A graphene modified anode to improve the performance of microbial fuel cells

Graphene with a Brunauer-Emmett-Teller (BET) specific surface area of 264 m² g⁻¹ has been used as anodic catalyst of microbial fuel cells (MFCs) based on Escherichia coli (ATCC 25922). The electrochemical activities of plain stainless steel mesh (SSM), polytetra?uoroethylene (PTFE) modified SSM (PMS) and graphene modified SSM (GMS) have been investigated by cyclic voltammetry (CV), discharge experiment and polarization curve measurement. The GMS shows better electrochemical performance than those of SSM and PMS. The MFC equipped with GMS anode delivers a maximum power density of 2668 mW m⁻², which is 18 times larger than that obtained from the MFC with the SSM anode and is 17 times larger than that obtained from the MFC with the PMS anode. Scanning electron microscopy (SEM) results indicate that the increase in power generation could be attributed to the high surface area of anode and an increase in the number of bacteria attached to anode.     

Treatment of carbon fiber brush anodes for improving power generation in air-cathode microbial fuel cells

Carbon brush electrodes have been used to provide high surface areas for bacterial growth and high power densities in microbial fuel cells (MFCs). A high-temperature ammonia gas treatment has been used to enhance power generation, but less energy-intensive methods are needed for treating these electrodes in practice. Three different treatment methods are examined here for enhancing power generation of carbon fiber brushes: acid soaking (CF-A), heating (CF-H), and a combination of both processes (CF-AH). The combined heat and acid treatment improve power production to 1370 mW m⁻², which is 34% larger than the untreated control (CF-C, 1020 mW m⁻²). This power density is 25% higher than using only acid treatment (1100 mW m⁻²) and 7% higher than that using only heat treatment (1280 mW m⁻²). XPS analysis of the treated and untreated anode materials indicates that power increases are related to higher N1s/C1s ratios and a lower C-O composition. These findings demonstrate efficient and simple methods for improving power generation using graphite fiber brushes, and provide insight into reasons for improving performance that may help to further increase power through other graphite fiber modifications.     

Polyaniline/carbon black composite-supported iron phthalocyanine as an oxygen reduction catalyst for microbial fuel cells

Polyaniline/carbon black (PANI/C) composite-supported iron phthalocyanine (FePc) (PANI/C/FePc) has been investigated as a catalyst for the oxygen reduction reaction (ORR) in an air-cathode microbial fuel cell (MFC). The electrocatalytic activity of the PANI/C/FePc toward the ORR is evaluated using cyclic voltammogram and linear scan voltammogram methods. In comparison with that of carbon-supported FePc electrode, the peak potential of the ORR at the PANI/C/FePc electrode shifts toward positive potential, and the peak current is greatly increased, suggesting the enhanced activity of FePc absorbed onto PANI/C. Additionally, the results of the MFC experiments show that PANI/C/FePc is well suitable to be the cathode material for MFCs. The maximum power density of 630.5 mW m⁻² with the PANI/C/FePc cathode is higher than that of 336.6 mW m⁻² with the C/FePc cathode, and even higher that that of 575.6 mW m⁻² with a Pt cathode. Meanwhile, the power per cost of the PANI/C/FePc cathode is 7.5 times greater than that of the Pt cathode. Thus, the PANI/C/FePc can be a potential alternative to Pt in MFCs.     

Performance improvement of air-cathode single-chamber microbial fuel cell using a mesoporous carbon modified anode

A novel mesoporous carbon (MC) modified carbon paper has been constructed using layer-by-layer self-assembly method and is used as anode in an air-cathode single-chamber microbial fuel cell (MFC) for performance improvement. Using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), we have demonstrated that the MC modified electrode exhibits a more favorable and stable electrochemical behavior, such as increased active surface area and enhanced electron-transfer rate, than that of the bare carbon paper. The MFC equipped with MC modified carbon paper anode achieves considerably better performance than the one equipped with bare carbon paper anode: the maximum power density is 81% higher and the startup time is 68% shorter. CV and EIS analysis confirm that the MC layer coated on the carbon paper promotes the electrochemical activity of the anodic biofilm and decreases the charge transfer resistance from 300 to 99 Ω. In addition, the anode and cathode polarization curves reveal negligible difference in cathode potentials but significant difference in anode potentials, indicating that the MC modified anode other than the cathode was responsible for the performance improvement of MFC. In this paper, we have demonstrated the utilization of MC modified carbon paper to enhance the performance of MFC.     

Analysis of carbon fiber brush loading in anodes on startup and performance of microbial fuel cells

Flat carbon anodes placed near a cathode in a microbial fuel cell (MFC) are adversely affected by oxygen crossover, but graphite fiber brush anodes placed near the cathode produce high power densities. The impact of the brush size and electrode spacing was examined by varying the distance of the brush end from the cathode and solution conductivity in multiple MFCs. The startup time was increased from 8 ± 1 days with full brushes (all buffer concentrations) to 13 days (50 mM), 14 days (25 mM) and 21 days (8 mM) when 75% of the brush anode was removed. When MFCs were all first acclimated with a full brush, up to 65% of the brush material could be removed without appreciably altering maximum power. Electrochemical impedance spectroscopy (EIS) showed that the main source of internal resistance (IR) was diffusion resistance, which together with solution resistance reached 100 Ω. The IR using EIS compared well with that obtained using the polarization data slope method, indicating no major components of IR were missed. These results show that using full brush anodes avoids adverse effects of oxygen crossover during startup, although brushes are much larger than needed to sustain high power.     

An overview of electrode materials in microbial fuel cells

Electrode materials play an important role in the performance (e.g., power output) and cost of microbial fuel cells (MFCs), which use bacteria as the catalysts to oxidize organic (inorganic) matter and convert chemical energy into electricity. In this paper, the recent progress of anode/cathode materials and filling materials as three-dimensional electrodes for MFCs has been systematically reviewed, resulting in comprehensive insights into the characteristics, options, modifications, and evaluations of the electrode materials and their effects on different actual wastewater treatment. Some existing problems of electrode materials in current MFCs are summarized, and outlooks for future development are also suggested.     

Effects of brush lengths and fiber loadings on the performance of microbial fuel cells using graphite fiber brush anodes

An alternative method for fabricating graphite fiber brush (GFB) electrodes was proposed. Two series of GFB electrodes with different lengths (L) and loaded fiber masses (m) were fabricated. The effects of m/L on the biomass distribution, active biomass content, electrochemical behavior and MFC performance were investigated. For the electrodes with a similar m but different L, substrate supply within the interior of GFB electrodes improved with L, leading to higher biomass content and consequently the improved performance. However, a complex trend was found for the electrodes with different m and similar L, due to the opposing trends of substrate supply and actual functional area for electrochemically active bacteria with m. Furthermore, m-normalized biomass content and power density of the GFB electrodes increased with decreasing of m/L ratio due to the improved graphite fiber utilization until 0.014 g mm⁻¹, below which they remained constant since the utilization of graphite fibers plateaued.     

Carbon nanotube/polyaniline composite as anode material for microbial fuel cells

A carbon nanotube (CNT)/polyaniline (PANI) composite is evaluated as an anode material for high-power microbial fuel cells (MFCs). Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) are employed to characterize the chemical composition and morphology of plain PANI and the CNT/PANI composite. The electrocatalytic behaviour of the composite anode is investigated by means of electrochemical impedance spectroscopy (EIS) and discharge experiments. The current generation profile and constant current discharge curves of anodes made from plain PANI, 1 wt.% and 20 wt.% CNT in CNT–PANI composites reveal that the performance of the composite anodes is superior. The 20 wt.% CNT composite anode has the highest electrochemical activity and its maximum power density is 42 mW m⁻² with Escherichia coli as the microbial catalyst. In comparison with the reported performance of different anodes used in E. coli-based MFCs, the CNT/PANI composite anode is excellent and is promising for MFC applications.     

Improved performance of microbial fuel cell using combination biocathode of graphite fiber brush and graphite granules

The efficiency and sustainability of microbial fuel cell (MFC) are heavily dependent on the cathode performance. We show here that the use of graphite fiber brush (GBF) together with graphite granules (GGs) as a basal material for biocathode (MFC reactor type R1) significantly improve the performance of a MFC compared with MFCs using GGs (MFC reactor type R2) or GFB (MFC reactor type R3) individually. Compared with R3, the use of the combination biocathode (R1) can shorten the start-up time by 53.75%, improve coulombic efficiencies (CEs) by 21.0 ± 2.7% at external resistance (R_EX) of 500 Ω, and increase maximum power densities by 38.2 ± 12.6%. Though the start-up time and open circuit voltage (OCV) of the reactor R2 are similar to R1, the CE (R_EX = 500 Ω) and maximum power density of R2 are 21.4 ± 1.7% and 38.2 ± 15.6% lower than that of R1. Fluorescence in situ hybridization (FISH) analyses indicate the bacteria on cathodes of R1 and R2 are richer than that of R3. Molecular taxonomic analyses reveal that the biofilm formed on the biocathode surface is dominated by strains belonging to Nitrobacter, Achromobacter, Acinetobacter, and Bacteroidetes. Combination of GFB and GGs as biocathode material in MFC is more efficient and can achieve sustainable electricity recovery from organic substances, which substantially increases the viability and sustainability of MFCs.     

Electrophoretic deposition of graphene oxide on carbon brush as bioanode for microbial fuel cell operated with real wastewater

Microbial fuel cell (MFC) is a promising technology for simultaneous wastewater treatment and energy harvesting. The properties of the anode material play a critical role in the performance of the MFC. In this study, graphene oxide was prepared by a modified hummer's method. A thin layer of graphene oxide was incorporated on the carbon brush using an electrophoretic technique. The deoxygenated graphene oxide formed on the surface of the carbon brush (RGO-CB) was investigated as a bio-anode in MFC operated with real wastewater. The performance of the MFC using the RGO-CB was compared with that using plain carbon brush anode (PCB). Results showed that electrophoretic deposition of graphene oxide on the surface of carbon brush significantly enhanced the performance of the MFC, where the power density increased more than 10 times (from 33 mWm^?2 to 381 mWm^?2). Although the COD removal was nearly similar for the two MFCs, i.e., with PCB and RGO-CB; the columbic efficiency significantly increased in the case of RGO-CB anode. The improved performance in the case of the modified electrode was related to the role of the graphene in improving the electron transfer from the microorganism to the anode surface, as confirmed from the electrochemical impedance spectroscopy measurements.     

Studies on the carbon reactions in the anode of deposited carbon fuel cells

The carbon reactions in the anode of deposited carbon fuel cells were studied experimentally and theoretically. Deposition experiments were conducted by decomposing methane in a thermogravimetric analyzer at 800 °C, with both NiO or YSZ powders and small chips of an unused anode-supported SOFC button cell used separately as bed materials. The carbon tended to deposit on the Ni surfaces with the NiO or YSZ powders, while with the anode chips, the deposited carbon formed particles comparable in size to the Ni or YSZ particles with little carbon deposited near the electrolyte where the electrochemical reactions occur. Thus, the results infer that the deposited carbon has little opportunity to participate in the electrochemical reactions. A two-dimensional isothermal model was then developed to examine the influence of the deposited carbon on the cell performance. The results show the diffusion coefficient of CO has the largest influence, followed by the gasifying reactivity and the electrochemical reactivity of the carbon. Finally, a short deposition time and a high methane concentration are favored to improve the performance of deposited carbon fuel cells.     

Landfill leachate: A promising substrate for microbial fuel cells

Landfill leachate emerges as a promising feedstock for microbial fuel cells (MFCs). In the present investigation, direct air-breathing cathode-based MFCs are fabricated to investigate the maximum open circuit potential from landfill leachate. Three MFCs that have different cathode areas are fabricated and studied for 17 days under open circuit conditions. The maximum open circuit voltage (OCV) of the cell is observed to be as high as 1.29 V which is the highest OCV ever reported in the literature using landfill leachate. The maximum cathode area specific power density achieved in the reactor is 1513 mW m^?2. Further studies are under progress to understand the origin of high OCV obtained from landfill leachate-based MFCs.     

Effect of cathode electron-receiver on the performance of microbial fuel cells

Performance of cathode electron receivers has direct effect on the voltage and power density of MFC. This paper explored the electrical performance of MFC with potassium permanganate, ferricyanide solution and dissolved oxygen (DO) as cathode electron receivers. The results showed that the internal resistance of MFC with DO depends on catalyst and is higher than that of MFC with potassium permanganate and potassium ferricyanide solution. The maximum volume power density is 4.35 W/m³, and the smallest internal resistance is only about 54 Ω. In case of DO, the internal resistance and power density is different depending on the catalyst and is not too much related to the membranes.     

Optimization of inner diameter of tubular bamboo charcoal anode for a microbial fuel cell

In the present study, the bamboo charcoal tube derived from the carbonization of the bamboo tube was employed as the anode. The effect of inner diameter of bamboo charcoal tube anodes was experimentally investigated on the microbial fuel cells (MFCs) performance to obtain an optimal structure. After successful star-up, bamboo charcoal tube anodes with different inner diameters (1 mm, 1.5 mm, 2 mm and 3 mm in inner diameter were named as MFC-D1, MFC-D1.5, MFC-D2 and MFC-D3) resulted in various voltage output. However, MFC-D2 and MFC-D3 still kept stable output while the MFC-D1 and MFC-D1.5 performances had a significant drop for a long-term operation (after operation for 30 days). Scanning electron microscope and electrochemical impedance spectroscopy results indicated that the reduction in the powder density for MFC-D1 and MFC-D1.5 attributed to a compact and thicker biofilm on the anode surface leading to the increased the internal resistance of MFCs. Furthermore, compared with other anodes, the highest power density (3303 W/m³) for MFC-D2 suggested that the tubular bamboo charcoal with 2 mm in diameter was more suitable for electricity generation.     

Facile microwave-assisted synthesized reduced graphene oxide/tin oxide nanocomposite and using as anode material of microbial fuel cell to improve power generation

A new nanocomposite material was fabricated by a facile and reliable method for microbial fuel cell (MFC) anode. Tin oxide (SnO₂) nanoparticles were anchored on the surface of reduced graphene oxide (RGO/SnO₂) in two steps. The hydrothermal method was used for the modification of GO and then microwave-assisted method was used for coating of SnO₂ on the modified GO. Nanohybrids of RGO/SnO₂ achieved a maximum power density of 1624 mW m⁻², when used as the MFC anode. The obtained power density was 2.8 and 4.8 times larger than that of RGO coated and bare anodes, respectively. The electrodes were characterized by scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX). The electrochemical characteristics were also studied by cyclic voltammetry (CV), linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS). The high conductivity and large specific surface of the nanocomposite were greatly improved the bacterial biofilm formation and increased the electron transfer. The results demonstrate that the RGO/SnO₂ nanocomposite was advantageous material for the modification of anode and enhanced electricity generation of MFC.     

Sulfonated graphene oxide/Nafion composite membranes for high-performance direct methanol fuel cells

An easy and effective method for producing low methanol-crossover membranes is developed by dispersing sulfonated graphene oxide (SGO) into a Nafion matrix. A SGO/Nafion mixture with low SGO content exhibits unique viscosity behavior and allows for better SGO dispersion within the Nafion. After film casting, the composite membranes show lower methanol and water uptakes, a reduced swelling ratio, improved proton conductivity in low relative humidity, and extremely high methanol selectivity, which can be implemented in direct methanol fuel cells (DMFCs). The regular backbone of the composite membrane shows a higher storage modulus, increased α-relaxation (transition temperature), and improved tolerance to pressure during membrane electrode assembly (MEA). The small angle X-ray spectra indicate the shrinkage of the ionic clusters in the composite membranes, which thus reduce methanol crossover. The hybrid membranes applied to DMFCs demonstrate performances superior to that of the commercial Nafion 115 in 1 M and 5 M methanol solutions.     

The effect of nitric acid,ethylenediamine, and diethanolamine modified polyaniline nanoparticles anode electrode in a microbial fuel cell

Anode materials are important in the power generation of microbial fuel cell. In this study, polyaniline was used as a conducting polymer anode in two chambers MFC. XPS and SEM were used for the characterization of functional groups of anode materials and the morphology. The power generation of microbial fuel cell was elevated by the modification of anode by nitric acid, ethylenediamine, and diethanolamine. The time that MFC reaches its maximum power generation was shortened by modification. Moreover the SEM photos prove that, it causes better attachment of microorganisms as biocatalysts on electrode surface. The best performance of among the MFCs with different anode electrodes, was the system working by polyaniline modified by ethylenediamine as that generated power of 136.2 mW/m² with a 21.3% Coulombic efficiency.     

Miniature microbial fuel cells and stacks for urine utilisation

MFCs are becoming a stronger contender in the area of alternative energy sources and show great promise in utilising a wide variety of organic sources. This paper describes the utilisation of neat undiluted urine as the main feedstock for different types of individual MFCs and stacks of small-scale MFCs, for direct electricity production, with conversion efficiencies of >50%. The smallest MFC (1.4 mL total volume) produced equal amounts of power to that produced by larger MFCs (6.25 mL), resulting in increased power densities. Power densities of 4.93 mW/m² (absolute power of 1.5 mW) were recorded when 48 small-scale MFCs were connected as a stack and fed with urine. This study demonstrates the feasibility of using urine as an untreated fuel and that improved power outputs can be achieved through MFC miniaturisation and multiplication into stacks.     

Unveiling characteristics of dye-bearing microbial fuel cells for energy and materials recycling: Redox mediators

This study disclosed why and how some decolorized intermediates (e.g., 2-aminophenol) could act as electron-shuttling mediator(s) to enhance the capabilities of reductive decolorization and bioelectricity generation. It also selected several model auxochrome-containing compounds structurally associated to 2AP to explore how chemical structure influenced the feasibility of possible electron shuttles for power producing capabilities in microbial fuel cells (MFCs). The selection criteria of electron-shuttling mediators were suggested for optimal reductive decolorization and bioelectricity generation in MFCs for practical application.     

Analysis of the carbon anode in direct carbon conversion fuel cells

The total electrochemical efficiency of a direct carbon fuel cell with molten carbonate electrolyte is dominated by the product of coulombic efficiency (electron yield (n) per carbon atom, divided by 4) and voltaic efficiency (ratio of cell voltage to theoretical voltage). The voltaic efficiency is acceptably high (70–80%) for many atomically-disordered carbon materials. High coulombic efficiency is more difficult to achieve but ranges from below 50% at low current densities in porous material to 100% in certain monolithic and particulate carbon anodes at high current densities where substantially pure CO₂ is the product gas. We find evidence for two competing anode reactions associated with distinct low- and high polarization segments, respectively: (1) a charge-transfer controlled, linear–polarization reaction occurring predominately within pores, proportional to specific area, and tending toward low efficiency by co-production of CO and CO₂; and (2) a flow-dependent reaction occurring on the exterior surface of the anode, requiring > 100 mV polarization and tending to produce CO₂. Based on this interpretation, high electrochemical efficiency of a carbon fuel cell is expected with anodes made of atomically disordered ("turbostratic") carbon that have negligible porosity, or with anodes of disordered carbon for which interior pores are intentionally blocked with an impervious solid material, such as an inert salt or readily carbonized pitch.