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ISSN : 1226-0088(Print)
ISSN : 2288-7253(Online)
Membrane Journal Vol.31 No.2 pp.120-132
DOI : https://doi.org/10.14579/MEMBRANE_JOURNAL.2021.31.2.120

Recent Advance in Microbial Fuel Cell based on Composite Membranes

Se Min Kim*, Rajkumar Patel**, Jong Hak Kim***†
*Life Science and Biotechnology Department (LSBT), Underwood Division (UD), Underwood International College, Yonsei University, Sinchon, Seoul 03722, South Korea
**Energy and Environmental Science and Engineering (EESE), Integrated Science and Engineering Division (ISED), Underwood International College, Yonsei University, 85 Songdogwahak-ro, Yeonsu-gu, Incheon 21983, South Korea
***Department of Chemical and Biomolecular Engineering, Yonsei University, 50 Yonsei-ro, Seodaemun-gu, Seoul 03722, South Korea
†Corresponding author(e-mail: jonghak@yonsei.ac.kr, http://orcid.org/0000-0002-5858-1747)
April 24, 2021 ; ; April 26, 2021

Abstract


Microbial fuel cell (MFC) is a bio-electrochemical device that generates electricity by utilizing bacterial catalytic activity that degrades wastewater. Proton exchange membrane (PEM) is the core component of MFC that decides its performance, and Nafion membrane is the most widely used PEM. In spite of the excellent performance of Nafion, it has drawbacks such as high cost, biofouling issue, and non-biodegradable property. Recent studies in MFC attempted to synthetize the alternative membrane for Nafion by incorporating various polymers, sulfonating, fluorinating, and doping other chemicals. This review summarizes characteristics and performances of different composite membrane based MFCs, mostly focusing on PEM.


microbial fuel cell , composite membranes , proton exchange membrane , ion conductivity

복합막 기반의 미생물 연료전지 연구에 대한 총설

김 세 민*, 라즈쿠마 파텔**, 김 종 학***†
*연세대학교 언더우드학부 생명과학공학과
**연세대학교 융합과학공학부 에너지환경융합과
***연세대학교 화공생명공학과

초록


미생물 연료전지(MFC)는 미생물의 촉매 반응을 이용하여 폐수 등 환경 오염물질을 처리함과 동시에 전기에너지 를 생성하는 생물전기화학 장치다. 미생물 연료전지의 주요 성분 중 하나인 양이온 교환막(PEM)은 미생물 연료 전지의 성능 에 결정적인 영향을 미치며, 현재 가장 많이 사용되고 있는 양성자교환막은 Nafion이다. Nafion은 우수한 성능을 가지고 있지 만, 단가가 높고, 생물오염에 취약하며, 생분해가 불가능하다는 단점이 있다. 따라서 Nafion을 대체하기 위한 새로운 복합막 을 개발하고자 하는 시도가 꾸준히 이루어졌다. 본 총설에서는 미생물 연료전지 분야에서 최근 개발된 복합막의 특징과 성능 을 고찰하며, 특히 양성자교환막을 중점적으로 다룬다.


    1. Introduction

    Microbial fuel cell (MFC) is a recently developed bio-electrochemical device which is well recognized as a promising renewable energy source due to its capability of generating electricity while treating wastewater [1-8]. The structure of MFC can be divided into three parts: cathode chamber, anode chamber, and separating membrane. The anaerobic anode chamber contains the organic waste with degrading microbes that produce electrons through an oxidation reaction. The generated electrons flow from the anode to the cathode through an external circuit while proton is transported through the separator [also known as the proton exchange membrane (PEM)][9-14]. Reduction reaction takes place in the aerobic cathode chamber, and the potential energy from electron transportation is directly used or stored in an external storage system i.e., battery[15].

    The performance of MFC, which is evaluated by its power density, COD removal, and coulombic efficiency, mainly depends on the performance of PEM. The role of the PEM is (1) separating cathode and anode chamber, (2) keeping the anode chamber deprived of oxygen, and (3) selectively transporting proton to the cathode chamber. Thus, ideal PEM should resist biofouling, prevent oxygen crossover, have low water uptake, and allow uninterrupted passage for protons[16-20]. Nafion, the sulfonated cation-exchange membrane produced by Dupont Company, is the most widely used PEM in MFC due to its high proton conductivity and low internal resistance. However, Nafion is expensive, hard to synthetize, not bio-degradable, and its biofouling issue is serious[21-23]. For these reasons, during the last couple of decades, researchers have attempted to find the alternative low-cost membrane materials for the Nafion membrane[17].

    The alternative membranes were synthetized with various polymers and fillers. To enhance PEM performance, different chemical groups such as sulfonated groups, fluorinated groups, or hydroxyl groups were incorporated to the polymers, and different chemicals were doped into the membrane. Moreover, some researchers looked for environmentally friendly, bio-degradable membranes. In the following, composite membranes from 20 papers from 2013 to 2021 were reviewed regarding their characteristics and their performances, especially their power densities, were compared. Schematic diagram of MFC is represented in Fig. 1 and membranes are summarized in Table 1.

    2. Composite Membrane

    A new PEM for MFC is presented, which is called a mild sulfonated polyether ketone ether ketone ketone (SPEKEKK) incorporated polysulfone (PSU) membrane [24]. PEEK is an aromatic semi-crystalline and non-fluorinated thermally stable polymer with excellent mechanical and chemical resistance. PEEK is sulfonated via incorporating sulfonic acid groups (-HSO3-1). Aromatic sulfonation improves ion exchange capacity (IEC) and hydrophilicity of the polymer by reducing its crystallinity. Also, sulfonation enhances proton conductivity since water molecules around PEM improves solubility and facilitates proton transport. 30 wt.% SPEKEKK is added to PSU, and this composite membrane showed the highest conductivity of 0.12 S/cm at 90°C. Water uptakes and swelling ratio of PSU/SPEKEKK membrane were higher than that of PSU membrane. Moreover, PSU/SPEKEKK membrane had excellent thermal stability property as its lowest decomposition temperatures occurred around ~300°C to ~500°C.

    An economical and biodegradable MFC membrane was developed for single use[25]. Chitosan (CS) has chosen for membrane fabrication since it is abundant natural polymer with free amine and hydroxyl groups that allow modifications to enhance its mechanical and thermal stability. Poly(vinyl alcohol) (PVA) is also a biodegradable polymer which is chosen for separator that promotes proton transfer and impedes oxygen crossover to anolyte. Three membranes, each based on CS, PVA, and PVA : CS were synthetized and analyzed. It was revealed that PVA : CS membrane outperform Nafion 4 times (power production while being 75 times more economic. Furthermore, PVA : CS membrane was incorporated into a paper-based micro-scale MFC biosensor.

    A new diamine monomer, 4,4’-((2’,5’-bis(benzyloxy)- 3,3”-bis(trifluoromethyl)-[1,1’:4,4”-terphenyl]-4,4”-diyl)bis (oxy))dianiline (TADBE), is designed and synthetized for proton exchange membrane (PEM) electrolyte material for fuel cells[26]. TADBE has 3F groups which enhance solubility and oxidative stability which hydrocarbon- based polyimides usually suffer from poor performance of these properties. 3F groups additionally reduce water uptake and help copolymers obtain better phase separated morphology, resulting in higher proton conductivity. Also, TADBE has self-assembling nature due to benzyl ether groups which create weak π-π stacking interactions or CH…π interactions. TADBE was synthesized into series of sulfonated copolyimides (S-coPIs) designated as DBN-XX (XX refers to DSDSA feed percentage). The new membranes showed high thermal (e.g., DBN-60, Td10 ~327°C) and mechanical stabilities (e.g., DBN-60, tensile strength ~94 MPa), good hydrolytic stability (e.g., DBN-60, > 99 retain wt.%), and low water uptake (e.g., DBN-60, ~17 wt.% at 80 °C). Its proton conductivity (e.g., DBN-90, ~244 mS cm-1) and microbial fuel cell performance (e.g., DBN-90, power density ~576 mW m-2) was comparable to that of Nafion 117 (power density ~563 mW m-2).

    A novel cardo diamine monomer, 9,9-bis (hydroxy- (4’-amino (3-trifluoromethyl) biphenyl-4-oxy)-phenyl)-9Hfluorene (mixture of isomers, HAPHPF) is designed and synthesized[27] (Figs. 2~5). Phenolic -OH groups in HAPHPF form additional hydrogen bonds with water molecules, enhancing electron conductivity compared to the analogous polymers without -OH groups. Incorporation of fluorine groups improved the electron density, the polymer solubility, and the peroxide radical resistance of the membrane. HAPHPF monomer is used along with 4,4’-diaminostilbene-2,2’-disulfonic acid (DSDSA) to prepare series of sulfonated copolyimides (DHN-XX) by polycondensation with 1,4,5,8-napthalenetetracarboxylic dianhydride (NDTA). XX denotes the mole percentage of DSDSA. The proton conductivity of the DHN-70 is 97 mS cm-1 at 80°C, which is 30% higher than that of the nonhydroxylated analogue. DHN-XX copolymer membranes in micro biotic fuel cells (MFCs) demonstrated power density and coulombic efficiency comparable with that of MFC using Nafion 117.

    2.1. Graphene oxide

    Incorporating crystalline poly - (R) - hydroxybutyrate (PHB) in medium - chain - length polyhydroxyalkanoates (mcl-PHA) matrix for PEM improves proton conductivity and other MFC performance[28]. Mcl-PHA is a biodegradable polymer. Thus, biofouling and slow biodegradation in PEM will result in the formation of micro- pores which ultimately improves ion exchange process. PHB is a biocompatible and biodegradable polymer with highly crystalline and brittle nature. The MFC setup with PHA composite membrane at 15 wt.% PHB showed improved proton transport, maximum voltage potentials and power densities, chemical oxygen demand (COD) removal, ammoniacal nitrogen (NH3-N) removal, and coulombic efficiency (CE) recovery. The membrane also exhibited low oxygen diffusivity.

    Sulfonated graphene oxide (SGO) is incorporated into sulfonated polyetheretherketone (SPEEK) to produce nanocomposite PEM for MFC[29]. SPEEK polymer was chosen due to its high mechanical strength, thermal and chemical stability, hydrophilicity, low cost, easy preparation, and better proton conductivity. Sulfonated graphene oxide (SGO) is added to SPEEK since SGO has functional groups like -SO3H, -OH, and -COOH that improves water uptake, IEC, and proton conductivity at ambient temperature. 2 wt.% SGO in SPEEK membrane exhibited improved proton conductivity and maximum power density (1,028 ± 7 mW/m2), water uptake, and ion-exchange capacity (IEC), compared with SPEEK, SPEEK-GO, and Nafion 115 membranes.

    PEM was synthesized that have better properties and longer durability than Nafion 117 membrane[30]. Two composite membranes, which are graphene oxide/sulfonated polyetheretherketone (GO-SPEEK) and silver graphene oxide/graphene oxide/sulfonated polyetheretherketone (AgGO-GO-SPEEK) composite membranes, were analyzed. SPEEK was selected due to its superior mechanical and thermal strength, GO was added to improve proton conductivity and mechanical strength, and GO was reduced with silver since silver is the most effective antibacterial material. It was revealed that AgGO-GO-SPEEK membrane has 54.2% higher proton conductivity and 76.7% lower oxygen diffusion coefficient than Nafion 117 membrane. Although GO-SPEEK membrane generated highest initial maximum power density (1134 mW/m2), AgGO-GO-SPEEK membrane maintained highest maximum power density (896 mW/m2) and lowest internal resistance after 100 days of operation due to silver’s antifouling effect. Thus, AgGO-GO-SPEEK membrane is a long-lasting and stable source of power for MFC.

    As a novel anode material for microbial fuel cells (MFCs), poly(diallyldimethylammonium chloride) (PDDA) synergizing reduced graphene oxide (rGO) modified carbon cloth, or CC-PDDA-rGO showed excellent power generation performance[31]. Anode for MFCs should have a large surface area for bacterial adhesion, and PDDA provides this property since it prepares multilayer nanocomposite structures. PDDA also enhances hydrophilicity owing to the quaternary ammonium functional groups with positive charge on its backbone. rGO also provides large surface area, and due to the oxygen-containing functional groups, rGO improves the electrical conductivity in terms of the electron shuttling. Comparing CC-PDDA-rGO, CC, CC-PDDA, and CC-rGO, CC-PDDA-rGO showed highest power density (2039.3 ± 57.5 mW m-2) and maximum net capacitance charge (11.25 ± 2.00 C m-2). Additionally, CC-PDDArGO formed stable and high electrochemically active biofilm.

    An efficient and inexpensive PEM membrane was developed for the single-chambered microbial fuel cell (sMFC)[32] (Figs. 6~9). Low-cost poly(vinyl alcohol)- (PVA-) based membranes show excellent dimensional and thermal stabilities, controllable physical properties, and good hydrophilic and electrochemical properties. To improve PVA- based membrane’s ion transport properties, inorganic dopants, heteropolyacids (HPAs) are added. STA is one kind of HPAs used in this study, and 30 wt.% of STA is incorporated into PVA-based membrane. Graphene oxide (GO) is also added as an ion-conductive filler to improve membrane’s conductivity. The resulting 0.5 wt.% GO-incorporated PVASTA- GO membrane showed excellent kinetic properties, better durability, and reduced oxygen crossover compared with Nafion 117. Also, PVA-STA-GO membrane’s maximum power density of 1/9 W/m3, which was higher than Nafion 117 membrane.

    A new highly catalytic cathode membrane was prepared through electro-depositing Pd-rGO on the PVDF/ carbon fiber cloth composite cathode membrane (abbreviated as Pd15-rGO PCCM)[33]. Carbon fiber cloth is an electric substrate for the cathode membrane, and it is coated with PVDF binder, forming PVDF/carbon fiber cloth composite membrane (PCCM). Pd and rGO on PCCM are catalysts that accelerate Oxygen reduction reactions (ORRs) in cathode, and 15 cycles of electrodeposition exhibited the highest catalyst activity. Under an electric field of -0.4 V cm-1, Pd15-rGO PCCM showed 1.9 times improvement of stable membrane flux. In MBR/MFC coupled system, the Pd15-rGO PCCM showed excellent performance in catalytic activity, membrane fouling reduction, energy recovery and contaminants removal towards both sewage and coking wastewater.

    Sulfonated polyetheretherketone (SPEEK) membrane composite was incorporated into graphene oxide (GO) by dry phase inversion method as a new PEM[34]. SPEEK was chosen due to its superior resistance, thermal and chemical stability, hydrophilicity, easy preparation, high mechanical strength, lower cost, and modest proton conductivity. GO, hydrophilic compound with oxygen-containing functional groups, was added because it exhibits high electrical conductivity due to a large number of free electrons GO also increases mechanical strength due to strong covalent bonding of sp2 carbon layer. 2% GO in SPEEK (SPEEK/GO3) membrane showed better performance in proton conductivity (2.88 mS/cm), water uptake, power density (53.12 mW/m2), voltage (833 mV), coulombic efficiency (3.74%), and chemical oxygen demand (COD) removal (88.7%) than that of Nafion membrane.

    PVDF-g-PSSA membrane possesses high proton conductivity, excellent chemical resistance, and good thermal stability[35]. However, hydrophobicity of PVDF causes biofouling on the membrane, and the degree of grafting is limited. Adding hygroscopic oxides, like graphene oxide (GO), to the polymer can improve this problem, but GO lacks proton-conductive groups to increase the proton conductivity. Sulfonated GO (SGO) was therefore incorporated into the PVDF-g-PSSA membrane in this research. As SGO has -SO3H groups, hydrophilicity of GO is improved, and thus anti-fouling property is enhanced. SGO/PVDF-g-PSSA composite membrane with 1.0 wt.% SGO had higher water uptake (32.56%), proton conductivity (0.083 S/cm), and excellent hydrophilicity (contact angle 70.78°) than that of Nafion 117. A quartz crystal microbalance with dissipation monitoring (QCM-D) revealed that SGO/PVDFg- PSSA composite membrane possesses better anti-fouling property than that of PVDF-g-PSSA, GO/PVDF-g- PSSA, and Nafion 117 membranes.

    Homogeneous PVDF-g-PSSA membrane itself is not appropriate for PEM because its proton conductivity and anti-fouling is lower than that of Nafion membrane[36]. Sulfonated graphene oxide (SGO) and SiO2 was added to PVDF-g-PSSA. SGO was added for higher proton conductivity. Graphene oxide (GO) can provide large surface area and a great number of oxygen-containing functional groups. SGO is a sulfonated GO, so SGO has higher hydrophilicity than GO. Interaction between -SO3H in SGO clusters increases proton conductivity and the moisture content of the membrane. Adding hydrophilic SiO2 nanoparticles improve PEM’s mechanical performance and prevents swelling. SiO2 also improves moisture retention and enhance anti-fouling ability. Researchers in this study blended hybrid particle SGO@SiO2 to the PVDF-g-PSSA and found that the new membrane had better proton conductivity and anti- fouling ability than Nafion membrane. SGO@SiO2/ PVDF-g-PSSA membrane showed best ability when the SGO@SiO2 addition amount was 1.0%.

    Medium-chain-length poly-3-hydroxyalkanoates (mcl- PHA) composited with -COOH functionalized multiwalled carbon nanotubes (MC) is a renewable biodegradable material for proton exchange membrane (PEM) in microbial fuel cell (MFC)[37]. MC is composited into PHA to enhance the electron conductivity and improve microbial electrochemical activities. Since mcl-PHA is biodegradable, biofouling on membrane would not be as detrimental to the MFC performance. mcl-PHA-MC10% membrane showed maximum power density of 361 mW/m2, which is comparable with Nafion 117 (372 mW/m2). Its internal resistance decrease, chemical oxygen demand (COD) removal, coulombic efficiency (CE), and electron conductivity were superior to Nafion 117.

    2.2. Titanium dioxide (TiO2)

    T-7 nanocomposite membrane (composed of 80% partially sulfonated PVDF-HFP, 13% wt.% Nafion and 7% wt.% TiO2) showed better performance as a proton exchange membrane (PEM) for microbial fuel cells (MFC) than Nafion-117 membrane[38]. The blend of partially sulfonated poly (vinylidenefluoride-co-hexafluoropropylene) S-PVDF-HFP has similar fluorinated-carbon backbone structure as Nafion but S-PVDF-HFP is cheaper and has better performance than Nafion. TiO2 nanoparticles are incorporated to the blend of Nafion and S-PVDF-HFP membrane to improve anti-biofouling effect. T-7 membrane exhibited enhanced 1) water uptake (up to 27.7%), 2) ion exchange capacity, 3) proton conductivity and 4) anti-biofouling effect than Nafion-117 membrane. T-7 membrane’s swelling was 34.7 mS/cm while Nafion-117’s was 30.2 mS/cm. T-7 membrane’s maximum current density was 1926 ± 89 mA/m2, maximum power density was 552.12 ± 26 mW/m2 and maximum COD removal was 88.97%.

    Sulfonated titanium dioxide (S-TiO2) was prepared by condensation reaction and was doped into the PVDF-g-PSSA, forming a new proton exchange membrane (PEM), S-TiO2/PPSSA[39]. PVDF-g-PSSA membrane has good proton conductivity with excellent physical and chemical stability. However, PVDF-g-PSSA membrane suffers from biofouling caused by the hydrophobicity of PVDF. Thus, sulfonated inorganic oxide, S-TiO2 is doped so that the hydrophilic sulfonic acid groups improve anti-fouling property of the membrane. Quartz crystal microbalance with dissipation (QCM-D) was newly used to reveal the formation process and mechanism of PEM membrane fouling in MFCs. QCM-D study showed that S-TiO2/PSSA-5.0 membrane has the least anti-fouling property. Additionally, S-TiO2/ PPSSA-5.0 membrane has increased water uptake (40.9%) and proton conductivity (0.067 S/cm) compared with the PVDF-g-PSSA membrane. S-TiO2/PPSSA-5.0 membrane has maximum power density of 130.54 mW/m2, while Nafion 117’s is 132.02 mW/m2, and has the highest COD removal of 91%.

    Self-standing and flexible membrane for energy applications is synthetized via completely green process [40]. The membrane is based on reduced graphene oxide (rGO)/SnO2 nanocomposite and cellulose fibers. rGO/SnO2 nanocomposite provides electrical/electrochemical features and catalytic activity that is suitable for the oxygen reduction reaction. Micro fibrillated cellulose (MFC) forms web-like structure that presents stable and flexible mechanical properties and it allows to operate in water solutions. rGO/SnO2 nanocomposite is synthetized by a microwave-assisted fast process with low energy consumption and high reproducibility. Then, it is assembled with MFC through a water-based process.

    2.3. Other inorganic fillers

    A noble organic-inorganic composite membrane is synthesized using sulfonated polyether-sulfone (SPES) and polydivinylflourdine (PVDF) with doping of zeolite 4A[41]. Firstly, PVDF is selected as it has high thermal, chemical, hydrolytic, and oxidative resistance with semicrystalline nature. Secondly, SPES is selected due to its easy sulfonation and film-forming properties. Thirdly, inorganic filler, zeolite is doped so that it provides a continuous phase that elevates proton conductivity and water sorption in PEM. 15 wt.% zeolite incorporated in 2 : 1 blend ratio of SPES and PVDF composite membrane exhibited high thermal (490°C) and mechanical stability (38.4 MPa), proton conductivity (0.141 S/cm), low oxygen diffusivity (7.21 × 10-8 cm2/s), and maximum power density (208 ± 5 mW/m2) with substantial COD removal efficiency (82.1%). Additionally, it was found that K+ cation hinders oxygen diffusion but allows higher diffusion of H3O+ in molecular dynamic (MD) simulation.

    Doping the phosphotungistic acid (PWA), a type of heteropolyacids (HPA), into the sulfonated poly (etheretherketone) (SPEEK)/poly amide imide (PAI) matrices enhances PEM performance for MFC[42]. Initially, SPEEK is chosen for the PEM material since it is highly stable and cheap, though its proton conductivity is lower than that of Nafion. To compensate this deficiency, the stable hydrophobic polymer, PAI is added. The addition of HPA, especially PWA in this research, enhances ion exchange capacity, water uptake, and proton conductivity (maximum conductivity was 5.6 × 10-2 S/cm). Due to the Keggin structure of PWA, the membrane retains good thermal stability. The maximum obtained voltage and power density are 786 mV and 113 mW/m2, respectively.

    Water-soluble conjugated oligoelectrolyte nanoparticles (COE NPs) are inserted into the microbial membrane of Escherichia coli to increase extracellular electron transfer (EET) between bacteria cells and anaerobic anode of microbial fuel cells (MFCs)[43] (Figs. 10~13). COE NPs perform better than the widely used COE, (4,4’-bis(4’-(N,N-bis(6”-(N,N,N-triethylammonuym)- hexyl)amino)-styryl)-stilbene tetraiodide) (DSSN+) in enhancing EET. This is possible because COE NPs take advantage of the structure of polyhedral oligomeric silisesquioxanes (POSS), a cage-like nanostructured material, which enhances the mechanical and optical properties due to its organic-inorganic hybrid structure. Pendant groups, -conjugated repeat units [i.e. oligo(pphenylenevinylene) electrolyte (OPVEs)] are attached at each corner of the cubic POSS like arms. OPVEs also enhance optical properties of COE NPs.

    3. Conclusion

    Various membranes for MFC were newly synthetized and studied, mainly aiming to replace the Nafion membrane. Nafion membrane has excellent proton conductivity and other features, but it is expensive and causes pollution. Thus, the important factors for evaluating the new membrane were cost, anti-fouling effect, environmental effect, and power density of the novel membrane based MFC. It was reported that most membranes have shown higher or similar power density compared to Nafion membrane. Membranes with graphene oxide (GO), reduced GO (rGO), or sulfonated GO (SGO) showed promising power density as GO has large surface area and it improves the proton conductivity and stability of membranes. Sulfonated polymers also enhanced MFC performance as the sulfonated groups improves ion exchange capacity and hydrophilicity. Biodegradable polymers such as PHA, PHB, PVA, and cellulose were possibly used as PEM material. Finally, the incorporation of SiO2, TiO2, Ag, and other inorganic fillers reduced biofouling of membrane.

    Figures

    MEMBRANE_JOURNAL-31-2-120_F1.gif

    Schematic diagram of MFC with composite membrane.

    MEMBRANE_JOURNAL-31-2-120_F2.gif

    Synthetic route for the preparation of the S-coPIs: (i) Benzoic Acid and (ii) 200°C 12 h (only one isomeric structure of the HAPHPF unit is shown) (Reproduced with permission from Kumar et al., 27, Copyright 2018, American Chemical Society).

    MEMBRANE_JOURNAL-31-2-120_F3.gif

    Schematic diagram of test MFC used to evaluate the newly developed PEMs. (Reproduced with permission from Kumar et al., 27, Copyright 2018, American Chemical Society).

    MEMBRANE_JOURNAL-31-2-120_F4.gif

    Ag+-stained TEM micrographs depict the morphology of DHN-XX copolymers (Reproduced with permission from Kumar et al., 27, Copyright 2018, American Chemical Society).

    MEMBRANE_JOURNAL-31-2-120_F5.gif

    AFM images of DHN-XX copolymer membranes (tapping mode) of scan area 2.5 × 2.5 μm. (a, c, e) Topographical height images, (b, d, f) phase images (Reproduced with permission from Kumar et al., 27, Copyright 2018, American Chemical Society).

    MEMBRANE_JOURNAL-31-2-120_F6.gif

    Cross-sectional SEM images of (a, b) PVA-STA and (c, d) PVA-STA-GO membranes. (e) EDX spectrum of the PVA-STA-GO membrane (Reproduced with permission from Khilari et al., 32, Copyright 2013, American Chemical Society).

    MEMBRANE_JOURNAL-31-2-120_F7.gif

    Comparison of polarization results for MFCs using Nafion 117, PVA-STA, and PVA-STA-GO membranes (Reproduced with permission from Khilari et al., 32, Copyright 2013, American Chemical Society).

    MEMBRANE_JOURNAL-31-2-120_F8.gif

    Comparison of polarization results for MFCs using GO-blended PVA-STA membrane-based MCAs with different diameters (2, 3, and 4.8 cm) (Reproduced with permission from Khilari et al., 32, Copyright 2013, American Chemical Society).

    MEMBRANE_JOURNAL-31-2-120_F9.gif

    A) Schematic diagram of tubular single chambered MFC, B) photograph of tubular single chambered MFC and C) front view of cathode of tubular single chambered MFC (Inset) (Reproduced with permission from Khilari et al., 32, Copyright 2013, American Chemical Society).

    MEMBRANE_JOURNAL-31-2-120_F10.gif

    Chemical structures of (a) DSSN+ and (b) COE NPs (Reproduced with permission from Zhao et al., 43, Copyright 2015, American Chemical Society).

    MEMBRANE_JOURNAL-31-2-120_F11.gif

    (a) HR-TEM image and (b) UV-vis spectrum and PL profile of the COE NPs (50 μM) in 2 mM PBS solution (Reproduced with permission from Zhao et al., 43, Copyright 2015, American Chemical Society).

    MEMBRANE_JOURNAL-31-2-120_F12.gif

    (a) Voltage generation and (b) power curves of E. coli MFCs with the control, COE NPs, OPVE, and DSSN+. The arrow indicates the addition of COE NPs, OPVE, and DSSN+ (Reproduced with permission from Zhao et al., 43, Copyright 2015, American Chemical Society).

    MEMBRANE_JOURNAL-31-2-120_F13.gif

    CLSM images of E. coli (a) without staining and (b and c) stained with COE NPs and DSSN+. (d) SEM image of E. coli adhered to carbon felt surface (Reproduced with permission from Zhao et al., 43, Copyright 2015, American Chemical Society).

    Tables

    Summary of the MFC Membrane

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