Journal of Molecular Liquids 232 (2017) 6293

Contents lists available at ScienceDirect

Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Review

Cellulose based grafted biosorbents - Journey from lignocellulose

biomass to toxic metal ions sorption applications - A review
Rajesh Kumar a,b,, Rajeev Kr. Sharma c,, Anirudh P. Singh a
a
I.K. Gujral Punjab Technical University, Kapurthala-Jalandhar Highway, Kapurthala, Punjab 144601, India
b
PG Department of Chemistry, Jagdish Chandra Dayanand Anglo Vedic (JCDAV) College, Dasuya, Punjab 144205, India
c
PG Department of Chemistry, Dayanand Anglo Vedic (DAV) College, Jalandhar, Punjab 144008, India

a r t i c l e i n f o a b s t r a c t

Article history: In the recent past, renewable biobased natural polymers have been explored for their variety of potential appli-
Received 8 December 2016 cations. Among the various biorenewable polymers, cellulose with ingrained robust characteristics such as biode-
Accepted 13 February 2017 gradability, nontoxicity, durability, availability, thermal and mechanical stability etc., is extensively studied. These
Available online 16 February 2017
properties can further be improved by different modication techniques, among which the grafting is considered
to be the most inuencive one. In this comprehensive review article, the general chemistry of the cellulose, dif-
Keywords:
Cellulose-graft-biosorbents
ferent biological, chemical, physical, physio-chemical extraction techniques for its extraction from lignocellulosic
Pre-treatment biomass, purication and bleaching techniques for extracted cellulose, methods of cellulose grafting, mechanism
Free radical grafting of free radical grafting initiated by a variety of chemical initiators, are reviewed. Further, recent developments in
Metal ion sorption the eld of metal ion sorption applications of grafted cellulosic copolymers, related factors affecting the metal ion
Adsorption isotherms sorption efciencies of these cellulosic biosorbents such as extent of grafting, contact time, temperature, pH, in-
Kinetic models terference of other metal ions, metal ion concentration, biosorbent dose, ionic strength of solution etc. are also
reviewed. Various adsorption isotherms models-Langmuir, Freundlich, Temkin, DubininRaduskevich and
RedlichPeterson; adsorption kinetic models-pseudo-rst-order, pseudo-second-order, and intra-particle-diffu-
sion models, useful for studying and evaluating the different sorption parameters, mechanism, and rate of sorp-
tion of toxic and hazardous heavy metal ions, are also summarized. In the last part of the review, adsorption
thermodynamics, desorption and regeneration studies for the grafted cellulosic biosorbents are also reviewed.
2017 Elsevier B.V. All rights reserved.

Abbreviations: AA, acrylic acid; AAm, acrylamide; AASO3H, 2-acrylamido-2-methylpropane sulfonic acid; AN, acrylonitrile; APBS, amidoximated polymerized banana stem; APS,
ammonium persulfate; ARP, ammonia recycle percolation; ATPR, atom transfer radical polymerization; ATR-FTIR, attenuated total reectance-fourier transform infrared spectroscopy;
BPO, benzoyl peroxide; CA, cellulose acetate; CA-g-AA-co-AAm, cellulose acetate-graft-acrylic acid-co-acrylamide; CAN, ceric ammonium nitrate; Cell-g-AA, cellulose-graft-acrylic acid;
Cell-g-GMA, cellulose-graft-glycidyl methacrylate; Cell-g-GMA-co-AA, cellulose-graft-glycidyl methacrylate-co-acrylic acid; Cell-g-GMA-I, cellulose-graft-glycidyl methacrylate-imidazole;
Cell-g-HEMA, cellulose-graft-hydroxyethyl methacrylate; Cell-g-HEMA-co-AA, cellulose-graft-hydroxyethyl methacrylate-co-acrylic acid; Cell-g-HEMA-co-AAm, cellulose-graft-
hydroxyethyl methacrylate-co-acrylamide; Cell-g-HEMA-co-AN, cellulose-graft-hydroxyethyl methacrylate-co-acrylonitrile; Cell-g-p(AA), cellulose-graft-polyacrylic acid; Cell-g-p(AA
AASO3H-NMBA), cellulose-graft-polyacrylic acid copolymer 2-acrylamido-2-methylpropane sulfonic acid crosslinked with N,N-methylene bisacrylamide; Cell-g-p(AAm), cellulose-
graft-polyacrylamide; Cell-g-p(AANMBA), cellulose-graft-polyacrylic acid crosslinked with N,N-Methylene bisacrylamide; Cell-g-p(AASO3H-NMBA), cellulose-graft-2-Acrylamido-2-
methylpropane sulfonic acid crosslinked with N,N-Methylene bisacrylamide; Cell-g-p(AN), cellulose-graft-polyacrylonitrile; Cell-g-p(EA), cellulose-graft-poly(ethylacrylate); Cell-g-p(EMA),
cellulose-graft-poly(ethyl methacrylate); Cell-g-p(GMA-co-AAm), cellulose-graft-glycidyl methacrylate-co-acrylamide; Cell-g-p(GMA-co-AN), cellulose-graft-glycidyl methacrylate-co-acryloni-
trile; Cell-g-p(MA), cellulose-graft-polymethylacrylate; Cell-g-p(MAN), cellulosegraft-polymethacrylonitrile; Cell-g-p(NIPAM), cellulose-graft-poly(N-isopropylacrylamide); Cell-g-PGMA-PEI,
cellulose-graft-polyglycidyl methacrylate-poly(ethylene imine); Cell-g-PMA-HZ, hydrazinolyzed cellulose-graft-polymethylacrylate; CMC, carboxymethylcellulose; CPADB, 4-cyano-4-
(phenylcarbonothioylthio) pentanoic acid; CRP, controlled radical polymerization; DBI, direct borohydride injection; DMAE-BC, methacryloxylethylbenzyldimethyl ammonium chloride;
DTAC, dodecyltrimethylammonium chloride; ECF, elemental chlorine free; EDTA, ethylene diamine tetraacetic acid; EGDMA, ethylene glycol dimethacrylate; EMA, ethyl methacrylate; GE,
grafting efciency; GMA, glycidyl methacrylate; GOx, glucose oxidase; GP, grafting percentage; HEC, hydroxyethylcellulose; HEMA, 2-hydroxyethyl methacrylate; HPMC, hydroxypropyl meth-
ylcellulose; KPS, potassium persulfate; LCESI/MS, liquid chromatography-electrospray ionization-tandem mass spectrometry; LHW, liquid hot water; Lignocell-g-p(AA), linocellulose-graft-
polyacrylic acid; LMA, lauryl methacrylate; MA, methyl acrylate; MAA, methacrylic acid; MAc, maleic acid; MAN, methacrylonitrile; MMA, methylmethacrylate; NIPAM, N-isopropyl acrylamide;
NMBA, N,N-Methylene bisacrylamide; NMP, nitroxide-mediated polymerization; p(AN)-co-p(MAA), poly(acrylonitrile-co-methacrylic acid); p(AN-co-MAA)-g-cell, poly(acrylonitrile-co-
methacrylicacid)-graft-cellulose; p(GMA)-g-Cell, poly(glycidyl methacrylate)-graft-cellulose; p(LA)-co-p(GMA), polylactide co-polyglycidyl methacrylate; p(MAA-co-MAc), poly(methacylic
acid-co-maleic acid); p(MAA-co-NIPAAM-co-EGDMA)@CS, poly(methyl acrylic acid-co-N-isopropylacrylamide-co-ethyleneglycol dimethacrylate) @ cellulose succinate; PDMAEMA, poly [2-
(dimethylamino)ethyl methacrylate]; PMAAC, polymethacrylic acid-graft-cellulose; PMMA, poly (Methylmethacrylate); RAFT, reversible addition fragmentation chain transfer; ROP, ring-open-
ing polymerization; ROS, reactive oxygenated species; SCF, supercritical uid; SET-LRP, single electron transfer-living radical polymerization; SLS, sodium lauryl sulfate; TCF, total chlorine free;
THF, tetrahydrofuran; VA, vinyl acetate.
Correspondence to: (R. Kumar) PG Department of Chemistry, Jagdish Chandra Dayanand Anglo Vedic (JCDAV) College, Dasuya, Punjab 144205, India.
Corresponding author.
E-mail addresses: rk.ash2k7@gmail.com (R. Kumar), rksharma_75@yahoo.co.in (R.K. Sharma).

http://dx.doi.org/10.1016/j.molliq.2017.02.050
0167-7322/ 2017 Elsevier B.V. All rights reserved.
 R. Kumar et al. / Journal of Molecular Liquids 232 (2017) 6293 63

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
2. General chemistry and different allomorphs of cellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
3. Pre-treatment techniques for the extraction of cellulose from lignocellulosic biomass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
3.1. Biological pre-treatments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
3.2. Chemical pre-treatments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
3.2.1. Acid pre-treatments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
3.2.2. Alkaline pre-treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
3.2.3. Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
3.2.4. Use of ionic solvents as greener solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
3.2.5. Organo-solvation or solvent extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
3.3. Physical pre-treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
3.3.1. Pyrolysis and torrefaction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
3.3.2. Mechanical comminution. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
3.3.3. Sonication. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
3.3.4. Irradiations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
3.3.5. LHW pre-treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
3.3.6. Pulsed-electric-eld . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
3.3.7. Extrusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
3.4. Physico-chemical pre-treatments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
3.4.1. Steam explosion/auto-hydrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
3.4.2. SCF pre-treatment\\CO2 explosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
3.4.3. AFEX . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
3.4.4. ARP . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
4. Cellulose purication and bleaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
4.1. Chlorinated bleaching agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
4.2. Oxygenated bleaching agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
4.3. Enzymatic bleaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
4.4. Fungal bleaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
4.5. DBI bleaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
5. Different techniques and methods of cellulose grafting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
6. Mechanisms of free radical grafting initiated by chemicals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
6.1. Free radical polymerization initiated by Ce+ 4 ions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
6.2. Free radical polymerization initiated by persulfates (S2O 2
8 ) ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
6.3. Free radical polymerization initiated by Fe2 +H2O2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
6.4. Free radical polymerization initiated by BPO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
6.5. Free radical polymerization initiated by potassium permanganate (KMnO4) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
6.6. Free radical polymerization initiated by AIBN . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
7. Metal ion sorption applications of cellulose grafted copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
7.1. Factors affecting the sorption capacity of grafted cellulosic bio-sorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
7.1.1. Effect of extent of grafting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
7.1.2. Effect of contact time. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
7.1.3. Effect of temperature. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
7.1.4. Effect of pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
7.1.5. Interference of other metal ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
7.1.6. Effect of metal ion concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
7.1.7. Effect of biosorbent dose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
7.1.8. Effect of ionic strength . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
7.2. Adsorption isotherms. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
7.2.1. Langmuir adsorption isotherm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
7.2.2. Freundlich adsorption isotherm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
7.2.3. Temkin adsorption isotherm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
7.2.4. DubininRaduskevich adsorption isotherm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
7.2.5. RedlichPeterson adsorption isotherm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
7.3. Adsorption kinetics. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
7.3.1. Pseudo-rst-order model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
7.3.2. Pseudo-second-order model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
7.3.3. Intra-particle-diffusion model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
7.4. Adsorption thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
7.5. Desorption and regeneration studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
8. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
9. Future scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
Funding sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
64 R. Kumar et al. / Journal of Molecular Liquids 232 (2017) 6293
1. Introduction
Biobased natural polymers are of great interest to the research fra-
ternity for their potential applications and the nature has provided a
vast variety of such materials. However, the major fraction of these eco-
nomic and eco-friendly biomaterials remain un-utilized and is usually
allowed to decompose naturally or articially, leading to the environ-
mental pollution related issues. Every year tons of agricultural waste
material is produced globally. But it is a common practice of burning ag-
ricultural waste material which directly increases the CO2 and particu-
late matter contents of the air, thereby resulting in global warming, a
key concern of every nation, presently. A number of policies and agree-
ments are made internationally to solve the environmental issues, par-
ticularly related to global warming. The agricultural waste biomass
constitutes cellulose, hemicellulose, lignin, extractives, proteins, oils,
waxes, starch etc. with active functional groups like alcohols, phenols,
carboxylic acids, carbonyl, and ether [13]. Owing to the presence of ac-
tive functional groups, these biomaterials can be modied for better and
versatile low-cost applications. Among the various constituents of the
biomaterials, cellulose is extensively used biopolymer for making
paper, paperboard, cellophane membranes, fabrics, water-soluble adhe-
sives, and binders etc. [46]. In addition to these common traditional ap-
plications, this biopolymer can also be used directly or in modied or
grafted form for the sorption of many heavy metal ions [79], adsorp-
tion of toxic and harmful dye from water [1012], in controlled drug de-
livery [13,14], as a renewable source of biofuels [15,16], in enzyme
immobilization [1719], Li-ion battery modications [2023] and as a
support material for the metallic catalyst [24,25]. The cellulose content
of cotton bers, hardwood stems, softwood stems, rice and wheat
straw are 9598%, 4055%, 4550%, and 3545%, respectively.
Herein, cellulose chemistry with special reference to its allomorphic
forms, pre-treatment techniques for extraction of cellulose from ligno-
cellulosic biomass and mechanism of free radical grafting of different
monomers onto cellulose being initiated by a variety of chemical initia-
tors are reviewed. Various factors affecting the metal ion sorption ef-
ciencies of grafted cellulose biosorbents, adsorption isotherms and
kinetic models for studying the different sorption parameters, adsorp-
tion thermodynamics, desorption and regeneration studies for the
grafted cellulosic biosorbents are reviewed.
Fig. 1. (a) Linear structure of cellulose showing three hydroxyl (OH) groups situated at C2, C3 and C6 atoms of each -D-glucopyranose unit and (b) Composite structure of lignocellulosic
biomass with amorphous and crystalline regions.
2. General chemistry and different allomorphs of cellulose
Cellulose, hemicellulose-a low molecular weight cellulose like struc-
ture and lignin-an aromatic non-saccharide polymer are the main con-
stituents of the plant cell wall. Cellulose is condensed, chiral,
biodegradable, water insoluble, tasteless and odorless linear polymer
of -D- anhydroglucopyranose units, linked through covalent C1C4 -
glycosidic linkages [26]. Methylation, nitration, and acetylation give
tri-substituted cellulose, suggesting that each unit of -D-glucopyranose
contains three hydroxyl (\\OH) groups situated at C2, C3, and C6 atoms.
Acetylation followed by hydrolysis gives cellobiose octa-acetate [27].
Hydrolysis of cellulose under milder conditions results in the formation
of cellobiose and other derivatives conrming the fact that all the -D-
glucopyranose units are connected through C1C4 -glycosidic linkages
(Fig. 1(a)). As a result of this linkage, the terminals of the cellulose chain
are chemically different, one end being polar and reducing in nature
with free C1 anomeric atom and the other one with non-reducing C4
atom of -D-glucopyranose units. The distribution of the -D-
glucopyranose units is not uniform throughout the length of the cellu-
lose microbril [26,27]. It contains closely and regularly packed crystal-
line regions along with loosely and randomly packed amorphous
regions [28] (Fig. 1(b)).
During the biosynthesis of cellulose, chains of varying lengths are
formed. An individual cellulose chain may contain one or more highly
ordered crystalline regions. It has been reported that it is the extent of
hydrogen bonding that decides the chemical reactivity of the different
cellulosic regions [29]. This extent of intramolecular and intermolecular
hydrogen bonding is low for randomly ordered amorphous regions as
compared to highly ordered crystalline regions. Different chemicals
can easily penetrate into the amorphous regions of cellulose, making
them more susceptible for reactions, while the crystalline regions re-
mains un-attacked [2931]. Additionally, amorphous regions can easily
absorb water and become more soft and exible [32]. As a result, under
harsh pre-treatment conditions, the amorphous regions are easily hy-
drolyzed, resulting in the formation of nanocrystalline and nano-
brillated cellulose [32,33].
Naturally, cellulose can be randomly formed into amorphous and
crystalline structure with different ratio in grassy and woody plants.
The general formula of cellulose is (C6H10O5)n where n is the number
 R. Kumar et al. / Journal of Molecular Liquids 232 (2017) 6293
repeating monomeric -D-glucopyranose units and the value of n dif-
fers from source to source. Wood pulp contains 3001700 units, cotton
bers and bacterial cellulose 80010,000 units, agro waste materials
such as rice husk and straw, wheat husk contain 60007000 units.
Due to the presence of equatorial conformations of the -D-
glucopyranose units and electronegative Oatoms and OH groups,
different cellulose chains are held together by strong inter as well as
intramolecular hydrogen bonding [34,35]. These intermolecular
dipole-dipole interactions are responsible for the formation of micro-
brils with physical and chemical stabilities along with high tensile
strength. Location of these hydrogen bonds is very crucial and decides
the nature and type of various crystalline forms of the cellulose [26,27,
34,36]. The basic and most common form of cellulose are native cellu-
lose I, with two different crystalline forms I-preferentially produced
by bacteria and algae and I-mainly present in plant cell walls [37].
Cellulose I comprises a single chain with slightly different conrma-
tions between alternating -D-glucopyranose units and triclinic unit
cells with a crystal density of 1.595 g cm3 while cellulose I consists
of double chains arranged in alternating sheets with a monoclinic unit
cell having crystal density of 1.615 gcm3 [36]. These two allomorphic
forms, with different compositions depending upon the source, are
present together within the same cellulose sheets as well as along a
given microbrils. The cellulose I chains are organized in a sheet-like
an arrangement with parallel-up fashion. The chains in cellulose I
and I are capable of forming intramolecular C2\\OH O\\C6,
C3\\OH O5 as well as intermolecular C6\\OH O\\C3 hydrogen
bonding but to different extents and strengths. The \\OH group at C6
of a cellulose chain are thus partly involved in intramolecular hydrogen
bonding with the O-atom of C2 atom of the adjacent -D-glucopyranose
unit and partly in intermolecular hydrogen bonding with an O-atom of
C3 atom of adjacent cellulose chain belonging to the same sheet. Further,
in the rst cellulose chain of every sheet, C2\\OHO\\C6 hydrogen bond
is reported to be short than the C3\\OHO5 hydrogen bond while in the
center chains the reverse is generally observed [36]. (See Fig. 2.)
It is reported that cellulose I form is metastable and can be easily
converted through annealing into cellulose I form [38]. Sheets of both
cellulose I and cellulose I forms are devoid of inter-sheet hydrogen
bonding and are held together by either hydrophobic interactions or
weak C\\H O van der Waals interactions [39,40]. It is interesting to
mention that all the \\OH groups present at C2 and C3 atoms are
equatorially bonded to a -D-glucopyranose units, while the OH
groups of \\CH2 moiety are axially bonded to a -D-glucopyranose
units (Fig. 3). As a result, the hydrophilic face is parallel to the glucopy-
ranose ring plane and hydrophobic face being perpendicular to it. Due to
these faces of opposite nature, cellulose is amphiphilic in character.
These intra, as well as inter-sheet non-covalent interactions, are
Fig. 2. Inter (- - - - - -) and intramolecular (- - - - - -) hydrogen bonding between cellulose I chains.
65
responsible for the formation of cellulose chains aggregate of various
ultra-structures, insoluble in common solvents [41].
In addition, to thermodynamically stable cellulose I form, other less
thermodynamic stable allomorphs of cellulose are cellulose II, III, and
IV [4244]. Cellulose II is more reactive than cellulose I and is used in
making cellophane membranes, rayon bers, natural yarns and fabrics
[45]. Through either regeneration or mercerization, cellulose I can be ir-
reversibly converted to stable cellulose II crystalline form. In regenera-
tion, a solution of cellulose I is prepared in a suitable solvent
subsequently followed by coagulation and recrystallization. Another
method of regeneration is the synthesis of an intermediate derivative
of the cellulose I. On the other hand in mercerization, cellulose I is treat-
ed with concentrated NaOH solution to induce intra-crystalline swelling
[46,47]. Mercerization also helps in removing hemicellulose and lignin,
an important requisite of cellulose microbrils extraction from a natural
source [48]. The regenerated and mercerized cellulose consists of P21
monoclinic unit cell comprising antiparallel chains [40]. Cellulose II
form, prepared through either regeneration or mercerization, however,
differ from each other in the conformational stereochemistry of the
CH2OH groups in the center chains. During this conversion, cellulose I
microbrils are completely disrupted leading to random orientations.
According to a report, complete transformation of parallel chain crystal
structure of cellulose I to the anti-parallel arrangement of chains in cel-
lulose II [49]. It was also found that the dominating C2\\OHO\\C6 and
C2\\OHO5 intramolecular hydrogen bonding in cellulose I is super-
seded by C6\\OHOC6, C2\\OHO\\C2 and C2\\OHO\\C6 inter-
molecular hydrogen bonding in cellulose II (Fig. 4) [50].
The two forms of Cellulose III, i.e. III1 and III2 can be obtained through
the liquid NH3 treatment of cellulose I and cellulose II, respectively [51].
Although under mild heat treatment conditions these forms can be eas-
ily reverted to their parent forms. The cellulose I and III1 forms differ
only in the intra-sheet shifts against each other. The unit cells of the
III1 and III2 structures are same except for the meridional reections
and parallel-antiparallel arrangements [52,53]. On treatment with glyc-
erol at 260 C temperature for 20 min cellulose III1 and III2 forms are
converted to cellulose IV1 and IV2 forms, respectively. The structure of
cellulose IV1 correlates very well to that of cellulose I form. Since,
cellulose III1 and III 2 forms have parallel and antiparallel arrange-
ments, respectively, the resulting IV1 and IV2 forms have the similar
features. Cellulose IV1 is considered as a mixture of cellulose I and IV2
forms.
In conclusion, the different forms of cellulose may be classied main-
ly into two categories based on chain orientations and polarities; one
containing parallel chains (I, I, III1, and IV1) and the other one with
anti-parallel chains (II and IV2). The anti-parallel form of cellulose III2
is, however, doubtful and not conrmed yet [51].
66 R. Kumar et al. / Journal of Molecular Liquids 232 (2017) 6293
Fig. 3. Representation of hydrophilic and hydrophobic faces of the cellulose sheets.
3. Pre-treatment techniques for the extraction of cellulose from lig-
nocellulosic biomass
The main constituents of the lignocellulosic biomass i.e. lignin, cellu-
lose, and hemicelluloses are held together by various types of inter-
polymer interactions that include, ethereal, ester, C\\C covalent and hy-
drogen bonds. These interactions, between the individual components
of lignocellulose are responsible for the complex nature of lignocellulos-
ic biomass. Lignin-polysaccharide complex primarily is composed of
ethereal and ester linkages [54]. Lignin through these inter-polymer
interactions is bounded to hemicelluloses as well as to cellulose.
Intra-ester linkage is also expected to occur within the hemicellulose
polymers. There is presence of intermolecular H-bonding between
hemicellulose and cellulose, though weak owing to the lack of primary
alcohol functional group external to the pyranoside rings in hemicellu-
lose [55]. Intermolecular H-bonding between hemicellulose and cellu-
lose polymers has also been reported due to the orientation of these
two polymers oriented parallel to each other. The cleavage of the
ether bond separates of lignin from polysaccharides matrix (cellulose
and hemicellulose) as well as the breakdown of glycosidic bonds-a
type of ether bond between glucopyranose units of polysaccharides.
The very high stability and the strength of lignin could be attributed to
the presence of strong intra-polymer C\\C covalent and ethereal
bonds. The former about 30% and later about 70% of the total bonds
are predicted to appear between either two aryl or two allyl or between
aryl and allyl carbon atoms [55,56].
Pre-treatment of the lignocellulosic biomass to get cellulose in terms
of quantity and quality is the prerequisite and involve the disruption of
the carbohydrate-lignin shield-a natural resistant which stabilizes it and
prevents the easy degradation of the lignocellulosic materials from the
Fig. 4. Inter () and intramolecular () hydrogen bonding between antiparallel cellulose II chains.
enzymes. Because of different physio-chemical properties of different
lignocellulosic biomasses, it is of utmost important to select a suitable
pre-treatment technique [57,58]. Before applying a pre-treatment, the
parameters like the degree of polymerization of cellulose, cellulose crys-
tallinity, surface area, and porosity etc. should be addressed as these are
few important issues related to biological pre-treatments. Broadly, the
various types and subtypes of the pre-treatment techniques are repre-
sented in Scheme 1.
3.1. Biological pre-treatments
The pre-treatment of lignocellulosic biomass is extremely essential
to prepare pure and highly crystalline cellulose for advanced applica-
tions. Both lignin and hemicellulose act as physical barriers for the
easy access to cellulose. Biological pre-treatment of the lignocellulosic
biomass, to remove lignin and hemicelluloses, provides a milder and al-
ternate environment friendly approach as compared to chemical,
physico-chemical and physical pre-treatments. The later techniques in-
volve the use of highly harsh, corrosive and toxic chemicals and drastic
conditions. Additionally, biological pre-treatment technique is more
economical over other delignication processes but suffers from a
major drawback of very low degradation rate and efciency.
Microorganisms such as wood rotting fungi, actinomycetes and bac-
teria are capable of attacking, de-polymerizing and disintegrating the
lignin contents of the biomass for easy and low-cost accessibility to cel-
lulose from lignocellulosic biomass through the action of lignin-
degrading enzymes [59].
Minimizing the cellulose loss during biological pre-treatments due
to fungal metabolism should be the pre-requisite. Among the white,
brown and soft wood fungi, the foremost is employed for
 R. Kumar et al. / Journal of Molecular Liquids 232 (2017) 6293
Scheme 1. Different lignocellulosic biomass pre-treatment techniques.
Reprinted and modied from Ref. [57]. Copyright 2016, Royal Society of Chemistry.
delignication, while brown-rotting fungi are effective against the deg-
radation of cellulose and hemicelluloses as compared to the lignin.
Phenoloxidases (laccases-copper containing enzymes) and peroxidases
are the two major categories of extracellular anaerobic lignin hydrolyz-
ing enzymes released by these wood rotting fungi. The enhancement of
the otherwise low degradation efciencies of the laccases to degrade
lignocelluloses in the presence of phenolic compounds like 3-
hydroxyanthranilic acid, 2,2p-azino-bis (3-ethylthiazoline-6-sulfonate)
redox mediators are reported [60]. On the other hand, the additives like
copper, manganese, linoleic acid, dirhamnolipid, and veratryl alcohol in-
crease the rate of the production of peroxidase enzyme by the fungi.
These additives initiate and accelerate the production of ROS such as
O
2 , HO , H2O2, which damage the lignocellulosic mass making it
more porous for better enzymatic action [61]. Two families of peroxi-
dases are further considered as effective delignifying enzymes: lignin
peroxidase (LiP) and manganese peroxidase (MnP) [62]. Both these en-
zymes are hematic glycoprotein and require H2O2 as oxidant. LiP prefer-
entially degrades non-phenolic lignin units, while MnP is associated
with the degradation of both phenolic as well as non-phenolic lignin
units, assisted through lipid peroxidation. Additionally, some other en-
zymes such as cellulase, xylanase, glyoxidase and aryl alcohol oxidase
are also reported to be produced during the fungal pre-treatments
[63]. For maximum degradation of the lignin from the native complex
biomass, very high dose of the enzyme is required [64].
Recently, it was formulated that the phenolic oxidation of the phenol
rings to phenoxy radicals through MnP involves the initial oxidation of
Mn2+ to Mn3+ [65].
Many white-rot fungi belonging to saprophytic and ligninolytic ba-
sidiomycetes group are reported in the literature for the delignication
process. Some white-rot fungi, with a high degree of delignication, are
Phanerochaete chrysosporium [63,66], Punctularia sp.TUFC20056 [67],
Pycnoporus cinnabarinus [68], Phlebia sp. [69], Pleurotus ostreatus,
Pleurotus pulmonarius [70], Echinodontium taxodii [71], Irpex lacteus
[72,73], and Pycnoporus sanguineus [74]. However, signicant
delignication was reported for Ceriporiopsis subvermispora [75], Phlebia
brevispora, P. oridensis, P. radiata [76], Echinodontium taxodii,
Gonoderma sp. [77], Oxysporus sp. [78], Pleurotus sajor-caju [79]. Most
commonly reported soft rot fungi used for rapid bio-delignication are
Paecilomyces sp. [80] and Cadophora sp. [81].
Bacteria, in contrast to wood rot fungi are less effective toward
delignication as the quantity of ligninolytic enzymes (extracellular
xylanases) produced by them is very low. Bacillus sp.AS3 [58], Bacillus
circulans and Sphingomonas paucimobilis [82], Cellulomonas and
Zymomonas sp. [83] have been reported for the biodegradation of ligno-
cellulosic biomass up to 50%. However, the addition of other enzymes
67
like manganese peroxidase, pectinase or -L-arabinofuranosidase ex-
hibits a synergism [84]. Actinomycetes are species with multicellular
lament-like structures and are capable of producing extracellular
peroxidaseLiP enzyme similar to white-rot and brown-rot fungi. Ther-
mophilic actinomycetes like Nocardia, Streptomyces,
Thermoactinomyces, and Micromonospora present in compost, through
their primary metabolic activities, degrade lignin with a high level of ni-
trogen contents in contrast to white-rot fungi [85].
The critical parameters, which affect the biological pre-treatment in-
clude the nature and the composition of the lignocellulosic biomass,
type of microorganism used for delignication, incubation temperature
and time, pH, inoculums concentration, moisture content and aeration
rate etc. [64].
3.2. Chemical pre-treatments
In contrast to biological pre-treatment techniques, chemical pre-
treatments of the lignocellulosic biomasses offer fast and convenient
methods with a high level of separation of components. Some of the
chemical pre-treatments are briey described in this section.
3.2.1. Acid pre-treatments
Acid pre-treatments of the lignocellulosic biomass can be carried out
using dilute as well as concentrated mineral acids although some critical
issues such as hazardous, toxic, highly corrosive nature are associated
with concentrated acids. The material of the reactors is also damaged
due to the corrosiveness of the mineral acids. Moreover, if the high qual-
ity of cellulose with a high degree of polymerization is required for the
formation of cellulose co-grafted polymers for organic dye and metal
ion sorption applications, concentrated acids can't be a good choice as
they cause the degradation of the cellulosic materials. However, if cellu-
lose and hemicelluloses are to be subjected to further enzymatic hydro-
lysis for the production of biofuels, concentrated acids are advantageous
in terms of the exibility of feedstock choice, hydrolysis of the con-
cerned biopolymers to fermentable sugar at even milder temperature
conditions. Through acid pre-treatments, hemicelluloses and to some
extent cellulose, only at the amorphous regions can be hydrolyzed but
this method of pre-treatment is quite ineffective for lignin hydrolysis.
As a result, cellulose brils with increase crystallinity index are obtained
after acid pre-treatment [86,87]. Dilute H2SO4, below 4 wt% is widely
and commonly used for a wide variety of biomass pre-treatments. It
can completely hydrolyze hemicellulose to monosaccharide xylose by
the hydrolysis of xylosidic bonds along with the cleavage of acetyl
ester linkages, which is being nally converted into furfural [88,89]. Al-
ternatively, HCl [90], H3PO4 [91], HNO3 [92], and organic acids like
68 R. Kumar et al. / Journal of Molecular Liquids 232 (2017) 6293
maleic acid and oxalic acids [93] are also under traditions for acid hydro-
lysis. Heteropolyacids (HPAs) like H5BW12O40 are also some emerging
strong homogeneous acid catalysts due to the presence of external, neg-
atively charged oxygen atoms with a very strong hydrogen-bond
accepting abilities responsible for lignocellulosic biomass composition
of rice plant straw, oil palm empty fruit bunch ber, and Japanese
cedar sawdust dissolution even at low temperature of 60 C [94]. Micro-
wave assisted acid pre-treatments are also reported to reduce the oper-
ating time, signicantly. Chen et al. [95] optimized microwave assisted
lignocellulosic structural disruption of sugarcane bagasse to 190 C for
5 min in the presence of acids. Thus, the concentration of the acid,
acid-biomass ratio, degradation temperature, and time are the most
common factors that affect the rate of acid pre-treatment process for lig-
nocellulosic biomasses.
3.2.2. Alkaline pre-treatment
Alkaline pre-treatments result in better delignication as compared
to acid pre-treatments. Under alkaline pre-treatments, ester linkages
and glycosidic side chains of the lignin are cleaved at specied condi-
tions of temperatures and pressures leading to its disruption [96].
NaOH, KOH, Ca(OH)2, Na2CO3 and NH3 are the common alkalies
employed for this process. In addition to delignication, these solutions
also result in partial hydrolysis of hemicelluloses, cellulose swelling, cel-
lulose decrystallization, lower degree polymerization of cellulose, in-
creased internal area and porosity of the polysaccharides- essentially
required for adsorption application, and signicant cleavage of linkages
holding lignin and polysaccharides, making cellulose more assessable in
the subsequent steps [97]. In order to reduce the extent of hydrolysis
and loss of hemicelluloses and cellulose, NH3 is a suitable candidate as
compared to other alkaline reagents [98]. Alkaline pre-treatments are
preferentially applicable for biomasses with low lignin contents (hard-
wood, herbaceous crops, and agricultural residues), in comparison to
softwood with a high level of lignin content. Lower temperature and
pressure conditions, less sugar degradation, easy recovery and removal
of alkalies at the end of the pre-treatment process are some signicant
advantages of these pre-treatment processes. However, longer pre-
treatment times and requirement of highly concentrated alkaline solu-
tions are some of the major drawbacks. Another approach to improve
the efciency of the alkaline pre-treatments is the use of alkaline solu-
tions in the presence of microwaves and radiofrequency wave radia-
tions. The effectiveness of microwavebased alkali pre-treatment as
compared to bare alkaline pre-treatments on the delignication of
switchgrass and coastal bermuda grass is also reported [99].
3.2.3. Oxidation
A variety of oxidizing agents such as H2O2, O2, O3, and even air can be
used as delignication agents of lignocellulosic biomass. Delignication
using ozone is generally referred to as ozonolysis. Ozone is very strong,
water soluble oxidant and preferentially attacks the conjugated C _C
bonds, olenic, aromatic, and phenolic compounds [100]. Lignin with
these structural properties is thus, most susceptible for ozonolysis lead-
ing to its disruption with the release of low molecular weight degrada-
tion products like organic acids, formic and acetic acids etc. [101]. In
contrary, the polysaccharides- hemicellulose and cellulose remain unaf-
fected and are hardly destroyed. These observations have been practi-
cally veried through potential techniques.
Kdr et al. [102] through ATR-FTIR, studied the chemical changes
occurred on the surface of ozone pretreated wheat straws. The ATR-
FTIR spectrum clearly indicated a decrease in the intensity of peaks re-
lated to aromatic rings of lignin. Initial electrophilic attack of the O3 on
the aromatic rings of the lignin is followed by hydroxylation, further fa-
voring electrophilic substitution reactions. Subsequent dipolar 1,3-cy-
cloaddition cleaves the olenic double bonds [103].
Ozonolytic pre-treatment of the different types of lignocellulosic
materials is signicantly affected by the moisture contents, the particle
size of the biomass, ozone concentration, type of biomass and air/ozone
ow rate [104]. The moisture content is considered to be critical in pre-
treatment process as ozone is highly soluble in water and initiates the
homogeneous reaction with the lignocellulosic biomass [105]. No pro-
duction of toxic degradation products, high level of delignication,
milder working conditions and most importantly, the minimized envi-
ronmental pollution are some of the major advantages of ozonolytic
pre-treatments. However, the requirement of a large amount of ozone,
make this process practically less applicable economically for industrial
applications.
Another most commonly applied oxidation process is the wet oxida-
tion, which operates with either oxygen or air in the presence of water
at an elevated temperature of 150350 C and high pressure of 5
20 MPa [106]. Lignin decomposes to CO2, H2O, aldehydes, alcohols and
carboxylic acids- succinic acid, formic acid, and glycolic acid etc. during
wet oxidation [107]. Wet oxidation can effectively remove 5070% of
the lignin, substantial hydrolysis of hemicelluloses along with exposing
the crystalline structure of cellulose depending upon the nature of the
biomass [108]. In addition to above-explained oxidants, peracetic acid
(C2H4O3), SO3, and ClO2 can also be utilized to oxidize hemicellulose
and lignin under milder alkaline or neutral conditions [109].
3.2.4. Use of ionic solvents as greener solvents
Ionic solvents generally are comprised of a large organic cation and a
small inorganic anion. Due to the different molecular structures, very
weak forces of attraction exist between the oppositely charged ions
resulting liquid state for the salt with very low vapor pressure [110].
This differential polarity can cause the selective dissolution of lignin
from lignocellulosic biomass making cellulose accessibility much easier
even under ambient and acid/base free conditions. High dissolution ca-
pacity, low melting point and viscosity, non-toxicity, and high water
stability etc. are some of the prerequisites of a better ionic liquid [111].
The most commonly applied organic cations for lignocellulosic pre-
treatment of biomasses include [Cnmmim]+: 1-alkyl-2,3-dimethyl
imidazolium (n = number of carbons in the alkyl chain); [C4mPy]+:
1-butyl-3-methylpyridinium; [Bmim]+: 1-butyl-3-methylimidazolium;
[Ammim]+: 1-allyl-2,3-dimethylimidazolium; [Ammim]+: 1-allyl-3-
methylimidazolium; [Emim]+:1-ethyl-3-methylimidazolium; [Bu4P]+:
tetra butyl phosphonium, while the corresponding inorganic anions
may be Cl, Br, SCN, HCOO, HOCH2COO, NH2CH2COO,
CH3COO, C6H5COO etc. [112]. Among these ionic liquids, 1-butyl-3-
methylimidazolium-chloride (Bmim-Cl) is considered to be highly
toxic, corrosive, and hygroscopic in nature, while chloride based
[Amim]+ are highly viscous having reactive side chains [113]. In con-
trast, the phosphate and acetate based ionic liquids are thermally
more stability with very low viscosity and toxicity [114]. In spite of
the extensive research related to the delignication of the biomasses
using ionic liquids, the cost of production, regeneration cost and high
loading of the ionic liquids restrict their industrial and large-scale appli-
cations [87].
3.2.5. Organo-solvation or solvent extraction
Organic solvents, either in pure form or in the form of mixtures with
water of appropriate compositions, are efciently used for
delignication and to some extent hydrolysis of hemicelluloses from
the lignocellulosic biomass in organo-solvation or solvent extraction.
MeOH, EtOH, ethylene glycol, butanols, benzene, triethylene glycol, tet-
rahydrofuran, dimethyl sulfoxides, ethers, ethyl acetate and ketones etc.
[58,115] are most commonly used solvents for the purpose. Presumably,
the HO ions from alcohols attack the acid-ester bonds of lignocellulosic
along with ethereal linkages of lignin components [33]. Recently,
Luterbacher et al. [116] recovered lignin from corn stover using -
valerolactone (GVL) and water (80:20 by weight) mixture, as a solvent
at working temperature of 393 K for a pre-treatment time of 30 min in a
high-solids batch reactor. Inorganic acid- HCl, H2SO4, organic acids-
oxalic acid, acetylsalicylic acid, and salicylic acid and salts- MgCl2,
Fe2(SO4)3 etc. are generally used as a catalyst [117]. These acids
 R. Kumar et al. / Journal of Molecular Liquids 232 (2017) 6293
simultaneously can also result in pre-acidic hydrolysis of the lignin. It is
reported that hemicellulose is hydrolyzed into soluble mono and oligo-
saccharides, and acetic acid, while lignin is primarily hydrolyzed into
low molar mass components, soluble in organic solvents employed
[118]. High cost, both in terms of organic solvents as well as equipment
along with environmental issues related to volatile organic compounds
restrict the use of these organo-solvents. However, the associated ease
of recovery of volatile organic solvents via distillation makes this pro-
cess somewhat favorable.
3.3. Physical pre-treatment
Physical pre-treatments are generally employed prior to chemical
and biological pre-treatments. The size reduction of the lignocellulosic
biomass is an essential step for increasing accessible surface area and
porosity, reducing the degree of polymerization, and decreasing crystal-
linity of biomass. In this section, different types of physical pre-
treatment methods are discussed briey.
3.3.1. Pyrolysis and torrefaction
The heat treatment of the lignocellulosic biomass is referred to as py-
rolysis. During pyrolysis, the brous structure of biomass is destroyed
leading to improved hydrophobicity and increased stability. A low-
temperature pyrolysis (150250 C) produces less volatile products
slowly whereas, a high-temperature treatment (N300 C) results in
rapid decomposition of cellulose to volatile products along with the for-
mation of residual char as one of the product [58,119]. A modied form
of the pyrolytic method is the torrefaction, which involves the thermal
treatment of the biomass between 200 and 300 C under an inert atmo-
sphere. Torrefaction removes the moisture contents and low molecular
weight organic compounds from the biomass. According to Chen et al.
[120] the torrefaction temperature largely affects the properties of the
torreed biomass. A low torrefaction temperature of 240 C majorly af-
fects the hemicellulose contents in contrast to lignin and cellulose,
while at high torrefaction temperature of 275 C, there was a drastic im-
pact on the depletion of lignocellulosic materials. A high torrefaction
temperature forms biomass with low oxygen contents, high densica-
tion, and high carbon contents [121]. As hemicellulose is thermally
less stable as compared to cellulose, a high torrefaction temperature of
330 C, removes up to 85% of hemicellulose contents from the biomass
in the form of volatile compounds [122].
3.3.2. Mechanical comminution
The main motive of mechanical comminution is the reduction of
crystallinity, particle size, and degree of polymerization for the polysac-
charide contents of the lignocellulosic biomass. Mechanical comminu-
tion can be carried out through either individual or combined effects
of chipping, grinding and milling. Milling techniques such as two-roll,
ball, vibratory ball energy, colloid, hammer, and wet disk etc. are used
generally depending upon the type of the biomass material. Among
these milling techniques, vibratory ball milling is considered to be ad-
vantageous over other techniques [123].
3.3.3. Sonication
In order to have the better accessibility of the plant biomass mate-
rials, it is of utmost importance to increase the reactivity of these mate-
rials through disintegration and removal of the lignin contents along
with disruption of highly ordered crystalline cellulose. Sonochemical
treatment of the plant biomass is an alternate, efcient, economic and
eco-friendly tool. A number of recent studies have been carried out to
study the effect of ultrasonic waves on the lignocellulosic biomass for ef-
cient removal and dissolution of lignin and better action of the chem-
ical reagents on the biomass contents [124126]. Moreover, the effect of
ultrasonic waves, in processing wood in water is more pronounced than
in air. Sonic waves are passed through the medium as acoustic waves
that generate acoustic cavitations i.e. micro bubbles, which grow to an
69
optimum size and nally collapse violently. According to Kuijpers
et al. [127] the cavitation bubble can have temperatures as high as
20005000 K and pressures up to 1800 atm. These drastic conditions
are responsible for the hemolytic cleavage of the organic contents of
the biomass to generate free radicals. Hydroxyl radicals and hydrogen
peroxide are also generated in the cavitation process in the medium.
Hydroxyl radicals and hydrogen peroxide further result in the selective
degradation of the biomass contents particularly lignin (Eqs. (1)(3)).
Ultrasonication
H2 O HO
H
1


OH O
HH2 O2 2
H2 O2 HO
HO
3
It is important to mention here that, the molecular mass of the com-
pound also affects its degradation rate. The compounds with relatively
higher molecular weights like lignin are most susceptible to degrada-
tion. High molecular mass compounds move slowly in the acoustic cav-
itation as compared to lower molecular mass compounds and are thus
easily attacked by the free radical species through C\\C bond cleavage
[124]. The optimized conditions, however, vary from material to mate-
rial [128]. Ultrasonic irradiation of intensity 368 W/cm2 for a duration
of only 15 min were considered to be highly efcient for disruption of
different biomasses.
3.3.4. Irradiations
Exposure of the lignocellulosic biomass to irradiation such as -rays,
electron beams and microwaves degrades cellulose to more fragile -
bers with low molecular weight constituting oligosaccharides and cello-
biose. These radiations preferentially attack the glycosidic bonds of the
cellulose chains [129]. Irradiation based technologies offer alternate
pathways of reduced energy demand, easy, uniform and selective pro-
cessing of the biomass. Microwave irradiation can impose thermal as
well as non-thermal effects on the biomass. These effects further pro-
duce hot spots, which increase the collision frequency between the
molecules, and faster microwave assisted rotation of water dipoles
[130]. Thermal effects generate internal heat and explosion effects due
to the vibrations of the molecular polar bonds of the biomass and the
water molecules of the reaction medium. These explosion effects result
in the disruption of lignocellulose materials releasing acetic acid which
further provides acidic conditions for its auto-hydrolysis [131]. In the
case of non-thermal electron-beam irradiation method, the polar
bonds of the chemical moieties undergo vibrations under the inuence
of the continuously changing magnetic eld. These changes prompt the
disruption of the polar bonds resulting physicochemical changes in the
biomass. These high energy radiations, alter the specic surface area,
the degree of polymerization and crystallinity of cellulosic contents
along with accelerated hydrolysis of hemicellulose and partial degrada-
tion of lignin [96,132]. In order to better explore the advantages of these
radiation techniques, these can be combined with other chemical pre-
treatment methods involving acid/alkali pre-treatments of lignocellu-
losic biomass.
3.3.5. LHW pre-treatment
In this process, liquid hot water with temperature ranging from 150
to 250 C at high pressure is used to disintegrate the lignocellulosic bio-
mass. Depending upon the nature and the source of the biomass, the
treatment time can vary from few minutes to many hours. Lignocellu-
losic material is disrupted through complete hydrolysis of the hemicel-
lulose to oligosaccharides and lignin to corresponding phenol
constituents [133]. However, hydrolysis of cellulose is also reported in
some cases, though to negligible (410%) extent [89]. The LHW pre-
treatment is advantageous as it is chemical free, eco-friendly, less corro-
sive and no neutralization of the nal products is required. However,
higher energy demands, higher pressure conditions and continuous
70 R. Kumar et al. / Journal of Molecular Liquids 232 (2017) 6293
supply of a large amount of water makes it somewhat less applicable
[111].
3.3.6. Pulsed-electric-eld
The treatment of the lignocellulosic biomass with high-intensity
voltage results in cell membrane breakdown, mass permeability, more
bioavailability, mechanical ruptures and many other local structural
changes. Electric shock treatment time may vary from few nanoseconds
to microseconds. In addition to this, pulse rate, the nature of the biomass
and the intensity of the electric shock are some other important factors.
The process can be performed even at ambient conditions with very low
energy demands.
3.3.7. Extrusion
In order to bring about physicochemical changes such as debrilla-
tion, brillation, and shortening or reducing the degree of polymeriza-
tion, the biomass materials are generally subjected to heating, mixing,
and shearing in a specially designed apparatus called extruder and the
respective treatment process is called extrusion. Two types- single and
twin screw extruders are employed for biomass treatment. Depending
upon the nature of the biomass extruding process can be modied
through screw design, screw speed, extrusion temperature and even
through supplemented acid and/or alkaline treatments. Extrusion pre-
treatment is more advantageous over other pre-treatment methods in
terms of cost and convenient. Alkaline pre-treatments are preferred
over acidic treatments, as the former lead to better delignication
with a low degradation rate of polysaccharides. Further, acidic medium
leads to the corrosion of the extruder material [134].
3.4. Physico-chemical pre-treatments
3.4.1. Steam explosion/auto-hydrolysis
Treatment of the lignocellulosic biomass with high temperature and
pressure steam followed by the sudden release of pressure to reduce the
biomass material to small brils is referred to as steam explosion or
autohydrolysis. The rupturing of the materials occurs due to the
thermo-mechanical action of the steam. Major fractions of the hemicel-
lulose and lignin are solubilized and subsequently removed from the
biomass. However, fractional hydrolysis of cellulose to glucose is also re-
ported [135]. The optimized temperature and pressure for the steam ex-
plosion are typically 160260 C and 0.694.83 MPa, respectively. The
treatment lasts for few seconds to few minutes depending upon the na-
ture of the biomass [136]. At elevated temperature, water acts as acid
and results in the hydrolysis of the glycosidic linkages of the polysaccha-
ride components [137].
3.4.2. SCF pre-treatment\\CO2 explosion
SCF is a gaseous material but has liquid-like properties when com-
pressed above its critical temperature and pressure. In supercritical
stage, the material passes diffusivity and viscosity like that of gases
and density of liquids. These features favor the penetration of SCFs
deep into the lignocellulosic biomass [138]. Supercritical CO2 with a crit-
ical temperature of 31.4 C, the critical pressure of 7.4 MPa, and compa-
rable size to water molecules make it a potential candidate for biomass
pre-treatments. It is also reported that there is co-existence of the H2O-
rich liquid phase and CO2-rich supercritical phase. In combination with
water, CO2 forms carbonic acid (H2CO3) which on ionization lowers the
pH and increases the acidic character of the medium to facilitate the
fractional hydrolysis of hemicellulose as well as cellulose but the almost
complete removal of the lignin. The treatment method though is ef-
cient and clean but suffers from a major drawback of the requirement
of very high operating pressure [111].
3.4.3. AFEX
The lignocellulosic biomass with low lignin contents is pretreated
preferentially through AFEX method. In this method, the biomass is
subjected to high temperature (60100 C) and pressure treatment
with anhydrous liquid ammonia. After the treatment for a shorter dura-
tion, pressure is released which results in swelling of biomass, lignin
separation from cellulose, hydrolysis of hemicelluloses and partial
decrystallization of cellulose. It is important to mention that the no lig-
nin is removed from the biomass, however; the lignin-carbohydrate
bonding is disrupted [139]. The efciency of the treatment through
AFEX depends on upon the temperature, time of depressurization, and
ammonia and water loading and the number of treatments are given
to the biomass etc. Due to volatile nature of ammonia, the process is dif-
cult to handle but have the advantage of easy recovery of the ammonia
[111,118]
3.4.4. ARP
In order to remove lignin from biomass more efciently, the AFEX
method is modied and the modied version is called ARP pre-
treatment. In contrast to AFEX which uses liquid ammonia treatment
for a short duration at 60100 C, (the ARP process utilizes 515 wt%
aqueous ammonia at moderately high temperatures of 140210 C)
and for the longer duration [140]. Through ARP 7585% lignin is solubi-
lized, 5060% hemicellulose is hydrolyzed while cellulose contents re-
main almost unaffected [141]. Similar to AFEX process, high energy
demands and high ammonia loadings, are some of the major drawbacks
of the ARP process and should be solved to make the pre-treatment pro-
cess more economic and advantageous [111].
4. Cellulose purication and bleaching
After the successful extraction of cellulose from different types of lig-
nocellulosic materials via a suitable pre-treatment method, it is subject-
ed to purication and bleaching. Incomplete delignication of the
biomass materials imparts brown shade to the cellulosic components.
During chemical and physicochemical pre-treatment methods, new
chromophores are also generated from lignin and hemicellulose [142].
The main motif of the bleaching is thus to remove the non-degraded lig-
nin for better access to the polysaccharide components i.e. cellulose and
hemicelluloses. For metal ions sorption and other application, pure cel-
lulose acts as backbone for the synthesis of grafted copolymers. Hence,
high degree of purity and crystallinity of the cellulose is desired. Any
fraction of lignin or hemicellulose remained in the pre-treated cellulose
can be removed by the use of oxidizing chemicals. These chemicals not
only remove the last fractions of lignin, hemicellulose and other compo-
nents such as xylose, mannose, galactose, rhamnose and arabinose, but
also weaken the inter and intra-cellulosic interactions among the cellu-
lose bers thereby making it more accessible.
4.1. Chlorinated bleaching agents
The conjugated aromatic rings of the phenolic components of the
lignin are most susceptible to redox reactions mediated through the
strong oxidizing character of bleaching agents. Chlorine (Cl2) and chlo-
rinated compounds such as hypochlorites (ClO) chlorites (ClO 2 ),
Chlorine dioxide (ClO2) are traditionally used as strong bleaching agents
[143145]. Through electrophilic substitution reactions, H-atoms of the
aromatic rings of paracoumaryl, coniferyl, and sinapyl alcohols are re-
placed by chlorine atoms, whereas the side chains of these lignin mono-
mers are oxidized to carboxylic acid (\\COOH) groups. It is reported
that at pH = 7, Cl2 also results in partial cellulose degradation. If chlori-
nation of the biomass is carried out at pH N 8, HClO is formed which is
also a very useful and strong delignifying agent [143]. Rojas et al.
[144] bleached and de-lignied agricultural waste products to micro-
crystalline cellulose after their treatment, with sodium hypochlorite
for 24 h at room temperature conditions. NaClO also efciently removed
other low-molecular-weight components like pectins, hemicelluloses,
and some mineral compounds like silica in the case of rice husk. There
are many reports for the utilization of sodium chlorite (NaClO2) as a
 R. Kumar et al. / Journal of Molecular Liquids 232 (2017) 6293
bleaching agent. Rezanezhad et al. [146] isolated nano-cellulose crystals
from rice waste, decolorizing the pretreated biomass using 0.7% (w/v)
sodium chlorite at pH = 4 through boiling for 2 h.
Lignin can also be removed from the treated biomass materials using
chlorine dioxide involving a series of a chemical reactions. In a slightly
basic medium, ClO2 reacts with HO ions to produce ClO 2 and ClO3
ions (Eq. (4)).
2ClO2 2HO ClO2 ClO3 H2 O 4 mediated through xylanases exposes the lignin [151,152]. The bio-
However, during the bleaching of biomass, HClO2 is predominantly
formed (Eqs. (5)(7)).
ClO2 Biomass HClO2 Oxidized biomass 5 The most common chemical mediator used in laccasemediator sys-
2HClO2 HClO ClO3 H 6 Hydroxybenzotriazole [153]. Valls et al. [154] reported reduced con-
2HClO2 HClO2ClO2 H2 O H Cl 7 hydroxybenzotriazole dose during eucalypt pulp bleaching assisted
Regeneration of ClO2 further improves its bleaching efciency. Alco-
holic side chains of the lignin monomers are also oxidized at high pH
along with the formation of chlorite ions. The important point here to
mention is the generation and release of many carcinogenic and muta-
genic chlorinated organic compounds into the environment during the
processing of biomass. These compounds are highly poisonous in nature
and have drastic effects on human health. Hence, ECF and TCF strategies
should be developed and encouraged to reduce the environmental
impacts.
4.2. Oxygenated bleaching agents
One of the favored TCF strategies to purify and delignify the
pretreated biomass is the use of oxygenated bleaching agents. The
most common oxygenated species include molecular oxygen (O2),
ozone (O3), and hydrogen peroxide (H2O2). Deprotonation of the phe-
nolic groups of paracoumaryl alcohol, coniferyl alcohol and sinapyl alco-
hol in strongly alkaline conditions (pH 12) provides electron rich
centers for the possible attack of O2 in the triplet state. Through the for-
mation of a variety of oxygenated anionic and free radical species such
as superoxides (O 2
2 ), peroxides (O2 ), hydroperoxides (HO2 ), hydrox-
yl radical (HO), hydroperoxy radical (HO2) and even hydrogen perox-
ides (H2O2), aromatic rings and side chains are converted to simple
molecular species [147]. The degradation can be catalyzed by the use
of transition metal compounds, particularly of Mn, Fe, Co and Cu with
variable oxidation states. The catalytic action of these moieties is attrib-
uted their tendencies to convert H2O2to HO which are non-selective
and very strong oxidizing agents [148]. However, these reactive
HO are also supposed to oxidize hydroxyl groups of the cellulose chains.
Under optimized conditions of temperature and pH, direct use of H2O2
in combination with O2 is thus more favorable to carry out the bleaching
process. Another substitute for chlorinating agents, particularly for ClO2,
is ozone which is environmental benign and is used for TCF bleaching of
the extracted cellulose [149]. Like HO radicals, O3 oxidizes the hydroxyl
groups to carbonyl groups and reduces the degree of polymerization of
cellulose components.
4.3. Enzymatic bleaching
Greener, ecofriendly bio-bleaching assisted through enzymes is still
another way of purifying polysaccharide components of pretreated lig-
nocellulosic biomasses. These enzymes have two fold actions i.e.
delinking of lignin components from the polysaccharides followed by
degradation of lignin. Other advantages of enzymatic bleaching are
milder operating conditions and lesser ber damage. The two main clas-
ses of enzymes capable of bio-bleaching are laccases and xylanases.
Laccases- a type of fungal enzymes, either in the presence of O2 or
71
H2O2 can catalyze the oxidation of phenolic and non-phenolic compo-
nents of the lignin and degradation of chromophores produced during
the pre-treatment stages [150]. On the other hand, xylanases, produced
from a number of bacteria and fungi are capable of complete hydrolysis
of xylan - the major constituent of hemicellulose and is a heterogeneous
carbohydrate composed of D-xylopyranose units linked through -1,4
glycosidic linkages and short side branches composed of O-acetyl, -L-
arabinofuranosyl and -D-glucuronyl moieties. Hydrolysis of the xylan
bleaching efciency thus can be improved by the synergic effect of
both xylanases and laccases enzymes in comparison to the individual
enzymes. However, the use of laccasemediator systems provides an al-
ternate and direct way to hydrolyze the lignin without using xylanases.
tems are 2,2-azinobis-(3-ethylbenzothiazoline-6-sulfonate) and 1-
sumption of reagents, lesser reaction duration, laccase and 1-
through xylanase and laccasemediator system.
Enzymatic bleaching assisted through ultrasonic treatment has also
shown fruitful and favorable results. As stated earlier in the Section
3.3.3, ultrasonication produces shock waves generated by cavitation
bubbles. These shock waves further, facilitate the transportation of en-
zyme molecules onto the ber surface [155]. Davulcu et al. [156] studied
the ultrasonic effect on the bleaching efciency of the glucose oxidase
(GOx) enzyme for the cotton fabrics. GOx is supposed to produce
H2O2, the concentration of which was increased upon ultrasonication.
Sufcient increase in the whiteness degree (75.6 Stensby) was observed
when bleaching was carried out under ultrasonication using GOx en-
zyme. The results were comparable to the conventional peroxide
bleaching process (76.7Stensby). Recently, Alghamdi et al. [157] report-
ed complete bleaching in a short duration of 30 min for the cotton bers
when treated with tetraacetylethylenediamine/hydrogen peroxide/
triethanolamine (TAED/H2O2/TEA) inuenced by ultrasonication as
compared to 60 min of treatment without ultrasonication at 70 C. Sim-
ilarly, the combined effect of laccase enzyme-hydrogen peroxide system
under ultrasonication also gave improved whiteness levels for cotton
fabrics as compared to the conventional methods [158].
4.4. Fungal bleaching
As stated earlier in Section 3.1, white-rot fungi, especially belonging
to saprophytic and ligninolytic basidiomycetes group can reduce the
kappa number-a parameter to determine the residual lignin contents
of pulp [150]. These fungi through their highly specic and effective at-
tack can even degrade the very low level of the lignin contents. The
delignication and bleaching under milder process conditions using
various fungal strains makes this technique an effective and alternative
as compared to other traditional bleaching techniques. However, the
technique suffers from some major drawback of long incubation time
of 514 days. To some extent, this disadvantage can be minimized by
performing the fungal bleaching in the presence of some chemical re-
agents such as H2O2, O2, and very dilute organic acid solutions [159].
4.5. DBI bleaching
This is another versatile technique for bleaching, which uses direct
use of a reductive bleaching liquor comprising borol solution- mixture
of sodium boronhydride (NaBH4) (strong reducing agent) and NaOH so-
lution and sodium bisulfate (weak reducing agent) solution. The process
is easy to operate, less time consumable and more economical.
Rangamannar et al. [160] reported better and economic bleaching per-
formances for DBI technique as compared to formamidine sulphinic
acid and sodium hydrosulphite-hydrogen peroxide methods.
To conclude, multistage bleaching involving the combination of an
oxidative and a reductive stage using strong but environmental benign
72 R. Kumar et al. / Journal of Molecular Liquids 232 (2017) 6293
oxidants and reductants respectively will be more suitable for different
chromospheres degradations [161].
5. Different techniques and methods of cellulose grafting
The hydroxyl groups (\\OH) present at C2, C3 and C6 atoms of each
-D-glucopyranose units of cellulose either directly or after modica-
tion, are the most suitable active sites for attack of other functionalities
of monomer units or polymers for the formation of grafted cellulose
polymers with advanced properties and potential applications as
compared to pure cellulose. In general, there are three basic techniques
i.e. grafting-to, grafting-from and grafting-through, reported in the
literature for the synthesis of grafted copolymers of cellulose (Fig. 5)
[162164].
In the grafting-to (polymer-to-polymer grafting) technique, already
grown polymer, with an active functional group is allowed to covalently
bond with the reactive sites of the cellulose chains. Bifunctional,
trifunctional or even polyfunctional polymers attached to cellulose
chains, further permit post-polymerization and formation of cellulose
based copolymers. Pre-synthesized polymers can be well characterized
in terms of their molar masses and other properties prior to their attach-
ment to cellulose chains. Due to low rates of reactions involving poly-
mer macromolecules grafting-to technique is less preferred as
compared to grafting-from technique (Monomer-to-polymer grafting)
[165]. The later involves the attachment of the monomer units on the
active sites of the cellulose backbone facilitated through macro-
initiators (generally free radicals) followed by the propagation of poly-
mer graft. However, the reaction conditions not only favor the grafting
but also results in the degradation of cellulose backbone along with
the formation of polydispersed homopolymers and block copolymers
which must be separated from the grafted polymer using suitable sol-
vents [166]. Another notable disadvantage of the grafted-from approach
is the characterization of the grafted polymer chains [167]. The
Fig. 5. Different grafting techniques employed for the synthesis of grafted cellulose.
characterization can be carried out only after the separation of polymer
grafts from the cellulose backbone through acid hydrolysis. Grafting
from approach may be initiated either through free radical, cationic or
anionic initiators, ring-opening polymerization, controlled/living radi-
cal polymerization, and enzymatic grafting. The chain length of the
grafted polymer chains and grafting densities are, however, difcult to
control through free radical polymerization as compared to ring-
opening and controlled/living radical polymerization [168].
Grafting-through involves the polymerization (or copolymerization)
of a macromonomer with one terminal end-group which further en-
ables polymerization. This end group is the most susceptible site for
other monomers to attack usually through vinyl and acrylate groups.
The percentage of grafting is largely affected by the ratio of molar con-
centrations of monomer to macromonomer and the copolymerization
behavior.
Among these reported grafting techniques, grafting-from is most
widely used one as many polymers can be grafted simultaneously to
form copolymers onto a principle polymer backbone, in contrast to a
grafting-through method which requires the pre-synthesis of a
macromonomer and grafting-to technique which suffers from the disad-
vantage of slow rates of polymerization reactions. Depending upon the
parameters like nature and functionalities of the polymer backbone and
side chains, concentration of the monomeric units, degree of the poly-
merization, graft distribution and polydispersity, different grafting
methods initiated through chemicals, radiations, plasma radiations, en-
zymes and light-induced are employed to engineer the physicochemical
properties and end use of the grafted cellulosic materials [162,163,166].
Various types and subtypes of these grafting methods are schematically
represented in Scheme 2.
Depending upon the nature of chemical initiators used and mono-
meric units, the free radical, living or CRP, ionic and ROP methods are re-
ported in the literature and the same along with their mechanisms are
reviewed in this section.
 R. Kumar et al. / Journal of Molecular Liquids 232 (2017) 6293
Scheme 2. Types and subtypes of various cellulose grafting techniques.
6. Mechanisms of free radical grafting initiated by chemicals
Owing to its applicability to polymerize a number of vinyl, acrylate,
acrylamides, dienes, styrenes, vinyl acetates and pyrrolidone mono-
mers, convenient and milder reaction conditions, inexpensive, and tol-
erance to wide temperature ranges, free radical polymerization
initiated through chemical initiators, is widely acceptable and applied
technique for the synthesis of variety of cellulose grafted copolymers.
Free radical polymerization involves chain reactions initiated through
chemical initiators which generate free radicals followed by propaga-
tion and chain termination steps. The extent of grafting is greatly inu-
enced by the nature and the concentration of the initiator used. The
extent of grafting may be inuenced either by increasing the number
of grafts per cellulose chain or by adding more number of monomer
units to the already grafted chains. The nal chain termination step is
the crucial one and can be brought about by either coupling of two
grafted chains to form a dead polymer or disproportionation or chain
transfer mechanisms. In the subsequent part, the routes to generate
free radicals directly or indirectly through the redox reactions by differ-
ent chemical initiators are explained.
6.1. Free radical polymerization initiated by Ce+4 ions
The most commonly used sources of Ce+4 ions are CAN;
((NH4)2Ce(NO3)6) and cerium (IV) sulfate [Ce(SO4)24H2O] salts.
Ce+4 ions are supposed to form an initial reversible intermediate che-
late complex with the \\OH groups of cellulose backbone followed by
dissociation through one electron transfer to generate free radicals
under acidic conditions [169]. During this process, Ce+4 ions are re-
duced to Ce+3 ions. These radicals can initiate the grafting polymeriza-
tion of many vinyl monomers. The hydroxyl group present at C1 of the
reducing hemiacetal end-unit and C2C3 glycol in the anhydroglucose
units rather than C6 are the preferred sites for grafting (Scheme 3.) [7,
170]. A number of monomers have been grafted the cellulose derived
Scheme 3. Mechanism for free radical grafting polymerization initiated Ce4+ ions.
73
from different sources through free radical polymerization initiated by
Ce+4 ions (Table 1).
6.2. Free radical polymerization initiated by persulfates (S2O2
8 ) ions
Persulfate ions (S2O2
8 ) are the best known free radical initiator for
grafting a variety of monomeric/polymeric chains onto the cellulose
polymers through the abstraction of H-atoms from \\OH moieties of
the cellulosic chains. The polymeric structure in a polymerization pro-
cess. The most common S2O2 8 ion sources are either potassium or am-
monium persulfate (K2S2O8, KPS and (NH4)2S2O8; APS). Both these
compounds are white solids with very high solubility in water. More-
over, they are much safer to use as compared to other initiators like or-
ganic peroxides. It is well known that persulfate ions (S2O28 ) undergo
uncatalyzed symmetrical cleavage in neutral medium to generate sul-
fate radical anions (SO4 ) (Eq. 8) [189]. These sulfate radical anions
are responsible for the generation of hydroxyl radicals (HO) and radical
anions (HO) either in aqueous or alcoholic medium (Eqs. (9)(10)).
The primary HO radicals as well as SO4 radical anions can initiate the
polymerization process (Eq. (11)).
S2 O2


8 SO4 SO4 8
SO

4 H2 OHSO4 HO
9



Cellulose SO4 Cellulose HSO
4 10


Cellulose HO Cellulose H2 O


11
Liu et al. [190] proposed two mechanisms for the probable attacks
for SO
4 radical anions onto the glucopyranose units of cellulose ber.
The C3 and C4 atoms of glucopyranose units are supposed to be the
most susceptible sites for the generation of free radical through oxida-
tive hydrogen abstraction in the absence of monomer units. According
to the one concept, SO 4 radical anions attack the cellulose chain to cre-
ate free radicals at C3, that can further combine with other SO 4 radical
anions or monomers to be grafted on cellulose chains for the formation
of cellulose grafted copolymers. Still another approach is the abstraction
of H from C1 position. Through electronic rearrangements, this C1 rad-
ical can be transferred to C4 of the linked glucopyranose unit. These two
approaches were well conrmed by the LCESI/MS analysis. The sec-
ondary alcoholic hydroxyl group present at C2 also activates the homo-
lytic cleavage of geminal C1\\H bond via anomeric effect. Lone pair of
electrons present on O-atoms of C2\\OH and glycosidic linkage, weaken
the C\\H bond through interactions with antibonding orbitals of C\\H
bond [191]. Many metal ions such as Fe2+, Co2+, Ag+, Cu2+, acidic inor-
ganic radicals such as S2O2
3 , HS2O3 , HSO3 , and organic acids like ascor-
bic acid are used as redox activators for the S2O2
8 ions to accelerate the
free radical formation (Eqs. (12)(14)) [164,192194].
2
S2 O2
2
8 Ag SO4 SO4 Ag 12
74 R. Kumar et al. / Journal of Molecular Liquids 232 (2017) 6293

Table 1
Cellulose grafted copolymers formed using Ce4+ ions as chemical initiator along with optimized grafting conditions.

Source of cellulose Backbone material Grafting Agent Reaction medium Temp (C)/Time (h) Grafted Copolymer formed Ref.

Wood pulp Cellulose GMA HNO3 30/2 Cell-g-GMA [171]

DMF 70/6 Cell-g-GMA-I
Bast bers of the kenaf plant Cellulose AN H2SO4/CH3COOH 30/3 Cell-g-p(AN) [172]
MAN Cell-g-p(MAN)
Commercial Cellulose AA AASO3H HNO3 30/3 Cell-g-p(AA) [173]
Cell-g-p(AANMBA)
Cell-g-p(AAAASO3H-NMBA)
Banana stem Lignocellulose AN Water 70/2 APBS [174]
Commercial Cellulose AA HNO3 30/3 Cell-g-p(AANMBA) [175]
AASO3H Cell-g-p(AASO3H-NMBA)
Ficus carica bers Lignocellulose AA Water Lignocell-g-p(AA) [176]
Commercial Cellulose EMA HNO3 30/2 Cell-g-p(AN) [177]
AN Cell-g-p(EMA)
Agave bers Cellulose AN Water 45/1 Cell-g-p(AN) [178]
EA Cell-g-p(EA)
Commercial Cellulose GMA Water 35/4 Cell-g-GMA [179]
uff pulp Cellulose AA Water 20,60/3 Cell-g-p(AA) [180]
AN Cell-g-p(AN)
Commercial Cellulose AAm HNO3 25/ Cell-g-p(AAm) [181]
MA Cell-g-p(MA)
Commercial Cellulose beads AA HNO3 35/ Cell-g-p(AA) [182]
Commercial Cellulose AAm HNO3 25/ Cell-g-p(AAm) [183]
EMA Cell-g-p(EMA)
Commercial cellulose CMC AAm Water 29/ Cell-g-p(AAm) [184]
Lantana camara -Cellulose AN HNO3 2025/14 Cell-g-p(AN) [185]
Wood pulp Cellulose GMA Water 30/2 Cell-g-GMA [186]
Commercial -Cellulose NIPAM HNO3 30/10 Cell-g-poly(NIPAM) [187]
Commercial Cellulose GMA HNO3 35/2 Cell-g-GMA [188]

S2 O2 2
2
8 S2 O3 SO4 SO4 S2 O3 13 Fe2+ ions on reaction with H2O2 produce HO radicals as are generated
in other redox initiators. However, as compared to other systems, the
initiation process can be carried out at lower temperatures. Following
S2 O2

2
8 HSO3 SO4 HSO3 SO4 14 reactions are reported for the generation of HO radicals from Fe2+
H2O2 system (Eq. (17)).
The various factors like nature and solubility of monomer, grafting
reaction time, monomer/cellulose mass ratio, initiator/monomer Fe2 H2 O2 Fe3 HO HO
17
molar ratio, initiator/cellulose mass ratio and reaction temperature,
are found to affect the grafting percentage or percent grafting (GP or If sufcient amount of H2O2 is not present in the reaction medium,
Pg) and grafting efciency (GE) of the different cellulose grafted poly- HO radicals can either reduce the Fe3+ ions back to Fe2+ ions or may
mers. The Eqs. (15) and (16) are used to calculate these grafting param- oxidize Fe2+ ions to Fe3+ ions (Eqs. (18), (19)). As Fe3+ ions are well
eters. reported to adversely, affect the grafting efciency, as appropriate
Fe2+/H2O2 molar ration is required [209].
Weight of cellulose grafted copolymerWeight of ungrafted cellulose
GP or Pg  100
Weight of ungrafted cellulose Fe3 HO
Fe2 HO 18
15
Fe2 HO
Fe3 HO 19
Weight of cellulose grafted copolymerWeight of ungrafted cellulose
GE  100
Weight of monomer
If an appreciable amount of H2O2 is present, it is decomposed by
16
HOradicals as follows (Eqs. (20)(21)).

Mondal et al. [195] compared the GP and GE for water soluble as well
as insoluble monomers grafted on cotton bers. It was reported that the
graft yields and grafting efciency were larger for water-insoluble
monomers with hydrophobic groups as compared to water-soluble
monomers. It was attributed that monomer afnity toward cotton bers
and the copolymerization efciency greatly affected the graft yields and
grafting efciency. Further, it is also reported that at higher APS concen-
tration grafting percentage is lowered, whereas for KPS the trends are
opposite which may be attributed to the different decomposition rates
of the said initiator [196].The various optimized conditions for different
cellulosic materials and monomers yielding highest GP and GE are listed
in Table 2.
6.3. Free radical polymerization initiated by Fe2+H2O2
Fe2+H2O2 (Fenton's reagent) is still another most effective redox
initiator used in the formation of cellulose based grafted copolymers.
HO
H2 O2 H2 O HO
2 20
HO
2 H2 O2 HO
H2 O O2 21
Another way to reduce the tragic negative effects of the Fe3+ ions on
various grafting parameters, grafting process is carried out in the pres-
ence of some complexing agents such as ascorbic acid, potassium uo-
ride, EDTA etc. [209210]. As H2O2 is decomposed in acidic medium,
the pH of the reaction medium greatly affects the grafting parameters.
Hence, the proper optimization of pH is also a necessary step to have
maximum grafting efciencies [211].
During the grafting process, Fe2+ ions are supposed to adsorb on the
surface of the cellulose material followed by generation of HOradicals
assisted through H2O2. These HOradicals initiate grafted polymeriza-
tion via an abstract of H from one of the\\OH group of the glucopyra-
nose units of the cellulose chains (Eq. (22)).
Cellulose OH + HO Cellulose O + H2O (22)
 R. Kumar et al. / Journal of Molecular Liquids 232 (2017) 6293 75

Table 2
Optimized conditions and grafting parameters for the grafting of cellulose using S2O2
8 as chemical initiator.

Source of Backbone material Grafting Reaction [Monomer]/[Initiator] Temp (C)/Time Initiator Grafting Parameters (%) Ref.
cellulose Agent medium (min) GE, GP*

Commercial CMC AA Water /10% 55/120 APS/NaHSO3 [193]

Bleached jute Cellulose AN Water 300%/22% 80/90 KPS/Fe2+ 4.5 [195]
ber MAN 280%/20% 11.0
Cotton Fibers Water and amine activated AA Water 100%/7% 80%/5% 70/120 KPS/CoSO4 16.6 [197]
cellulose MAA 120%/7% 60/100 25.1
AAm 90%/6% 80%/5% 55/150 11.3
MA 100%/4% 55/100 39.8
MMA 60/120 51.5
VA 65/120 27.2
Cotton linter Cellulose MMA DMSO 100%/12% 80/120 APS 76 [198]
Commercial CMC AAm Water /180 APS 323* [199]
Grewia optiva Cellulose MMA Water 0.35 M/12 mM 60/180 KPS 1525* [200]
Pine needles Lignocellulose EA Water 0.32 M/8.6 mM 55/135 KPS 27.55* [201]
Commercial CMC NIPAM Water 60%/10% 50/180 KPS [202]
Pine needles Lignocellulose MMA Water 0.33 M/8.85 mM 55/140 KPS 23.28* [203]
Wood pulp Cellulose nanocrystals PDMAEMA Water 100%/15% 70/180 APS [204]
Commercial HPMC AAm Water 5075/6 h KPS [205]
Bamboo pulp Cellulose AAm NaOH-urea 100%/25% 50/60 APS [206]
Commercial HEC AA Water / 70/300 APS [207]
Cotton linter Cellulose MMA DMAc/LiCl 100%/12% 80/120 APS 76* [208]

Since vinyl monomers are also susceptible to the HOradicals attack,
a major amount of these monomers is converted into their respective
homopolymers. As a result, both Fe2+\\H2O2 and S2O2 8 ions as initia-
tors suffer from a low degree of grafting percentage and efciency as
compared to Ce4+ ions as initiators, which directly attack the glucopy-
ranose units of the cellulose chains as stated earlier in this section. Var-
ious monomers such as MMA, AA, AAm, GMA, DMAE-BC etc. are grafted
on the different types of cellulosic materials derived from various natu-
ral sources using Fe2+\\H2O2 as initiator (Table 3).
6.4. Free radical polymerization initiated by BPO
When heated to ~ 65 C, the peroxide bond (O\\O) undergoes ho-
molytic cleavage to generate two benzyloxy free radicals. The bond dis-
sociation energy for O\\O is very low (35 kcal mol1) as compared to
the bond dissociation energies of C\\H (100 kcal mol 1) and C\\C
(kcal mol1) bonds. The benzyloxy free radical is unstable and can eas-
ily liberate CO2 gas to form resonance stabilized phenyl free radicals.
Both benzyloxy, as well as phenyl free radicals, are supposed to initiate
the polymerization process [218] (Scheme 4). Homopolymerization of
the monomers is initiated to form macroradicals which subsequent ab-
stract H from one of the\\OH group of the glucopyranose units of the
cellulose chains. However according to the proposed mechanism by
Routray et al. [219] benzyloxy free radicals can directly remove H rad-
icals from one of the\\OH groups to generate Cellulose O radicals for
further grafting (Eq. (23))
23
Benzoyl peroxide is the most commonly used chemical initiator to
initiate the polymerization followed by their grafting onto the cellulosic
materials [Table 4].
The concentration of the BPO initiator extensively affects the
grafting parameters. Chauhan et al. [226] reported a gradual decrease
in GP and GE when the BPO concentration was increased from
2.76 102 to 13.77 102 mol L 1 for polyglycidylmethacrylate
grafted cellulose extracted from pine needles. The monomer- initiator
molar ratio is also a critical factor in affecting the GP and GE. For CA
grafted with an equimolar binary mixture of AA and AAm, Abdelwahab
et al. [220] observed 133.5 and 124.3% GP and GE, respectively for
monomer: initiator molar ratio of 10, grafting temperature of 80 C
and grafting reaction time of 3 h. A higher initiator dose is expected to
terminate the growing macroradicals of the monomer through the mu-
tual coupling, thus leading to homopolymer formation instead of
grafted copolymers [221]. In addition to water, other solvents such as
acetone, DMSO, DMAc, and 1,4-dioxane etc. are also used for the prepa-
ration of cellulose grafted polymers. Routray et al. [219] analyzed the ef-
fect of DMSO, DMAc, 1,4-dioxane and acetone on the grafting
efciencies of PMMA onto CA using BPO as an initiator. Initiator efcien-
cy of BPO was better in DMAc, 1,4-dioxane, and acetone as compared to
DMSO as solvents. The optimum grafting temperatures were 70, 60 and
55 C for DMAc, 1,4-dioxane and acetone, respectively. No doubt, BPO is
a potential candidate as a free radical initiator, but care should be taken
during its use as concentrated BPO is highly explosive and catches res
without any external ignition. Hence, it always recommended using it in
the form of a solution or a paste.
6.5. Free radical polymerization initiated by potassium permanganate
(KMnO4)
Owing to the very low energy difference between 4s and 3d sub-
shell, manganese (Mn) can exhibit variable oxidation states such as
+ 2, + 3, + 4, + 5, + 6, and + 7 in its compounds. It is well known
that +7 oxidation state of Mn in permanganate (MnO 4 ) ion is easily re-
duced to + 2 through the formation of highly unstable + 3 oxidation
state in acidic medium. These intermediate Mn3+ ions are considered
the most important entities to induce grafting copolymerization in
many polymeric materials including cellulose. Additionally, there are
some reports that also considered Mn4+ ions to initiate the free radical
formation [228].
The most susceptible sites for the free radical formation are the C2
and C3 positions in the glucopyranose units of cellulose chains. The
exact mechanism of the free radical formation at these sites is still de-
batable. According to one view, MnO 4 initially oxidize the\ \OH groups
at C2 or C3 positions to aldehydic (\\CHO) groups followed by
tautomerization to enol form which nally on reaction with Mn4+ or
Mn3 + ions generate free radicals [228,229] (Scheme 5(a)). Another
view suggested the direct abstraction of H from\\OH groups of the glu-
copyranose units to yield free Cellulose O radicals [230] (Scheme 5(b)).
Another effect, which the permanganate treatment results, is the reduc-
tion of the hydrophilicity of the cellulose bers to lower the water
76 R. Kumar et al. / Journal of Molecular Liquids 232 (2017) 6293

Table 3
Optimized conditions for cellulose grafting in aqueous medium using Fe2+\
\H2O2 initiator.

Source of cellulose Backbone material Grafting Agent [Monomer]/[Initiator] Temp (C)/Time (min) Ref.

Eucalyptus pulp Nanobrillate cellulose MAA /1 mM 50/120 [212]

MAc
Cotton linter Cellulose nanocrystals MMA 500%/0.5% 70/120 [213]
Banana stalk (Musa paradisiaca) Lignocellulose AAm 500%/0.02 M 60/240 [214]
Cotton gauzes Cellulose GMA / 80/ [215]
Commercial Cellulose bers Cellulose thiocarbonate DMAE-BC / 30/240 [216]
Rice husk Lignocellulose MAA / 70/60 [217]

absorption capacities. There is a negative correlation between the con-
centration of the KMnO4 and hydrophilicity.
As mentioned above the initiator activities of the KMnO4 occur only
under the acidic conditions of the medium, the choice of the acid is also
an important aspect. Many strong acids such as HCl, HClO4, H2SO4, and
HNO3 etc. and weak acids like citric acid, tartaric acid, oxalic acid, and
ascorbic acid etc. are reported in the literature (Table 5). The optimiza-
tion of the acid concentration is a critical issue. A high strong acid con-
centration either coagulates the polymer material or may induce side
reactions of the KMnO4 that may lead to the formation of molecular
oxygena strong inhibitor of free radical polymerization. Moreover,
stronger acids are also highly corrosive in actions. Moreover, when
solid KMnO4 reacts with concentrated H2SO4, manganese (VII) oxide
(Mn2O7)-a highly explosive compound, is formed. In addition, it is not
preferable to use the alcoholic medium for free radical grafting poly-
merization as solid KMnO4 reacts with simple alcohols to undergo a vi-
olent combustion reaction.
In order to minimize the effect of these limitations, weaker acids in
the form of aqueous solution are generally used. These acids not only
maintain the acidic conditions for a free radical generation but also
help in the formation of some secondary free radicals, which further as-
sist in grafting polymerization reactions (Eqs. (24)(25)) [194].
In addition to the described chemical initiators, other chemical spe-
cies such as quinquevalent vanadium (V+5) [241], and ABCN [23] are
also reported in the literature as chemical initiators for free radical poly-
merization of unsaturated vinylic monomers onto the cellulose.
7. Metal ion sorption applications of cellulose grafted copolymers
Fast industrialization and blooming growth in the elds like power
generation, mining, and metallurgy, electronic, electrochemical, auto-
mobile, chemical, paint, and dye, pesticide and insecticide, textile and
tannery around the globe is substantially contributing to environmental
pollution. Efuents released from these industries are usually rich in
heavy metal ions contents and are transported easily to the water re-
sources. From these water resources, highly poisonous, toxic and non-
biodegradable metal ions such as Cd2 +, Pd2 +, Hg2 +, Cu2 +, Ni2 +,
Co2 +, Co3 +, Zn2 +, Mn2 +, As3 +, Mo2 +, V3 +, Cr6 +, Sb3 + are easily
bioaccumulated into the food chains. The presence of these metal ions
in water beyond a permissible level is fatal to aquatic animals as well
as humans. These metals can result in nerve damage, malfunctioning

Mn3 C2 O2
4 Mn
2
CO2 CO

2 24

Mn 4
C2 O2
4 Mn
3
CO2 CO

2 25
6.6. Free radical polymerization initiated by AIBN

AIBN is another organic white compound, soluble in many organic

solvents and alcohols but insoluble in water, which restricts its applica-
tions as free radical initiator were greener and eco-friendly graft poly-
merizations processes in an aqueous medium are involved. However,
it is safer than BPO in terms of its explosive nature. AIBN produces
free radicals when heated or exposed to VU radiations. Grafting efcien-
cy is found to be lower for AIBN as compared to one-electron-transfer
agents which are attributed to the formation of resonance stabilized
free radical (Scheme 6) [237240].
Recently, Anzlovar et al. [237] grafted PMMA onto the CPADB mod-
ied nanocrystalline cellulose in THF using AIBN as initiator at 75 C for
24 h. Keplinger et al. [238] introduced methacryl groups into wood cell
walls of Norway spruce (Picea abies) followed by subsequent AIBN initi-
ated grafting of the styrene in pyridine. The grafting was performed at
75 C for 20 h. Li et al. [239] synthesized p(LA)-co-p(GMA) copolymer
in xylene at 70 C and the reaction continued for 5 h. As synthesized
p(LA)-co-p(GMA) was grafted to the bacterial cellulose. The bonding
between p(LA)-co-p(GMA) and bacterial cellulose was conrmed by
FTIR analysis. This surface modication reduced the interfacial tension
of bacterial cellulose and polylactide, in order to make these materials
more compatible and the dispersible. Metaxa et al. [240] reported the
synthesis of biocompatible hollow p(MAA-co-NIPAAM-co-EGDMA)@
CS biocompatible hollow microspheres on uniform silica-MPS micro-
spheres template. EGDMA and AIBN were used as crosslinker and initi-
ator, respectively. The materials were further subjected to evaluate their
drug delivery applications for anticancer drug daunorubicin in acidic as Scheme 4. Schematic representation of the free radical mechanism for cellulose grafting
well as slightly basic conditions. initiated through BPO.
 R. Kumar et al. / Journal of Molecular Liquids 232 (2017) 6293 77

Table 4 side chains with those of the metal ions from the efuent solution
Optimized conditions for cellulose grafting in aqueous medium using BPO initiator. (Fig. 6).
Source of Backbone Grafting Reaction Temp Ref. From Tables 15, it can be clearly seen that in order to increase the
cellulose material Agent medium (C)/Time adsorbing power of the cellulosic bio-sorbents a number of monomeric
(h) species such as GMA, AA, AAm, AN, 4-vinylpyridine, AASO3H and HEMA
Cotton CA MMA DMAc/LiCl 70/6 [219] etc. are used for the fabrication of cellulose grafted copolymers and cor-
linters Acetone 55/6 responding binary copolymers. These monomers usually contain acidic
1,4-Dioxane 60/6
\\COOH,\\SO3H,\\COONa,\\SO3Na and basic -NH2 functional group
Commercial CA AA Toluene 30100/14 [220]
AAm moieties. Metal ions can very easily form a chelate with the lone pair
Pine Cellulose HEMA Water 70/2 [221] of electrons present of O-atoms of these functional groups.
needles AA The adsorption amount of the metal ions q adsorbed onto the
AAm grafted cellulosic biomaterials is calculated using Eq. (26).
AN
Commercial Cellulose GMA Water 7080/3 [222]
Commercial Cellulose GMA Water 70/2.5 [223] C o C e
q V 26
microcrystalline W
Bamboo Cellulose LMA 80/4 [224]
powder
where, Co, Ce = Initial, and equilibrium metal ion concentrations,
Pine Cellulose MMA Water 70/2 [225]
needles HEMA respectively.
GMA V = Volume of the sample solution
AAm W = Weight of the adsorbent taken
AAc
AN
7.1. Factors affecting the sorption capacity of grafted cellulosic bio-sorbents
Pine Cellulose GMA Water-Acetone 70/2 [226]
needles phosphate AA
AAm 7.1.1. Effect of extent of grafting
AN As mentioned earlier in Section 7, the extent of adsorption of metal
Commercial Cellulose GMA Water 70/3 [227]
ions directly depends on the density of active functional groups on the
grafted cellulose backbones. Grafting percentage or percent grafting
(GP/GE/GY or Pg) is a direct measure of the active site density for ad-
sorption. In order to achieve maximum percent grafting, the optimiza-
of liver, kidney, glands and enzymes, gastrointestinal upsets and various tion for proper solvent and its volume in which the grafting is carried
types of allergies etc. Additionally, these metal ions are also highly carci- out, monomer concentration, initiator concentration, grafting time and
nogenic in nature [242]. Economic, easy, fast and eco-friendly removal temperature, cross-linker concentration and co-monomer concentra-
of these metal ions from water is the key concern of the modern day tion is necessary. Singha et al. [247] observed an increased adsorption
research. uptake of Cu2+, Zn2+, Cd2+ and Pb2+ toxic metal ions from wastewater
Solid phase extraction is highly recommended and utilized a tech- with percent grafting of p(AN)-co-p(MAA) polymer chains with cya-
nique for pre-concentration of toxic heavy metal ions as compared to nide and carboxyl functionalities, grafted on cellulosic ber extracted
other traditional techniques like chemical precipitation, carbon adsorp- from okra plant. However, a very high percent grafting or grafting ef-
tion, co-precipitation, coagulation-occulation, otation, membrane ciency may decrease the swelling properties of the cellulose based
separation, electrolytic reduction to neutral form, ion exchange, electro- grafted copolymers due to more compactness and less penetrable na-
chemical treatment, hydroxide and sulde precipitation, ultraltration ture for the diffusion of the metal ions [248]. Fig. 7 represents the vari-
and electrodialysis etc. Adsorbents required for SPE should be a stable ations of adsorption of Ni2 +, Cu2 + and Co2 + ions by PMAAC with
and insoluble matrix with a high density of active site in the form of different percent grafting yields. For Cell-g-GMA copolymers, based on
functional groups, in order to effectively interact with toxic heavy different binary monomers such as AA, AAm and AN, the sorption be-
metal ions present in water [243]. havior was found to be maximum for Cell-g-GMA-co-AA as compared
Biosorption using biodegradable, natural, stable and reusable bioma- to other two binary monomers. This can be attributed to the maximum
terials is now becoming a promising technique for the removal of toxic grafting efciency and swelling tendency for Cell-g-GMA-co-AA. Fur-
metal ions from wastewater. Low-cost, high adsorption capacity, mini- ther, the hydrolysis of a carboxylic acid group of grafted AA increases
mized with biochemical sludge, recovery, and regeneration of the availability of negatively charged carboxylate groups for better
biosorbent material, and easy desorption of metal ions for their possible metal ion sorption. Partial hydrolysis of the biosorbents also improves
recovery are some of the major advantages of this technique [244]. The the charge density and water uptake properties which further augment
most abundant agro-based biomaterial cellulose can be chemically the metal ion uptake behavior [249]. Jia et al. [250] also studied the var-
modied or grafted in order to improve its adsorption capacity toward iations of adsorption amounts of Cu2+ ions on Cell-g-PMA-HZ surface as
toxic metal ions. Owing to the insoluble behavior of modied or grafted a function of grafting yield. The adsorption capacity of the Cell-g-PMA-
forms of cellulose, it can be easily separated from the aqueous medium HZ adsorbent exhibited an increase from 101.6 mgg 1 to
after the adsorption process. Grafting of vinyl and other monomers onto 206.9 mgg1 with the grafting yield percentage from 130% to 326%.
cellulose backbone introduces grafted side chains with multi-functional For higher grafting yields, however, adsorption capacity decreased due
groups. These grafted copolymers formed, through various physical at- to above-stated reasons.
tractions such as van der Waals forces, hydrophobicity, hydrogen
bonds, polarity and steric interaction, dipole-induced dipole interaction 7.1.2. Effect of contact time
etc. adsorb the different metal ions onto their surfaces very easily. Re- Maximum adsorption of the metal ions from the medium in a lesser
cently, Hokkanen et al. [245] and Zhu et al. [246] elaborated the various contact or agitation time is one of the very important requisite features
adsorption mechanisms. These mainly include chemisorption, of the adsorbent materials. Depending upon the nature of functional
physisorption, redox reactions, complex formation between the metal groups present on grafted polymers and percent grafting, different opti-
ions and the anionic functional groups of the cellulose grafted copoly- mized contact times for maximum adsorption capacities are reported in
mer and ion exchange-replacement of cationic counterparts (\\COOH, the literature. Further, after an optimized contact time, adsorption ca-
\\SO3H,\\COONa,\\SO3Na) from the functional groups of the grafted pacity becomes constant which may be attributed to saturation of the
78 R. Kumar et al. / Journal of Molecular Liquids 232 (2017) 6293

Scheme 5. Different proposed mechanisms for free radical grafting of cellulose initiated by KMnO4.

adsorption sites and attainment of thermodynamic equilibrium Not only the functional groups of cellulose graft copolymers are af-
[247248]. In Fig. 8, the extent of Co2+ ions adsorbed by PMAAC as a fected by the pH of the medium, concentration and the chemistry of
function of time as well as temperature is shown. Irrespective of the some metal ions such as Cr+ 6 and V5 + etc. is also affected. These
temperature of the reaction medium, there is a signicant fast increase metal ions from a variety of cationic, anionic and neutral species at dif-
in the adsorption of Co2+ ions during the initial 20 min. ferent pH values. As the pH is lowered, chromate ions (Cr+6) undergo a
series of protonation and dimerization reactions (Eqs. (27)(29)).
7.1.3. Effect of temperature

A high adsorption temperature increases the kinetic energy and thus CrO2
4 H HCrO4 27
favors their fast and easy diffusion and penetration of the metal ions
from the medium into the polymer phase to undergo reactions with HCrO
4 H H2 CrO2 28
the active sites present on the grafted cellulosic biosorbents [248]. Fig.
8 indicates the effect of temperature on the adsorption extent of Co2+
H2 CrO2 Cr2 O2
7 H2 O 2H 29
ions on PMAAC. As the temperature is increased from 30 to 50 C, the
adsorption capacity is also increased. In addition, temperature also af-
fects the swelling behavior and internal structure of grafted cellulose, Under strongly acidic conditions, dehydration process precipitate
out red chromium (VI) oxide with innite linear chains of CrO4 tetrahe-
enhancing the rate of penetration of metal ions. The temperature varia-
tions during metal ion sorption process are also helpful in deciding be- dra (Eq. (30)).
tween physisorption and chemisorption behaviors. Most of the metal n n

ion sorption studies conducted so far suggested the involvement of Cr2 O2
7 nH CrO3 n H2 O 30
2 2
weak van der Wall interactions between the metal ions and the
biosorbents materials. Due to this feature, desorption of the metal ions It has been reported that Cr6+ exist as HCrO 2 2
4 , Cr2O7 , and CrO4
and hence regeneration of the biosorbents is easier at higher tempera- ions at pH = 2, 24 and above 4, respectively. Cr2O2 a form of Cr6+
7
tures [247]. ions is found to adsorb to maximum extent on Ficus carica ber Cell-g-
p(AA) at pH = 3.5. Beyond this pH, a decrease in the extent of adsorp-
7.1.4. Effect of pH tion was attributed to a competitive approach of OH ions (Fig. 9) [176].
Protonation-deprotonation of the functional groups controlled by Vanadium has much more complicated chemistry as compared to
the pH of the medium severely affects the adsorption capacity of the chromium. V+5 ions exist as vanadate (VO3 4 ) ions in extremely basic
grafted cellulose biosorbents. The initial pH of the medium inuences solution. Under very dilute conditions, if the pH of the medium is
the surface charge density and ionization degree of the cellulose based lowered, protonation occurs to give different monomeric species (Eqs.
grafted biosorbents [248]. High concentration of the H+ ions (low pH) (31)(33)).
favors the protonation process that blocks the anionic active sites such
as\\COO and SO 3 present on grafted cellulosic biosorbents, making
VO3 2
4 H HOVO3 31
the surface positively charged and thereby lowering the adsorption ca-
pacities due to electrostatic repulsions. At very low pH, metal ions face a
proton-competitive sorption reactions. In contrast, at very high pH of HOVO2
3 H HO2 VO2 32
the medium, some metal ions are converted to their soluble/insoluble
metal hydroxides (Scheme 7) [171,251]. Thus, for maximum metal ion HO2 VO
2 HO3 VO2 VO2 33
uptake, the biosorbents surface should have maximum negative charge
density [247]. At pH b 2, predominantly VO+ 2 exists that can be very easily adsorbed
As far as the amine and related functional groups are concerned, pro- on negatively charged active sites. When solutions are more concentrat-
tonation at low pH is favored as it helps in the binding of the metal ions ed, however, protonation and dehydration occur to form V2O4 7 , V3O9
3
4
as anionic species [227,252]. Cellulose based grafted polymers with and V4O12 anionic species at high pH values [240,241]. Thus, cellulose
these protonated positively charged active sites may thus be utilized grafted copolymers with negatively and positively charged active sites
for the adsorption of anionic species like F, Cl, CO2 2
3 , HCO3 , SO4 , preferably adsorb Vanadium ions at low and high pH values,

CrO2
4 , Cr O2
2 7 , MnO4 , PO3
4 , S O2
2 3 , AsO3
4 and AsO 2 etc. respectively.
 R. Kumar et al. / Journal of Molecular Liquids 232 (2017) 6293 79

Table 5
Some of the reported KMnO4 based initiator systems, monomers and optimized condi-
tions for cellulose grafting.

Source of Backbone Grafting Reaction Initiator Temp Ref

cellulose material Agent medium system (C)/Time
(h)

Corn stalk Cellulose AN Water KMnO4 40/1 [228]

(NMBA)
Saw dust of Cellulose AA Water KMnO4 69/2 [231]
Picea abies
and Fagus
sylvatica
Pine cone Cellulose AA Hexane KMnO4 70/2 [232]
Scheme 6. Proposed free radical grafting mechanism initiated by AIBN.
Sunower Cellulose AN Water KMnO4-citric 5080/ [233]
Stalks acid
Bleached Cellulose AN Water KMnO4-citric 70/3 [234]
Egyptian acid Interestingly, it was reported that the adsorption capacities during com-
cotton petitive adsorption, as compared to the non-competitive adsorption
Non-mulberry Cellulose MMA Water KMnO4-Oxalic 3060/15 [235]
were low and high in SLS and DTAC, respectively. It was concluded
silk-Antheraea acid
assama that, in the presence of SLS, there was an increased competition be-
Cotton bers Cellulose AN Water KMnO4-Oxalic 50/1 [236] tween the metal ions for the Cell-g-p(NIPAM) copolymer, while in the
acid case of DTAC, the highest afnity of metal ions experienced strong inter-
actions between quaternized ammonium groups in DTAC [259,260].

7.1.6. Effect of metal ion concentration

7.1.5. Interference of other metal ions
The adsorption capacity of the biosorbents for a particular metal ion
may be affected by the simultaneous presence of other metal ions in the
solution, their concentrations, electro-negativities, hydration capacities,
polarisabilities, hard-soft nature and tendency to show cation- interac-
tions with the active site [7,255]. The active sites in the form of negative-
ly charged functional groups on the surface of bio-sorbent preferably
bind smaller metal ions with greater positive charge density. Singha
et al. [247] observed a decrease in adsorption capacity of poly(acryloni-
trile-co-methacrylic acid)-g-cellulose biosorbents for Zn2+, Cd2+ and
Pb2 + metal ions in the presence of Cu2 + ions. Ionic radii of Cu2 +,
Ni2+, Zn2+, Cd2+ and Pb2+ ions are 73, 83, 88, 109 and 133 pm, respec-
tively. Smaller ionic radii and thus higher positive charge density of
Cu2+ ions, as compared to Zn2+, Cd2+ and Pb2+ ions may be attributed
to the lower sorption of the later ions in the presence of Cu2+ ions [247].
In contrast, Maatar et al. [212] reported a preferential adsorption order
of Pb2 + N Cd2 + N Zn2 + Ni2 + over p(MAA-co-MAc) grafted nano-
brillated cellulose. The order may be explained on the basis of -
interactions between the unsaturated functional groups such as
\\CONH2,\\COOH and\\SO3H of the grafted polymers and highly po-
larizable transition metal ions especially Cu2+, Cd2+, Hg2+, and Pb2+.
Rahman et al. [256] reported adsorption order Cu2+ N Fe3 + N Mn2+-
Co3+ N Cr3+ N Ni2+ N Zn2+ over the surface of Cell-graft-p(MA) with
poly(hydroxamic acid) bidentate ligands with very strong chelating ca-
pabilities. In addition to nature, the concentration of the interfering
metal ions is another crucial factor that affects the adsorbing capacity
of the cellulose based grafted biosorbents. The adsorption of Pd2+ ions
on 2-mercaptobenzothiazole impregnated cellulose was decreased
drastically in the presence of Zn2 +, Cd2 + and Pb2 + ions above
200 mg/L concentration. In contrast, anionic species like Cl, SO24 ,
NO 3
3 and PO4 interfere to a very small extent with the metal adsorp-
tion process [257,258].
Recently Ozbas et al. [187] studied the competitive and non-
competitive adsorption properties of the thermoresponsive Cell-g-
p(NIPAM) copolymer for metal ions such as Cu2 +, Pb2 +, Ni2 + and
Cd2+ ions through temperature swing adsorption (TSA) process in the
presence of SLS and DTAC. The adsorption rates for different metal
ions during non-competitive adsorption followed the order Cd2 +-
Cu2+ Ni2+ in the presence of SLS (Fig. 10(a)), and Cu2+ N Cd2+ N Ni2+-
Pb2+ in the presence of DTAC surfactant (Fig. 10(b)). These orders were
based on relative stabilities of Mn+-surfactant complexes. During com-
petitive adsorption however the rates followed the orders
Ni2+ N Cu2+ = Cd2+ in SLS and Cu2+ N Pb2+ N Cd2+ N Ni2+ in DTAC.
Another factor that affects the metal ion sorption is the initial con-
centration of the metal ions present in the medium. Through many
studies, it has been observed that the adsorption capacity exhibits a pos-
itive correlation with initial metal ion concentrations. However, at
higher metal ion concentrations the adsorption capacity either de-
creases or becomes constant due to the saturation of active sites on
biosorbents (Fig. 11) [246247]. In a recent study, poly(hydroxamic
acid) ligand synthesized using ester functionalities of Cell-g-p(MA) co-
polymer was efciently utilized for the adsorption of many transition
metal ions such as Cu2+, Fe3+, Mn2+, Co3+, Cr3+, Ni2+, and Zn2+. Re-
ectance spectra were found to increase with concentrations of the
metal ions from 0 to 15 ppm. The origin of the color was attributed to
charge transfer - transitions. The visual color investigation of transi-
tion metal ions adsorbed on poly(hydroxamic acid) ligand of Cell-g-
p(MA) copolymer revealed excellent physical and textural properties
[256].
7.1.7. Effect of biosorbent dose
The adsorption capacity and metal ion uptake of the cellulose based
grafted biosorbents directly depends on the surface area, the density of
the active sites and ion exchange capacity. A high dose of biosorbent
thus increases the availability of the active sites and hence favors larger
extent of metal ion uptake from the medium. However, at very high
biosorbent dose, the sorption capacity may show a decremental trend
due to the aggregation and overlapping of active sites leading to de-
creased surface area and rate of metal ion diffusion into the biosorbent
matrix [261]. From Fig. 12, the optimized dose for maximum percentage
sorption and residual Pb2+ ion concentration using CA-g-AA-co-AAm as
biosorbents was found to be 0.5 g L1 [8,220].
7.1.8. Effect of ionic strength
Ionic strength expresses the total concentration of coexisting ions
and greatly affects the acid-base and electron-donor properties of the
cellulose based grafted biosorbents, exibility, and orientation of the
grafted hydrophilic polymer chains and swelling behavior of the grafted
polymer in water. All these factors, in turn, affect the adsorption ef-
ciency of the adsorbent materials [214]. As electrostatic forces of attrac-
tion are the signicant forces, operating between the cellulose grafted
adsorbent and metal ions; adsorption is highly sensitive to the ionic
strength of the medium. During the process of adsorption, metal ions
or their reactive intermediate species form a xed layer on the surface
of the adsorbent, further surrounded by a mobile/diffused layer of oppo-
sitely charged ions from the medium. Higher the concentration of the
80 R. Kumar et al. / Journal of Molecular Liquids 232 (2017) 6293

Fig. 6. Various proposed mechanism for the adsorption of Cu2+ from aqueous solution onto epoxidized and aminated bagasse pulp cellulose. Reprinted with permission from [246].
Copyright 2015 Elsevier Ltd.

electrolyte in the medium more is the thickness of this electrically
charged double layer. The metal ion uptake by the adsorbent signi-
cantly decreases with the thickness of this electrical double layer. The
Higher ionic strength of the medium produces a higher shielding effect
for positively metal ions at the surface, thereby resulting a decreased ex-
tent of adsorption. Further, metal ions may be involved in the formation
of some charged or neutral species in the medium stuffed with electro-
lytes. It has been reported that an increased concentration of the Cl
ions converts Cd2 + ions into CdCl+, CdCl2 andCdCl 3 stable chloro-
complexes that are adsorbed to the very lesser extent as compared to
Cd2 + and Cd(OH)+ ions [262]. The adsorption of many metal ions
such as Cu2+, Cd2+, Zn2+ and Cr6+ is decreased with a rise in the con-
centration of NaCl in the adsorption medium using grafted cellulosic
biosorbents [174,222,262].
7.2.1. Langmuir adsorption isotherm
The model is based upon two basic assumptions. Firstly, a saturated
unimolecular chemisorbed layer of the metal ions is formed on the ho-
mogeneous surface of the adsorbent and secondly, there are no interac-
tions between the metal ions adsorbed. In other words, adsorption of
metal ions occurs at a xed number of identical localized sites, which
are sterically independent to each other [8,241,246,258,269,270]. Ac-
cording to Langmuir adsorption model (Eq. (34))
qm K L C e
qe 34
1 K LCe
The linear form of the Langmuir adsorption isotherm equation is as
follows (Eq. (35))

Ce Ce 1
35
7.2. Adsorption isotherms qe qm qm K L

In order to investigate the adsorption equilibrium of metal ions, var- where,

ious adsorption isotherms such as Langmuir, Freundlich, Temkin, Co, Ce = Initial and equilibrium metal ion concentrations, respective-
DubininRaduskevich, RedlichPeterson etc. are reported in the ly in mg L1.
literature. qe = Amount of metal ions adsorbed on the adsorbent at equilibri-
um (mgg1)

Fig. 7. Variations of adsorption of Ni2+, Cu2+ and Co2+ ions by PMAAC with different
percent grafting yields. Reprinted with permission from [248]. Copyright 2011 Fig. 8. Effect of temperature on the extent of Co2+ ion adsorption onto PMAAC. Reprinted
Elsevier Ltd. with permission from [248]. Copyright 2011 Elsevier Ltd.
 R. Kumar et al. / Journal of Molecular Liquids 232 (2017) 6293 81

7.2.2. Freundlich adsorption isotherm

Freundlich adsorption isotherm represents the isothermal variation
of extent adsorption of metal ions adsorbed per unit mass of the
cellulose-based biosorbents. The amount of the metal ions adsorbed
can be calculated using linear Eqs. (37) and (38).

qe K F :C 1=n
e 37

1
logqe logK F logC e 38
n
Scheme 7. Protonation-deprotonation of different functional groups of cellulose grafted
biosorbents.
For favorable tting, 0b 1n b1where,
KF = Freundlich adsorption isotherm constant.
qm = Monolayer saturation adsorption (Saturation capacity of ad- n = Heterogeneity factor that denes the adsorption intensity of the
sorbent in mgg1) adsorbent
KL = Langmuir adsorption isotherm constant. From the slope and intercept of the linearized plot between logqe
For better tting, a plot between Cq e and Ce should follow a straight and logCe, the values of 1n and KF, respectively can be calculated. The mag-
e

line. The values of qm and KL can be computed from the slope and inter- nitude of KF indicates the adsorption capacity, whereas the magnitude
cept, respectively of the linear graph [220,227,241]. In Table 6, the qm of 1n expresses the strength of adsorption [220].
values for the adsorption/sorption of different metal ions on various cel- In contrast to Langmuir isotherm model, Freundlich adsorption iso-
lulose grafted and functionalized copolymers are presented. therm assumes a multilayer adsorption, with non-uniform distribution
Another dimensionless factor called separation constant, RL is used of heat of adsorption over the heterogeneous adsorbent surface [250].
to describe the afnity between the metal ions and cellulose based
grafted copolymers and hence the shape and favorability of the Lang- 7.2.3. Temkin adsorption isotherm
muir adsorption isotherm (Eq. (36)), where The model is based on the assumption that the heat of adsorption
and binding energy of all the adsorbed molecules/ions of adsorbate de-
crease linearly rather than logarithmically with the binding of the ad-
1 sorption sites present on the surface of adsorbent species at a
RL 36
1 Co K L particular temperature [271]. Secondly, it was assumed that there is a
uniform distribution of the binding energies during adsorption. Follow-
ing equations express the Temkin isotherm model (Eqs. (39)(42)).
For linear and irreversible Langmuir adsorption isotherm RL = 1 and
0, respectively. For favorable tting, RL = 0 1, whereas for unfavor- RT
qe ln AT C e 39
able tting, RL N 1 [8,250,254]. RL values of 0.45460.8929 were reported b
for the adsorption of Cu2+ ions for solutions with 50500 mg L1 con-
centrations onto cotton cellulose-graft-polycaprolactone copolymer RT RT
qe ln AT lnC e 40
[269]. In another study, the RL values were 0.14 and 0.095 for Cu2 + b b
and Hg2+ ions, respectively when adsorbed on Cellulose-g-GMA func-
qe B lnAT B ln C e 41
tionalized with diethylenetriamine [227]. For the adsorption of Cu2+
and Ni2 + ions onto hydrazinolyzed Cell-g-p(MA), the RL values were where
0.04419 and 0.72486, respectively [250].
RT
B 42
b

where,
R = Gas constant (8.314 Jmol1K1)
T = Absolute temperature (K)
AT = Temkin isotherm equilibrium binding constant (mLmg1)
B = Constant heat of sorption
b = Adsorption capacity of the adsorbent (Jmol1)
KDR = Parameter for expressing free energy of sorption per mole of
adsorbate (mol2/KJ2)
The factor B is a direct measure of adsorbentadsorbate interac-
tions. The factors like AT, b, and B can be computed from slope and inter-
cept of the graph obtained by plotting qe vs lnCe.

7.2.4. DubininRaduskevich adsorption isotherm

Fig. 9. Effect of pH on the adsorption of Cr6+ onto acrylic acid grafted lignocellulosic
adsorbent.
Reprinted with permission from [176]. Copyright 2012 Elsevier B.V.
DubininRadushkevich adsorption isotherm is generally applied to
estimate the porosity of the adsorbent, to distinguish between
physisorption and chemisorption of metal ions with its mean free ener-
gy (E) and to express the adsorption mechanism with a Gaussian energy
distribution onto the heterogeneous surface of the adsorbent [220]. The
model has often successfully tted high solute activities and the inter-
mediate range of concentrations data well (Eqs. (43)(45)).
qe qm :eK DR 2
43
82 R. Kumar et al. / Journal of Molecular Liquids 232 (2017) 6293

Fig. 10. Effect of time on the adsorption capacities of heavy metal ions in the presence of (a) SLS and (b) DTAC.
Reprinted with permission from [187]. Copyright 2016 Elsevier Ltd.

ln qe ln qm K DR 2 44 temperature-dependent model calculates the adsorption mean free en-

ergy (E) (Eq. (46))
where,
1

 E p 46
1 2K DR
RT ln 1 45
Ce
Positive E value is a direct indication of the endothermic nature of
where, the sorption of metal ions on the surface of grafted cellulosic adsorbents.
KDR = Parameter for expressing free energy of sorption per mole of For the adsorption of Pb2+ ions onto Cellulose acetate-g-acrylic acid-co-
adsorbate (mol2/KJ2) acrylamide binary copolymer, E-value was reported to be
= DubininRadushkevich isotherm constant also called Polanyi 14.01 kJmol1 [220]. For E = 816 kJmol1, the sorption is excep-
potential. tionally governed by ion-exchange mechanism [272273]. For refer-
The values of qm and KDR can be calculated from the intercept and ence, the typical Langmuir, Freundlich, DubininRadushkevich and
slope respectively, of the graph plotted between ln qe and 2. Higher Temkin adsorption isotherms for the adsorption of Cu2 + and Ni2 +
the value of qm, greater is the adsorption capacity of the adsorbent (cel- ions onto cellulose-g-polycaprolactone copolymer synthesized by via
lulose grafted copolymers in this case). The factor, KDR in this ring-opening polymerization carried out in ionic liquid 1-N-butyl-3-
methylimidazolium chloride are shown in Fig. 13. The adsorption of
Cu2+ tted well with Langmuir, Freundlich, and Temkin adsorption iso-
therm models while the adsorption of Ni2+ followed Freundlich iso-
therm model only [269].

Fig. 11. Effect of initial concentration of Cu2+ on adsorption capacity on epoxidized and Fig. 12. Pb2+ ions sorption by CA-g-AA-co-AAm at 25 0.2 C, initial [Pb2+] = 10 ppm,
aminated bagasse pulp cellulose. pH = 4.55.0.
Reprinted with permission from [246]. Copyright 2015 Elsevier Ltd. Reprinted with permission from [220]. Copyright 2015 Elsevier B.V.
 R. Kumar et al. / Journal of Molecular Liquids 232 (2017) 6293 83

Table 6
Grafting parameters, optimized conditions for sorption of different metal ions and adsorption capacities for grafted cellulose based biosorbents.

S.N. Grafted cellulosic biosorbent Pg Metal ions pH Contact Sorbent Volume T [Mn+] qmaxa Pu (%) Ref.
(%) time (h) dose (g) (mL) (C) (mg/L) (mg/g)

1 Cell-g-p(AAm) 170 Cr3+ 1 0.1 25 RT 20 94.5 [7]

Pb2+ 90.0
Mn2+ 92.5
Ni2+ 82.0
Hydrolyzed Cell-g-p(AAm) 190 Cr3+ 1 0.1 25 RT 20 97.0
Pb2+ 92.0
Mn2+ 95.0
Ni2+ 90.0
2 Cell-g-p(AN) Cr6+ 5 6 1 100 30 200 371.9 86.2 [8]
3 Cell-g-p(AN) 22.0 Cd2+ 2 1 100 29 100 13.26 [9]
Cu2+ 12.96
Cell-g-p(AA) 26.0 Cd2+ 2 1 100 29 100 21.21
Cu2+ 15.22
4 Cell-g-GMA-I Ni2+ 46 6.67 0.2 50 40 204000 48.3 [171]
5 APBS 78.6 Cu2+ Zn2+ 26 3 0.1 50 30 100 47 [174]
(GE) 1012 45.8
6 Ficus carica ber Cell-g-AA Cr6+ 3.5 3 0.5 100 30 400 28.90 [176]
7 Nano magnetic Cell-g-p(GMA) (immobilized Hg2+ Cu2+ 2 35b 0.1 100 25 7c 2.00 [179]
with tetraethylenepentamine) Ag+ 1.50
1.20
8 Cell-g-GMA-I Cu2+ 7 1 0.2 25 23 1000 97.33 [186]
9 p(MAA-co-MAc)-g-nanobrillated cellulose Pb2+ Cd2+ 5 3 0.2 RT 165 [212]
Zn2+ 135
Ni2+ 138
117
10 CA-g-(AA-co-AAm) 135.2 Pb2+ 25 1.5 0.252 1000 25 10100 66.67 86.3 [220]
11 Cell-g-HEMA 245.1 Cr6+ Cu2+ 7 2 0.1 20 RT 5.0 9.84 [221]
Fe2+ 3.0 8.5
0.6 24.03
Cell-g-HEMA-co-AAm 383.6 Cr6+ Cu2+ 7 2 0.1 20 RT 5.0 19.67
Fe2+ 3.0 16.26
0.6 20.14
Cell-g-HEMA-co-AAc 330.9 Cr6+ Cu2+ 7 2 0.1 20 RT 5.0 13.13
Fe2+ 3.0 32.10
0.6 32.16
Cell-g-HEMA-co-AN 404.9 Cr6+ Cu2+ 7 2 0.1 20 RT 5.0 16.39
Fe2+ 3.0 14.56
0.6 3.53
12 GMA-g-densied cellulose with quaternary Cr6+ 4.5 1 0.1 50 30 100 123.6 [222]
ammonium groups
2+
13 Cell-g-PGMA-PEI 170 Cu 5 1 0.05 30 28 300 102.0 94.0 [223]
14 Cell-g-GMA-diethylene triamine Cu2+ Hg2+ 5.3 10b 0.1 100 25 5c [227]
4
15 Corn stalk grafted acrylonitrile copolymer 42.3 Cd2+ 7 6 0.5 50 20 22.17 99.2 [228]
(AGCS)
16 Cell-g-GMA 91.6 Hg2+ 5 0.5 25 RT 50 37.03 [241]
17 p(AN-co-MAA)-g-cell 53.78 Cu2+ Zn2+ 5.5 3 0.05 50 25 1001000 76.82 [247]
Cd2+ 6.5 62.89
Pb2+ 6.0 141.73
5.5 268.32
18 PMAAC 100 Cu2+, 7 1 1.0 50 1000 247 [248]
Co2+ 252
Ni2+ 242
19 Cell-g-p(GMA) 271.3 Cu2+ Fe2+ 7 2 0.1 20 RT 20 3.37 [249]
Cr6+ 51.86
9.84
Cell-g-p(GMA-co-AAm) 398.4 Cu2+ 7 2 0.1 20 RT 20 12.38
Fe2+ 25.80
Cr6+ 24.59
Cell-g-p(GMA-co-AN) 308.8 Cu2+ Fe2+ 7 2 0.1 20 RT 20 5.34
Cr6+ 6.36
21.31
Cell-g-p(GMA-co-AA) 448.0 Cu2+ Fe2+ 7 2 0.1 20 RT 20 22.82
Cr6+ 39.93
16.39
20 Hydrazinolyzed Cell-g-p(MA) Cu2+ Ni2+ 5 24 0.05 250 28 100500 229.36 [250]
4.5 173.91
6+ b
21 Quaternary ammonium functionalized cellulose Cr 3 50 1 1000 25 1.0 ~100 [252]
nanobers
5+
22 Amine-Modied p(GMA)-g-Cell 81.3 V 6 3 0.56.0 1000 30 25 197.75 99.6 [253]
(GE)
23 Cellulose-g-calix [4]arene Co2+ Ni2+ 1 0.025 10 25 0.02c 20.4 [255]
Cu2+ 30.5
Cd2+ 25.0

(continued on next page)

84 R. Kumar et al. / Journal of Molecular Liquids 232 (2017) 6293

Table 6 (continued)

S.N. Grafted cellulosic biosorbent Pg Metal ions pH Contact Sorbent Volume T [Mn+] qmaxa Pu (%) Ref.
(%) time (h) dose (g) (mL) (C) (mg/L) (mg/g)

Hg2+ 22.1
Pb2+ 21.4
21.5
24 Cell-g-p(MA) with poly(hydroxamic acid) ligand Cu2+ 6 2 0.15 10 30 0.1 M 320 99.0 for each [256]
Fe3+ 255 metal ion
Mn2+ 260
Co3+ 300
Cr3+ Ni2+ 280
Zn2+ 233
223
25 2-Mercaptobenzothiazole impregnated cellulose Hg2+ 4 0.2 30 100 204.08 [257]
26 2-Mercaptobenzothiazole impregnated cellulose Pd2+ 5 0.5 25 RT 10 5.0 99.0 [258]
27 4-Vinylpyridine-grafted- U6+ 7 3 2.5 1000 30 10 133.95 100 [263]
vinyltriethoxysilane-cellulose 40 137.05
50 146.88
60 147.16
28 Cell-g-p(AA) 40 Pb2+ 7 2 0.2 100 30 250 100 [264]
29 Luffa cylindrical ber Cell-g-AA 90.8 Mg2+ 7 2.5 0.5 100 25 300 45 [265]
Ni2+ 20
Zn2+ 8
30 Cell-g-p(AAm)/Hydroxyapatite Cu2+ 5.8 12 0.04 50 20 3.6c 175.4 [266]
31 Cell-g-p (AA) Cu2+ Ni2+ 7 72 0.1 25 RT 1000 181 [267]
183
32 Cell-g-p(AA) with poly(amidoxime) ligand 135 Cu2+ 6 2 0.15 10 30 0.1d 236.4 [268]
Fe3+ 213.2
Co3+ 191.9
Cr3+ Ni2+ 205.3
170.0
a
Amount of metal ions adsorbed on the adsorbent at equilibrium as calculated from Langmuir adsorption isotherms.
b
Time in min.,
c
Concentrations in mM units,
d
Concentrations in M units,

7.2.5. RedlichPeterson adsorption isotherm
This is a hybrid isotherm which can be applied to heterogeneous as
well as homogeneous systems over a wide range of adsorbate concen-
trations and incorporates Langmuir and Freundlich isotherms equations
into one empirical equation [274276]. The linear form of the Redlich
Peterson isotherm is expressed as shown in Eq. (47).


Ce
ln K R 1 ln aR ln C e
qe
where,
is the exponent such that = 1 0.
aR and KR = RedlichPeterson isotherm constants
When = 0, equation follows Henry's Law and when = 1, it fol-
lows Langmuir isotherm.
Various studies conducted have revealed that the experimental data
better ts into Langmuir isotherm model as compared to the Freundlich
model with few exceptions. These results thus conrm the fact that
chemisorption is mainly responsible for adsorption of the dye molecules
onto the surface of the grafted cellulose based adsorbents as compared
to physisorption.
7.3. Adsorption kinetics
providing the information about the mechanism of biosorption and
the efciency of the biosorbent. Additionally, it also helps in optimizing
the reaction conditions and parameters [277]. Many kinetic models
such as pseudo-rst-order, pseudo-second-order, intra-particle-diffu-
sion, and liquid lm-diffusion models reported in the literature to eval-
uate the kinetic parameter of the adsorption [8,179,220,227,246,276].
7.3.1. Pseudo-rst-order model
47
The model is based on the basic assumption that rate of change of
sorption of metal ions on grafted cellulose biosorbents, is directly relat-
ed to the difference in saturation concentration, the quantity of metal
ions sorbed with time and number of free sites available for sorption
[278]. The Lagergren equation for pseudo-rst-order model can be
expressed as follows (Eq. (48)) [279].
dqt
k1 qe qt 48
dt
After integrating Eq. (48) within suitable limits i.e. t = 0 to t = t and
qt = 0 to qt = qt, the integrated linearized forms of this are represented
in following Eqs. (49) and (50)

The speed with which the metal ions are adsorbed/sorbed from the Inqe qt In qe k1 t 49
medium onto the surface of cellulose graft copolymers is dened as the
rate of adsorption. This rate and hence kinetics of the sorption of differ-
ent metal ions on the active sites of the grafted cellulose based k1
logqe qt logqe t 50
biosorbents depends on many factors. These factors include electrostat- 2:303
ic forces of attractions between the functional groups (active sites) of
the biosorbent and metal ion species, ease of approachability of metal where,
ions to these active site, metal ion-solvent interactions, steric hindrance k1, = Equilibrium rate constant for pseudo-rst-order model (T1).
of the active sites, charge density and ionic radii of metal ions, pH of the qe, qt = Amounts of metal ions adsorbed at equilibrium and at any
medium, sorption mechanism etc. Kinetic studies are very helpful in contact time t (mgg1 or mmolg1).
 R. Kumar et al. / Journal of Molecular Liquids 232 (2017) 6293
Fig. 13. Different adsorption isotherms for the adsorption of Cu2+ and Ni2+ ions on cellulose-g-polycaprolactone copolymers (a) Langmuir, (b) Freundlich, (c) DubininRadushkevich and
(d) Temkin adsorption isotherms.
Reprinted with permission from [269]. Copyright 2015, Royal Society of Chemistry.
From the intercept and slope of the straight-line graph plotted be-
tween log(qe qt) vs t the values of qe and k1, respectively can be com-
puted (Fig. 14).
In the majority of the cases reported so far, a high degree of nonlin-
earity makes pseudo-rst-order kinetic model inefcient and inapplica-
ble for sorption studies related to metal ion sorption on grafted and
modied cellulose-based biosorbents. For higher metal ion concentra-
tions, the nonlinearity is further increased. This may be due to the esti-
mation of the amount of metal ions adsorbed at equilibrium (qe) from
the y-intercept corresponding to t = 0. The metal ion uptake reected
from the intercept is usually lower than the equilibrium uptake amount.
Hence metal ion uptake by cellulosic biosorbents does not follow a rst-
order kinetics, though the correlation coefcient values may be high
[174,212,220,222,228,241,243,252,264266].
7.3.2. Pseudo-second-order model
In this model, the rate-limiting step is the surface adsorption that in-
volves chemisorption, where the removal from a solution is due to
physicochemical interactions between the two phases [280]. The rate
of metal ion sorption is directly proportional to the square of the num-
ber of unoccupied sites [281]. The general form for the pseudo-second-
order model is represented in Eqs. (51) and (52).
dqt
k2 qe qt 2
dt
dqt
k2 dt
qe qt 2
Integrating Eq. (52) within suitable limits i.e. t = 0 to t = t and qt = 0
to qt = qt, the integrated linear forms of the pseudo-second-order are
represented as follows (Eq. (53))
t t 1
qt qe k2 q2e
85
For t = 0, the initial sorption rate h can be dened as follows
(Eq. (54)):
h k2 q2e 54
where,
k2 = Equilibrium rate constant for pseudo-second-order kinetic
model (gmg1 T1).
qe, qt = Amounts of metal ions adsorbed at equilibrium and at any
contact time t (mgg1 or mmolg1).
The values of qe and k2 can be determined experimentally from the
slope and intercept of the graph obtained by plotting qt against contact
t
timet (Fig. 14).
In contrast to pseudo-rst-order kinetic model, a high degree of lin-
earity along with correlation coefcient is observed for the pseudo-
second-order kinetic model. The adsorption capacities obtained from
this model match well with experimental results. The use of pseudo-
second-order model is further advantageous as it shows a regular
change in rate constant values over an appreciable range of initial
metal ion concentration [176,185,214,239,246,256,262263,265]. The
major disadvantage of the pseudo-second-order kinetic model is that
it cannot predict the diffusion mechanism [282].
51
7.3.3. Intra-particle-diffusion model
52 The unexplained limitation of diffusion mechanism in pseudo rst
and second-order kinetics is well explained through intra-particle diffu-
sion model proposed by Weber and Morris [283]. This model describes
the rate of adsorption as the speed at which metal ions diffuse out from
the solution phase toward the cellulose grafted porous biosorbent. This
diffusibility plays a crucial role in deciding the overall rate of the adsorp-
tion process [284]. It was predicted that during a solid/liquid adsorption
53
process, metal ion uptake by the porous biosorbent depends on the
86 R. Kumar et al. / Journal of Molecular Liquids 232 (2017) 6293
Fig. 14. Different kinetics models for the adsorption studies of Pd2+ onto 2-Mercaptobenzothiazole impregnated cellulose (a) Pseudo-rst-order kinetics (b) Pseudo-second-order kinetics
(c) Intra-particle diffusion model.
Reprinted with permission from [258]. Copyright 2013 Elsevier B.V.
intra-particle mass diffusion - probably the slowest and hence rate de-
termining step [285]. In general, literature reported three stages
representing multi-linearity for the metal ion sorption process. First
and initial stage involves fast and instantaneous adsorption, the second
stage involves slow intra-particle diffusion controlled adsorption and
the third and nal stage involve diffusion of metal ions slowly from larg-
er pores to micropores of the adsorbent. This stage also marks the nal
equilibrium stage. The rate adsorption in the second intra-particle diffu-
sion controlled stage depends on the metal ion concentration, tempera-
ture, and density of active sites on the surface of adsorbent [286]. The
linear equation for intra-particle diffusion model is given in Eq. (55)
p
qt kIP t C
where,
kIP = Intra-particle diffusion rate constant [mg/(gT)1/2 or mmol/
(gT)1/2]
C = Constant parameter corresponding to boundary layer thickness
(mgg1 or mmolg1)
p RT
A plot between qt and t gives an intercept equivalent to boundary
layer thickness (Fig. 14). Higher is the value of intercept, greater is the
extent of boundary layer thickness, more pronounced are the boundary
layer effects, and hence lesser is the rate of Intra-particle diffusion [258,
286287].
Among the various models discussed for adsorption kinetic studies
so far, the pseudo-second-order kinetic model is the most suitable
one. A high degree of linearity can be clearly seen for the pseudo-
second-order kinetic model as compared to other two models for the
adsorption of Pd2+ ions onto 2-Mercaptobenzothiazole impregnated
cellulose (Fig. 14).
Various kinetic parameters for different kinetic models are repre-
sented in Table 7 for the sorption of Cu2 +, Ni2+, Cd2+ and Pb2+ ions
onto thermo-responsive Cell-g-p(NIPAM) copolymer based biosorbent
the presence of DTAC at 50 C temperature. A comparison of the corre-
lation coefcient (R2) values for different kinetic models for different
metal ions clearly reveals that the pseudo-second-order kinetic model
is best suited for the kinetic studies of metal ions sorption onto the sur-
face of cellulose grafted biosorbents [187].
7.4. Adsorption thermodynamics
55
From Langmuir adsorption isotherm constant KL, the thermodynam-
ic parameters for the adsorption of metal ions on the grafted cellulosic
biosorbents can be estimated using van't Hoff equation (Eq. (56))
[179,288].
H o So
ln K L 56
T
where, H (kJmol1), S (kJmol1K1) = enthalpy and entropy
changes, respectively,
R = Gas constant, and T = Absolute temperature (K).
It is a straight-line equation and from the slope and intercept of the
graph plotted between lnKL vs 1 T1, the values of H/R and S/R,
respectively can be calculated (Fig. 15). A negative value of H/R indi-
cates the exothermic nature of adsorption.
 R. Kumar et al. / Journal of Molecular Liquids 232 (2017) 6293 87

Table 7 morphologies even after 4 adsorptiondesorption cycles for Cr6+ ions.

Kinetic parameters for pseudo-rst-order kinetics, pseudo-second-order kinetics and The desorption percentage can be calculated using Eq. (59).
intra-particle diffusion models for the adsorption of heavy metal ions sorbed on Cell-g-
p(NIPAM) copolymer based biosorbent.
Concentration of metal ions desorbed
Reprinted with permission from [187]. Copyright 2016 Elsevier Ltd. Desorption%  100 59
Concentration of metal ions adsorbed
Kinetic Model Heavy metal ions

Cu2+ Ni2+ Cd2+ Pb2+ For the removal of metal ions from adsorbents with acidic functional
Pseudo-rst-order
groups, the use of a concentrated mineral acid solution like HCl, HNO3,
qe (mmolg1) 0.8132 0.0948 0.0872 0.0915 H2SO4 etc. is favored [9,221,250,256]. In contrast, for adsorbents with
K1 (h1) 0.0883 0.2528 0.2802 0.2902 basic functional groups like quaternary ammonium salts, concentrated
R2 0.9451 0.8447 0.9425 0.9761 alkaline solutions are utilized as eluting agents [222,252]. Another ap-
Pseudo-second-order
proach is the use of strong complexing agents such as EDTA, thiourea,
qe (mmolg1) 1.0537 0.4360 0.8505 0.3849
K2 (gmol1 h1) 0.2656 1.2195 1.2963 0.7283 urea, thiocyanates etc., which are capable of strongly binding the
R2 0.9905 0.9927 0.9986 0.9938 metal ions as compared to the active sites of the cellulosic grafted poly-
Intra-particle diffusion mers [179,212,258]. Some halo compounds such as KI and KCl are also
KIP (1) [mmol/(gh)1/2] 0.1328 0.0420 0.0683 0.0787 reported in the literature for the efcient desorption of Hg2 + ions
C1 (mmolg1) 0.2231 0.2045 0.5362 0.0246
R21 0.9673 0.9665 0.9472 0.9309
through the formation of respective tetra half derivatives [257]. Maatar
KIP (2) [mmol/(gh)1/2] 0.0954 0.0264 0.0273 0.0266 et al. [212] compared the eluting efciencies of EDTA and HNO3 solution
C2 (mmolg1) 0.3645 0.2472 0.6568 0.1850 for the elution of Pb2+, Cd2+, Zn2+ and Ni2+ from p(MAA-co-MAc)-g-
R22 0.9787 0.9494 0.9387 0.9780 nano brillated cellulose as biosorbent. The higher stability constant
The parameters and symbols used in the above adsorption isotherms expression are as follows values (logK = 1214) for metal ion-EDTA complexes as compared to
k1, k2 = Equilibrium rate constants for pseudo-rst-order (T1) and pseudo-second-order metal ion-maleic acid complexes (logK = 23) favor the removal of
kinetic models (gmg1 T1), respectively. adsorbed metal ions by EDTA as compared to mineral acids (Fig. 16).
qe, qt = The amount of metal ions adsorbed at equilibrium and at any contact time t
(mgg1 or mmolg1).
kIP = Intra-particle diffusion rate constant [mg/(gT)1/2 or mmol/(gT)1/2] 8. Conclusion
C = Constant parameter corresponding to boundary layer thickness (mgg1 or
mmolg1) Grafted cellulose based copolymers are reported as potential candi-
dates for the effective metal ion sorption applications. Among the vari-
ous grafting techniques, free radical grafting using chemical initiators is
the most recognized and applied technique as it is cost effective, facile,
The value of KL, equivalent to the equilibrium constant (K) can also fast, with a higher degree of polymerization, and devoid of complicated
be calculated from the concentration of adsorbed metal ions and instrumentations. Grafting of the cellulose backbone can control the
metal ions present in the solution at equilibrium (Eq. (57)) [258]. structural, physical, chemical, mechanical and thermal properties of
the cellulose. Proper optimization of the grafting parameters and condi-
 n 
M tions, choice of proper monomer species to be grafted and type of initi-
K  n ads 57 ator used etc. increase the density of the active sites in the form of
M sol
functional groups that act as excellent adsorption sites for a variety of
Gibb's free energy change (G) can also be estimated from H and toxic heavy metal ions. Nature of metal ions to be adsorbed, nature of
S values using Eq. (58) the active sites, the extent of grafting and swelling properties of the
grafted cellulose based biosorbents greatly affect the adsorption behav-
G H TS 58 ior. Various studies conducted so far reveal that the adsorption experi-
mental data better ts into Langmuir adsorption isotherm and
If G = Ve, the adsorption process is spontaneous in nature. For pseudo-second-order kinetics models as compared to the other adsorp-
maximum cases reported in the literature as H N TS, enthalpy factor tion and kinetic models with few exceptions. Desorption and adsorption
rather that entropy factor dominates during adsorption process [188, studies up to few cycles studied in many reports showed a marginal de-
289]. High temperature favors endothermic cellulose grafted crease in adsorption behavior of the grafted cellulose biosorbents. Che-
copolymermetal ion interaction, which in turn increase the value of lating agents were a quite effective eluting agent in desorption of
equilibrium constant. Increased degree of randomness, dispersion of
grafted polymer into medium and electrostatic interactions between
the polymer and solvent are indicated by the positive entropy changes
[241].

7.5. Desorption and regeneration studies

Desorption and regeneration studies not only help in the recycling of

the adsorbent by removing the metal ions loaded on it, but also help in
elucidating the mechanism of adsorption and in predicting the nature of
interactions between the metal ions and the adsorbent [222]. Recycling
of the adsorbent through a number of cycles is economical, environ-
ment benign and reduces the cost of production. Owing to the strong
cross-linking between monomers and cellulosic component, such ro-
bust biosorbents can withstand the harsh mechanical and chemical con-
ditions. Additionally, the separation of such microscopic biosorbents is
Fig. 15. van't Hoff plots for the determination of thermodynamic parameters for the
also easier as compared to other inorganic nano-sized adsorbents. Stud- adsorption of Hg2+, Cu2+ and Ag+ ions on Nano magnetic cellulose-g-GMA
ies carried out by He et al. [252] have shown that quaternary ammoni- (immobilized with tetraethylenepentamine).
um functionalized cellulose nanobers based aerogel maintained their Reprinted with permission from [179]. Copyright 2012 Published by Elsevier B.V.
88 R. Kumar et al. / Journal of Molecular Liquids 232 (2017) 6293
adsorbed metal ions as compared to mineral acids and base solutions.
Thus cellulose based grafted biosorbents can denitely help the human-
ity with an adequate supply of pure and drinkable water throughout the
world.
9. Future scope
1. The choice of the pre-treatment method depends on various factors
including nature and source of lingo-cellulosic biomass and applica-
tion of the pre-treated biomass. Further improvements for the devel-
opment of cost-effective, eco-friendly, fast, non-corrosive and
chemical free pre-treatment techniques are still required for com-
mercial and large-scale dissociation of the complex hierarchical
structure of lingo-cellulose biomass.
2. Purication and bleaching of the extracted cellulose from lingo-
cellulose biomass are another critical issues that still need to be ad-
dressed. Chlorine (Cl2) and chlorinated compounds such as hypo-
chlorites (ClO) chlorites (ClO 2 ), chlorine dioxide (ClO2) are
traditionally used as strong bleaching agents which may generate
and release many carcinogenic and mutagenic chlorinated organic
compounds into the environment during the processing of bio-
masses. These compounds are highly poisonous in nature and have
drastic effects on human health. The future research should thus
focus on the development of ECF, TCF and physicochemical tech-
niques such as ultrasonication, irradiation, photocatalytic degrada-
tion of various chromophores generated during the pre-treatment
process in order to reduce the environmental impacts.
3. From the literature review, it was observed that various grafting pa-
rameters for grafting monomers like GMA, AA, AAm, AN, MMA, EMA,
MAc, MA, MAA, etc., onto the cellulose have been optimized and the
same has been used as biosorbents for various metal ions and dyes.
However, there is a limited literature which reports other monomers
such as AASO3H, NIPAM, HEMA, 4-Vinylpyrrolidine etc. for the syn-
thesis of pristine and binary copolymer grafted cellulosic
biosorbents. Future research thus should focus on the utilization of
new monomeric species, optimization of grafting parameters for
these monomer, and subsequent use of the grafted biosorbents as
super-adsorbents for metal ion and dye sorption applications.
4. Recent developments in the eld of nanotechnology has already
stimulated the research to solve world's current problems. One of
the major applications of nanotechnology and nanoscience includes
the use of a number of n- and p-type metal oxide semiconductor
nanomaterials such as ZnO, CuO, and TiO2 to generate free radical
Fig. 16. Adsorption-Desorption behavior of metal ions onto p(MAA-co-MAc)-g-
nanobrillated cellulose using EDTA and HNO3 striping solution [212].
Copyright 2015 Elsevier Ltd.
species under UV or visible light irradiation. These radical species
may be the potential substitutes for already existing chemical initia-
tors in polymerization reactions. Many of these metal oxide
nanomaterials are easy to synthesise, non-toxic, and biocompatible
and can be developed as new eco-friendly initiators for grafting
monomers to cellulose backbone. In addition, these nanomaterials
can also be used along with traditional chemical initiators to enhance
the rate of the free radical polymerization process.
5. The studies reported for the metal ion sorption applications using
grafted cellulose biosorbents so far has been largely conducted only
for very dilute metal ion solutions. In-depth research is still required
to study the metal ion sorption behavior for different metal ions
when present simultaneously in the solution. The future research
thus should focus on the commercialization of these cellulose-
based biosorbents and subsequent use for the real sample purica-
tion applications.
6. Recycling of the adsorbent through a number of cycles is economical
as well as environment benign. Thus, regeneration and desorption of
these cellulose grafted biosorbents are other critical issues, which
still need improvements. Extensive and fruitful future research for
the synthesis of cellulose based grafted biocompatible, biodegrad-
able, economic, stimuli-responsive and nontoxic biosorbents will
denitely help the humanity and future generations with an ade-
quate supply of pure and drinkable water.
Funding sources
This research did not receive any specic grant from funding agen-
cies in the public, commercial, or not-for-prot sectors.
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