Vous êtes sur la page 1sur 9

See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/312107259

Application of Wet Nanostructured Bacterial Cellulose as a Novel Hydrogel


Bioanode for Microbial Fuel Cells

Article  in  ChemElectroChem · January 2017


DOI: 10.1002/celc.201600868

CITATIONS READS

8 277

6 authors, including:

Mehrdad Mashkour Mostafa Rahimnejad


University of Bologna Babol Noshirvani University of Technology
13 PUBLICATIONS   63 CITATIONS    147 PUBLICATIONS   1,777 CITATIONS   

SEE PROFILE SEE PROFILE

Mahdi Mashkour Gholamreza Bakeri


Gorgan University of Agricultural Sciences and Natural Resources Babol Noshirvani University of Technology
23 PUBLICATIONS   123 CITATIONS    64 PUBLICATIONS   580 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

‫ ﻣﺸﺨﺼﺎت ﻓﯿﺰﯾﮑﯽ و ﻣﮑﺎﻧﯿﮑﯽ ﺑﻠﻮک ﺳﺎﺧﺘﻪ ﺷﺪه از ﻣﯿﺴﻠﯿﻮم‬Physical and Mechanical Properties of Mycelium Bricks View project

MFC Based Biosensors View project

All content following this page was uploaded by Mehrdad Mashkour on 05 April 2017.

The user has requested enhancement of the downloaded file.


DOI: 10.1002/celc.201600868 Articles
1
2
3
4
Application of Wet Nanostructured Bacterial Cellulose as a
5 Novel Hydrogel Bioanode for Microbial Fuel Cells
6
7 Mehrdad Mashkour,[a] Mostafa Rahimnejad,*[a] Mahdi Mashkour,[b] Gholamreza Bakeri,[c]
8 Rafael Luque,[d] and Sang-Eun Oh[e]
9
10
11
In this study, wet bacterial cellulose (BC) with a water content of system by using cyclic voltammetry (CV), electrochemical
12
more than 98 % was utilized as a novel scaffold to design impedance spectroscopy (EIS), and polarization curves. A power
13
bioanodes for microbial fuel cells (MFCs). At first, unmodified density of 136 mW/m2 and a current density of 662 mA/m2 were
14
wet BC was used a bioanode. Then a simple in situ synthesis of found for BC-PPYR, which are superior to those of graphite
15
polypyrrole (PPYR) at various pyrrole concentrations was (1 mW/m2 and 9 mA/m2, respectively). The results were attrib-
16
subsequently performed on the BC‘s fibers to generate the uted to a good adhesion of bacterial cells to the fibrous surface
17
novel bioanodes. Characterization of the BC-PPYR nanobiocom- of BC, permanent capillary transfer of nutrients, the conductive
18
posites was conducted by using ATR-FTIR, XRD, and FESEM. The content of hydrogel BC, and good conductivity and catalytic
19
performance of the nanobiocomposites was studied in a MFC activity of PPYR in the nanocomposite.
20
21
22
23 1. Introduction transfer between microorganisms and anode surface restraining
24 its feasible applications.[6,7]
25 MFCs have been extensively investigated in recent years as Considerable works are underway with a focus on electro-
26 highly relevant devices capable of decomposing organic waste des to improve performance of MFC devices.[8] Fabrication of
27 materials and producing electricity.[1] With current needs of conventional anode electrodes such as graphite,[9] carbon
28 renewable energy, MFC’s technology can offer a potential cloth[10], carbon paper,[11] and evolved generations of carbon
29 alternative renewable energy source.[2–4] In MFC, degradation of based materials including CNT modified,[12] graphene,[13] gra-
30 the organic substrates is generally performed by bacteria at the phene oxide-polypyrrole[14] and graphene-ionic liquid[15] compo-
31 anode (oxidation reactions).[5] The electrons and protons site electrodes involve a relevant role of a stable and high
32 released throughout the microbial metabolite react with oxy- performing anodes in MFCs.
33 gen at cathode. Though, the chemical energy is electrochemi- Conductive polymers including polyaniline (PANI) and
34 cally converted to electrical power in above process, MFC’s polypyrrole (PPYR) have been used in various anode structures
35 generated power is still low because of the slow electron because of their acceptable conductivity and explored catalytic
36 properties in MFC technology.[16–18] The environmentally friendly
37 nature, charge capacitance, lower price and rather simple
[a] M. Mashkour, Dr. M. Rahimnejad
38 Biofuel and Renewable Energy Research Center synthesis of these polymers makes them potentially suitable
39 Department of Chemical Engineering alternatives for CNT, graphene and graphene oxide in compo-
40 Babol Noshirvani University of Technology (BNUT) site anode electrodes.[14,19] Anode porosity is another relevant
47148-71167 Babol (Iran)
41 Fax: (+ 98)-11-32334204 property to be taken into account in the design of advanced
42 E-mail: Rahimnejad@nit.ac.ir MFCs. It can provide an extended surface for bacteria adhesion
43 [b] Dr. M. Mashkour and colonization and suitable support for exoelectrogenic
Department of Wood Engineering and Technology
44 Faculty of Wood and Paper Engineering microorganisms to the anode as well as enhanced electron
45 Gorgan University of Agricultural Sciences and Natural Resources transfer surface. The low porosity of the scaffolds is a problem
46 49189-43464 Gorgan (Iran) in conventional electrodes and even composite electrodes
[c] Dr. G. Bakeri
47 Advanced Membrane and Biotechnology Research Center based on stainless steel, nickel, carbon cloth and carbon paper.
48 Department of Chemical Engineering A more comfortable method to achieve an appropriate porosity
49 Babol Noshirvani University of Technology(BNUT) is choosing suitable scaffolds. Some scaffolds including tex-
47148-71167 Babol (Iran)
50 [d] Prof. R. Luque tiles,[20] titanium dioxide,[21] natural loofah sponge[22] and
51 Departamento de Quimica Organica chitosan[6,23] have been previously reported.
52 Universidad de Cordoba Bacterial Cellulose (BC) is a sustainable and renewable
Campus de Rabanales, Edificio Marie Curie
53 14014 Cordoba (Spain) biological material derived from wet spinning activity of some
54 [e] Prof. S.-E. Oh bacterial species such as Acetobacters. BC’s features are three-
55 Department of Biological Environment dimensional (3D) nano- and microfibrous porous network[24,25]
Kangwon National University
56 192-1, Hyoja 2-dong, Chuncheon with remarkable and potentially tunable properties including
57 Kangwon-do 200-701 (South Korea) low density, high specific surface area, high sorption capacity,

ChemElectroChem 2017, 4, 1 – 8 1  2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

These are not the final page numbers! ÞÞ


Articles
1 high strength and high aspect ratio.[26,27] The water content of MFC Configuration and Electrode Fabrication
2 BC accounts for over 98 % and its capacity for liquid sorption
A simple H-type dual chamber MFC with working volume of
3 has been reported to be outstanding.[28,29] Mentioned properties 250 mL for each chamber was used in this study. The cathode was
4 turned BC into an ultrafine scaffold capable of being coated by graphite (ENTEGRIS, INC. USA). Graphite, BC and BC-PPYR nano-
5 conductive materials such as CNT, PANI and PPYR in electrodes biocomposite sheets were utilized as anodes. Nafion 117 (Sigma
6 and supercapacitor applications.[30–35] Aldrich, USA) was treated by the method studied by Ghasemi
et al.[36] and applied as proton exchange membrane between two
7 Profiting from the excelling properties of BC and in
chambers. All the anodes and also the cathode prepared in
8 continuation with research endeavors of the group, BC-PPYR dimensions of 2 cm  4 cm. Graphite plates, wet BC and wet BC-
9 nanobiocomposites have been synthesized in this work and PPYR sheets were connected to copper wire by stainless steel
10 further utilized as anodes in a dual chamber MFC device. connectors. Figure 1 shows the MFC system before cultivation. PBS
11 Initially, investigations on BC as anode compared to graphite as concentration for both electrodes was the same in the MFC.
12 a commercial electrode were conducted, followed by the
13 design of BC-PPYR nanobiocomposites using a low cost in situ
14 polymerization of pyrrole on BC porous scaffolds. The designed
15 bio-anode exhibited high conductive surface and related
16 excelling properties as microbial support which provided
17 improved MFC’s performance.
18
19
20 Experimental Section
21
22 Synthesis of BC-PPYR Nanobiocomposite
23
The synthesis of polypyrrole on BC fibers was performed based on
24 a previous method reported by Muller et al.[34] Different volumes of
25 distilled pyrrole (15, 30, 45 and 60 mL) each one was added to
26 10 mL of deionized water (to achieve 0,01, 0.02, 0.03, 0.04 m pyrrole
27 solution) and then the four mixtures were stirred for 10 minutes. A
piece of BC sheet (Nano Novin Polymer, Iran) (4 cm  5 cm) was
28
soaked in each mixture under shaking at 5 8C until the pyrrole Figure 1. Double-chamber MFC configuration employed in this study.
29 solution replaced water in BC (for 1 hour). 10 mL of FeCl3 aqueous
30 solution as polymerization initiator with constant molar ratio (1 : 2
31 pyrrole: FeCl3) was then poured into each prepared mixture
32 (aqueous solution of pyrrole and BC). After reaction overnight,
33 PPYR coated films were washed by deionized water and dilute HCl Power and Current Densities
(0.1 M) solution to remove remained monomers and possible
34 Power and current was measured by MFC test device (DGHS-
impurities on the films. The obtained hydrogel BC-PPYR composites
35 EL25101, Iran) loading various resistances (from higher to lower) on
were put in deionized water.
36 the MFC external circuit then calculating power and current of each
point by ohm’s law and finally plotting power density versus
37
Characterization of BC-PPYR Nanobiocomposite current density to reach the power density peak.
38
39 Chemical and crystalline structures of BC’s fibers before and after
40 PPYR coating for different concentrations of monomers were Electrochemical Analysis
41 characterized by ATR-FTIR spectroscopy (Shimadzu IR-Prestige 21,
All electrochemical measurements were accomplished in a PGSTAT
42 Japan) and XRD (Rigaku Ultima-IV) respectively. The morphology of
IVIUM (Vertex, Netherlands) in the MFC with three electrodes
the composites was studied by FESEM (Hitachi S4800, Japan). For
43 contained an anode as the working electrode, a near reference
ATR-FTIR and FESEM, dry films were used and dry powder was
44 electrode (KCl saturated Ag/AgCl) at the anode compartment and
prepared for XRD.
45 graphite as counter electrode at the other side of the MFC device.
For CV, the scan rate was 50 mV/Sec similar to previous works.[12,37]
46
Bacterial Culture EIS experiments were carried out over frequency range of 10 mHz
47 to 100 kHz at OCP which was different for each electrode.
48 Anaerobic sludge from Ghaemshahr wastewater treatment com-
49 plex located in north of Iran was used as inoculums. The mixed
50 culture was grown in a phosphate buffer solution (PBS) media
51 consisted of 10 g of glucose, 3 g of yeast extract and 1 g of 2. Results and Discussion
peptone per liter under 30 8C for 12 h and in stationary phase. PBS
52 was made in two different concentrations, namely 0.1m and 0.5m.
53 Bacterial bio-films then formed on the anode surface after 50 h The successful synthesis of PPYR on BC fibers was supported by
54 under a 1 kW external resistance. In order to remove oxygen and Field Emission Scanning Electron Microscopy, Attenuated Total
55 keep anaerobic condition, nitrogen was purged for 20 min before Reflectance Fourier Transform Infrared (ATR-FTIR) spectroscopy
56 adding inoculums. and X-Ray Diffraction (XRD) spectra. Figure 1A displays the
57 characteristic patterns of different PPYR concentrations in the

ChemElectroChem 2017, 4, 1 – 8 www.chemelectrochem.org 2  2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

These are not the final page numbers! ÞÞ


Articles
1 nanocomposites. Absorption bands at 1470 and 1560 cm 1 can At first, performance of untreated wet BC and graphite as
2 be ascribed to stretching vibrations of C N and C=C in pyrrole anode electrodes was studied. Power and current density
3 rings, respectively.[33] Increasing pyrrole concentration in the produced by MFC in the presence of graphite as anode was
4 polymerization process led to a reasonable increase of C N 0.94 mW/m2 and 7 mA/m2 (Figure 3C and D), respectively in
5 absorption band intensity at 1470 cm 1. The characteristic
6 bands at 1290 cm 1 are the result of C–N bending mode in-
7 plane ring. Observable peaks in the regions of 1036 cm 1 and
8 1161 cm 1 can also be attributed to bending mode of C H.[38]
9 By comparing the four composites’ spectra with BC, a pyrrole
10 concentration of 0.01 m obviously resulted in a weak coating of
11 PPYR on BC. Besides qualitative detection, the observed
12 intensity increase of PPYR peaks denoted a higher concen-
13 tration of PPYR on BC’s fibers.
14 XRD patterns in Figure 2B depict the phase of cellulose I in
15 BC and the PPYR coated BC via characteristic (110) and (200)
16
17
18
19
20
21 Figure 3. FESEM images of A) graphite and B) untreated wet BC, as well as
22 the box plot for the C) power density and D) current density.

23
24
25 0.1 m PBS. It was in good agreement with recent reported
26 results by Mashkour et al.[41] Untreated wet BC exhibited a low
27 power density (0.57 mW/m2) in 0.1 m PBS (usual concentration
28 of PBS in anolyte) compared to graphite under similar
29 conditions. With higher PBS concentration (0.5 M), the MFC
30 generated 2.2 mW/m2 using BC as anode. Unlike BC, for
31 graphite the obtained power was only 1 mW/m2 (in 0.5m PBS),
32 somewhat closer to that recorded for graphite anode at 0.1m
33 PBS concentration. Similar results were recorded for the
34 generated current density as demonstrated in Figure 3D. The
35 measured conductivity for 0.1m and 0.5m PBS were 13 and
36 54 mS, respectively. Regards to the above results, increasing
37 PBS conductivity[42] improved electron transfer in BC and also,
38 the effect of anolyte (PBS) conductivity on the performance of
39 untreated wet BC was more than graphite. In order to explain
40 the difference of the effect of anolyte conductivity on wet BC
41 and graphite, the nature of MFC should be reminded.
42 Figure 2. ATR-FTIR (A) and XRD (B) spectra of BC. BC-PPYR with concen- Exoelectrogens, the electron generators in MFC, create colonies
43 tration of a) 0.01, b) 0.02, c) 0.03, and d) 0.04m pyrrole. on the anode surface. The porosity and morphology of BC give
44 rise to an improved adhesion of microbial cells. Because of the
45 high liquid content of BC and consequently more extended
46 planes. The degree of crystallinity for BC as calculated using contact surface of bacteria with the anolyte, the liquid
47 Segal’s equation was 94 %.[39] PPYR synthesized on BC’s fibers conductivity is expected to be more effective on power and
48 rendered nanocomposites with a decreased degree of crystal- current produced by BC as compared to graphite. For more
49 linity (ranging from 92.8 to 88 %) for concentrations between concentrated PBS (over 0.5 M), the lag phase of bacteria in the
50 0.01, to 0.04 m of pyrrole which indicated a good preservation anode chamber was too high and it was inexcusable to increase
51 of BC crystallinity upon deposition despite the amorphous even more the concentration of PBS.
52 nature of PPYR.[34] These findings can be attributed to the low In previous paragraph, it was shown that conductivity of
53 temperature (5 8C) and particularly mild acidic condition untreated BC in wet state depends on the conductivity of liquid
54 employed during polymerization process. Based on previous by which BC is wetted. Another approach to make BC
55 research, cellulose degrades at high temperatures and under conductive involves deposition of a conductive layer on BC’s
56 strong acidic conditions.[40] fibers. For this purpose, in this study BC was coated with PPYR
57 as a conductive polymer through a trouble-free in situ

ChemElectroChem 2017, 4, 1 – 8 www.chemelectrochem.org 3  2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

These are not the final page numbers! ÞÞ


Articles
1 method.[34] In addition to conductivity, PPYR provides a
2 protecting layer on BC’s nano fibers against microbial degrada-
3 tion which was a big concern for long-term use of untreated BC
4 anode in MFC. CV experiments represented in Figure 4B (nano-
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26 Figure 5. A) Power output and B) polarization curves of the MFC with a) BC,
27 b) BC-PPYR 0.01, c) BC-PPYR 0.02. d) BC-PPYR 0.03, and e) BC-PPYR 0.04.
28 Figure 4. A) Power output and polarization curves of MFC with a) BC and b)
graphite. B) Cyclic voltammograms of a) graphite, b) BC, and c) BC-PPYR 0.01
29
in the anolyte containing mixed cultures in anaerobic conditions.
30 results in charge (electron) accumulation in the anolyte. Total
31 extended surfaces of BC’s fibers became wet by the buffer
32 composite formed by polymerization of 0.01m pyrrole solution solution by which the wet fibers became conductive. The
33 on BC’s fibers) demonstrated a superior catalytic activity of number of stored charges transferred by the extended
34 modified BC, in good agreement with similar findings .[43] The conductive surface of BC’s fibers were far superior as compared
35 sharp anodic and cathodic peaks were obtained around 0.25 V to those transferred by the limited conductive surface of
36 and 0.1 V respectively (in anolyte electroactive solution). graphite during power output tests.
37 These results were in contrast to the weak current of FESEM images in Figure 6 show the morphologies of
38 unmodified BC and graphite and pointed to the excelling redox synthesized BC-PPYR nanobiocomposites. PPYR nano spheres
39 properties of BC-PPYR. The fabricated electrode was further
40 tested in the MFC device and power density and current
41 density were extraordinarily enhanced with respect to BC and
42 graphite. As illustrated in Figure 5, BC-PPYR generated 76 mW/
43 m2 power which was 38 times superior to that measured for BC.
44 Another parameter improved by PPYR coating was capacitance
45 which is calculated by integrating the CV curve area at a
46 specific scan rate.[30,44]
47 Another operational parameter in MFC is the internal
48 resistance (Rin) of the system which is calculated from the slope
49 of the linear part of the polarization curve.[45] From Figure 4A
50 (slope of polarization curve), the measured Rin of the MFC with
51 graphite and uncoated BC as anodes were 12.63 KW and
52 17.5 KW, respectively. Comparatively, a significant decline in Rin
53 was recorded for BC-PPYR nanocomposites (481 to 305 W for
54 pyrrole concentrations between 0.01 to 0.04 m) (Figure 5B).
55 Higher power density of uncoated BC after similar test time Figure 6. FESEM images of BC-PPYR with concentrations of A) 0.01, B) 0.02,
C) 0.03, and D) 0.04m of pyrrole.
56 period as compared to graphite may be attributed to charge
57 capacitance of BC. In other words, the microorganisms’ activity

ChemElectroChem 2017, 4, 1 – 8 www.chemelectrochem.org 4  2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

These are not the final page numbers! ÞÞ


Articles
1 created aligned and ultrafine conductive layers on the BC fibers. loaded systems, CNT coating, etc.), with a comparable perform-
2 Comparing Figure 3B (untreated BC) with Figure 6 demon- ance to recent similar work.[37]
3 strated formation of PPYR layer around BC’s fibers. Better EIS tests were subsequently conducted in the two chamber
4 coating of PPYR leads to more conductive BC’s fibers and H-type MFC (Figure 7). The reference electrode was located
5 consequently more conductive electrode. The optimized con-
6 centration of pyrrole in order to get fully conductive fibers was
7 found to be 0.04 m (Figure 6D). Lower concentrations clearly
8 showed some parts from BC remained uncovered. These
9 findings were also supported by ATR-FTIR spectra, particularly
10 at 0.01 M. Interestingly, the nanocomposites porosity was
11 influenced by PPYR concentration. As expected, more compact
12 (less porous) nanocomposites were obtained at higher PPYR
13 concentrations. The pore sizes under 1 mm observed for the
14 fabricated composites is attributed to a slight shrinkage in BC
15 fibers during drying (to prepare composites for FESEM imag-
16 ing).[46] Comparably, wet BC-PPYR composite electrodes utilized
17 under working conditions in MFC exhibited a good conductivity Figure 7. Nyquist diagrams of BC-PPYR with concentration of a) 0.01, b) 0.02,
18 as well as acceptable pore sizes. c) 0.03, and d) 0.04m of pyrrole.
19 Concentrations of 0.01, 0.02, 0.03 and 0.04 m pyrrole in the
20 nanocomposite synthesis generated maximum power densities
21 (mW/m2) of 76, 96, 119 and 136 at current densities (mA/m2) of adjacent to the working electrode (BC/PPYR) in the anode
22 397, 557, 619 and 662, respectively (Figure 5A). With respect to compartment and graphite played the role as counter electrode
23 aforementioned results, it was found that conductivity and in cathode chamber. The aim of EIS was to measure charge
24 catalytic activity of extended surface of BC’s nano fibers (which transfer resistance (Rct). Straight lines with the Slope of 458 in
25 exoelectrogens adhere to them) are enhanced by completely high frequencies of Nyquist diagrams in Figure 7 could be
26 PPYR coating around them. Maximum power and current ascribed to porosity of anodes and verify the porous nature of
27 density (136 mW/m2 and 662 mA/m2) of the designed optimum BC/PPYR composites.[21] A Randle equivalent circuit was applied
28 nanocomposite were subsequently compared with literature to analyze the results. In the method, the diameter of the
29 work, taking into account parameters such as microorganisms, semicircle part of the EIS graph is proportional to Rct. Electrons
30 cathode electrode material, mediators, oxidizing agent and transfer faster on electrodes (interface of electrode and electro-
31 MFC’s configuration (Table 1). Results summarized in Table 1 lyte) representing the semicircles with smaller diameter.[50]
32 clearly demonstrate the potential of the proposed bio-anode According to Figure 7, Rct is reduced by increasing the
33 for MFCs as compared to expensive devices and systems (i.e. Pt concentration of PPYR on BC fibers. Uncoated BC clearly
34
35
36 Table 1. Comparison of some MFCs with various condition.
37
MFC configura- Double chamber Double cham- Double cham- Double cham- Double cham- Single chamber Dual gas diffusion
38 tion ber ber ber ber cathode
39
Anode Carbon felt Graphite CNT-125/PANI/ rGO/PPy-modi- BC-PPYR Carbon mesh Carbon cloth
40 GF fied carbon
41 cloth
42 Anolyte PBS and HNQ/ PBS (0.1 M), me- PBS, mediator PBS, HNQ PBS, mediator - PBS (Neutral pH)
thionin diator less less less
43 Cathode Pt loaded carbon CNT/Pt loaded plain carbon – graphite Activated car- Gas diffusion elec-
44 felt carbon paper cloth bon-PTFE-GDL trode
45 Catholyte K3[Fe(CN)6 and Distilled water 50 mM K3[Fe — PBS gas gas
5 ml of and PBS (CN)6, 100 mM
46 KCl
47 Membrane Nafion Nafion 117 Nafion – Nafion 117 Without mem- Ion permeable sepa-
48 brane rators (Zirfon)
Bio catalyst E. coli Mixed culture Shewanella pu- E. coli Mixed culture - Farm manure
49 trefaciens
50 Anode area 2.25 cm  2.25 cm 8 cm2 3.24 cm2 1.5 cm2 8 cm2 - 110 cm2
51 Cathode area 2.25 cm  2.25 cm 8 cm2 11.25 cm2 – 8 cm2 7 cm2 110 cm2
Power density 700 mW/m2 16.26 mW/m2 300 mW/m2 1100 mW/m2 136 mW/m2 800 mW/m2 19.79 mW/m2
52 (normalized by) (Anode surface) (Cathode sur- (Anode surface) (Anode surface) (Anode sur- (Cathode sur- (anode or cathode
53 face) face) face) area)
54 Maximum 354 mW 13 mW 97 mW 165 mW 109 mW 560 mW 217 mW
power
55 Working volume 10 cc (each 760 cc (each 45 cc (each – 250 cc (each 28 cc 100 cc
56 chamber)
[47]
chamber)
[41]
chamber)
[37] [14]
chamber) [48] [49]
57 Ref. This work

ChemElectroChem 2017, 4, 1 – 8 www.chemelectrochem.org 5  2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

These are not the final page numbers! ÞÞ


Articles
1 possessed high electron transfer resistivity, even in the hydrogel PPYR coating, with BC-PPYR nanocomposites exhibiting a
2 state. For hydrogel BC/PPYR composites, calculated amounts of remarkable power and current density in MFC in comparison to
3 Rct (W) were 375, 317, 293 and 160 for concentrations of 0.01, unmodified BC. Additionally, the mentioned novel bio-anode
4 0.02, 0.03 and 0.04 m of pyrrole, respectively. The higher pyrrole possessed an excellent biocompatibility and ability of trans-
5 concentration, the lower charge transfer resistance as expected ferring water soluble nutrients to microorganisms by which an
6 due to an increasing degree of PPYR coating on BC fibers. EIS active biofilm formed on the electrode surface. A simple MFC’s
7 results were also fully consistent with FESEM images, ATR-FTIR, configuration and commercial graphite cathode pointed BC-
8 spectra power output and also polarization curves. PPYR as high performance bioanode with a significant potential
9 The rapid growth of microorganisms and biofilm formation for further developments due to its simplicity, tunability and
10 on the fabricated BC-PPYR nanobiocomposite could also be renewable origin that will be reported in due course.
11 demonstrated in FESEM images (Figure 8). Mixed culture cells
12
13 Acknowledgments
14
15 The authors would like to thank Prof. Tsunehisa Kimura and Prof.
16 Fumiko Kimura from Kyoto University for their help with ATR-FTIR,
17 XRD, and FESEM measurements, People at Biofuel & Renewable
18 Energy Research Center at BNUT as well as Mr. M. Taher Motahari
19 at Danesh Gostar Hamgam ba Sanat Company who facilitated
20 the MFC test device for this project.
21
22
23 Conflict of Interest
24 Figure 8. Microbial growth on the surface of BC-PPYR nanobiocomposite
after A) 2 days and B) 7 days.
25 The authors declare no conflict of interest.
26
27 Keywords: bacterial cellulose · hydrogel bionode · micobial
28 were attached to the anode surface by connecting a 1 KW fuel cells · nanobiocomposites · polypyrrole
29 resistance for 50 h to the MFC in which cathode and anode
30 were respectively graphite and BC-PPYR (0.04 m pyrrole). The
31 unique coverage of the nanobiocomposite by bacteria could be
[1] P. Pandey, V. N. Shinde, R. L. Deopurkar, S. P. Kale, S. A. Patil, D. Pant,
32 clearly visualized on Figure 8, indicating the optimum biocom- Appl. Energy 2016, 168, 706–723.
33 patibility of the fabricated anode. Dense population of free [2] S. K. Chaudhuri, D. R. Lovley, Nat. Biotechnol. 2003, 21, 1229–1232.
34 floating exoelectrogen bacteria can result in two phenomena: [3] B. E. Logan, Nat. Rev. Microbiol. 2009, 7, 375–381.
[4] M. Rahimnejad, M. Ghasemi, G. Najafpour, M. Ismail, A. Mohammad, A.
35 an extended electroactive surface for bacteria and on the other Ghoreyshi, S. H. Hassan, Electrochim. Acta 2012, 85, 700–706.
36 hand, hindering nutrient transfer to internal bacteria and [5] M. Rahimnejad, A. A. Ghoreyshi, G. Najafpour, T. Jafary, Appl. Energy
37 subsequent bacterial death also decreasing the internal con- 2011, 88, 3999–4004.
[6] Z. He, J. Liu, Y. Qiao, C. M. Li, T. T. Y. Tan, Nano Lett. 2012, 12, 4738–4741.
38 ductive surface of electrode. The later phenomenon usually [7] K. Rabaey, P. Clauwaert, P. Aelterman, W. Verstraete, Environ. Sci. Technol.
39 occurs in convectional electrodes as graphite and even in 2005, 39, 8077–8082.
40 porous anodes including carbon cloth and carbon paper in [8] M. Zhou, M. Chi, J. Luo, H. He, T. Jin, J. Power Sources 2011, 196, 4427–
4435.
41 which the pores are clogged by microbial growth.[20] The use of [9] H. Liu, R. Ramnarayanan, B. E. Logan, Environ. Science Technol. 2004, 38,
42 BC as a hydrogel scaffold and subsequently perdurable 2281–2285.
43 diffusion of glucose to the inner part by capillary between [10] Y. Fan, H. Hu, H. Liu, J. Power Sources 2007, 171, 348–354.
[11] H. Liu, S. Cheng, B. E. Logan, Environ. Sci. Technol. 2005, 39, 658–662.
44 fibers[51] could also minimize death of cells for internal [12] X.-W. Liu, Y.-X. Huang, X.-F. Sun, G.-P. Sheng, F. Zhao, S.-G. Wang, H.-Q.
45 bacteria.[52] Therefore, the free floating and internal exoelectro- Yu, ACS Appl. Mater. Interfaces 2014, 6, 8158–8164.
46 gens can play synergic roles to improve the performance of [13] A. ElMekawy, H. M. Hegab, D. Losic, C. P. Saint, D. Pant, Renewable
Sustainable Energy Rev. 2016.
47 designed bioanodes. [14] G. Gnana Kumar, C. J. Kirubaharan, S. Udhayakumar, K. Ramachandran,
48 C. Karthikeyan, R. Renganathan, K. S. Nahm, ACS Sustainable Chem. Eng.
49 2014, 2, 2283–2290.
[15] C. Zhao, Y. Wang, F. Shi, J. Zhang, J.-J. Zhu, Chem. Commun. 2013, 49,
50 3. Conclusions 6668–6670.
51 [16] D. Sarauli, C. Wettstein, K. Peters, B. Schulz, D. Fattakhova-Rohlfing, F.
52 Bacterial cellulose with 3D fibrous, highly porous and hydro- Lisdat, ACS Catal. 2015, 5, 2081–2087.
[17] Y. Qiao, C. M. Li, S.-J. Bao, Q.-L. Bao, J. Power Sources 2007, 170, 79–84.
53 philic structure could be successfully employed as effective and [18] Y. Zou, J. Pisciotta, I. V. Baskakov, Bioelectrochemistry 2010, 79, 50–56.
54 sustainable anode scaffold in MFC. Due to its excelling proper- [19] C. Lai, G. Li, Y. Dou, X. Gao, Electrochim. Acta, 2010, 55, 4567–4572.
55 ties, BC exhibited an improved performance compared to [20] X. Xie, L. Hu, M. Pasta, G. F. Wells, D. Kong, C. S. Criddle, Y. Cui, Nano
Lett. 2010, 11, 291–296.
56 graphite, as a conventional electrode. Capacitance and electro- [21] Y. Qiao, S.-J. Bao, C. M. Li, X.-Q. Cui, Z.-S. Lu, J. Guo, Acs Nano 2007, 2,
57 chemical properties of BC could be considerably enhanced by 113–119.

ChemElectroChem 2017, 4, 1 – 8 www.chemelectrochem.org 6  2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

These are not the final page numbers! ÞÞ


Articles
1 [22] Y. Yuan, S. Zhou, Y. Liu, J. Tang, Environ. Science Technol. 2013, 47, [38] H. Wang, L. Bian, P. Zhou, J. Tang, W. Tang, Journal of Materials Chemistry
14525–14532. A 2013, 1, 578–584.
2
[23] S. R. Higgins, C. Lau, P. Atanassov, S. D. Minteer, M. J. Cooney, ACS Catal., [39] S. Park, J. O. Baker, M. E. Himmel, P. A. Parilla, D. K. Johnson, Biotechnol
3 2011, 1, 994–997. Biofuels 2010, 3.
4 [24] T. D. Gadim, A. G. Figueiredo, N. C. Rosero-Navarro, C. Vilela, J. A. [40] C. Luo, S. Wang, H. Liu, Angew. Chem. Int. Ed. 2007, 46, 7636–7639.
Gamelas, A. Barros-Timmons, C. P. Neto, A. J. Silvestre, C. S. Freire, F. M. [41] M. Mashkour, M. Rahimnejad, Biofuel Res. J. 2015, 2, 296–300.
5
Figueiredo, ACS Appl. Mater. Interfaces 2014, 6, 7864–7875. [42] W. M. Haynes, CRC handbook of chemistry and physics, CRC press,
6 [25] L. W. Dalton, Chem. Eng. News 2004, 82, 24–25. 2014.
7 [26] S. Tanpichai, F. Quero, M. Nogi, H. Yano, R. J. Young, T. Lindstrçm, W. W. [43] Z. Shi, Y. Li, X. Chen, H. Han, G. Yang, Nanoscale 2014, 6, 970–977.
Sampson, S. J. Eichhorn, Biomacromolecules 2012, 13, 1340–1349. [44] W. Chen, Z. Fan, L. Gu, X. Bao, C. Wang, Chem. Commun.2010, 46, 3905–
8
[27] E. Trovatti, A. J. Carvalho, S. J. Ribeiro, A. Gandini, Biomacromolecules 3907.
9 2013, 14, 2667–2674. [45] B. E. Logan, Microbial fuel cells, John Wiley & Sons, 2008.
10 [28] T. Maneerung, S. Tokura, R. Rujiravanit, Carbohydr. Polym. 2008, 72, 43– [46] S. Yamanaka, K. Watanabe, N. Kitamura, M. Iguchi, S. Mitsuhashi, Y. Nishi,
51. M. Uryu, J. Mater. Sci. 1989, 24, 3141–3145.
11
[29] M. L. Cacidedo, I. E. Len, J. S. Gonzalez, L. M. Porto, V. A. Alvarez, G. R. [47] P. I. Ho, G. G. Kumar, A. Kim, P. Kim, K. S. Nahm, Bioelectrochemistry
12 Castro, Colloids Surf., B. 2016. 2011, 80, 99–104.
13 [30] H. Wang, E. Zhu, J. Yang, P. Zhou, D. Sun, W. Tang, J. Phys. Chem. C [48] H. Dong, H. Yu, X. Wang, Q. Zhou, J. Feng, Water Res. 2012, 46, 5777–
2012, 116, 13013–13019. 5787.
14
[31] Z. Lin, Z. Guan, Z. Huang, Ind. Eng. Chem. Res. 2013, 52, 2869–2874. [49] S. B. Pasupuleti, S. Srikanth, S. V. Mohan, D. Pant, Int. J. Hydrogen Energy
15 [32] Y. Liu, J. Zhou, J. Tang, W. Tang, Chem. Mater. 2015, 27, 7034–7041. 2015, 40, 12424–12435.
16 [33] S. Li, D. Huang, J. Yang, B. Zhang, X. Zhang, G. Yang, M. Wang, Y. Shen, [50] N. Sekar, R. P. Ramasamy, J Microb Biochem Technol S 2013, 6.
Nano Energy 2014, 9, 309–317. [51] M. Mashkour, T. Kimura, F. Kimura, M. Mashkour, M. Tajvidi, Biomacromo-
17
[34] D. Mller, C. Rambo, D. Recouvreux, L. Porto, G. Barra, Synth. Met. 2011, lecules 2013, 15, 60–65.
18 161, 106–111. [52] M. Mashkour; M. Rahimnejad, M. Mashkour, J. Power Sources 2016, 325,
19 [35] F. Wang, H.-J. Kim, S. Park, C.-D. Kee, S.-J. Kim, I.-K. Oh, Compos. Sci. 322–328.
Technol. 2016, 128, 33–40.
20
[36] M. Ghasemi, W. R. W. Daud, M. Ismail, M. Rahimnejad, A. F. Ismail, J. X.
21 Leong, M. Miskan, K. B. Liew, Int. J. Hydrogen Energy 2013, 38, 5480–
22 5484.
[37] H.-F. Cui, L. Du, P.-B. Guo, B. Zhu, J. H. Luong, J. Power Sources 2015, Manuscript received: December 19, 2016
23
283, 46–53. Final Article published: && &&, 0000
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57

ChemElectroChem 2017, 4, 1 – 8 www.chemelectrochem.org 7  2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

These are not the final page numbers! ÞÞ


Articles
1
2
ARTICLES
3
M. Mashkour, Dr. M. Rahimnejad*,
4
Dr. M. Mashkour, Dr. G. Bakeri,
5
Prof. R. Luque, Prof. S.-E. Oh
6
7 1–8
8
9 Application of Wet Nanostruc-
10 tured Bacterial Cellulose as a
11 Novel Hydrogel Bioanode for
A permanent change: Bacterial density. With this new bioanode,
12 Microbial Fuel Cells
cellulose (BC) is wet nanostructured because of capillaries between BC
13 porous framework for fabricating a bi- fibers and permanent transfer of
14 ocompatible anode for microbial fuel nutrients, the risk of microorganism
15
cells. Polypyrrole, as a conductive spoilage and clogging of the pores in
16
polymer, improves the conductivity of the anode become minimized.
17
BC and boosts the generated power
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57

View publication stats