Tailoring Iron-Ion Release of Cellulose-Based Aerogel-Coated Iron Foam for Long-Term High-Power Microbial Fuel Cells

The presence of iron(Fe) has been found to favor power generation in microbial fuel cells(MFCs). To achieve long-term power production in MFCs, it is crucial to effectively tailor the release of Fe ions over extended operating periods. In this study, we developed a composite anode(A/IF) by coating iron foam with cellulose-based aerogel. The concentration of Fe ions in the anode solution of A/IF anode reaches 0.280 μg/mL(Fe^(2+) vs. Fe^(3+) = 61%:39%) after 720 h of aseptic primary cell operation. This value was significantly higher than that(0.198 μg/mL, Fe^(2+) vs. Fe^(3+) = 92%:8%) on uncoated iron foam(IF), indicating a continuous release of Fe ions over long-term operation. Notably, the resulting MFCs hybrid cell exhibited a 23% reduction in Fe ion concentration(compared to a 47% reduction for the IF anode) during the sixth testing cycle(600-720 h). It achieved a high-power density of 301 ± 55 mW/m^(2) at 720 h, which was 2.62 times higher than that of the IF anode during the same period. Furthermore, a sedimentary microbial fuel cell(SMFCs) was constructed in a marine environment, and the A/IF anode demonstrated a power density of 103 ± 3 mW/m^(2) at 3240 h, representing a 75% improvement over the IF anode. These findings elucidate the significant enhancement in long-term power production performance of MFCs achieved through effective tailoring of Fe ions release during operation.

The biofilm characteristics and enhanced performance of a marine microbial-electrolysis-cell-based biosensor under positive anodic potential

Microbial fuel cells have already been used as biosensors to monitor assimilable organic carbon(AOC).However,their signal production from AOC is known to be completely suppressed by dissoved oxygen(DO).In this study,two identical microbial electrolysis cell(MEC)based biosensors were inoculated with marine sediment and operated at two different anodic potentials,namely-300 mV and+250 mV relative to Ag/AgCl.The MEC biosensor operated under positive anodic potential conditions had electrochemically active microbial communities on the anode,including members of the Shewanellaceae,Pseudoalteromonadaceae,and Clostridiaceae families.However,the strictly anaerobic members of the Desulfuromonadaceae,Desulfobulbaceae and Desulfobacteraceae families were found only in the negative anodic potential MEC biosensor.The positive anodic potential MEC biosensor showed several other advantages as well,such as faster start-up,significantly higher maximum current production,fivefold improvement in the AOC detection limit,and tolerance of low dissolved oxygen,compared to those obtained from the negative anodic potential MEC biosensor.The developed positive anodic potential MEC biosensor can thus be used as a real-time and inexpensive detector of AOC concentrations in high saline and low DO seawater.

Scalability of biomass-derived graphene derivative materials as viable anode electrode for a commercialized microbial fuel cell: A systematic review

Microbial fuel cell(MFC) is an advanced bioelectrochemical technique that can utilize biomass materials in the process of simultaneously generating electricity and biodegrading or bio transforming toxic pollutants from wastewater. The overall performance of the system is largely dependent on the efficiency of the anode electrode to enhance electron transportation. Furthermore, the anode electrode has a significant impact on the overall cost of MFC setup. Hence, the need to explore research focused towards developing cost-effective material as anode in MFC. This material must also have favourable properties for electron transportation. Graphene oxide(GO) derivatives and its modification with nanomaterials have been identified as a viable anode material. Herein, we discussed an economically effective strategy for the synthesis of graphene derivatives from waste biomass materials and its subsequent fabrication into anode electrode for MFC applications. This review article offers a promising approach towards replacing commercial graphene materials with biomass-derived graphene derivatives in a view to achieve a sustainable and commercialized MFC.

Bimetallic catalysts as electrocatalytic cathode materials for the oxygen reduction reaction in microbial fuel cell:A review

Microbial fuel cell(MFC) is one synchronous power generation device for wastewater treatment that takes into account environmental and energy issues, exhibiting promising potential. Sluggish oxygen reduction reaction(ORR) kinetics on the cathode remains by far the most critical bottleneck hindering the practical application of MFC. An ideal cathode catalyst should possess excellent ORR activity, stability, and costeffectiveness, experiments have demonstrated that bimetallic catalysts are one of the most promising ORR catalysts currently. Based on this, this review mainly analyzes the reaction mechanism(ORR mechanisms, synergistic effects), advantages(combined with characterization technologies), and typical synthesis methods of bimetallic catalysts, focusing on the application effects of early Pt-M(M = Fe, Co, and Ni) alloys to bifunctional catalysts in MFC, pointing out that the main existing challenges remain economic analysis, long-term durability and large-scale application, and looking forward to this. At last, the research trend of bimetallic catalysts suitable for MFC is evaluated, and it is considered that the development and research of metal-organic framework(MOF)-based bimetallic catalysts are still worth focusing on in the future, intending to provide a reference for MFC to achieve energy-efficient wastewater treatment.

Three-Dimensional N-Doped Carbon Nanotube/Graphene Composite Aerogel Anode to Develop High-Power Microbial Fuel Cell

Optimizing the structure of electrode materials is one of the most effective strategies for designing high-power microbial fuel cells(MFCs).However,electrode materials currently suffer from a series of shortcomings that limit the output of MFCs,such as high intrinsic resistance,poor electrolyte wettability,and low microbial load capacity.Here,a three-dimensional(3D)nitrogen-doped multiwalled carbon nanotube/graphene(N-MWCNT/GA)composite aerogel is synthesized as the anode for MFCs.Comparing nitrogen-doped GA,MWCNT/GA,and N-MWCNT/GA,the macroporous hydrophilic N-MWCNT/GA electrode with an average pore size of 4.24μm enables high-density loading of the microbes and facilitates extracellular electron transfer with low intrinsic resistance.Consequently,the hydrophilic surface of N-MWCNT can generate high charge mobility,enabling a high-power output performance of the MFC.In consequence,the MFC system based on N-MWCNT/GA anode exhibits a peak power density and output voltage of 2977.8 mW m^(−2)and 0.654 V,which are 1.83 times and 16.3%higher than those obtained with MWCNT/GA,respectively.These results demonstrate that 3D N-MWCNT/GA anodes can be developed for high-power MFCs in different environments by optimizing their chemical and microstructures.

The growth of biopolymers and natural earthen sources as membrane/separator materials for microbial fuel cells:A comprehensive review

Microbial fuel cell(MFC)technology has emerged as an effective solution for energy insecurity and bioremediation.However,identifying suitable components(particularly separators or membranes)with the required properties,such as low cost and high performance,remains challenging and restricts practical application.Commercial membranes,such as Nafion,exhibit excellent performance in MFC.However,these membranes have high production costs,which considerably increase the overall MFC unit cell cost.Among the numerous types,the separators or membranes developed from biopolymers and naturally occurring earthen sources have proven to be a novel and efficient concept due to their natural abundance,cost-effectiveness(approximately$20 m^(-2),$5 m^(-2),and$1 kg-1for biopolymers,ceramics,and earthensources,respectively),structural properties,proton transportation,manufacturing and modification ease,and environmental friendliness.In this review,we emphasize cost-effective renewable green materials(biopolymers,bio-derived materials,and naturally occurring soil,clay,ceramics or minerals)for MFC applications for the first time.Biopolymers with good thermal,mechanical,and water retention properties,sustainability,and environmental friendliness,such as cellulose and chitosan,are typically preferred.Furthermore,the modification or introduction of various functional groups in biopolymers to enhance their functional properties and scale MFC power density is explored.Subsequently,separator/membrane development using various bio-sources(such as coconut shells,banana peels,chicken feathers,and tea waste ash)is described.Additionally,naturally occurring sources such as clay,montmorillonite,and soils(including red,black,rice-husk,and Kalporgan soil)for MFC were reviewed.In conclusion,the existing gap in MFC technology was filled by providing recommendations for future aspects based on the barriers in cost,environment,and characteristics.

Influence of Cathode Modification by Chitosan and Fe^(3+)on the Electrochemical Performance of Marine Sediment Microbial Fuel Cell

The electrochemical performances of cathode play a key role in the marine sediment microbial fuel cells(MSMFCs)as a long lasting power source to drive instruments,especially when the dissolved oxygen concentration is very low in seawater.A CTS-Fe^(3+)modified cathode is prepared here by grafting chitosan(CTS)on a carbon fiber surface and then chelating Fe^(3+)through the coordination process.The electrochemical performance in seawater and the output power of the assembled MSMFCs are both studied.The results show that the exchange current densities of CTS and the CTS-Fe^(3+)group are 5.5 and 6.2 times higher than that of the blank group,respectively.The potential of the CTS-Fe^(3+)modified cathode increases by 138 mV.The output power of the fuel cell(613.0 mW m^(-2))assembled with CTS-Fe^(3+)is 54 times larger than that of the blank group(11.4 mW m^(-2))and the current output corresponding with the maximum power output also increases by 56 times.Due to the valence conversion between Fe^(3+)and Fe^(2+)on the modified cathode,the kinetic activity of the dissolved oxygen reduction is accelerated and the depolarization capability of the cathode is enhanced,resulting higher cell power.On the basis of this study,the new cathode materials will be encouraged to design with the complex of iron ion in natural seawater as the catalysis for oxygen reduction to improve the cell power in deep sea.

Electricity generation during wastewater treatment by a microbial fuel cell coupled with constructed wetland

A membrane-less constructed wetland microbial fuel cell （CW-MFC） is constructed and operated under continuous flow with a hydraulic retention time （HRT） of 2 d. Fed with glucose, the CW-MFC generates a stable current density of over 2 A/m3 with a resistor of 1 kΩ and has a chemical oxygen demand （COD） removal efficiency of more than 90% after the startup of 2 to 3 d. A series of systems with the electrode spacings of 10, 20, 30 and 40 cm are compared. It is found that the container with the electrode spacing of 20 cm gains the highest voltage of 560 mV, the highest power density of 0. 149 W/m 3, and the highest Coulombic efficiency of 0.313%. It also has the highest COD removal efficiency of 94. 9%. In addition, the dissolved oxygen （DO） concentrations are observed as the lowest level in the middle of all the CW-MFC reactors. The results show that the more COD is removed, the greater power is generated, and the relatively higher Coulombic efficiency will be achieved. The present study indicates that the CW-MFC process can be used as a cost-effective and environmentally friendly wastewater treatment with simultaneous power generation.

Identification of the Electricity-Producing Bacteria in Wastewater for Microbial Fuel Cells （MFCs）

A microbial fuel cell （MFC） is a device that converts chemical energy to electrical energy during substrate oxidation by microorganisms. The characterization and identification of these microbial communities will allow better control of this electricity generation with simultaneous removal of carbon and nitrogen. This study aims to investigate the role of natural bacteria in electricity generation by studying three different sources of wastewater： the raw wastewater （RW）, wastewater from an aeration tank （AEW） and returned activated sludge （RAS） from an activated sludge treatment plant. The result showed that after the MFC treatment, the number of bacterial strains was reduced from twenty strains to eight strains. Microscopic observation further showed that fifteen isolate before the treatment were gram-positive, and five were gram-negative whereas all isolates after the treatment were gram-positive rods or cocci The four strains isolated from the RAS inoculums, β-Comamonas sp., γ-Enterobacter sp., Bacillus cereus sp. and Clostridium sp. produced the highest power density of 67.57 mW/m^2 which made them potential candidates for electrochemically active bacteria in MFCs. However, the level of chemical oxygen demand （COD） removal was 20% and the total kjeldahl nitrogen （TKN） removal was 66.7%. Key words：

Recovery of copper from copper slag using a microbial fuel cell and characterization of its electrogenesis

The microbial fuel cell, which can convert the chemical energy of organic matter into electricity via the catalytic action of microorganisms, is a novel environmentally friendly technology for wastewater treatment and energy generation. The electrical energy generated by the microbial fuel cell can be used as an alternative to a traditional external power source required to extract copper via electrolytic treatment. A dual-chamber microbial fuel cell(DMFC) for the treatment of copper slag sulfuric acid leach liquor was constructed. The electrogenesis performance of the DMFC and its ability to extract copper from the copper slag leachate were investigated. The results demonstrated that the maximum voltage was 540 mV when the DMFC achieved steady-state operation. The removal rate of copper ions was greater than 80.0%, and the maximum value was 92.1%. Moreover, X-ray diffraction and scanning electron microscopy were used to characterize the cathodal products. The results showed that the product deposited onto the cathode was copper and that its morphology was similar to that of the electrolytic copper powder. The DMFC can generate electricity and recover copper from copper slag simultaneously.

Melamine modified carbon felts anode with enhanced electrogenesis capacity toward microbial fuel cells

Surface electropositivity and low internal resistance are important factors to improve the anode performance in microbial fuel cells (MFCs). Nitrogen doping is an effective way for the modification of traditional carbon materials. In this work, heat treatment and melamine were used to modify carbon felts to enhance electrogenesis capacity of MFCs. The modified carbon felts were characterized using X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), atomic force microscopy (AFM) and malvern zeta potentiometer. Results show that the maximum power densities under heat treatment increase from 276.1 to 423.4 mW/m(2) (700 degrees C) and 461.5 mW/m(2) (1200 degrees C) and further increase to 472.5 mW/m(2) (700 degrees C) and 515.4 mW/m(2) (1200 degrees C) with the co-carbonization modification of melamine. The heat treatment reduces the material resistivity, improves the zeta potential which is beneficial to microbial adsorption and electron transfer. The addition of melamine leads to the higher content of surface pyridinic and quaternary nitrogen and higher zeta potential. It is related to higher MFCs performance. Generally, the melamine modification at high temperature increases the feasibility of carbon felt as MFCs's anode materials. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.

A system combining microbial fuel cell with photobioreactor for continuous domestic wastewater treatment and bioelectricity generation

A coupled system consisting of an upflow membrane-less microbial fuel cell (upflow ML-MFC) and a photobioreactor was developed, and its effectiveness for continuous wastewater treatment and electricity production was evaluated. Wastewater was fed to the upflow ML-MFC to remove chemical oxygen demand (COD), phosphorus and nitrogen with simultaneous electricity generation. The effluent from the cathode compartment of the upflow ML-MFC was then continuously fed to an external photobioreactor for removing the remaining phosphorus and nitrogen using microalgae. Alone, the upflow ML-MFC produces a maximum power density of 481 mW/m 3 , and obtains 77.9% COD, 23.5% total phosphorus (TP) and 97.6% NH4+-N removals. When combined with the photobioreactor, the system achieves 99.3% TP and 99.0% NH4+-N total removal. These results show both the effectiveness and the potential application of the coupled system to continuously treat domestic wastewater and simultaneously generate electricity and biomass.

Electricity Generation Using Membrane-less Microbial Fuel Cell during Wastewater Treatment

An upflow mode membrane-less microbial fuel cell （ML-MFC） was designed for wastewater treatment. Granular graphite electrodes, which are flexible in size, were adopted in the ML-MFC. Microbes present in anaerobic activated sludge were used as the biocatalyst and artificial wastewater was tested as substrate. During the electrochemically active microbe enrichment stage, a stable power output of 536 mW.m-3 with reference to the anode volume was generated by the ML-MFC running in batch mode. The voltage output decreased from 203 mV to about 190 mV after the ML-MFC was changed from batch mode to normally continuous mode, indicating that planktonic electrochemically active bacterial strains in the ML-MFC may be carried away along with the effluent. Cyclic voltammograms showed that the attached microbes possessed higher bioelectrochemical activity than the planktonic microbes. Forced aeration to the cathode benefited the electricity generation obviously. Higher feeding rate and longer electrode distance both increased the electricity generation. The coulombic yield was not more than 20% throughout the study, which is lower than that of MFCs with membrane. It is proposed that dissolved oxygen diffused from the cathode to the anode may consume part of the substrate.

Sustainable biochar as an electrocatalysts for the oxygen reduction reaction in microbial fuel cells

Microbial fuel cells(MFCs)have gained remarkable attention as a novel wastewater treatment that simultaneously generates electricity.The low activity of the oxygen reduction reaction(ORR)remains one of the most critical bottlenecks limiting the development of MFCs.To date,although research on biochar as an electrocatalyst in MFCs has made tremendous progress,further improvements are needed to make it economically practical.Recently,biochars have been considered to be ORR electrocatalysts with developmental potential.In this review,the ORR mechanism and the essential requirements of ORR catalysts in MFC applications are introduced.Moreover,the focus is to highlight the material selection,properties,and preparation of biochar electrocatalysts,as well as the evaluation and measurement of biochar electrodes.Additionally,in order to provide comprehensive information on the specific applications of biochars in the field of MFCs,their applications as electrocatalysts,are then discussed in detail,including the uses of nitrogen-doped biochar and other heteroatom-doped biochars as electrocatalysts,poisoning tests for biochar catalysts,and the cost estimation of biochar catalysts.Finally,profound insights into the current challenges and clear directions for future perspectives and research are concluded.

Nitrogen and Sulfur Co-doped Porous Carbon Derived from ZIF-8 as Oxygen Reduction Reaction Catalyst for Microbial Fuel Cells

Nitrogen and sulfur co-doped porous nanocarbon (ZIF-C-N-S) catalyst was successfully synthesized derived from ZIF-8 and thiourea precursors.The electrochemical measurements indicate that the as-obtained ZIF-C-N-S catalyst exhibits higher electrocatalytic activity for oxygen reduction reaction (ORR) in alkaline electrolyte and superior durability-longer than commercial Pt/C catalyst.The enhancment of electrocatalytic activity mainly be come from the open pore structure,large specific surface area as well as the synergistic effect resulted from the co-doping of N and S atoms.In addition,the ZIF-C-N-S catalyst is also used as the air cathode catalyst in the microbial fuel cell (MFC) device.The maximum power density and stable output voltage of ZIF-C-N-S based MFC are 1315 mW/m2 and 0.48 V,respectively,which is better than that of Pt/C based MFC.

Carbon material-based anodes in the microbial fuel cells

For the performance improvement of microbial fuel cells(MFCs),the anode becomes a breakthrough point due to its influence on bacterial attachment and extracellular electron transfer(EET).On other level,carbon materials possess the following features:low cost,rich natural abundance,good thermal and chemical stability,as well as tunable surface properties and spatial structure.Therefore,the development of carbon materials and carbon-based composites has flourished in the anode of MFCs during the past years.In this review,the major carbon materials used to decorate MFC anodes have been systematically summarized,based on the differences in composition and structure.Moreover,we have also outlined the carbon material-based hybrid biofilms and carbon material-modified exoelectrogens in MFCs,along with the discussion of known strategies and mechanisms to enhance the bacteria-hosting capabilities of carbon material-based anodes,EET efficiencies,and MFC performances.Finally,the main challenges coupled with some exploratory proposals are also expounded for providing some guidance on the future development of carbon material-based anodes in MFCs.

Characterization of Fe/N-doped graphene as air-cathode catalyst in microbial fuel cells

This work proposed a simple and efficient approach for synthesis of durable and efficient non-precious metal oxygen reduction reaction（ORR） electro-catalysts in MFCs. The rod-like carbon nanotubes（CNTs）were formed on the Fe–N/SLG sheets after a carbonization process. The maximum power density of1210 ± 23 m W·mobtained with Fe–N/SLG catalyst in an MFC was 10.7% higher than that of Pt/C catalyst(1080 ± 20 mW ·m) under the same condition. The results of RDE test show that the ORR electron transfer number of Fe–N/SLG was 3.91 ± 0.02, which suggested that ORR catalysis proceeds through a four-electron pathway. The whole time of the synthesis of electro-catalysts is about 10 h, making the research take a solid step in the MFC expansion due to its low-cost, high efficiency and favorable electrochemical performance. Besides, we compared the electrochemical properties of catalysts using SLG, high conductivity graphene（HCG, a kind of multilayer graphene） and high activity graphene（HAG, a kind of GO） under the same conditions, providing a solution for optimal selection of cathode catalyst in MFCs.The morphology, crystalline structure, elemental composition and ORR activity of these three kinds of Fe–N/C catalysts were characterized. Their ORR activities were compared with commercial Pt/C catalyst.It demonstrates that this kind of Fe–N/SLG can be a type of promising highly efficient catalyst and could enhance ORR performance of MFCs.

Comparative Study of Two Carbon Fiber Cathodes and Theoretical Analysis in Microbial Fuel Cells on Ocean Floor

Cathode activity plays an important role in the improvement of the microbial fuel cells on ocean floor （BMFCs）. A comparison study between Rayon-based （CF-R） and PAN-based carbon fiber （CF-P） cathodes is conducted in the paper. The two carbon fibers were heat treated to improve cell performance （CF-R-H ＆ CF-P-H）, and were used to build a new BMFCs structure with a foamy carbon anode. The maximum power density was 112.4mWm-2 for CF-R-H, followed by 66.6mWm-2 for CF-R, 49.7 mWm-2 for CF-P-H and 21.6mWm-2 for CF-P respectively. The higher specific area and deep groove make CF-R have a better power output than with CF-P. Meanwhile, heat treatment of carbon fiber can improve cell power, nearly two-fold higher than heat treatment of plain fiber. This improvement may be due to the quinones group formation to accelerate the reduction of oxygen and electron transfer on the fiber surface in the three phase boundary after heat treatment. Compared to PAN-based carbon fiber, Rayon-based carbon fiber would be preferentially selected as cathode in novel BMFCs design due to its high surface area, low cost and higher power. The comparison research is significant for cathode material selection and cell design.

Simultaneous Denitrification and Carbon Removal in Microbial Fuel Cells

In this article,microbial fuel cell( MFC) was used for simultaneous denitrification and carbon removal to ascertain their electricity generation performance. The results showed that strengthening domestication and enrichment of electrogenic bacteria had the best start-up effect. An increase in volumetric loading reduced the rate of pollutant removal but promoted the output voltage. The changes of working conditions such as influent concentration,sludge concentration and temperature had a great influence on the electricity generation performance of MFC,and their optimum values were 500 mg/L,2 000 mg/L and 35℃,respectively.

A Comprehensive Review on Oxygen Reduction Reaction in Microbial Fuel Cells

The focus of microbial fuel cell research in recent years has been on the development of materials,microbes,and transfer of charges in the system,resulting in a substantial improvement in current density and improved power generation.The cathode is generally recognized as the limiting factor due to its high-distance proton transfer,slow oxygen reduction reaction(ORR),and expensive materials.The heterogeneous reaction determines power gen-eration in MFC.This comprehensive review describes-recent advancements in the development of cathode mate-rials and catalysts associated with ORR.The recent studies indicated the utilization of different metal oxides,the ferrite-based catalyst to overcome this bottleneck.These studies conclude that some cathode materials,in parti-cular,graphene-based conductive polymer composites with non-precious metal catalysts provide substantial ben-efits for sustainable development in the field of MFCs.Furthermore,it also highlights the potentiality to replace the conventional platinum air cathode for the large-scale production of the next generation of MFCs.It was evi-dent from the experiments that cathode catalyst needs to be blended with conductive carbon materials to make cathode conductive and efficient for ORR.This review discusses various antifouling strategies for cathode biofoul-ing and its effect on the MFC performance.Moreover,it also depicts cost estimations of various catalysts essential for further scale-up of MFC technology.