Emerging Applications of Graphene and Its Derivatives in Carbon Capture and Conversion: Current Status and Future Prospects PDF

Renewable and Sustainable Energy Reviews 41 (2015) 15151545
Contents lists available at ScienceDirect
Renewable and Sustainable Energy Reviews

journal homepage: www.elsevier.com/locate/rser
Emerging applications of graphene and its derivatives in carbon

capture and conversion: Current status and future prospects
Amin Taheri Najafabadi n
Department of Chemical and Biological Engineering, Clean Energy Research Center, The University of British Columbia, 2360 East Mall, Vancouver, BC,
Canada V6T 1Z3
art ic l e i nf o
a b s t r a c t
Article history:
Received 1 March 2014
Received in revised form
9 August 2014
Accepted 17 September 2014
Available online 1 November 2014
Alarming carbon dioxide emissions and its detrimental environmental impacts (e.g. climate change and
global warming) are the major consequences of the undue reliance of the modern civilization on fossil
fuels. Long-term solutions to address these issues are based on developing sustainable alternatives for
the human energy thirst. However, the versatilities offered by the carbonaceous fuels have still
preserved their popularity as the main source of energy for a wide variety of applications. After decades
of practicing conventional carbon capture and storage, researchers believe the ultimate solution of
realistically facing with CO2 sequestration problem is the chemical conversion of carbon dioxide to
valuable products. However, substantial development of state-of-the-art materials remains the major
bottleneck of such technologies. Graphene, as the rising star of the materials world in 21st century, offers
game-changing prospects towards a more sustainable future for fossil-fuel-based economies. This twodimensional planar sheet of sp2-bonded carbon atoms is the most widely studied nanomaterial since its
discovery in 2004. Here we aim to highlight various aspects of graphene research in carbon dioxide
capture and conversion from materials viewpoint. After presenting an overview of the most common
and effective synthesis and doping/functionalization methods, the application of graphene and its
derivatives in CO2 capture and conversion is discussed in detail. Catalytic, electrocatalytic and
photoelectrocatalytic use of graphene-based compounds could potentially revolutionize some of the
current techniques for CO2 transformation to valuable chemical commodities. CO2 to graphene
conversion pathways are also covered extensively in this review paper as another intriguing relation
of graphene with CO2.
& 2014 Elsevier Ltd. All rights reserved.
Keywords:
CO2
Carbon capture and conversion
Graphene
Catalysis
Electrocatalysis
Photoelectrocatalysis
Contents
1.
2.
3.
4.
5.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1516
Graphene synthesis overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1517
2.1.
Scalable top-down production techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1518
2.2.
Chemical doping/functionalization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1520
2.2.1.
Doping (condensed matter). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1520
2.2.2.
Functionalization (chemical synthesis) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1522
CO2-assisted graphene production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1525
Graphene-assisted CO2 capture. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1527
4.1.
CO2 capture background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1527
4.2.
Graphene-based sorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1527
Graphene-assisted CO2 conversion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1531
5.1.
CO2 conversion background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1531
5.2.
Catalytic reduction of CO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1532
5.2.1.
Hydrogen-assisted CO2 reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1532
5.2.2.
Methane-assisted CO2 reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1533
Tel.: 1 604 827 3418; fax: 1 604 822 6003.

E-mail address: ataheri@chbe.ubc.ca
http://dx.doi.org/10.1016/j.rser.2014.09.022
1364-0321/& 2014 Elsevier Ltd. All rights reserved.
1516
A. Taheri Najafabadi / Renewable and Sustainable Energy Reviews 41 (2015) 15151545
5.3.
Electrocatalytic reduction of CO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.4.
Photoelectrocatalytic reduction of CO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6. Concluding remarks. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1. Introduction
Energy and environmental issues are two of the major challenges facing modern civilization by the mid-century [1]. From this
perspective, fossil fuels are double-edged swords that require a
delicate balance between their benets and drawbacks. On one
hand, they are unquestionably versatile energy supplies; where oil
and natural gas supply close to 90% of our current energy needs,
making so many industrial activities economically feasible [2]. The
adaptabilities offered by the carbonaceous fuels have still preserved their popularity as the main source of energy for a wide
variety of applications. Firstly, they are available in a wide range of
physical formats (gas, liquid and solid) spreading almost all over
the world. Secondly, myriad of technological advances are made
with respect to their implementation for various applications in
different scales. Thirdly, owing to high energy density and portability, their superior properties as fuels in transportation industry
cannot be overstated [3]. On the other hand, the increasingly
alarming climate change issues have occurred due to notable
amounts of carbon dioxide emissions from undue consumption
of fossil fuels [4]. Burning each gram of carbon in fossil fuels
releases more than 3.5 g of carbon dioxide (CO2), accumulation of
which is now approaching 1 Tt in the atmosphere [5]. In order
to limit the consequent global mean temperature increase by
2.02.4 1C, the world-wide CO2 emission must be reduced
5080% by 2050 versus that of 2000 [6,7].
Long-term solutions to address the aforementioned problems
are based on the development of sustainable alternatives for
quenching the ever-increasing human energy thirst. Meanwhile,
in the current fashion of runaway fossil fuel intakes, CO2 reduction
strategies particularly from large-scale energy consumers (e.g.
power stations and cement works) rely mainly on three proposed
1534
1535
1537
1537
generic solutions for CO2 capture and storage (CCS): pre- and postcombustion capture, and oxy fuel combustion [8,9]. Afterwards,
the puried CO2 is sent for physical storage options such as
deep ocean sequestration [10], geological storage [11], limited
industrial uses (e.g. mineral processing and soda companies)
[12], etc. However, researchers believe that storing CO2 somewhere other than atmosphere is not the permanent solution to the
problem [13,14]. In fact, the long term ecological and environmental impacts of using the earth as a gigantic reservoir for carbon
dioxide are not well-understood [10,15]. The potential hazards of
CO2 leakage to the earth surface remarkably increases the risk of
this approach [16,17]. It also imposes signicant nancial burdens
on the industrial rms from expensive CO2 capture equipment to
hefty sequestration costs ultimately translated into higher prices
for the end-users [18,19].
Based on the facts mentioned, chemical transformation of CO2
can be the realistic solution to the CO2 sequestration concerns;
which could ultimately lead to the utopia for fossil-fuel-based
economies with taking full advantage of the carbonaceous fuels
while minimizing their negative environmental impacts. This
approach of recovering CO2 in order to synthesize useful products
is capable of sustainable reduction of carbon emissions, and is
known as carbon capture and conversion (CCC) [20]. The economic
advantages of producing valuable chemicals from CO2 provide
further incentives for major emitters to move towards this
direction.
The author has recently published a critical review paper on the
state-of-the-art CCC technologies, addressing more efcient material development as the main bottleneck in this eld of research
[21]. Graphene, as the rising star of the materials world in 21st
century, offers game-changing prospects towards a more sustainable future for fossil-fuel-based economies. This two-dimensional
Fig. 1. Graphene, the mother of all carbon dimensions with myriad of applications (right, Reprinted with permission from Ref. [22], Copyright 2011, American Physical
Society).
Nomenclature
NMP
NPD
ARPES
APCVD
Eg
CCC
CCS
CMS
CNT
CCM
CVD
DRM
CB
DFT
DOS
DMF
ERC
EF
FLG
FWHM
f-HEG
GCMC
GO
GN
G-silica
GMNO
GIC
HOMO
HRTEM
HEG
IGCC
1-methyl-2-pyrrolidone
4-nitrophenyl diazonium
angle-resolved photoemission spectroscopy
atmospheric pressure chemical vapor deposition
band-gap energy
carbon capture and conversion
carbon capture and storage
carbon molecular sieve
carbon nanotube
catalytic combustion of methane
chemical vapor deposition
CO2 reforming of methane
conduction band
density functional theory
density of states
dimethylformamide
electrochemical reduction of carbon dioxide
Fermi energy
few-layer graphene
full-width at half-maximum
functionalized hydrogen exfoliated graphene
grand canonical Monte Carlo
graphene oxide
graphene sheets
graphene-based mesoporous silica
graphene-Mn3O4 hybrid
graphite intercalation compound
highest occupied molecular orbital
high-resolution transmission electron microscopy
hydrogen exfoliated graphene
integrated gasication combined cycle
planar sheet of sp2-bonded carbon atoms is the most widely studied

nanomaterial since its discovery in 2004 by Dr. Andre Geim and
Dr. Konstantin Novoselov [22,23]. Considering its numerous unique
properties, graphene can be implemented promisingly within many
areas of energy and environmental research [24,25]. It has a large
theoretical specic surface area (2630 m2 g 1) [26], high intrinsic
charge mobility (200,000 cm2 v 1 s 1) [27], strong Young's modulus ( 1.0 TPa) [28], and excellent thermal conductivity
( 5000 W m 1 K 1) [29], while having signicant optical transmittance ( 97.7%) for application as transparent conductive electrodes [30,31].
Graphene has been used for many key applications, particularly: (i) in energy-related areas, modied graphene materials
have been used in solar cells [32,33], while metallic/metal
oxides combined with graphene are utilized in lithium ion
batteries [34,35], supercapacitors [36,37], andfuel cells [38,39];
(ii) in the environmental pollution remediation area, graphene
and magnetic graphene nanomaterials have been employed as
adsorbents for heavy metal ions and organic pollutants [40],
while several transition-metal oxide graphene hybrids are studied
for the degradation of toxic organic pollutants [41]. Graphenebased materials have been also examined as the pollutant
sensors [42] including CO2 sensing applications [43,44]. Importantly, chemical treatment of graphene remarkably broadens
its applications in cross-disciplinary areas with structural
doping and surface functionalization [45,46]. Fig. 1 demonstrates
graphene as the mother of all carbon dimensions with myriad of
applications.
LDH
LUMO
MOF
OFET
ORR
POM
PGNB
PES
PECVD
PANI
PEI
PPy
PS
PT
PC
rGO
RWGS
RTIL
SWCNT
SEG
sccm
H0
S0
G0
SMR
g
SOCl2
TiNS
TEM
VB
WE
XPS
1517
layered double hydroxide

lowest unoccupied molecular orbital
metal organic framework
organic eld effect transistors
oxygen reduction reaction
partial oxidation of methane
periodic graphene nanobuds
photoemission spectroscopy
plasma-enhanced chemical vapor deposition
polyaniline
polyethyleneimine
polypyrrole
polystyrene
polythiophene
propylene carbonate
reduced graphene oxide
reverse water-gas shift
room temperature ionic liquid
single wall carbon nanotube
solvent exfoliated graphene
standard cubic centimeters per minute
standard enthalpy change
standard enthropy change
standard Gibbs free energy change
steam methane reforming
structural parameter for C60 fullerene
thionyl chloride
TiO2 nanosheets
transmission electron microscopy
valence band
working electrode
X-ray photoelectron spectroscopy
This paper aims to highlight various aspects of graphene

research in carbon dioxide capture and conversion from materials
perspective. After presenting an overview of the most common
and effective synthesis and doping/functionalization methods, the
application of graphene and its derivatives in CO2 capture and
conversion is discussed in detail. Catalytic, electrocatalytic and
photoelectrocatalytic use of graphene-based compounds could
potentially revolutionize some of the current techniques for CO2
transformation to valuable chemical commodities. CO2 to graphene conversion pathways are also covered extensively here as
another intriguing relation of graphene with CO2. Since this review
paper is multi-disciplinary in nature, the audience across the
associated areas might not be necessarily familiar with all the
aspects. Therefore, the author has provided a concise background
for each section, and depending on their expertise, readers can
certainly skip some of the introductory sections. Such approach
maintains the comprehensiveness of the paper without requiring
to reach other references for some of the crucial terminologies and
background.
2. Graphene synthesis overview

There are two fundamentally different approaches to prepare
graphene sheets (GNs) as single-(or a few) layers of atoms, namely
top-down and bottom-up [47,48]. The top-down approach starts
with macroscopic structures, breaking them down into smaller
ones. In fact, Geim and Novoselov developed a top-down approach
1518
so-called micromechanical cleavage to extract single sheets of

atoms from three dimensional graphitic crystals using scotch tape
exfoliation [23]. Graphite, as an earth-abundant starting material
for the top-down preparation of graphene, offers a cost-efcient
and environmentally-friendly alternative to bottom-up nano-carbon based synthesis. However, the key challenge here is to
surmount the strong cohesive energy of the -stacked layers in
graphite (5.9 kJ mol 1 carbon) [49,50]. Other top-down methods
include wet chemical or electrochemical synthesis from graphite
intercalation compounds (GICs) [5153], direct liquid phase exfoliation [54], and solution-based chemical reduction of graphene
oxide (GO) [55,56]. GNs produced by the top-down approach are
usually mixtures of monolayers, bilayers and multilayers (typically
composed of three to ten monolayers), in the form of irregularly
structured akes (at or folded sheets) [57]. Such morphologies
still suit the majority of GNs applications in the energy sector, both
for energy storage and conversion [24,58].
On the other hand, production of GNs with only a few layers
and defect-free is certainly looked-for. Furthermore, employing a
straightforward top-down pathway is difcult to produce large
pieces of GNs (in the size of mm) that would be needed for
fabricating chips or other electronic devices. Therefore, bottom-up
techniques have been intensely investigated for technological
applications, in which single-layers of graphene are grown in
a step-wise manner from carbon atoms. This is mainly achieved
via epitaxial growth of GNs on a substrate by chemical vapor
deposition (CVD) [59,60], plasma-enhanced CVD (PECVD) [61,62],
solvothermal synthesis [63,64], pyrolysis [65,66], and thermal
decomposition of silicon carbide (SiC) wafer under ultrahigh
vacuum conditions [67,68].
All the above-mentioned processes have been studied in detail,
and described in several review articles [6971]. Additionally, a
high-throughput approach to determine the number of atomic
planes in GN samples has been recently introduced via optical
microscopy and subsequent image processing [72,73]. Here, we
mostly focus on scalable top-down GNs production techniques
considering the demanding industrial applications of graphene

especially in carbon capture and conversion. The complementary
doping/functionalization aspects, which greatly broaden graphene
applications, are also covered to provide the reader with sufcient
background for the subsequent sections.
2.1. Scalable top-down production techniques
At present, chemical oxidation of graphite to graphite oxide
followed by exfoliation to graphene oxide (GO), and then reducing
GO to graphene usually by chemical or thermal reduction has
emerged as a promising method due to its low-cost and mass
production potential [7478]. Graphite oxide is usually synthesized by oxidizing graphite via concentrated sulfuric acid, nitric
acid and potassium permanganate based on the Hummers method
[79,80]. It is important to note that although graphite oxide and
GO share similar chemical properties (i.e. surface functional
groups), their structures are different. GO is a monolayer material
produced by the exfoliation of graphite oxide [69]. Fig. 2 depicts
the graphene production pathway via effective reduction of the
mono-layered graphene oxide sheets.
Several reducing agents are proposed for chemical reduction of
GO sheets including hydrazine [8285], and sodium borohydrate
[86,87]. Hydrazine (N2H4), unlike other strong reductants, is
nonreactive with water and is suggested to be the most effective
in synthesizing ultrathin and ne graphene sheets [69]. Throughout the reduction process, the brownish GO dispersion in water
turns black, and the reduced sheets begin to agglomerate and
precipitate in the reaction vessel [77,88]. Such trends in color
changes and dispersibility of the reduced GO (rGO) in water are
rendered by the removal of oxygen atoms from the GO sheets,
making the nal product more blackish and less hydrophilic [69].
The restoration mechanism of the conjugated GN network through
hydrazine-assisted GO reduction has been proposed by Stankovich
et al. in Scheme 1 [77]. First, hydrazine partakes in a ring-opening
reaction with epoxides and transforms the epoxides into
Fig. 2. Graphene production pathway via effective reduction of the mono-layered graphene oxide sheets. Reprinted with permission from Ref. [81], Copyright 2011, WileyVCH.
hydrazino-alcohols [89]. This derivative then reacts further, converting to an amino-aziridine moiety which goes through thermal
elimination of di-imide to form a double bond [77]. Stable aqueous
suspensions of rGOs were obtained via pH adjustments
using ammonia solutions during reduction with hydrazine [90].
However, without surfactant-assisted stabilization, rGOs tend to
agglomerate in organic solvents due to their hydrophobicity
[77,88].
Sodium borohydride (NaBH4), as another promising reductive
agent, is reported to be more effective in removal of GO's oxygencontaining groups compared to hydrazine [86]; although borohydride is prone to hydrolysis by water [69]. The resulting rGOs show
lower sheet resistances of 59 k/m2 (comparing with 780 k/m2
for a hydrazine-reduced sample under similar circumstances), and
higher C:O ratios of 13.4:1 (compared to 6.2:1 for hydrazine) [86].
Other GO chemical reduction pathways include the use of hydroquinone [91], gaseous hydrogen (after thermal expansion) [92],
strong alkaline solutions [93], and solvothermal methods [94].
While hydrogen-assisted GO reduction was proved to be promising (C:O ratio of 10.814.9:1), hydroquinone and alkaline solutions
did not emerge as effective as hydrazine and sodium borohydride
based on semi-quantitative results [69].
Nonetheless, most of the reported chemical production techniques use harsh oxidizers (e.g. H2SO4/KMnO4), and an excess of
Scheme 1. Proposed reaction pathway for epoxide reduction with hydrazine.

Reprinted with permission from Ref. [77], Copyright 2007, Elsevier.
1519
organic solvents (e.g. dimethylformamide/tetrahydrofuran), which

are not environmentally benign [70,95]. Besides, the successive
reduction of GO sheets to graphene typically requires a strong
chemical reducer (e.g. hydrazine/sodium borohydride), and high
temperature heating in order to recover the graphitic structure by
lowering the lattice defects [56,96,97]. The severe poisonous and
explosive characteristics of hydrazine or sodium borohydride
derivatives dictate safety measures when large quantities are
used, making the process challenging in real conditions [98].
A handful of scalable environmentally friendly processes are
available to reduce GO to graphene either by chemical or electrochemical pathways [93,99]; however, developing more integrated
green approaches to the synthesis of graphene is still of great
interest.
To address the above-described issues, researchers have utilized electrochemical methods as a part of the GN fabrication
process [100106]. In principle, GN electrosynthesis employs an
ionically conductive solution (electrolyte) and a power source
to drive the structural changes through the graphite precursor
(e.g. rod, plate, or wire) placed as the working electrode (WE). This
offers a number of potential advantages including ease of operation and control over the entire synthesis process, being more ecofriendly with elimination of harsh oxidizers/reducers, relatively
fast fabrication rates, and high mass production potential at
ambient pressure/temperature. Presumably, direct exfoliation of
the graphene sheets from graphite would overcome the low
electronic conductivity of graphene lms chemically reduced from
GO derivatives [77,105]. As shown in Fig. 3, GNs electrosynthesis
particularly in the aqueous media is typically perceived to involve
the partial oxidation (or reduction) of the host graphite (WE) that
Fig. 3. Electrochemical approaches of (a) oxidation, intercalation and exfoliation (negative ions are shown in red color), and (b) reduction, intercalation and exfoliation to
produce single and multilayer GN akes (positive ions are shown in deep blue color). Reprinted with permission from Ref. [52], Copyright 2013, Elsevier. (a) Positive current
to produce "oxidised" GN akes and (b) Negative current to produce "non-oxidised" GN akes. (For interpretation of the references to color in this gure legend, the reader is
referred to the web version of this article.)
1520
leads to the intercalation of anions (or cations) from the electrolyte. The intercalation process prompts structural expansion in the
graphite matrix which was reported as blisters in early investigations [107]. This has been suggested to yield ultrathin GNs when
high voltages are applied to the graphitic electrodes in sulfuric
acid [101], and KOH solutions [108] at the anode and cathode,
respectively. Nonetheless, the exact exfoliation mechanism is still
debated, and more exhaustive experiments are required to verify
the described pathways illustrated in Fig. 3.
Due to limitations imposed by water electrolysis in aqueous
electrolytes, non-aqueous solvents or mixtures of aqueous with
non-aqueous components are generally employed to provide a
wider electrochemical window [103105]. Accordingly, amongst
anodic electro-exfoliations, large anions of PF6 , and/or BF4 in
ionic liquids have shown remarkable tendency to intercalate
graphite electrodes, yielding gram-scale quantities of carbon
nanostructures especially GN akes [105,106]. Air- and moisturestable room temperature ionic liquids (RTILs), salts of large organic
cations with relatively bulky inorganic counter-ions, are molten
salts with melting points close to room temperature [109,110].
Owing to low vapor pressure, high chemical and thermal stability,
solvating capability, non-ammability with potential recyclability,
RTILs have received much interest as green solvents in organic
synthetic processes to replace classic, toxic and volatile molecular
solvents [111,112]. Consequently, ILs are extensively used as a
reaction medium for the fabrication of conducting polymers and
nanoparticles [113116]. Additionally, their tunable physicochemical properties enable in-situ functionalization of GNs which is the
most important approach for expanding the graphene applications
throughout many key research themes [117,118].
Among the cationic electro-exfoliation reports, lithium
co-intercalation with propylene carbonate (PC) has been proposed
for high-yield production of few-layer graphene (FLG) ( 470%)
[103]. The process resembles the destructive effects of PC as a
molecular solvent on the graphitic electrodes in lithium-ion
batteries [119,120]. Intercalation of tetraalkylammonium cations
from 1-methyl-2-pyrrolidone (NMP) solutions is also reported
with signicant exfoliation rates as a viable choice for GN synthesis with low energy consumption and ease of operation [121].
In any case, a subsequent sonication treatment is suggested to
have complementary role in improving the quality of the electrosynthesis products particularly with boosting the exfoliation of the
expanded akes into the ultrathin sheets [103,106,121].
2.2. Chemical doping/functionalization
Any effort toward tailoring graphene characteristics by inserting external atoms or molecules to its sp2 network falls into
chemical doping/functionalization category. Physicists and chemists look at this subject from quite different perspectives, which
we have aimed to combine them here. Physicists are mostly
inclined to view this from electronic point of view, where any
external impurities can affect the band structure of graphene,
therefore focusing on the doping concept [122,123]. This is also
paraphrased as the adatom phenomenon for creating new body
states that do not appear in pure graphene [124,125]. On the other
hand, chemists are more interested in such modications for
functionalization and improving the processability of graphene;
hence they tend to discuss the concept from chemical synthesis/
activation approach [117,118]. This has often caused confusion
with misplacing the related categorizations which we tried to
address here.
In the most general classication, any impurity introduced to
graphene can interact in two major states. First, the impurity can
disrupt the sp2 network and cause sp3 defect regions via bonding
with graphene. This is something which is typically associated
with substitutional doping or covalent functionalization. Second

group consists of adatoms that tend to interact with graphene less
rigorously therefore do not cause sp3 defects in the graphene
lattice. Such modications, so-called surface transfer doping or
noncovalent functionalization, are typically reversible under especial circumstances. Importantly, substrate, chemical remnants and
ambient gases can render involuntary electronic effects in graphene [126128]. Here, the author briey overviews the concept
from condensed mater to chemical synthesis aspects.
2.2.1. Doping (condensed matter)

From condensed matter standpoint, graphene is constructed
via hybridization of s, px and py atomic orbitals forming sp2bonded carbon atoms via three strong bonds with three adjacent
atoms. The remaining pz orbital on each carbon center overlaps
with those from the neighboring atoms, establishing a lled band
of orbitals (valence band), and an empty band of n orbitals
(conduction band). Since the valence and conduction bands touch
at the Brillouin zone corners, graphene emulates a zero-band-gap
semiconductor [60]. Fig. 4A depicts the described energy distribution in graphene, and the corresponding inset for zero-band-gap at
one of the Dirac points (i.e. the intersection of the valence and
conduction bands) [129].
From vast amount of literature, doping of graphene can be
classied as (i) electrical doping (via changing gate voltage)
[132,133], (ii) substrate-induced doping (via interactions with
the support) [131], and (iii) chemical doping (via insertion of
external chemical species) [130,134]. Fig. 4B illustrates the strong
ambipolar eld effect in pristine graphene (i.e. mismatch between
Fermi level and Dirac point), resulted from electrical doping.
Fig. 4C shows the transference of the Dirac point relative to the
Fermi level prompted by chemical doping and draws a simultaneous comparison with the substrate-induced doping. We mainly
focus on the graphene chemical doping concept here, considering
its paramount importance to the context of this review article.
Before putting graphene to the test, chemical doping was
recognized to extend carbon nanotubes (CNTs) application in
variety of research areas [135139]. As previously described, two
chemical categories for ne-tuning of the graphene electronic
properties via doping include (i) adsorption of gas [42], metal
[140], or organic molecules to the graphene surface [141] (i.e.
surface transfer doping [142,143]), and (ii) substitutional doping,
which introduces heteroatoms, such as nitrogen [144], and boron
[145], into the conjugated graphene lattice [146,147]. Consequently, graphene band gap tuning via doping is employed to
fabricate high performance electronic devices [148,149].
The mechanism of chemical doping in graphene resembles that
of carbon nanotubes, however the latter is still debated [150153].
Surface transfer doping occurs through charge transfer from the
adsorbed dopant (or graphene) to graphene (or dopant) [131,142].
Charge transfer direction is determined by the relative position of
density of states (DOS) at the highest occupied molecular orbital
(HOMO) and lowest unoccupied molecular orbital (LUMO) of the
dopant compared to the Fermi level of graphene. If the dopant's
HOMO is above the graphene's Fermi level, charge ows from
dopant to graphene, and the dopant is considered donor; conversely, if the LUMO is below the Fermi level of graphene, charge
transfers from graphene layer to dopant, and the dopant acts as an
acceptor [129,154]. Consequently, graphene can be p-type or ntype doped according to the described electron exchange patterns
[154,155]. p-type doping lifts the graphene's Dirac points above
the Fermi level, while n-type doping pushes the Dirac points
below the Fermi level. In general, surface-adsorbed molecules
with electron-withdrawing groups (electronegativity) induce
p-type doping in electronic structure of graphene, and molecules
1521
Fig. 4. (A) Left: the electronic structure of the sp2 bonded graphene. Right: zoom-in of the Dirac point where valance and conduction bands intersect. Reprinted with
permission from Ref. [129], Copyright 2009, American Physical Society. (B) Ambipolar electric eld effect in single-layer graphene (the position of the Dirac point and the
Fermi energy (EF) are shown in the insets as a function of gate voltage). Reprinted with permission from Ref. [130], Copyright 2007, Nature Publishing Group. (C) A schematic
diagram for the Dirac point and the Fermi level positions as a function of doping; where the upper panel is n-type doped, pristine and p-type doped free-standing graphene
(ac), and the lower section illustrates n-type doped, pristine and p-type doped epitaxial graphene grown on silicon carbide (SiC) (df). Reprinted with permission from Ref.
[131], Copyright 2008, American Chemical Society.
with donating groups (electropositivity) lead to n-type doping.

In contrast, the substitutional doping mechanism in pristine
graphene still remains uncertain. For this category, p-type doping
mostly takes place by adding atoms with fewer valence electrons
than carbon (e.g. boron), while n-type doping is induced by adding
atoms with more valence electrons than carbon (e.g. nitrogen).
Three main characterization tools are generally employed
to monitor the chemical doping including: (i) photoemission
spectroscopy (PES), especially X-ray photoelectron spectroscopy
(XPS), and angle-resolved photoemission spectroscopy (ARPES),
(ii) Raman spectroscopy, and (iii) charge mobility measurements.
From XPS spectrum, the dopant presence can be conrmed by the
characteristic peak of the representative dopant's element, and the
corresponding peak area characterizes the doping level (i.e. survey
scan analysis). Furthermore, the chemical and electronic states of
the dopant can be obtained by analyzing the high-resolution
spectra of the element (i.e. narrow scan analysis). ARPES is
commonly employed as a strong probe to explore the band
structure of graphene at Fermi level near the Dirac point in the
Brillouin zone [156158]. This is achieved by relating the energy
distribution of electrons to their momentum along the high-
symmetry directions measured by ARPES. Comparing the Fermi

level position (at zero bonding energy) with the Dirac point (near,
below or above the Fermi level) determines whether the graphene
is pristine or doped.
Raman spectroscopy is another useful technique to analyze the
number of layers, disorder and doping in graphene [159163]. Due
to the relatively facile recognition of single- and few-layer graphene akes by optical microscopy on silicon substrates with
typically 300 nm of SiO2 deposits, most of Raman studies are
carried out on a similar substrate [130]. For electrically doped
graphene, it is well-known that the G band, the main characteristic
band in graphene, sharpens and upshifts in both electron and hole
doping [133,164]. The full-width at half-maximum (FWHM) of G
band also decreases for both kinds of doping.
The corresponding carbonaceous G peak in graphene is also
inuenced by chemical doping. In the case of surface transfer
doping, there is a handy empirical correlation to identify the
doping type: n-type doping downshifts and stiffens the G peak,
while p-type doping upshifts and softens the representative G
peak (Fig. 5) [165167]. Adsorption of aromatic groups is also
reported to induce an asymmetry or splitting in the G band for
1522
effect transistors (OFETs) has exhibited competitive work functions similar to those for Ag and Cu [194,195]. Moreover, the
analogous molecular structure of graphene and organic semiconductors like pentacene affords strong interactions amongst
them, lowering the carrier injection barriers, thus improving the
device overall performance (Fig. 6d).
Other applications have also been reported including use of
nitrogen-doped graphene as an efcient metal-free electrocatalyst
for oxygen reduction reaction (ORR) in fuel cells (Fig. 7) [196,197],
and graphene doping with thionyl chloride (SOCl2) for achieving high
electrical conductivities [198]. More practical applications are anticipated to emerge soon due to the rapid progress on graphene
research. This is further elaborated in the upcoming sections relating
doping to graphene competence for CO2 capture and conversion.
Fig. 5. Raman shift trends for the graphene's G band upon interaction with (a) 1 M
solutions of monosubstituted benzenes, and (b) with various concentrations of
aniline and nitrobenzene. Reprinted with permission from Ref. [165], Copyright
2008, Royal Society of Chemistry.
graphene-containing samples (Fig. 5) [168]. Nonetheless, the trend

for substitutional doping is entirely different, where both nitrogen- and boron-doped graphene show upshifted G bands [169].
Electrical conductivity (or resistance) of any graphenecontaining substrate is measurable by eld effect devices. The
conductivity (or resistivity) relation with gate voltage of pristine
graphene is a characteristic V-shaped curve (Fig. 4). Typically, the
minimum conductivity (or maximum resistivity) point (i.e. the
Dirac point of pristine graphene) is observed at the zero gate
voltage; while p-type (n-type) doping of graphene shifts the point
toward positive (negative) gate voltages. In the case of band-gap
opening, graphene-based transistors will exhibit higher on/off
current ratios, where theoretical/experimental studies have suggested many novel properties for such pn junctions often shaped
by local top gate control [170174]. Promising pn junctions have
been generated via selective chemical doping, and their properties
have been investigated extensively [175].
As mentioned earlier, graphene is highly sensitive to surface
transfer doping, and most of such doping processes are reversible.
This two-dimensional material with its ultrahigh conductivity,
which alters swiftly upon atomic/molecular absorbance, is therefore
an excellent candidate for high-precision sensors. A linear conductivity response to various NO2 concentrations is reported (Fig. 6a),
which greatly facilitates the application of graphene-based sensors
to detect even individual NO2 molecules [42]. This has become a
strong incentive to develop high performance sensors based on
graphene chemical manipulations [176180]. Fig. 6 presents other
encouraging cases of gas sensing and the related electronic effects
on GNs. Graphene-based biosensors for detecting bacteria [181],
glucose [182], pH and proteins [183,184] have also been successfully
fabricated. Additionally, DNA detection via GO is reported [185,186],
while graphene is suggested to be an ideal material for DNA
sequencing [187192].
It is important to achieve controllable, air-stable and highperformance n-type, p-type or even ambipolar eld effect
throughout the doping process. Pristine graphene and rGO often
share similar p-type characteristics at ambient conditions due to
the involuntary doping originated from chemical residues or
oxygen molecules in the air, which is not fully explored yet.
However, graphene embedded in insulating polymer matrices,
like polystyrene (PS), is noticeably less affected by such ambient
doping [193]. Consequently, graphene as a buffer layer between
the electrodes and the organic semiconductors of organic eld
2.2.2. Functionalization (chemical synthesis)

From chemistry viewpoint, functionalization and dispersion of
graphene sheets are of crucial importance for their end applications. This enables graphene to be processed by solvent-assisted
techniques, such as layer-by-layer assembly, spin-coating, and
ltration [117,199]. It also avoids agglomeration of graphene
monolayers throughout GO reduction process, and preserves
graphene's intrinsic properties. Hence, surface modied graphene
has been utilized for the fabrication of polymer nanocomposites
[200], super-capacitor devices [201], drug delivery systems [202],
solar cells [203], memory devices [204], transistor devices [205],
biosensors [206], etc. Moreover, it is indicated in the next sections
that functionalization has a remarkable role in enhancing graphene's CO2 capture capacities along with introducing new catalytic properties for CO2 conversion.
GO is widely used as a precursor for the synthesis of processable graphene, owing to its highly oxygenated surface with
abundant hydroxyl, epoxide, diol, ketone, and carboxyl functional
groups [207,208]. As shown in Fig. 8, such oxygen-containing
functionalities can result in a broad range of dispersibility in water
and various organic solvents via alteration of the van der Waals
interactions [209213]. Edge-positioned carbonyl and carboxyl
groups afford strong hydrophilicity for the GO sheets, making
them readily dispersed in water [214,215]. As illustrated in Fig. 9,
according to various functionality scenarios, different model
structures have been proposed for GO [213,216].
As discussed in Section 2.1, chemical reduction of GO lead to a
rapid irreversible precipitation due to the agglomeration of GNs,
unless a stabilizer is used. Therefore, to address this issue, GO
surface is modied prior to reduction, which is usually performed
either by noncovalent or covalent functionalization [199,217].
Serving an example, reduction of alkylamine-modied GO results
in stable dispersion of functionalized graphene sheets in organic
solvents. Impregnation of carboxylic or sulfonate groups on the
basal planes of graphene is also reported to afford producing
water-dispersible graphene sheets [218220]. On the other hand, a
number of papers have discussed synthesis of functionalized
graphene sheets directly from natural graphite [221223]. For
instance, ionic-liquid-assisted graphene electrosynthesis from
graphitic anodes remains functional groups on the ultrathin
exfoliates [104,106]. Nonetheless, obtaining high-yield dispersions
of non-functionalized GNs has still sustained a wave of research
[106,222].
Discussing the aforementioned classications, noncovalent
graphene functionalization mainly involves physical surface
adsorption of molecules/atoms via hydrophobic, van der Waals,
and electrostatic forces (equivalent to surface transfer doping).
Successful cases include adsorption of surfactants or small aromatic molecules, polymer wrapping, and biochemical interactions
with DNA and peptides [224227]. Similar to doping, noncovalent
1523
Fig. 6. (a) Linear dependency of chemically induced charge transport, n, to various concentration, C, of NO2. Lower inset: graphene characterization by the electric eld
effect. (b) Changes in resistivity, , at zero-band-gap point of graphene induced by exposure to various diluted gases (1 ppm). The positive (negative) sign of changes indicate
electron (hole) doping. (c) Constant mobility of charge carriers in graphene with increasing chemical doping. The parallel shift is caused by a negligible scattering effect of the
charged impurities induced by chemical doping. Reprinted with permission from Ref. [42], Copyright 2007, Nature Publishing Group. (d) Schematic of charge transfer at the
F4-TCNQ/graphene interface. Reprinted with permission from Ref. [141], Copyright 2007, American Chemical Society.
Fig. 7. (a) Metal-free nitrogen-doped graphene as an efcient electrocatalyst for oxygen reduction reaction. Reprinted with permission from Ref. [144], Copyright 2013, Royal
Society of Chemistry. (b) Schematic illustration of various types of nitrogen-doped graphene (gray for the carbon, blue for the nitrogen, and white for the hydrogen atom).
A possible defect structure is shown in the middle of the ball-stick model. Reprinted with permission from Ref. [182], Copyright 2010, American Chemical Society. (For
interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)
functionalization is a well-practiced concept for the surface

modication of carbon-based materials, and it has been frequently
employed to alter the physicochemical properties of the sp2
networks in CNTs [228233]. Consequently, similar techniques

can be borrowed for further surface modication of graphene via
various types of organic compounds.
1524
Fig. 8. As-prepared graphite oxide dispersions in water and 13 organic solvents by bath ultrasonication for 1 h. Top: Dispersions immediately after sonication. Bottom:
Dispersions three weeks after sonication. The yellow color of the o-xylene sample is due to the solvent itself. Reprinted with permission from Ref. [211], Copyright 2008,
American Chemical Society. (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)
Fig. 9. Variations in the proposed model structures for the GO sheets regarding the presence (left, Reprinted with permission from Ref. [212], Copyright 1998, American
Chemical Society) or absence (right, Reprinted with permission from Ref. [213], Copyright 2009, Nature Publishing Group) of carboxylic acids on basal plane edges.
In contrast with noncovalent interactions, covalent functionalization involves rehybridization of sp2 carbon atoms through the
graphene network into the sp3 conguration, associating with the
loss of electronic conjugation (equivalent to substitutional doping)
[234]. This is mainly due to the rigorous interactions of the dopant
with the honeycomb graphene, and it is often irreversible. Such
strong surface modications can be achieved in a variety of ways
including nucleophilic substitution, electrophilic addition, condensation, and combinatory addition; which most of them use
GO as the starting material [235237].
Briey, the epoxy functionalities of GO are the target groups for
the nucleophilic substitution reaction. It involves attacking amine
(single bond NH2) groups of the organic modiers, bearing a lone
pair of electrons, to the GO's epoxy groups. Comparing with other
techniques, nucleophilic substitution is more facile and takes place
at room temperature in an aqueous medium. Thus, it has emerged
as a promising scalable production method for GNs functionalized
with all types of aliphatic and aromatic amines, amino acids,
amine-terminated biomolecules, ionic liquids, low molecular
weight polymers, and silane compounds [235246].
Electrophilic substitution occurs when an electrophile agent
displaces a hydrogen atom. Impulsive insertion of aryl diazonium
via reduction of 4-nitrophenyl diazonium (NPD) tetrauoroborate
is a prominent example for such electrophilic reactions with
graphene surface [247]. Stable dispersions of functionalized GNs
in organic solvents have also been obtained via electrophilic
substitution of aryl diazonium salt on the surface of surfactantwrapped graphene [248,249].
In condensation reaction, two molecules (or functional groups)
combine to form one single molecule with a loss of entropy.
It occurs when isocyanate, di-isocyanate, and amine compounds
form amides and carbamate ester linkages with GO body.
Stankovich et al. used a series of isocyanate compounds for the

surface modication of GO [51,250]. The reaction took place in
dimethylformamide (DMF) under nitrogen atmosphere. In the case
of using solid isocyanates, both the isocyanate and GO were loaded
into a ask prior to the DMF addition. The resulting functionalized
GO was readily dispersed in DMF therefore useful in the preparation of polymer nanocomposites [51]. Similar to the organic
isocyanate, organic di-isocyanate is also emerged successfully in
GO functionalization and cross-linking [251].
In organic addition reactions, two or more molecules merge to
form a larger molecule. A promising case is put forward recently
with 1,3-dipolar cycloaddition of azomethine ylide on the surface
of graphene. Thus, a similar concept has been employed for the
functionalization of epitaxial graphene by cycloaddition of azidotrimethylsilane [252]. After removing N2, nitrene reacts with
graphene via an electrophilic cycloaddition reaction or a biradical
pathway to form functionalized graphene. The GNs obtained from
direct liquid-phase exfoliation of graphite in pyridine and NMP
have been functionalized using a similar procedure [253,254]. The
resulting graphene sheets are easily dispersible, making them
more compatible with the processes that involve mixing, blending,
or dispersion.
As mentioned earlier, it has become more evident that both
covalent and noncovalent modications signicantly improve the
processability of graphene [255257]. However, this adversely
affects the electrical conductivity of surface modied GNs, and is
observed to decrease the electron mobility noticeably comparing
to that of pristine graphene [208,251]. In addition, both functionalization techniques severely decrease the surface area of the
modied GNs due to the structural damages induced by graphite
chemical oxidation, subsequent sonication, functionalization and
chemical reduction [117,199]. To address the aforementioned
1525
issues, several studies have examined preparing functionalized GNs directly from graphite in a one-step process using,
for instance, ionic liquids and surfactants via direct liquidand electro-exfoliation methods [102,106]. Nonetheless, the
bottom line is that all the related studies have appreciated the
effectiveness of graphene functionalization in preventing GNs
agglomeration in various solvents, and affording more physicochemical properties for a broad range of applications.
3. CO2-assisted graphene production

Following the discussions in Section 2.1, there is a great interest
towards sustainable production of graphene for preserving the
green image of this material. Consequently, new methodologies
are pursued upon using CO2 as the graphene precursor to hit two
birds with one stone. This provides a unique opportunity with
large-scale chemical conversion of CO2 to graphene and its
derivatives considering their increasing global demand. The products could be even employed afterwards as excellent CO2
sorbents (see Section 4.2). Due to the paramount importance of
this newly born research concept, we have particularized all the
critical synthesis parameters as they could spark more out-of-thebox ideas in this eld.
Recently, it was found that burning magnesium ribbons in a
CO2-rich environment produces ultrathin carbonaceous sheets via
the reaction presented in Scheme 2 [258]. Although the metalCO2
propulsion system for Mars missions had been explored in early
90s [259], thorough characterization of the resulting carbon
products remained untouched until 2011 [258]. Indeed, formation
of few-layer graphene from combustion of magnesium metal in
carbon dioxide was unprecedented, and prompted further incentives to explore more pathways from CO2 to carbon nanostructures
[260]. It was also a signicant development over the previous
report which had suggested graphene synthesis by CO reduction
(rather than CO2) using Al2S3 [261].
In the initial studies, 3 g of Mg ribbon was ignited inside a dry
ice vessel covered with another dry ice block. After the completion
of Mg combustion in CO2, the black deposits were collected and
treated with 1 M HCl solution to remove the MgO and any
remaining Mg metal. Both Mg and MgO react with hydrochloric
acid to form MgCl2 which is water-soluble. Thus, pure carbon
material was obtained as the product by ltration and subsequent
vacuum drying with the yield of 680 mg (92%). Fig. 10a and b
shows transmission electron microscopy (TEM) images of the FLG
prepared by the described technique, in which graphene sheets
with varying lengths between 50 nm and 300 nm have been
isolated [258]. Fig. 10c clearly shows the large crystalline graphene
structures as the combustion products, while high-resolution TEM
(HRTEM) (Fig. 10d) suggests the number of layers ranging from
37. The measured lattice spacing of this material was about 3.5 ,
which is in good agreement with the thickness of a monolayer
graphene (3.4 ) [28]. The inset image in Fig. 10d corresponds to
the diffraction pattern of FLG, which is an indication of crystallization. Although the exact graphene formation mechanism is still
under investigation, the high temperature generated during magnesium combustion undoubtedly plays a crucial role. It is hypothesized that magnesium ignition in gaseous CO2 renders quick
escape of the solid products from the reaction center. Thus, the
sp2 bonded carbon atoms have very low retention times to
develop their 3D multi-layer structure (graphite), and only FLG
synthesis is kinetically favored. Catalyst morphology effect on
Scheme 2. Burning magnesium metal in a CO2-rich environment to produce

graphene heterostructures.
Fig. 10. TEM images of few-layer graphene obtained from magnesium combustion
with CO2. (a) Graphene nanosheets with an average length of 50100 nm.
(b) Larger size graphene sheets with average lengths of 300 nm. (c) Crystalline
GNs with an average length of 200 nm. (d) High-resolution TEM image of few-layer
graphene with the number of layers ranging from 37. Inset: the electron
diffraction pattern of GNs. Reprinted with permission from Ref. [258], Copyright
2011, Royal Society of Chemistry.
monolayer graphene formation with higher yields using similar

techniques is still subject to more studies.
Apart from the above-mentioned report, it is still challenging to
directly break the CQO bonds due to the thermodynamical
stability of CO2, limiting the practicality of CO2 to graphene
conversion. Moreover, nding reliable ways to precisely rule over
the GNs layer number, morphology, crystallinity, size, edge structure, and even spatial orientation of the products is of great
interest. Delicate control of the aforementioned characteristics
during graphene synthesis is crucial to ne-tuning its electric
properties and device performance. Yet, the discussed chemical
transformation of CO2 into graphene has not completely fullled
these aspects. In this regard, a more controllable epitaxial growth
of single-layer graphene domains was recently put forward via
catalytic activation of CO2 [262]. Graphene domains, with a shape
evolution from hexagonal to more rounded, were fabricated on
copper foils in an atmospheric pressure chemical vapor deposition
(APCVD) chamber by chemical activation of CO2 [262]. Unlike CH4,
decomposition of CO2 under CVD conditions is more difcult due
to the signicant energy barriers for CO2 conversion. Therefore,
the corresponding CVD apparatus for CO2-assisted graphene
synthesis was modied with a catalytic activation module to
generate more reactive intermediates such as methanol, formic
acid, and methane as indirect carbon precursors [263]. The utilized
catalyst for CO2 activation in the recent study was a Ni-based
catalyst (Ni/Al2O3), which is among the most successfully examined materials for CO2 conversion to synthetic natural gas [263
266]. In fact, CO2 reduction to form CC and CH bonds is of
intense interest in the context of viewing CO2 as a feedstock to
produce valuable chemical commodities via organic synthesis (see
Section 5) [264266].
Fig. 11a shows the modied CVD apparatus diagram based on
the described scheme for graphene synthesis from CO2. Comparing
with the previous CVD growth routes, the Ni-based catalyst for
1526
Fig. 11. Graphene CVD growth on copper foils via catalytic activation of CO2.
(a) Schematic diagram. (bf) SEM images of graphene domains development on
copper foils with 200 sccm H2 and different ow rates of CO2 (330 sccm) after
30 min of growth time. (g) The characteristic length of the domains as the function
of CO2 ow rates. Reprinted with permission from Ref. [262], Copyright 2013, Royal
Society of Chemistry.
CO2 activation is loaded at the upstream of the copper foil which

was placed at the center of the quartz tube. The Cu foils were rst
annealed at 1000 1C at a 200 sccm H2 ow rate for 30 min.
Subsequently, the alumina-supported nickel catalyst was heated
with a heating tape while maintaining the 200 sccm H2 ow, and
then a mixture of 5 sccm CO2 and 200 sccm H2 was introduced to
the chamber for graphene growth during 30 min. Afterwards, CO2
injection was stopped and 150 sccm Ar was put through until the
H2 ow reduced to 50 sccm. Finally, the substrates were slowly
quenched from 1000 1C to 800 1C, and the furnace was swiftly
cooled down to room temperature by opening the joints.
Beside the efforts to produce carbon nanostructures directly
from CO2, there has been another line of research looking into
utilizing other sources of CO2 [267]. Since it is not much convenient to carry out magnesium combustion using dry ice, the
new study reported GNs production by the co-calcination of
calcium carbonate (CaCO3) with magnesium powder (Mg) [267].
This offers a facile and scalable approach to synthesize few-layer
graphene by calcining the mixture of magnesium metal and
calcium carbonate. The number of layers are reported to vary from
4 to 10 by a simple calcination at 850 1C, where the reaction
temperature was observed to be vital for graphene formation
[267]. GNs were only detected for calcinations at 850 1C, while
other temperatures (ranging from 700 to 900 1C) led to the
formation of amorphous carbon materials. In addition to graphene
sheets, CaO and MgO were also collected after the reaction. It is
noteworthy that CaO is currently used as a recyclable sorbent for
carbon capture in uidized bed chemical looping congurations,
where it efciently adsorbs CO2 and converts to CaCO3 [268,269].

The described graphene synthesis method using calcium carbonate opens up the possibility of large-scale in-situ production of
carbon nanostructures in a continuous CaO/Mg regeneration mode
linked with the main CO2 capture process.
The melting point of magnesium is 649 1C with boiling point of
1090 1C while calcium carbonate decomposes at 825 1C. Therefore,
in the reaction at 850 1C magnesium remains liquid with very low
vapor pressure. It is observed that magnesium droplets wrap
calcium carbonate powder tightly, where the CaCO3 contents were
far greater than that of Mg. Thus, the molten magnesium
surrounding calcium carbonate surface forms a nano-stretched
lm. Also, magnesium combustion in pure CO2 is suggested to
occur at two reaction zones [270]: (i) an outer zone (shell) where
magnesium initially reduces carbon dioxide to CO and coverts to
magnesium oxide, and (ii) an inner zone, at the particle surface,
where CO is further reduced by the remaining liquid magnesium
and results in producing solid carbon and solid magnesium oxide.
Accordingly, calcium carbonate decomposition into carbon dioxide
and then carbon dioxide reduction by magnesium into graphene
can be presumed to follow the Scheme 3. In this case, since the
reducing agent (Mg) was effectively wrapped and stretched
around the CaCO3 particles to form a nanoscale layer, the ultrathin
carbon sheets were produced as the result.
Other attractive options for CO2 conversion to carbon allotropes
include reducing CO2 to diamonds [271,272], and nanotubes
[273,274], either through direct CO2 splitting or via reaction with
metals at pressures higher than 70 MPa. Recently, porous carbon
synthesis from high-pressure supercritical CO2 was reported using
alkali metals for CO2 reduction [275]. As a notable follow up, CO2
reaction with sodium borohydride enabled producing borondoped porous carbon at more moderate conditions [276]. The
results introduced a more energy efcient pathway for CO2
reduction to porous carbon under atmospheric pressure at temperatures below 500 1C; while XPS analysis conrmed doping of
the products with boron throughout the synthesis process [276].
Nevertheless, complete CO2 reduction to carbon nanomaterials
without using metal-containing co-reactants and applying
extreme conditions remains unmapped. Just recently, a novel
metal-free pathway for CO2 conversion to graphene oxide was
put forward using ammonia borane (NH3BH3) [277]; which is
known to have a signicant hydrogen storage capability [278]. The
reported CO2-to-GO pathway comprises two consecutive steps of
carbon xation and then graphenization. The carbon xation is the
CO2 reaction with NH3BH3 under mild temperature and pressure
(T o100 1C and Po3 MPa) to produce a solid compound containing methoxy (OCH3), formate (COOH), and aliphatic groups. Afterwards, the graphenization phase takes place with the pyrolysis of
the obtained solid at high temperatures (T 4600 1C), and atmospheric pressure of nitrogen to produce graphene oxide-boron
oxide nanocomposites. Fig. 12 shows the reaction pathway for
CO2-to-GO using ammonia borane with representative TEM micrograph. After all, more extensive studies are required for advancing
this concept, and turning it to a feasible process for cost-effective
CO2 remediation in large scales.
Scheme 3. Underlying reactions of calcium carbonate conversion to graphene

nanosheets via magnesium reduction.
Fig. 12. Formation of graphene oxide nanocomposites from carbon dioxide using
ammonia borane with representative TEM micrograph showing curled and stacked
akes. Reprinted with permission from Ref. [277], Copyright 2012, American
Chemical Society.
4. Graphene-assisted CO2 capture

4.1. CO2 capture background
Concerning negative impacts of CO2 as a greenhouse gas on
global warming and climate change [279,280], it is crucial to
nd inexpensive, effective, and robust solutions for substantial
CO2 reduction from industries that heavily rely on fossil fuels
[281,282]. For instance, in pulverized-coal plants, post-combustion
CO2 capture is a common practice where CO2 removal is carried
out from the typically dilute (o15 % by volume) ue gas (i.e.
exhaust gas). Aside from the current infrastructures, several
alternative power plant designs have been proposed that may
allow for more efcient CO2 capture [283285]. In pre-combustion
capture, the fuel is gasied with steam, air, or O2 to produce
synthesis gas (H2/CO mixtures). CO is typically further oxidized to
CO2 by H2O in a shift reactor to produce additional hydrogen.
The gas mixture (now mostly H2 and CO2) is then separated into a
H2-rich fuel and CO2 for storage/conversion. In contrast to typical
post-combustion capture conditions, the target gas stream for
separation in this case is typically pressurized, containing appreciable CO2 concentrations (4 15 %). Pre-combustion capture is thus
mostly related to the coal-red plants with integrated gasication
combined cycle (IGCC) [286,287]. Oxy-combustion is another
alternative power plant design that could lead to more efcient
CO2 capturing. In this case, a hydrocarbon fuel is combusted with
pure O2, rather than air, producing an exhaust of CO2 and H2O
vapor. This leads to a ue gas with an easily separable component,
H2O, remaining an essentially pure CO2 stream for storage or other
dispositions. Importantly, such designs require an air separation
unit, which adds to the monetary burdens of this technology
[288]. After CO2 separation by any of the described methods, the
puried CO2 can be considered whether for (semi-)permanent
storage [289291] or conversion into useful products [14,292,293].
Considering the above-mentioned criteria, three types of gas
mixtures are targeted for CO2 capture and separation technologies:
the components of ue gases (mainly CO2/N2), pre-combustion gas
mixtures (H2/CO2), and natural gas streams containing CO2
(mainly CH4/CO2). However, aside from the major components in
ue gases, natural gases, and hydrogen, other gases/compounds
can be found in these mixtures. For instance, trace amounts of
water are inevitable in most systems which generally add more
complexities to the separation process; while under certain
circumstances it may positively contribute to it [294,295]. Still,
only a handful of computational investigations have included
water to study its possible effects more extensively [280,296].
Consequently, different adsorbents may better suit one application
or another, on the basis of the operating temperature, pressure,
CO2 mole fraction, presence of impurities, and other factors.
According to various adsorption behaviors of graphene and its
1527
derivatives, their suitability for each of the three described major

CO2 mixtures is conceivable throughout this paper.
In general, employing high capacity nanostructured materials
potentially reduces the costs associated with carbon capture (or
separation). For instance, membranes or particle-based adsorption-driven processes can be used for CO2 separation from N2-rich
ue gases [297,298]. CO2 is currently removed from ue gas
streams via absorption by amine-based aqueous solutions like
simple alkanolamines or liqueed NH3 [299,300]. CO2 selectivity is
a key factor for the cost-effectiveness of the adsorption-mediated
separation of CO2 from ue gases [301,302]. To address this issue,
numerous adsorbent materials have been put to test recently
including zeolites [303,304], metal organic frameworks (MOFs)
[305,306], and highly alkaline adsorbents [294,307]; where alkaline systems have shown a high selectivity for CO2 adsorption over
N2 [308,309]. Moreover, carbon [310,311] and silica [312,313]
materials have also received a great attention in this regard.
Complementarily, chemical looping combustion congurations are
proposed to continuously circulate the sorbent via regenerative
cycles [314,315]. Among materials for solution-based separation,
ionic liquids have also exhibited promising uptakes with high
selectivity towards CO2 [316,317].
Quality (or utility) of ideal CO2 adsorbents is characterized by
several parameters [318,319], which generally includes fast adsorption/desorption kinetics, large adsorption capacity, high regenerability/stability, and a wide yet exible operability range.
Nevertheless, no ideal adsorbent exists in reality, and the practicality
of each adsorbent must be decided over its strengths and weaknesses in the context of a particular process design. Ultimately, those
adsorbents that perform reasonably well within a specic CO2
separation process scenario would emerge as viable candidates.
4.2. Graphene-based sorbents
Carbon-based adsorbents are among the most promising
materials for CO2 capture due to their chemical inertness, high
surface area, and low cost [320]. Porous carbons have revealed a
signicant advantage over zeolites in terms of hydrophobicity for
CO2 capture. However, the competitive adsorption of water on
other hydrophilic carbonaceous surfaces still reduces their CO2
uptake capacities [280,321]. Several types of carbon materials have
been studied for CO2 capture including activated carbons
[322,323], carbon molecular sieves (CMS) [324,325], carbon nanotubes (CNT) [326,327], and graphene heterostructures as the most
recent constructs [328,329]. Among those, graphene has the
largest surface area (2630 m2 g1) [26], and is thus presumed to
outperform the others [330,331].
As pointed out in Section 2.1, scalable top-down graphene
syntheses, mainly via GO reduction, do not usually result in a
pristine monolayer of graphite, rather producing a few-layer
graphene with lattice defects [332,333]. Therefore, CO2 capture
behaviors of GNs prepared by such methods have been unexpected to some degree [328,333,334]. Recently, relatively high
uptakes of hydrogen and carbon dioxide by rGO sheets with a
wide range of surface areas is reported [335]. A reasonable
hydrogen uptake of 1.7 wt% was observed at 1 atm and 77 K,
where the values were linearly correlated with the surface area.
Thus, upon extrapolation, the hydrogen uptake by single-layer
graphene was projected to exceed 3 wt%. The H2 adsorption at
100 atm and 298 K was found to surpass 3 wt%, which suggests
much higher uptakes by the monolayer graphene via linear
extrapolation [335]. On the other side, rGOs showed remarkably
higher uptakes for CO2, approaching 35 wt% at 1 atm and 195 K.
This was further backed by another study on rGOs obtained from
various thermal reduction conditions showing high CO2 capture
capacities (248 wt% under 298 K and 30 bar) for the samples
1528
reduced at 300 1C [336]. Such uptakes were signicantly higher

than those for commercial zeolites ( 7-fold) and activated carbons ( 3.5-fold) under similar experimental conditions [336].
Fig. 13 compares the typical sorption isotherms for H2 and CO2
on a graphene supercell, and depicts various adsorption orientation scenarios. The rst-principles calculations show parallel and
perpendicular orientation for hydrogengraphene interactions
[154,328], suggesting up to 7.7 wt% of theoretical hydrogen
adsorption on monolayer graphene. On the other hand, CO2
molecules sit parallel to the honeycomb network, resulting in a
maximum uptake of 37.9 wt% for single-layer graphene [335].
It is found that stacking the graphene layers in the samples
decreases the H2 uptake, while the edge sites signicantly contribute to CO2 adsorption on GNs [337]. Since the related uptake
calculations have only taken basal planes into account, edge effects
can be the source of discrepancy between theoretical estimations
and experimental values of adsorption onto GNs [338]. The
aforementioned discrimination between the edge sites and basal
planes in graphitic carbons is also observed using molecular
orbital calculations, based on SO2 and CO2 adsorptions [339].
Moreover, strong interactions of CO2 and H2O with graphene
nanoribbons at room temperature have been reported experimentally with less reversible adsorption; comparing to N2 molecules
adsorbed less rigorously with perfectly reversible cycles at 77 K
[340]. Therefore, the meaningful pattern of edge effects in graphene nanoribbons became more evident; while basal-planedominant GNs had exhibited reversible adsorption for CO2 and
H2O.
A few theoretical works have explored the determining role of

edges on the physicochemical properties of nanographenes as they
contain numerous edge sites with various types of defects [341
344]. The edges' contribution to the molecular adsorption by GNs
was isolated from that for basal planes using grand canonical
Monte Carlo (GCMC) simulations [329]. The edge sites of GNs
show relatively strong Coulombic interactions due to the partial
charging at the vertices, while basal planes hardly afford such
interactions. The modeling results revealed that the edge sites are
more inclined toward CO2 adsorption, while N2 mostly sits on the
basal planes. This leads to an extremely high selectivity for CO2
adsorption over N2 on the edge sites, which the number exceeds
30 in pressures below 0.02 MPa [329]. Therefore, ne-tuning of
the edge sites versus basal planes in GNs can suit their applications
for selective adsorptions, reactions, and separations. Fig. 14 illustrates the discriminating effect of the nanographene edges for
selective CO2 adsorption with related comparisons.
From surface chemistry standpoint, basic adsorbents show
more afnity towards CO2 capture due to the slightly acidic nature
of CO2 [345]. Consequently, adsorbents functionalized with amines
have shown high CO2 adsorption uptakes [346348], which
improves further when nitrogen is effectively incorporated within
the support's framework [349351]. Thus, researchers have aimed
to improve the CO2 capture characteristics of amine-based carbon
materials by increasing the surface density of the amine groups on
the support as well as strengthening the amine-support immobilization [352354]. Along this approach, polyaniline (PANI), as a
rich source of nitrogen-containing groups, has been impregnated
Fig. 13. (a) Hydrogen sorption isotherms at 1 atm and 77 K. (b) Carbon dioxide sorption isotherms. (c) Binding energies of a single molecule on a graphene supercell as a
function of distance with various adsorption orientations (shown in insets) for hydrogen (upper panel) and carbon dioxide (lower panel). Reprinted with permission from
Ref. [328], Copyright 2008, American Chemical Society.
1529
Fig. 14. (a) CO2 and N2 adsorption isotherms at 273 K on nanographenes ( for CO2, for N2), edge sites (solid curve), and basal planes (dashed curve), and (b) snapshots.
Reprinted with permission from Ref. [329], Copyright 2012, American Chemical Society.
on various supports and membranes with promising results [355

358]. The suitable supports for such applications should meet
several criteria including strong attraction for the aminecontaining molecules, high surface area with proper pore size
distribution, reasonable mechanical strength and hydrothermal
stability. Graphene matches very well with the stated requirements, and therefore polyanilinegraphene nanocomposites have
shown encouraging CO2 capture performance [356,358].
In the rst study, GNs were prepared via hydrogen-induced
thermal exfoliation of GO, named as hydrogen exfoliated graphene
(HEG) [359]. HEGs alone reached the adsorption capacities of 21.6,
18 and 12 mmole g 1 at temperatures of 25, 50 and 100 1C,
respectively (pressure was xed at 11 bar) [360]. These values
were found to outperform other carbon nanostructures (e.g.
activated carbons and carbon nanotubes) as well as zeolites under
similar operating conditions [360]. HEG was then functionalized
with oxygen-containing functional groups to form functionalized
graphene (f-HEG). This initial functionalization created anchoring
sites for the subsequent addition of PANI molecules to the f-HEG,
providing more uniform accommodation for nitrogen-rich groups
over the f-HEG surface. The f-HEG was further coated with
nanostructured PANI, yielding a PANI-f-HEG nanocomposite via a
chemical impregnation process [361]. CO2 adsorption capacities at
the pressure of 11 bar and temperatures of 25, 50 and 100 1C were
observed as 75, 47 and 31 mmol g 1, respectively. Comparing with
the above-mentioned CO2 uptake values for non-functionalized
HEG, this is a far greater performance accompanied by a higher
degree of recyclability [356].
In the other study, PANI-rGO composites were synthesized
using chemical activation starting from pretreatment with 7 M
KOH solutions followed by activation at various temperatures
between 400 and 800 1C under nitrogen ow inside a tube furnace
[358]. This was inspired by the recent synthesis of high surface
area porous carbons (3100 m2 g 1) via chemical activation of
graphene for application in supercapacitors with high-capacity
energy storage [362]. KOH partially reacts with graphene at high
temperatures and remains a signicant pore volume within the
nal product after being washed away by HCl solutions [363]. PANI
was grafted to the surface of GO sheets prior to the reduction with
hydrazine (a typical protocol for GN functionalization, see Section
2.2.2) [358]. A highly reversible CO2 uptake of 2.7 mmol g 1 at
298 K and 1 atm (5.8 mmol g 1 at 273 K and 1 atm) was observed
over the samples activated at 700 1C. The N-doped graphene
maintained a practical stability in the course of recycling, showing
only an initial decrease of 10% (32.7 mmol g 1) in CO2 storage
capacity before reaching the cycling equilibrium. The synthesized
materials also displayed selectivity towards CO2 adsorption compared to H2, N2, Ar or CH4. Fig. 15 represents the described
recyclability and gas selectivity for the NG7 samples (979.6 m2 g 1
surface area), which showed the highest CO2 uptakes (NG7 stands
for chemical activation at 700 1C).
N-doped porous carbons are also synthesized via chemical
activation of polypyrrolegraphene composites using KOH solutions [364]. Polypyrrole (PPy) is an environmentally benign basic
CO2 sorbent with excellent thermal stability and can be easily
produced in large scales [365]. However, the low surface area
along with costly nature of PPy have constrained its application for
CO2 capture at the industrial level. In this regard, interfacing PPy
with graphene substantially increases its surface area, and the
resulting composites have also exhibited a high adsorption capacity for aqueous mercury [366]. After chemical activation, nitrogen
was found to be doped within the porous carbon rather than the
graphene matrix. The PPyGN nanomaterials showed a selective
and reversible adsorption for CO2 (4.3 mmol g 1) over N2
(0.27 mmol g 1) at 298 K and 1 bar [364]. The scalability of the
synthesis method and excellent recyclability of the N-doped
porous carbons make them highly competitive for practical
applications.
As the latest follow up to the abovementioned line of research,
S-doped microporous carbon materials, obtained by the chemical
activation of polythiophene (PT) grafted rGOs, were examined for
CO2 adsorption [367]. With a signicant CO2 uptake of
4.5 mmol g 1 at 298 K and 1 atm, the S-doped samples showed
remarkable selectivity over N2, CH4 and H2 with a stable recycling
adsorption capacity of 4.0 mmol g 1 [367]. The microporosity
(0.6 nm pore size), surface area (1567 m2 g 1), and oxidized S
content of the porous carbon ( 6.5 wt%) were found to be the
determining factors for the remarkable CO2 adsorption resulted
from chemical activation at 700 1C. Noticeably, S-doped chemically
activated graphene reached higher CO2 adsorption values than
those for N-doped materials prepared and examined under similar
conditions [367].
Successful synthesis of graphene-based mesoporous silica
(G-silica) sheets is reported recently with sandwich-like structure
and high surface area [368]. Conning GNs within individual porous
silica sheets enables the end product to have broader applications
particularly in ultrafast energy storage [368,369]. It was found that
G-silica sheets can serve as an effective host for immobilizing
polyethyleneimine (PEI), as another amine-rich compound (denoted
as PEI-G-silica) [370]. The resulting PEI-G-silica sheets not only
had an ultrathin structure with high PEI surface density, but
also exhibited superior thermal conductivities originated from GNs
1530
Fig. 15. (a) Recycling of the NG7 composite material, and (b) its selectivity towards CO2 adsorption over Ar, N2, H2 and CH4. NG7 stands for chemical activation at 700 1C.
Reprinted with permission from Ref. [358], Copyright 2013, IOP Science.
presence. Such features afforded the synthesized nanocomposite an

efcient CO2 diffusivity/adsorption as well as rapid thermal transfer
for faster regeneration kinetics. Accordingly, high CO2 uptake of
19 wt% with reasonable regenerability at 75 1C and atmospheric
pressure was achieved by PEI-G-silica sheets [370].
GrapheneMn3O4 (GMNO) hybrid porous materials have also
shown promising carbon dioxide adsorption capacities [371].
Metal oxides that offer various basic sites are extensively studied
as alkaline CO2 adsorbents [372,373]. Obviously, the surface area is
another determining factor, and specic strategies are followed to
better benet from basicity on higher accessible areas. This
includes synthesis of porous metal oxide materials [374], and
impregnating metal oxide nanoparticles on high surface area
materials [375]. Particularly, in the synthesis of GMNO hybrids
(second strategy), MnO(OH)2 colloid, obtained by the hydrolysis of
Mn2 in basic solution, was used as the Mn3O4 precursor. After
hydrothermal reaction of GO and MnO(OH)2, they were simultaneously reduced to graphene and Mn3O4, respectively, with an
enhanced crystallization. Finally, as-prepared GMNO hybrid materials showed a high specic surface area ranging from 140 to
680 m2 g 1. The CO2 uptakes reached up to 11 wt% for the samples
prepared with initial Mn2 /GO mass ratios of 4 (541 m2 g 1
surface area) under sorption isotherm conditions [371]. This was
signicantly higher than CO2 adsorption capacity of pristine
graphene (7.7 wt%) and Mn3O4 (0.6 wt%) in similar experimental
settings [371].
In a separate study, graphene oxide enhanced the CO2 adsorption capacity of the layered double hydroxides (LDHs) [376]. LDHs,
also known as hydrotalcite-like compounds, are a large class of
inorganic materials with some unique basic properties useful for
diverse applications [377,378]. They are composed of synthetic 2D
nanostructures with basic anionic clays conned by the positively
charged brucite-like Mg(OH)2 layers. A fraction of divalent cations
in LDHs, octahedrally bonded with hydroxyl groups, is typically
substituted by trivalent cations. This results in an excess of positive
charge which is then balanced by the intercalating anions. The
remaining interlayer space is usually lled by the water molecules
which weakly interact with the material [379,380]. LDHs, as
promising CO2 sorbents, require lower regeneration energies with
better long-term stability than other alkali metal oxides (e.g.
calcium oxides) [296]. In addition, they exhibit fast adsorption/
desorption kinetics, particularly in the water presence, which not
only makes them applicable to pre-combustion CO2 capture, but
also enables them for sorption-enhanced hydrogen production
[381]. Despite the described advantages, LDHs have shown relatively low CO2 adsorption capacities [382]. The recent study
demonstrated that GO assembly with LDHs provides a lightweight
charge-harmonizing 2D material that boosts the CO2 uptake

capacity, and multicycle stability of the end product. Consequently,
this increased the CO2 storage capacity of LDH by 62% with
only 7 wt% of GO incorporation [376]. The experimental procedure
for producing GOLDH composites was based on the direct
precipitation of the LDH nanoparticles onto GO using wet
impregnation technique. Unsupported LDHs were synthesized by
co-precipitation with Mg/Al ratio of 2, which is reported to be
optimal for CO2 capture [383]. Fig. 16 presents the schematic for
the LDHGO assemblies with related CO2 sorption data as a
function of GO loading at 573 K and P(CO2) of 0.2 bar.
Interest in the inorganic graphene analogs containing boron,
carbon, and nitrogen, BxCyNz, has arisen by a recent study on a
graphene-like borocarbonitride (BCN) sample with high surface
area and noticeable CO2 uptakes at low temperatures [384];
similar to the behavior of hexagonal (graphene-like) boron nitride
(g-BN) based on computational modeling [385]. Therefore, more
experimental research is conducted on the adsorption of CO2 and
CH4 by graphene-like BxCyNz compounds with compositions close
to BC2N [386]. The synthesized materials showed large surface
areas (15001990 m2 g 1), and a very high uptake for both CO2
(up to 64 wt%) and CH4 (up to 15 wt%) at 298 K and 5 MPa; which
were increasing exponentially with the surface area of the adsorbent. The CH4 uptakes changed proportionally to those for CO2,
and they were both considerably higher than the values reported
for their adsorption on nanographenes [329].
On the theoretical track, grand canonical Monte Carlo (GCMC)
simulations are performed to design new constructs via evaluating
fullerene-intercalated graphene nanocontainers (NanoBuds) for
adsorption of CH4 and CO2 [387]. It was found that the fullerenes
of type C180 other than C60, as intercalation reagents for constructing the model structure, could improve the storage capacity [387].
Afterwards, further in-depth GCMC studies were conducted on
adsorption of CH4 and CO2 gases and CO2 purication from CH4/
CO2 and N2/CO2 binary mixtures by the C60 intercalated graphite
(Fig. 17) [388]. First, it was perceived that the pristine material is
not suitable for gas storage, mainly due to its low porosity (0.45)
and large crystal density (1.57 g/cm3). Accordingly, the maximum
uptakes of 4.04 mmol/g for CH4 and 4.96 mmol/g for CO2 were
calculated for room temperature adsorption. However, the material exhibited a remarkable selectivity for CO2 at ambient conditions, reaching up to 8 and 50 for the CH4/CO2 and N2/CO2
mixtures, respectively. Prior to that nding, a novel construct socalled periodic graphene nanobud (PGNB) was reported using the
rst-principles method, where the C60 fullerenes were covalently
bonded to the graphene monolayer [389]. Therefore, it opened the
possibility of controlling the distance between the C60 fullerenes
1531
Fig. 16. (a) Schematic of the LDH-GO hybrids for CO2 capture. (b) Average CO2 uptakes as a function of GO content at 573 K and P(CO2) 0.2 bar. Reprinted with permission
from Ref. [376], Copyright 2012, American Chemical Society.
Fig. 17. Absolute CO2 uptakes of C60 intercalated graphite versus g at 298 K with equimolar compositions of: (a) CH4/CO2 mixture; (b) N2/CO2 mixture. (c) Snapshots of pure
gas adsorption in C60 intercalated graphite at 298 K and 6 MPa (top for top view, and bottom for side view). Reprinted with permission from Ref. [388], Copyright 2010,
American Chemical Society.
for further modication of the material. This affords up to 200%

increase in CO2 adsorption, approaching 12 mmol/g at 6 MPa for
both mixtures without degrading the selectivity to CO2 [388]. Such
improvements are mainly achieved via decreasing crystal density,
thus increasing porosity originated from enlargement of g
(structural parameter for C60). Ultimately, it implies that C60
intercalated graphite could be still an excellent material for CO2
purication, especially for N2/CO2 systems at room temperature
under aforementioned circumstances. Fig. 17(a and b) demonstrates the effect of structural parameter enlargement on the
absolute CO2 uptakes in C60 intercalated graphite at 298 K with
equimolar mixtures of CH4/CO2, and N2/CO2, respectively.
5. Graphene-assisted CO2 conversion

5.1. CO2 conversion background
Carbon dioxide, as the most oxidized state of carbon, is a
nonpolar linear molecule which is highly stable from thermodynamics angle. Both terms of enthalpy and entropy changes (H 0
and S0 , respectively) of the Gibbs free energy change G0 are

not favorable for converting CO2 to other useful chemical commodities [390]. Therefore, reactions involving CO2 reduction
require signicant energy input to overcome the costs associated
with thermodynamical barriers. It also necessitates proper catalysis to boost the conversion kinetics, and enhance the product
selectivity [391].
Undoubtedly, energy supplies for CO2 conversion should be
provided from sustainable low-carbon sources to effectively control atmospheric CO2 levels. As the most scientically sound
scenario, energies from intermittent resources (e.g. electricity
and hydrogen produced by solar, wind, wave, geothermal, biofuel
or nuclear) must be employed to chemically transform CO2.
In association with hydrogen (or methane), CO2 can be converted
into high-density fuels perfectly compatible with the current
energy infrastructures. Additionally, a wide range of useful products can be synthesized from CO2, which are currently produced
by unsustainable carbonaceous reagents. This intriguing approach
offers the prospect of decarbonizing fossil-fuel-based economies
without any revolutionary change in the platform required by
substituting other alternatives such as electricity and hydrogen.
1532
In fact, there are numerous theoretical pathways proposed for

CO2 chemical transformation which are studied extensively by
several researchers in the past few years [392401]. The majority
of them mainly rely upon use of CO2 as a co-reactant with other
chemicals owning higher Gibbs free energies (e.g. hydrogen,
methane, unsaturated compounds, small-membered ring compounds, organometallics, etc.) for facilitating chemical reduction
of carbon dioxide. Such energetic chemicals meaningfully enhance
CO2 reducibility with releasing high chemical energies in the
course of reaction [392]. Fig. 18 exemplies the appropriate
selection of reactions that can lead to a negative Gibbs free energy
change for the overall CO2 reduction route.
Among the suggested solutions for CO2 chemical conversion,
graphene and its derivatives can serve remarkably in three major
categories of catalytic, electrocatalytic, and photoelectroncatalytic
CO2 reduction to primary fuels and chemical commodities (i.e.
methanol and formic acid), using methane (Scheme 4) and
hydrogen (Scheme 5) as the main co-reactants. Each of the
mentioned categories will be discussed in detail throughout this
section with more emphasis on the future prospects by elaborating
the theoretical aspects. Fig. 19 portrays the critical role of advanced
catalytic materials, in this case graphene, to achieve carbon-
Fig. 18. Appropriate reactions that can lead to a negative Gibbs free energy change
for organic synthesis using CO2 as a co-reactant.
Scheme 4. Carbon dioxide conversion to syngas using methane as co-reactant.
Scheme 5. Carbon dioxide conversion to methanol using hydrogen as co-reactant.
Fig. 19. Ideal carbon-neutral energy cycle via coupling carbon capture technologies
with renewable carbonaceous fuel production from CO2 upon successful graphene
utilization.
neutral cycles for carbonaceous fuels by efcient CO2 chemical

conversion.
Scheme 4 is known as the dry reforming of CO2 comparing with
steam reforming which utilizes steam to produce syngas from
methane [402]. On the other side, methanol synthesis from CO2
using hydrogen as the co-reactant (Scheme 5) is viewed as the
chemical liquefaction of hydrogen to increase its volumetric
energy density. This process can be potentially carbon-neutral if
the required energies for the water electrolysis (i.e. hydrogen
production), carbon capture and release are supplied from
carbon-neutral resources (Fig. 19).
5.2. Catalytic reduction of CO2
Rapid developments in scalable and cost-efcient production
methods for graphene and its derivatives have encouraged assessment of catalytic properties of this class of 2D materials [403]. The
overall advantage of carbon-based catalysts over their conventional metal-based rivals, aside from cost-effectiveness, is the
elimination of the surface poisoning issue (common among
metallic compounds) which leads to a signicant increase in the
number of working cycles [404]. Particularly in carbon family,
there are notable differences between graphene and other allotropes which include (i) superior surface/weight ratios, (ii) greater
surface accessibility, and (iii) extreme exibility in chemical
doping/functionalization (see Section 2.2). Here, we aim to elaborate more on these versatilities with respect to their ability to
address the CO2 catalytic reduction criteria.
5.2.1. Hydrogen-assisted CO2 reduction
Theoretically, graphene and its derivatives meet some of the
key requirements for catalytic reduction of CO2 with H2; which is
currently practiced using multi-component heterogeneous catalysts at high temperatures for elevating production yields
[405,406]. In fact, the reverse water-gas shift reaction (RWGS)
shown in Scheme 6 has a key role in the catalytic hydrogenation of
CO2. RWGS results in the initial conversion of the H2/CO2 stream to
CO and H2O; where the produced water acts as an inhibitor on the
catalyst surface, and deviates from the subsequent methanol
synthesis step. This is the most critical issue in the underlying
reaction mechanism for CO2 reduction with H2, obstructing the
process to reach higher efciencies at lower temperatures with
water tolerance.
Wide-ranging studies have been carried out on catalyst development for more improved CO2 hydrogenation to methanol
[407,408]. CuZn oxides are among the most researched materials
for this process along with various additives and promoters such
as ZrO2, Ga2O3, and SiO2 [409,410]. The latter materials certainly
enhance the intrinsic reactivity, active surface area (via dispersion), thermal stability, and recyclability; however, water intolerance still remains problematic with low per pass conversions of
about 10% [405]. Thus, multicomponent heterogeneous catalysts
(Cu/ZnO/ZrO2/Al2O3/SiO2) have emerged as better alternatives
especially under practical reaction conditions [411,412]. Furthermore, using pure CO2 as feedstock results in typically 310 times
lower conversion rates compared to that of CO/CO2 mixtures as the
feed (CO reacts with water and lowers the inhibitory impact of
RWGS) [413]. Therefore, the feasibility studies on methanol synthesis from CO2/H2 mixtures are mainly divided by two different
approaches; one separates RWGS reaction vessel from methanol
Scheme 6. Reverse water-gas shift reaction (RWGS) as the main bottleneck of CO2
hydrogenation.
production step, and the other integrates two stages in a single

reactor. The rst concept offers higher catalyst performance, lower
gas recycle and reactor size; while the latter proposal requires
lower xed investments with simpler reactor designs (the complexities are all lumped into the efcient catalyst synthesis here)
[414].
Prior to the recent interest in graphene, the CNT-based materials decorated by transition metals had been reported as promising
support and/or promoter for the catalysts related to CO/CO2
hydrogenation to alcohols [415]. This includes hybridization of
multiwall CNTs with CuZnAlZr (as promoter) [416], and
PdZnO (as support) [417]. Although both CNTs and GNs share
similar sp2 constructed surfaces, with the previously described
superiorities of GNs over other carbonaceous frameworks, it is
projected that hybrid materials of GN and transition metals emerge
as a robust support/promoter for CO2 hydrogenation process. Aside
from hydrophobicity of graphene [418,419], the edges and basal
planes of GNs are remarkably active for CO2 adsorption [329]. It was
also discussed that graphene doping with nitrogen has a synergetic
impact on both adsorption and reactivity of the nanographenes
which is another distinct advantage [364,420].
Moreover, a new research has investigated the possibility of
using graphene oxide as a metal-free catalyst for CO2 reduction
based on density functional theory (DFT) modeling [421]. GO
substrates are impermeable against various gases [422], and
recently, several catalytic applications have been reported for
them at moderate temperatures [423]. Consequently, DFT-based
modeling conrmed the possibility of the CO2/CO reduction via
employing GO as the hydrogen source for the hydrogenation
process [421]. It is shown that the transformation of hydroxyl
groups on the graphene surface to epoxy functionalities is reversible in the presence of water at room temperature [424]. Also,
addition of the transition metal oxides signicantly decreases the
energy costs of the CO2 reduction [421]. Such a novel approach
with benetting from surface groups of GO as a regenerable
hydrogen source while lowering the energy barriers with metallic
additives certainly requires further detailed explorations. At present, the estimated yields for complete reduction of carbon mono-
1533
and di-oxide to methane are 0.01% and 0.07% for pure GO and its
composite with metal oxides (in this case iron and vanadium),
respectively. Increasing the temperature up to 100 1C is projected
to afford the total conversion of CO/CO2 [421]. The calculated
reaction rates compete fairly with more expensive catalysts
(platinum- and ruthenium-based), but in terms of yield per gram
(or cm2) by far outweigh the costly rivals due to the superior
surface over weight ratios of GO [421]. Fig. 20 illustrates the
optimized atomic structure and energy costs of initial (a, d),
intermediate (b, e) and nal (c,f) stages of CO2 to HCOOH conversion using pure graphene oxide (ac) as well as GO hybrids with
metal oxides (df).
5.2.2. Methane-assisted CO2 reduction
Three major classes based on transition metals are broadly
examined as catalysts for carbon dioxide reforming with methane
[425427]: (i) non-noble metals (Ni, Co and Fe), (ii) noble metals
(Ru, Rh, Pd, Pt, Ir), and (iii) transition metal carbide catalysts. Noble
metallic nanoparticles are highly resistant to coke formation (the
main catalyst deactivator here) [428]; however, their costly nature
remains the limiting factor. Ni-based materials have shown the
closest performance comparing with the noble metals, incurring
intense attention due to their non-preciousness and earth abundance. However, they still suffer from rapid coke formation and
subsequent catalyst deactivation which is mostly linked with the
methane cracking reaction [429,430]. In such situations, the
adsorbed oxygen atoms on the surface are supposed to eliminate
the deposited carbon and release CO as the result. However, this
does not occur efciently on the surface of non-noble metals such
as Ni due to the insufcient oxygen adsorption and/or severe
solubility/diffusivity of carbon in the metal. There have been a
number of studies to address the oxygen activation issue via
surface engineering of the catalyst. For instance, it is reported that
metal oxide composites such as CeO2/ZrO2 [431], Y2O3/ZrO2 [432],
TiO2/ZrO2 [428], and Nb2O5/ZrO2 [433] as the carriers can improve
the catalytic performance relative to the pure oxides. Moreover,
the most recent studies have revealed that synthesizing NiO
MgOZrO2 alloys inhibit the coke formation process on Ni1 more
effectively under dry reforming conditions [425].
As mentioned in earlier sections, metal-free carbonaceous
materials have recently gained a signicant ground with their
low cost, high temperature stability, and the absence of sulfur
poisoning [434437]. They are also strong absorbers of microwave (i.e. highly heated under microwave radiation) [438440].
As the result, improved yields for dry reforming are achieved by
microwave heating of carbon-based catalysts compared to the
conventional heating methods, with an optimum temperature
ranges between 700 and 800 1C [436]. The better outcome via
microwave heating is attributed to the presence of microplasmas
within the porous carbon which act both as catalyst and as
microwave receptor (C/MR), thus boosting the homogeneous and
heterogeneous catalytic reactions [436,441,442]. In this situation, dry reforming mechanism is proposed to be a combination
of the catalytic methane decomposition (Scheme 7), and the CO2
gasication (Scheme 8) [441,443]. CH4 decomposition takes
place on the active sites of C/MR, and the nature of these
centers has been suggested to fall into the following categories:
Scheme 7. Catalytic decomposition of methane over graphene heterostructures.
Fig. 20. Optimized atomic structure and energy costs of initial (a, d), intermediate
(b, e) and nal (c,f) stages of CO2 to HCOOH conversion using pure graphene oxide
(ac) as well as GO hybrids with metal oxides (df). Reprinted with permission
from Ref. [421], Copyright 2013, Scientic Research.
Scheme 8. CO2 gasication rendered by the carbonaceous deposits from methane

decomposition on GNs.
1534
(i) surface functionalities at the edges of the graphene sheets

[444]; (ii) delocalized electron-rich regions of the GN
basal planes [444]; and, (iii) carbine type (free armchair sites)
or carbene type (free zigzag type) edge (or defect) sites at
the GNs boundaries [445]. The deposits resulting from surface
CH4 decomposition are diversied in nature and reactivity
[446]; which then render CO2 gasication, leading to the insitu regeneration of the active centers for dry reforming
[436,437].
The above-described role of the edges and basal planes in GNs
as the reaction centers with complementary functionalization
effects for the microwave-assisted dry reforming opens a wide
window of opportunity for more research in this section. Flexibility in doping, tunability of the edge-to-surface ratios, and the
extraordinary microwave absorption of graphene heterostructures
[439] bolster their competitiveness in this area amongst metalfree catalysts.
5.3. Electrocatalytic reduction of CO2

Graphene offers many versatilities for electrochemical applications, and CO2 electroreduction is no exception. Experimental
studies on electrochemical reduction of carbon dioxide (ERC) have
been commonly conducted in neutral to alkaline medium
(pH47), where the generation of formate ions (HCO2 ) is more
favored via the reaction shown in Scheme 9. However, the pH
above 9 is also not recommended as it renders CO2 sequestration
in the form of bicarbonate/carbonate and deviates CO2 from the
main reduction pathway [14,447]. Yet, competitive reduction of
water to hydrogen remains the major issue of this process
(Scheme 10) [448,449].
The reaction in Scheme 10 is more thermodynamically favored
over that of Scheme 9. Still, formate ions can be selectivity
produced through cathodic electrocatalysis, where the water
reduction to hydrogen (Scheme 10) is kinetically hindered relative
to the reaction in Scheme 9. As another alternative to address this
issue, non-aqueous solvents, particularly ionic liquids with a wide
electrochemical window have been employed successfully for CO2
electroreduction without any water interference [450453].
The preferred cathode materials here are Cu, Hg, In, Pb, and Sn,
which are also suitable candidates for the reaction under acidic
conditions [454458]. However, the concerns regarding their slow
turnover rates, high overpotential, poor product selectivity, and
low stability are not fully addressed yet [447,459]. Recently, new
classes of the organometallic complexes are explored with signicant afnity toward carbon dioxide activation. The developed
electron-rich and earth-abundant metal complex frameworks
have shown excellent stability in both basic and acidic environments [393,460].
From electrochemistry viewpoint, the cited metallic electrocatalysts hold high hydrogen overpotential which lowers the
exchange current densities for water reduction to hydrogen
(Scheme 10). This equates applying a cathodic bias of at least
0.5 V relative to its Nernst equilibrium potential for maintaining
a reasonable rate of the water reduction [447,454]. Hence, the
exchange current densities for the CO2 reduction reaction
Scheme 9. Formate ion formation resulting from carbon dioxide electroreduction

in aqueous solutions.
Scheme 10. Competitive reduction of water to hydrogen as the main issue for CO2
electroreduction.
(Scheme 9) on the surface of these metals is remarkably higher

than that for the water reduction (Scheme 10), and other parasitic
reactions [454,461]. Briey, a proper electrocatalyst for ERC should
fulll three important criteria: (i) active in reducing CO2/CO (i.e.
low cathodic overpotential), (ii) high faradaic efciency toward
CH4/CH3OH production, and (iii) excellent chemical stability (i.e.
resistant to poisoning by adsorbed H or OH).
Among the metallic compounds, copper is the only one that
can afford the complete electroreduction of CO2 to produce
signicant amounts of hydrocarbons, mostly CH4 and C2H4. However, high overpotential along with a low faradaic efciency
resulting from the competing hydrogen evolution reaction
(Scheme 10) are still troublesome in this case [462,463]. Surprisingly, methanol (CH3OH) is not among the electroreduction
products while copper catalysts are widely employed for selective
methanol production from mixtures of CO2, CO, and H2 [464,465].
The origin of cathodic overpotential on copper electrodes
remained mysterious until a recent DFT modeling mapped out
the entire underlying reaction mechanism in conjunction with the
computational hydrogen electrode method [466,467]. The results
revealed that the CO protonation step to form adsorbed CHO
species is the main bottleneck for efcient CO2 electroreduction to
hydrocarbons on copper electrocatalysts. CHO intermediates must
be stabilized on Cu surface to facilitate further electroreduction
steps, and reach a signicant drop in overpotential. However, weak
CO interaction with copper surface leads to large quantities of gasphase CO production. Therefore, materials with strong tendency
towards CHO adsorption, while showing similar tenacity about CO,
may be the best candidates for the future ERC electrocatalyst
developments [466,467]. Recently, a novel class of coppergraphene hybrids is synthesized, exhibiting signicantly lower overpotential and higher current densities [468]. Presumably,
graphene addresses the described CO/CHO adsorption issue on
the electrocatalyst surface. As suggested by other researchers, a
noticeable CO adsorption capacity is anticipated for graphene
nanosheets [154,469], and their presence in a close proximity to
the copper nanoparticles certainly increases the electroreduction
chance under more energy-efcient circumstances.
Nonetheless, the inefciencies of metallic electrocatalysts for
ERC have urged scientic community to search for more forwardlooking material designs. Consequently, a new class of metalfunctionalized porphyrin-like graphene is recently investigated for
CO2 electroreduction based on DFT calculations (Fig. 21a) [470].
The model structure is composed of a metal atom coordinated to a
porphyrin ring attached to the graphene. The framework is
different from the typical porphyrin structures with the metal
coordinated to four adjacent nitrogen atoms, which ultimately
creates ve- and six-atom-long rings along neighboring carbon
atoms. This specic 4-fold coordination was therefore named as
the porphyrin-like functionalized metalGN composite, which is
proved to be the most stable state of binding between metal and
nitrogen atoms in graphene [471].
The described porphyrin-based functionalization has also been
exercised successfully on carbon nanotubes and other graphitic
materials; where some of these chemical modications have led to
excellent catalytic characteristics for methanol oxidation and
oxygen reduction reactions [472,473]. In this case, two major
factors inuenced the model structure design of the grapheneporphyrin hybrids: (i) signicant activities of some porphyrinbased electrocatalysts for ERC applications [474,475]; and (ii) the
unique electrochemical properties of graphene itself [476,477].
Accordingly, the computational studies using the late transition
metals in the center of the porphyrin ring revealed a quite
different trend in catalytic properties; which is originated from
electronic structure modication of the active sites in the model
comparing with the extended metal surfaces (Fig. 21b). Ultimately,
1535
Fig. 21. (a) Model structure of porphyrin-like functionalized metalGN composite. The central metal is coordinated to four adjacent nitrogen atoms, creating a porphyrin
ring attached to the graphene network. (b) Comparison of density of states projected onto the d orbitals of the Pt atom at the porphyrin ring center, and the Pt surface atom
in Pt(111) surface. Reprinted with permission from Ref. [470], Copyright 2013, American Chemical Society.
the Rhporphyrin-like functionalized graphene emerged as the

most active catalyst for CO2 electroreduction with the minimum
overpotential of 0.22 V [470], which is a remarkable improvement
over that of copper ( 1 V) [466].
5.4. Photoelectrocatalytic reduction of CO2
As the third and the last category, graphene-based materials
have been employed for photocatalytic CO2 conversion to solar
fuels [46,478481]. The photoelectrochemical reduction of CO2 by
water begins with the excitation of a semiconductor via absorption
of external photons with energies exceeding its band-gap level
(Eg). This creates photo-induced electrons and holes in the conduction band (CB) and the valence band (VB) of the semiconductor, respectively (Fig. 22a). The photoexcited electronhole pairs
generated in the bulk of the material should then migrate
separately to the surface (paths i and ii in Fig. 22b), and concurrently compete with the unwanted electronhole recombination
process (path iii in Fig. 22b). Finally, at the semiconductor surface,
the successfully migrated electrons and holes reduce and oxidize
the adsorbed CO2 and water molecules to produce methane (or
methanol) and oxygen, respectively. Accordingly, the semiconductor should meet the redox potential requirements for the ratedetermining steps of water oxidation (Scheme 11) and CO2 reduction (Scheme 12). Thus, thermodynamics dictates a band gap of at
least 2.88 eV with suitable band edges' positions to drive redox
reactions effectively.
Three key advantages of performance, stability, and cost have
been lumped in TiO2-based materials with their superior photocatalytic characteristics [482484]. Titania application for photocatalytic
CO2 reduction has also been put forward successfully in gas- and
aqueous-phase photoreactions. Various strategies are implemented
to enhance the performance of the TiO2-based photocatalysts which
can be mostly generalized for other semiconductors as well
[485,486]: (i) uniform synthesis of the single-phase titania crystalline
structure to avoid charge recombination on the lattice defects and
phase boundaries, (ii) band-gap engineering to employ a greater
portion of the external light source, (iii) cocatalyst deposition on the
surface to catalyze redox reactions and reduce activation energies,
(iv) use of sensitization effect for increasing photo-induced electrons,
and (v) utilizing nanofabrication techniques to control the size and
morphology of the material.
Extensive research is carried out to address some of the abovementioned approaches based on the impregnation of TiO2 and
Fig. 22. Photocatalytic CO2 reduction by water using PtTiO2: (a) photo-excitation
of the electronic band structure of the semiconductor, and (b) migration of photoinduced electronhole pairs to the photocatalyst surface for driving redox
reactions.
Scheme 11. Water oxidation half-reaction during photocatalytic reduction of CO2.
Scheme 12. CO2 reduction half-reaction as the heart of carbon dioxide photocatalytic conversion.
other semiconductors on the support materials [487495]. The

major benets of using the supported photocatalysts are:
(i) lowering back-electron transfer as a determining factor in
photocatalytic reactions, (ii) taking advantage of nano-sized semiconductors while using them on an easily-separable micro-sized
support, (iii) providing more solid chemical promoters with the
aid of support, and (iv) useful structural and chemical characteristics of the support itself.
Graphene alone cannot be used as an antenna or a light
harvester due to its transparency against visible and UV lights
[496,497]. However, as a support, it can enhance the
1536
photocatalytic performance of TiO2 (or any other suitable semiconductor) especially by boosting charge separation [498,499].
Photo-excited electrons in the CB of TiO2 are delocalized via swift
migration to graphene, which keeps them reasonably distant from
recombination with the localized holes generated on TiO2 surface
[500]. Charge transport efciency on graphene surface is also vital
to preserve the reactivity power of electrons for driving CO2
reduction reasonably [481,501]. Additionally, it is recently
reported that graphene can elevate the conduction band of WO3
toward more effective CO2 reduction into hydrocarbon fuels under
visible light irradiation [479].
The inuence of lattice defects in honeycomb graphene on the
photocatalytic reduction of CO2 is investigated using two major
solution-based GN synthesis techniques (rGOs and solvent exfoliated) [502]. It was revealed that the TiO2GN composites prepared with solvent exfoliated graphene (SEG) exhibit higher
activities due to lesser defects and more enhanced electron
mobility. Comparing with unsupported TiO2, the optimized TiO2
GN hybrids led to 7-fold improvement in the photoreduction of
CO2 [502].
Moreover, the dimensionality role of the carbon nanomaterial
as the support on the photoreduction of CO2 with TiO2-based
nanosheets (TiNS) is studied by comparing two photocatalysts of
SEGTiNS and SWCNTTiNS [503]. As the result, SEGTiNS nanocomposites afforded 73.5% more CH4 production compared to
SWCNTTiNS [503]. Such improvements were attributed to more
compatible electronic and physical coupling of 2D SEG with TiNS
comparing with 1D SWCNT. This intimate interconnection through
Fig. 23. Schematic of TiO2-graphene hybrids for more efcient photoexcited charge
separation during photocatalytic conversion of CO2 to methane/methanol.
SEGTiNS nanostructure suppresses recombination of the photogenerated pairs more effectively [503].
Robust hollow spheres composed of alternating TiNS and GNs
(GTi0.91O2) are recently fabricated via a layer-by-layer deposition
method with dramatic improvements in photocatalytic CO2 conversion rates [480]. Compared to the conventional synthesis
procedures for TiO2graphene nanocomposites by impregnation
of TiO2 nanoparticles on the graphene surface, GTi0.91O2-based
samples showed a 9-fold enhancement in the photoreduction of
CO2 [480]. This was mainly linked to three key aspects of: (i) the
extreme thinness of Ti0.91O2 nanosheets which allows rapid charge
transfer to the surface; (ii) the compact pile of ultrathin TiNS with
GNs that enables fast interface electron exchange between the two
components and increases the lifetime of electronhole pairs; and
(iii) the hollow structure that acts as a photon-collector and
renders maximum absorption of multi-scattered incident light.
Fig. 23 depicts the schematic of TiO2graphene hybrids for more
efcient photoexcited charge separation during photocatalytic
conversion of CO2 to methane/methanol.
Graphene oxide has also emerged as a promising photocatalyst
for CO2 to methanol conversion [478]. The modied Hummers
method was used for the synthesis of the GO-based photocatalysts
with the enhanced catalytic activities [504]. CO2 conversion rates
of up to 0.172 mol g 1 h 1 were achieved under visible light,
which was reported to be six-fold higher than the results for the
pure TiO2. The wide and tunable band gap of GO via controlling
the oxygenated functional groups unprecedentedly rendered
noticeable photocatalytic activities for CO2 to methanol conversion. Only a small fraction of oxygenated groups in GO was lost
and slightly affected the initial methanol formation before reaching the rate stabilization region (up to 2 h). Fig. 24a illustrates the
underlying mechanisms of photocatalytic CO2 reduction to
methanol on GO.
The stoichiometric carbon-to-oxygen atomic ratios in GO
determine the electronic structure and band gap properties of this
semi-insulating material with a wide band gap [505,506]. Studies
suggest covalent functionalization of GO basal plane with the
epoxide and hydroxyl groups, while proposing the presence of
carboxyl functional groups at the edges (see more in Section 2.2.2)
[209,507]. Thus, owing to several types of oxygenated functional
groups on different locations, GO can undergo a series of complex
covalent/noncovalent interactions with the neighboring molecules. The diversity of surface components also provides a blended
2D network of sp2 and sp3 bonded atoms in GO, which ultimately
results in a specic band gap depending on the sp2/sp3 domain
ratios [118,508]. Consequently, based on the disruption severity of
the graphene sp2 network with sp3 defects, the resulting material
Fig. 24. (a) Schematic illustration of the underlying mechanisms for photocatalytic CO2 reduction to methanol on GO. (b) Photocatalytic methanol formation rates via
different graphene oxide samples (GO-1, GO-2, GO-3) comparing with TiO2. Reprinted with permission from Ref. [478], Copyright 2013, Royal Society of Chemistry.
ranges from a graphene-like semi-metal to a semiconductor and

nally an insulating compound [84,509]. In this regard, protection
of basal planes from breakage and overoxidation is proved to be
one of the key factors in superior activity of the GO-3 sample
presented in Fig. 24b. This was mainly achieved via utilizing a
balanced mixture of strong (e.g. KMnO4) and mild (e.g. H3PO4)
oxidants proposed by the modied Hummers method for GO
production [80,478].
6. Concluding remarks
This review paper presented the latest theoretical and experimental studies on versatilities of graphene and its derivatives for
carbon capture and conversion. Imposing effective CO2 remediation strategies as one of the top urgencies of 21st century requires
state-of-the-art materials development and graphene could play a
game-changing role in this regard. The author did not overlook
theoretical studies as they offer numerous key guidelines for
future material synthesis and development based upon graphene
heterostructures.
The overview of the most common and effective preparation,
doping/functionalization methods was presented along with
detailed discussions on the current and potential applications of
graphene and its derivatives for CO2 capture and conversion.
In addition to the extraordinary CO2 capture capability of
graphene-based materials, their catalytic, electrocatalytic and
photoelectrocatalytic use were elaborated, accompanied by some
of the key DFT investigations. CO2-assisted graphene production is
another intriguing pathway for carbon dioxide chemical transformation, which was covered extensively in this review paper. In
fact, it represents a high interconnectivity between multidisciplinary branches of research on materials for energy and environment
applications.
Finally, there is no doubt that solutions to climate change are in
debt of CO2 annihilation. The worldwide budget to encourage
industries' actions toward efciency improvements, process modications, CCS, and so forth is not sufcient for achieving globally
set visions of hindering the accelerated warming. Without promoting economically oriented CCC technologies, the CO2 regulation mission will fail. Subsequently, without introducing more
cutting-edge materials and processes for CO2 chemical conversion,
the entire concept cannot emerge viably.
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Emerging Applications of Graphene and Its Derivatives in Carbon Capture and Conversion: Current Status and Future Prospects PDF

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Renewable and Sustainable Energy Reviews 41 (2015) 15151545

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews

Emerging applications of graphene and its derivatives in carbon

Tel.: 1 604 827 3418; fax: 1 604 822 6003.

A. Taheri Najafabadi / Renewable and Sustainable Energy Reviews 41 (2015) 15151545

A. Taheri Najafabadi / Renewable and Sustainable Energy Reviews 41 (2015) 15151545

planar sheet of sp2-bonded carbon atoms is the most widely studied

layered double hydroxide

This paper aims to highlight various aspects of graphene

2. Graphene synthesis overview

A. Taheri Najafabadi / Renewable and Sustainable Energy Reviews 41 (2015) 15151545

so-called micromechanical cleavage to extract single sheets of

considering the demanding industrial applications of graphene

A. Taheri Najafabadi / Renewable and Sustainable Energy Reviews 41 (2015) 15151545

Scheme 1. Proposed reaction pathway for epoxide reduction with hydrazine.

organic solvents (e.g. dimethylformamide/tetrahydrofuran), which

A. Taheri Najafabadi / Renewable and Sustainable Energy Reviews 41 (2015) 15151545

with substitutional doping or covalent functionalization. Second

2.2.1. Doping (condensed matter)

A. Taheri Najafabadi / Renewable and Sustainable Energy Reviews 41 (2015) 15151545

with donating groups (electropositivity) lead to n-type doping.

symmetry directions measured by ARPES. Comparing the Fermi

A. Taheri Najafabadi / Renewable and Sustainable Energy Reviews 41 (2015) 15151545

graphene-containing samples (Fig. 5) [168]. Nonetheless, the trend

2.2.2. Functionalization (chemical synthesis)

A. Taheri Najafabadi / Renewable and Sustainable Energy Reviews 41 (2015) 15151545

functionalization is a well-practiced concept for the surface

networks in CNTs [228233]. Consequently, similar techniques

A. Taheri Najafabadi / Renewable and Sustainable Energy Reviews 41 (2015) 15151545

Stankovich et al. used a series of isocyanate compounds for the

A. Taheri Najafabadi / Renewable and Sustainable Energy Reviews 41 (2015) 15151545

3. CO2-assisted graphene production

Scheme 2. Burning magnesium metal in a CO2-rich environment to produce

monolayer graphene formation with higher yields using similar

A. Taheri Najafabadi / Renewable and Sustainable Energy Reviews 41 (2015) 15151545

CO2 activation is loaded at the upstream of the copper foil which

where it efciently adsorbs CO2 and converts to CaCO3 [268,269].

Scheme 3. Underlying reactions of calcium carbonate conversion to graphene

A. Taheri Najafabadi / Renewable and Sustainable Energy Reviews 41 (2015) 15151545

4. Graphene-assisted CO2 capture

derivatives, their suitability for each of the three described major

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reduced at 300 1C [336]. Such uptakes were signicantly higher

A few theoretical works have explored the determining role of

A. Taheri Najafabadi / Renewable and Sustainable Energy Reviews 41 (2015) 15151545

on various supports and membranes with promising results [355

A. Taheri Najafabadi / Renewable and Sustainable Energy Reviews 41 (2015) 15151545

presence. Such features afforded the synthesized nanocomposite an

charge-harmonizing 2D material that boosts the CO2 uptake

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for further modication of the material. This affords up to 200%

5. Graphene-assisted CO2 conversion

and S0 , respectively) of the Gibbs free energy change G0 are

A. Taheri Najafabadi / Renewable and Sustainable Energy Reviews 41 (2015) 15151545

In fact, there are numerous theoretical pathways proposed for

Scheme 4. Carbon dioxide conversion to syngas using methane as co-reactant.

Scheme 5. Carbon dioxide conversion to methanol using hydrogen as co-reactant.

neutral cycles for carbonaceous fuels by efcient CO2 chemical

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production step, and the other integrates two stages in a single

Scheme 7. Catalytic decomposition of methane over graphene heterostructures.