Hydrogen production in microbial electrolysis cells with biocathodes.

Electroautotrophic microbes at biocathodes in microbial electrolysis cells (MECs) can catalyze the hydrogen evolution reaction with low energy demand, facilitating long-term stable performance through specific and renewable biocatalysts. However, MECs have not yet reached commercialization due to a lack of understanding of the optimal microbial strains and reactor configurations for achieving high performance. Here, we critically analyze the criteria for the inocula selection, with a focus on the effect of hydrogenase activity and microbe-electrode interactions. We also evaluate the impact of the reactor design and key parameters, such as membrane type, composition, and electrode surface area on internal resistance, mass transport, and pH imbalances within MECs. This analysis paves the way for advancements that could propel biocathode-assisted MECs toward scalable hydrogen gas production.

Thin-Film Composite Membranes for Hydrogen Evolution with a Saline Catholyte Water Feed.

Hydrogen gas evolution using an impure or saline water feed is a promising strategy to reduce overall energy consumption and investment costs for on-site, large-scale production using renewable energy sources. The chlorine evolution reaction is one of the biggest concerns in hydrogen evolution with impure water feeds. The "alkaline design criterion" in impure water electrolysis was examined here because water oxidation catalysts can exhibit a larger kinetic overpotential without interfering chlorine chemistry under alkaline conditions. Here, we demonstrated that relatively inexpensive thin-film composite (TFC) membranes, currently used for high-pressure reverse osmosis (RO) desalination applications, can have much higher rejection of Cl- (total crossover of 2.9 ± 0.9 mmol) than an anion-exchange membrane (AEM) (51.8 ± 2.3 mmol) with electrolytes of 0.5 M KOH for the anolyte and 0.5 M NaCl for the catholyte with a constant current (100 mA/cm2 for 20 h). The membrane resistances, which were similar for the TFC membrane and the AEM based on electrochemical impedance spectroscopy (EIS) and Ohm's law methods, could be further reduced by increasing the electrolyte concentration or removal of the structural polyester supporting layer (TFC-no PET). TFC membranes could enable pressurized gas production, as this membrane was demonstrated to be mechanically stable with no change in permeate flux at 35 bar. These results show that TFC membranes provide a novel pathway for producing green hydrogen with a saline water feed at elevated pressures compared to systems using AEMs or porous diaphragms.

Reducing Chloride Ion Permeation during Seawater Electrolysis Using Double-Polyamide Thin-Film Composite Membranes.

Low-cost polyamide thin-film composite membranes are being explored as alternatives to expensive cation exchange membranes for seawater electrolysis. However, transport of chloride from seawater to the anode chamber must be reduced to minimize the production of chlorine gas. A double-polyamide composite structure was created that reduced the level of chloride transport. Adding five polyamide layers on the back of a conventional polyamide composite membrane reduced the chloride ion transport by 53% and did not increase the applied voltage. Decreased chloride permeation was attributed to enhanced electrostatic and steric repulsion created by the new polyamide layers. Charge was balanced through increased sodium ion transport (52%) from the anolyte to the catholyte rather than through a change in the transport of protons and hydroxides. As a result, the Nernstian loss arising from the pH difference between the anolyte and catholyte remained relatively constant during electrolysis despite membrane modifications. This lack of a change in pH showed that transport of protons and hydroxides during electrolysis was independent of salt ion transport. Therefore, only sodium ion transport could compensate for the reduction of chloride flux to maintain the set current. Overall, these results prove the feasibility of using a double-polyamide structure to control chloride permeation during seawater electrolysis without sacrificing energy consumption.

A comprehensive analysis of key factors influencing methane production from CO2 using microbial methanogenesis cells.

With increasing attention on carbon capture and utilization (CCU) technologies for the conversion of CO2 into chemical products, microbial methanogenesis cells (MMCs) have been extensively studied over the past few decades for biomethane production. Using rapidly accumulating data for MMCs with varying configurations and operating conditions, a comprehensive analysis was conducted here to investigate the critical factors that influence methane production rates (MPR) in these systems. A comparison of MPR and set potentials or current densities showed weak linear relationships (R2 < 0.6, p < 0.05), indicating the significant contributions of other important factors impacting methane production. A non-quantitative analysis of these additional parameters indicated the potential importance of using metal catalysts for anode materials where oxygen evolution reaction occurs, while most previous MMC research focused more on cathode materials where the biocatalytic reaction occurs. The use of undefined mixed anaerobic cultures as inocula was found to be sufficient for producing high MPRs, as the electrochemical environment at the cathode provides a strong selective pressure to converge on desirable methanogenic cultures. Other operational parameters, such as catholyte pH control and CO2 supply methods, were also important factors impacting MPR in MMCs, indicating the cumulative impact of these various factors will require careful consideration in future research.

Relative Insignificance of Polyamide Layer Selectivity for Seawater Electrolysis Applications.

Low-cost polyamide thin-film composite (TFC) membranes are being explored as alternatives to cation exchange membranes for seawater electrolysis. An optimal membrane should have a low electrical resistance to minimize applied potentials needed for water electrolysis and be able to block chloride ions present in a seawater catholyte from reaching the anode. The largest energy loss associated with a TFC membrane was the Nernstian overpotential of 0.74 V (equivalent to 37 Ω cm2 at 20 mA cm-2), derived from the pH difference between the anolyte and catholyte and not the membrane ohmic overpotential. Based on analysis using electrochemical impedance spectroscopy, the pristine TFC membrane contributed only 5.00 Ω cm2 to the ohmic resistance. Removing the polyester support layer reduced the resistance by 79% to only 1.04 Ω cm2, without altering the salt ion transport between the electrolytes. Enlarging the pore size (∼5 times) in the polyamide active layer minimally impacted counterion transport across the membrane during electrolysis, but it increased the total concentration of chloride transported by 60%. Overall, this study suggests that TFC membranes with thinner but mechanically strong supporting layers and size-selective active layers should reduce energy consumption and the potential for chlorine generation for seawater electrolyzers.

Impact of reactor configuration on pilot-scale microbial fuel cell performance.

Different microbial fuel cell (MFC) configurations have been successfully operated at pilot-scale levels (>100 L) to demonstrate electricity generation while accomplishing domestic or industrial wastewater treatment. Two cathode configurations have been primarily used based on either oxygen transfer by aeration of a liquid catholyte or direct oxygen transfer using air-cathodes. Analysis of several pilot-scale MFCs showed that air-cathode MFCs outperformed liquid catholyte reactors based on power density, producing 233% larger area-normalized power densities and 181% higher volumetric power densities. Reactors with higher electrode packing densities improved performance by enabling larger power production while minimizing the reactor footprint. Despite producing more power than the liquid catholyte MFCs, and reducing energy consumption for catholyte aeration, pilot MFCs based on air-cathode configuration failed to produce effluents with chemical oxygen demand (COD) levels low enough to meet typical threshold for discharge. Therefore, additional treatment would be required to further reduce the organic matter in the effluent to levels suitable for discharge. Scaling up MFCs must incorporate designs that can minimize electrode and solution resistances to maximize power and enable efficient wastewater treatment.

Thermodynamic and Kinetic Analyses of Ion Intercalation/Deintercalation Using Different Temperatures on NiHCF Electrodes for Battery Electrode Deionization.

Prussian blue analogues are used in electrochemical deionization due to their cation sorption capabilities and ion selectivity properties. Elucidating the fundamental mechanisms underlying intercalation/deintercalation is important for the development of ion-selective electrodes. We examined the thermodynamic and kinetic properties of nickel hexacyanoferrate electrodes by studying different temperatures effects on intercalation/deintercalation with monovalent ions (Li+, Na+, K+, and NH4+) relevant to battery electrode deionization applications. Higher temperatures reduced the interfacial charge transfer resistance and increased the diffusion coefficient of cations in the solid material. Ion transport in the solid material, rather than interfacial charge transfer, was found to be the rate-controlling step, as shown by higher activation energies for ion transport (e.g., 31 ± 3 kJ/mol for K+) than for interfacial charge transfer (5 ± 1 kJ/mol for K+). The largest increase in cation adsorption capacity with temperature was observed for NH4+ (28.1% from 15 to 75 °C) due to its smallest activation energy. These results indicate that ion hydration energy determines the intercalation potential and activation energies of ion transport in solid material control intercalation/deintercalation rate. Together with the endothermic behavior of deintercalation and exothermic behavior of intercalation, the higher operating temperature results in improvement of ion adsorption capacity depending on specific cations.

High-rate microbial electrosynthesis using a zero-gap flow cell and vapor-fed anode design.

Microbial electrosynthesis (MES) cells use renewable energy to convert carbon dioxide into valuable chemical products such as methane and acetate, but chemical production rates are low and pH changes can adversely impact biocathodes. To overcome these limitations, an MES reactor was designed with a zero-gap electrode configuration with a cation exchange membrane (CEM) to achieve a low internal resistance, and a vapor-fed electrode to minimize pH changes. Liquid catholyte was pumped through a carbon felt cathode inoculated with anaerobic digester sludge, with humidified N2 gas flowing over the abiotic anode (Ti or C with a Pt catalyst) to drive water splitting. The ohmic resistance was 2.4 ± 0.5 mΩ m2, substantially lower than previous bioelectrochemical systems (20-25 mΩ m2), and the catholyte pH remained near-neutral (6.6-7.2). The MES produced a high methane production rate of 2.9 ± 1.2 L/L-d (748 mmol/m2-d, 17.4 A/m2; Ti/Pt anode) at a relatively low applied voltage of 3.1 V. In addition, acetate was produced at a rate of 940 ± 250 mmol/m2-d with 180 ± 30 mmol/m2-d for propionate. The biocathode microbial community was dominated by the methanogens of the genus Methanobrevibacter, and the acetogen of the genus Clostridium sensu stricto 1. These results demonstrate the utility of this zero-gap cell and vapor-fed anode design for increasing rates of methane and chemical production in MES.

Pilot scale microbial fuel cells using air cathodes for producing electricity while treating wastewater.

Microbial fuel cells (MFCs) can generate electrical energy from the oxidation of the organic matter, but they must be demonstrated at large scales, treat real wastewaters, and show the required performance needed at a site to provide a path forward for this technology. Previous pilot-scale studies of MFC technology have relied on systems with aerated catholytes, which limited energy recovery due to the energy consumed by pumping air into the catholyte. In the present study, we developed, deployed, and tested an 850 L (1400 L total liquid volume) air-cathode MFC treating domestic-type wastewater at a centralized wastewater treatment facility. The wastewater was processed over a hydraulic retention time (HRT) of 12 h through a sequence of 17 brush anode modules (11 m2 total projected anode area) and 16 cathode modules, each constructed using two air-cathodes (0.6 m2 each, total cathode area of 20 m2) with the air side facing each other to allow passive air flow. The MFC effluent was further treated in a biofilter (BF) to decrease the organic matter content. The field test was conducted for over six months to fully characterize the electrochemical and wastewater treatment performance. Wastewater quality as well as electrical energy production were routinely monitored. The power produced over six months by the MFC averaged 0.46 ± 0.35 W (0.043 W m-2 normalized to the cross-sectional area of an anode) at a current of 1.54 ± 0.90 A with a coulombic efficiency of 9%. Approximately 49 ± 15 % of the chemical oxygen demand (COD) was removed in the MFC alone as well as a large amount of the biochemical oxygen demand (BOD5) (70%) and total suspended solid (TSS) (48%). In the combined MFC/BF process, up to 91 ± 6 % of the COD and 91 % of the BOD5 were removed as well as certain bacteria (E. coli, 98.9%; fecal coliforms, 99.1%). The average effluent concentration of nitrate was 1.6 ± 2.4 mg L-1, nitrite was 0.17 ± 0.24 mg L-1 and ammonia was 0.4 ± 1.0 mg L-1. The pilot scale reactor presented here is the largest air-cathode MFC ever tested, generating electrical power while treating wastewater.

Vapor-Fed Cathode Microbial Electrolysis Cells with Closely Spaced Electrodes Enables Greatly Improved Performance.

Hydrogen can be electrochemically produced in microbial electrolysis cells (MECs) by current generated from bacterial anodes with a small added voltage. MECs typically use a liquid catholyte containing a buffer or salts. However, anions in these catholytes result in charge being balanced predominantly by ions other than hydroxide or protons, leading to anode acidification. To enhance only hydroxide ion transport to the anode, we developed a novel vapor-fed MEC configuration lacking a catholyte with closely spaced electrodes and an anion exchange membrane to limit the acidification. This MEC design produced a record-high sustained current density of 43.1 ± 0.6 A/m2 and a H2 production rate of 72 ± 2 LH2/L-d (cell voltage of 0.79 ± 0.00 V). There was minimal impact on MEC performance of increased acetate concentrations, solution conductivity, or anolyte buffer capacity at applied voltages up to 1.1 V, as shown by a nearly constant internal resistance of only 6.8 ± 0.3 mΩ m2. At applied external voltages >1.1 V, the buffer capacity impacted performance, with current densities increasing from 28.5 ± 0.6 A/m2 (20 mM phosphate buffer solution (PBS)) to 51 ± 1 A/m2 (100 mM PBS). These results show that a vapor-fed MEC can produce higher and more stable performance than liquid-fed cathodes by enhancing transport of hydroxide ions to the anode.

Long-Term Succession Shows Interspecies Competition of Geobacter in Exoelectrogenic Biofilms.

Geobacter spp. are well-known exoelectrogenic microorganisms that often predominate acetate-fed biofilms in microbial fuel cells (MFCs) and other bioelectrochemical systems (BESs). By using an amplicon sequence variance analysis (at one nucleotide resolution), we observed a succession between two closely related species (98% similarity in 16S RNA), Geobacter sulfurreducens and Geobacter anodireducens, in the long-term studies (20 months) of MFC biofilms. Geobacter spp. predominated in the near-electrode portion of the biofilm, while the outer layer contained an abundance of aerobes, which may have helped to consume oxygen but reduced the relative abundance of Geobacter. Removal of the outer aerobes by norspermidine washing of biofilms revealed a transition from G. sulfurreducens to G. anodireducens. This succession was also found to occur rapidly in co-cultures in BES tests even in the absence of oxygen, suggesting that oxygen was not a critical factor. G. sulfurreducens likely dominated in early biofilms by its relatively larger cell size and production of extracellular polymeric substances (individual advantages), while G. anodireducens later predominated due to greater cell numbers (quantitative advantage). Our findings revealed the interspecies competition in the long-term evolution of Geobacter genus, providing microscopic insights into Geobacter's niche and competitiveness in complex electroactive microbial consortia.

Comparison of different chemical treatments of brush and flat carbon electrodes to improve performance of microbial fuel cells.

Anodes in microbial fuel cells (MFCs) can be chemically treated to improve performance but the impact of treatment on power generation has not been examined for different electrode base materials. Brush or flat anodes were chemically treated and then compared in identical two-chambered MFCs using the electrode potential slope (EPS) analysis to quantify the anode resistances. Flat carbon cloth anodes modified with carbon nanotubes (CNTs) produced 1.42 ± 0.06 W m-2, which was 3.2 times more power than the base material (0.44 ± 0.00 W m-2), but less than the 2.35 ± 0.1 W m-2 produced using plain graphite fiber brush anodes. An EPS analysis showed that there was a 90% decrease in the anode resistances of the CNT-treated carbon cloth and a 5% decrease of WO3 nanoparticle-treated brushes compared to unmodified controls. Certain chemical treatments can therefore improve performance of flat anodes, but plain brush anodes achieved the highest power densities.

The impact of different types of high surface area brush fibers with different electrical conductivity and biocompatibility on the rates of methane generation in anaerobic digestion.

The addition of electrically conductive materials may enhance anaerobic digestion (AD) efficiency by promoting direct interspecies electron transfer (DIET) between electroactive microorganisms, but an equivalent enhancement can also be achieved using non-conductive materials. Four high surface area brush materials were added to AD reactors: non-conductive horsehair (HB) and polyester (PB), and conductive carbon fiber (CB) and stainless steel (SB) brushes. Reactors with the polyester material showed lower methane production (68 ± 5 mL/g CODfed) than the other non-conductive material (horsehair) and the conductive (graphite or stainless steel) materials (83 ± 3 mL/g CODfed) (p < 0.05). This difference was due in part to the higher biomass concentrations using horsehair or carbon (135 ± 43 mg) than polyester or stainless steel or materials (26 ± 1 mg). A microbial community analysis indicated that the relative abundance of electroactive microorganisms was not directly related to enhanced AD performance. These results show that non-conductive materials such as horsehair can produce the same AD enhancement as conductive materials (carbon or stainless steel). However, if the material, such as polyester, does not have good biomass retention, it will not enhance methane production. Thus, electrical conductivity alone was not responsible for enhancing AD performance. Polyester, which has been frequently used as a non-conductive control material in DIET studies, should not be used for this purpose due to its poor biocompatibility as shown by low biomass retention in AD tests.

Metal-Ion Depletion Impacts the Stability and Performance of Battery Electrode Deionization over Multiple Cycles.

Prussian blue hexacyanoferrate (HCF) materials, such as copper hexacyanoferrate (CuHCF) and nickel hexacyanoferrate (NiHCF), can produce higher salt removal capacities than purely capacitive materials when used as electrode materials during electrochemical water deionization due to cation intercalation into the HCF structure. One factor limiting the application of HCF materials is their decay in deionization performance over multiple cycles. By examining the performance of CuHCF and NiHCF electrodes at three different pH values (2.5, 6.3, and 10.2) in multiple-cycle deionization tests, losses in capacity (up to 73% for CuHCF and 39% for NiHCF) were shown to be tied to different redox-active centers through analysis of dissolution of electrode metals. Both copper and iron functioned as active centers for Na+ removal in CuHCF, while iron was mainly the active center in NiHCF. This interaction of Na+ and active centers was demonstrated by correlating the decrease in performance to the concentration of these metal ions in the effluent solutions collected over multiple cycles at different pHs (up to 0.86 ± 0.14 mg/L for iron and 0.42 ± 0.17 mg/L for copper in CuHCF and 0.38 ± 0.05 mg/L for iron in NiHCF). Both materials were more stable (<11% decay for CuHCF and no decay for NiHCF) when the appropriate metal salt (copper or nickel) was added to the feed solutions to inhibit electrode dissolution. At a pH of 2.5, there was an increased competition between protons and Na+ ions, which decreased the Na+ removal amount and lowered the thermodynamic energy efficiency for deionization for both electrode materials. Therefore, while an acidic pH provided the most stable performance, a circumneutral pH would be useful to produce a better balance between performance and longevity.

Separation and recovery of ammonium from industrial wastewater containing methanol using copper hexacyanoferrate (CuHCF) electrodes.

Ammonium is typically removed from wastewater by converting it to nitrogen gas using microorganisms, precluding its recovery. Copper hexacyanoferrate (CuHCF) is known to reversibly intercalate alkali cations in aqueous electrolytes due to the Prussian Blue crystal structure. We used this property to create a carbon-based intercalation electrode within an electrochemical cell. Depending on the electrode potential, it can recover NH4+ from wastewater via insertion/regeneration while leaving organics. In the first phase, different binders were evaluated towards creating a stable electrode matrix, with sodium carboxymethyl cellulose giving the best performance. Subsequently, based on voltammetry, we determined an intercalation potential for NH4+ removal of + 0.3 V vs. Ag/AgCl, while the regeneration potential of the electrode was + 1.1 V (vs. Ag/AgCl). Using the CuHCF electrodes 95% of the NH4+ in a synthetic wastewater containing 56 mM NH4+ and 68 mM methanol was removed with an energy input of 0.34 ± 0.01 Wh g-1 NH4+. A similar removal of 93% was obtained using an actual industrial wastewater (56 mM NH4+, 68 mM methanol, 0.02 mM NO2-, 0.05 mM NO3-, 0.04 mM SO42- and 0.34 mM ethanol), with an energy input of 0.40 ± 0.01 Wh g-1 NH4+. In both cases, there was negligible removal of organics. The stability of CuHCF electrodes was evaluated either by open circuit potential monitoring (61 h) or by cyclic voltammetry (50 h, 116 cycles). The stability during cycling of the electrode was determined in both synthetic and real streams for 25 h (125 cycles). The charge density (C cm-1) of the CuHCF electrodes declined by 17 % and 19% after 125 cycles in the synthetic stream and the actual wastewater, respectively. This study highlights the possibility of low-cost CuHCF coated electrodes for achieving separation of NH4+ from streams containing methanol. The stability of electrodes has been improved but needs to be further enhanced for large-scale applications and long-term operation.

Magnetic seeding coagulation: Effect of Al species and magnetic particles on coagulation efficiency, residual Al, and floc properties.

Magnetic seeding coagulation (MSC) process has been used to accelerate flocs sedimentation with an applied magnetic field, offering large handling capacity and low energy consumption. The interactions of three typical Al species, aluminum chloride (AlCl3), Al13O4(OH)247+ polymer (Al13), and (AlO4)2Al28(OH)5618+ polymer (Al30), with magnetic particles (MPs) were examined to clarify the MSC process. In traditional coagulation (TC) process, the aggregation of primary Ala-dissolved organic matter (DOM) complexes with in-situ-formed polynuclear species generated a large average floc size (226 µm), which was proved to be efficient for DOC removal (52.6%). The weak connections between dissolved Ala-DOM complexes and MPs led to the negligible changes of dissolved Al after seeding with MPs in AlCl3. A significant interaction between MPs and Al13 was observed, in which the MPs-Al13-DOM complexes were proposed to be responsible for the significant improvement of DOC removal (from 47% to 52%) and residual total Al reduction (from 1.05 to 0.27 mg Al L-1) with MPs addition. Al30 produced a lower floc fractal dimension (Df = 1.88) than AlCl3 (2.08) and Al13 (1.99) in the TC process, whereas its floc strength (70.9%) and floc recovery (38.5%) were higher than the others. Although more detached fragments were produced with MPs addition, the effective sedimentation of these fragments with the applied magnetic field led to the decrease of residual turbidity and colloidal Al in Al30. The dependence of coagulation behavior to MPs and different Al species can be applied to guide the application of an effective MSC process.

Unveiling the correlation of Fe3O4 fractions upon the adsorption behavior of sulfamethoxazole on magnetic activated carbon.

Magnetic particles (MPs) assisted powdered activated carbon (PAC) is a promising composite material for adsorption removal of micropollutants. The fractional amount of Fe3O4 impacts the balance between adsorption capacity and magnetic property of magnetic activated carbons (MPACs), and therefore it affects the extent of sulfamethoxazole (SMX) removal. Here, five MPACs with different mass ratios of Fe3O4: PAC (1:1, 1:2, 1:4, 1:6, and 1:8) were prepared using a hydrothermal method and characterized by various spectroscopic methods. The spherical shaped MPs were monolayerly deposited on PAC with fewer pores blocked when the mass ratio of Fe3O4 was comparatively low (≤ 20%). MPAC6 (14.3 wt% of Fe3O4) had the best overall performance, with good Langmuir adsorption capacities for SMX (173.0 mg g-1) and excellent magnetic properties (9.0 emu g-1). Corresponding adsorption kinetics fitted well with the pseudo second-order kinetic model. The negative ΔG0 (-25.6 to -27.2 KJ mol-1) and ΔH0 (-9.14 KJ mol-1), and positive ΔS0 (0.55 KJ mol-1 K-1) properties indicated the spontaneous and exothermic nature of the adsorption process accompanied by an increase in entropy. The strong cation-assisted electron donor-acceptor and hydrophobic interactions were contributed to a high extent of SMX removal in the pH range of 2-4. Formation of negative charge-assisted H-bonds was responsible for the adsorption of hydrophilic SMX- on negatively charged MPAC6 in alkaline solution. Desorption and regeneration experiments showed SMX removal was still 92.3% in the 5th cycle. These findings give valuable insights into the interactions between SMX and MPACs and guide for choosing sustainable magnetic adsorbents for environmental applications.

Addition of a carbon fiber brush improves anaerobic digestion compared to external voltage application.

Two methods were examined to improve methane production efficiency in anaerobic digestion (AD) based on adding a large amount of surface area using a single electrically conductive carbon brush, or by adding electrodes as done in microbial electrolysis cells (MECs) to form a hybrid AD-MEC. To examine the impact of surface area relative to electrodes, AD reactors were fitted with a single large brush without electrodes (FB), half a large brush with two electrodes with an applied voltage (0.8 V) and operated in closed circuit (HB-CC) or open circuit (HB-OC) mode, or only two electrodes with a closed circuit and no large brush (NB-CC) (equivalent to an MEC). The three configurations with a half or full brush all had improved performance as shown by 57-82% higher methane generation rate parameters in the Gompertz model compared to NB-CC. The retained biomass was much higher in the reactors with large brush, which likely contributed to the rapid consumption of volatile fatty acids (VFAs) and therefore improved AD performance. A different microbial community structure was formed in the large-size brushes compared to the electrodes. Methanothrix was predominant in the biofilm of large-size carbon brush, while Geobacter (anode) and Methanobacterium (cathode) were highly abundant in the electrode biofilms. These results demonstrate that adding a high surface area carbon fiber brush will be a more effective method of improving AD performance than using MEC electrodes with an applied voltage.

Impact of cathodic electron acceptor on microbial fuel cell internal resistance.

Ferricyanide is often used in microbial fuel cells (MFCs) to avoid oxygen intrusion that occurs with air cathodes. However, MFC internal resistances using ferricyanide can be larger than those with air cathodes even though ferricyanide results in higher power densities. Using a graphite fiber brush cathode and a ferricyanide catholyte (FC-B) the internal resistance was 62 ± 4 mΩ m2, with 84 ± 8 mΩ m2 obtained using ferricyanide and a flat carbon paper cathode (FC-F) and only 51 ± 1 mΩ m2 using a 70% porosity air cathode (A-70). The FC-B MFCs produced the highest maximum power density of all configurations examined: 2.46 ± 0.26 W/m2, compared to 1.33 ± 0.14 W/m2 for the A-70 MFCs. The electrode potential slope (EPS) analysis method showed that electrode resistances were similar for ferricyanide and air-cathode MFCs, and that higher power was due to the larger experimental working potential (500 ± 12 mV) of ferricyanide compared to the air cathode (233 ± 5 mV).

Impact of external resistance acclimation on charge transfer and diffusion resistance in bench-scale microbial fuel cells.

Reducing the external resistance (Rext) for microbial fuel cell (MFC) acclimation can substantially alter the anode performance in terms of charge transfer (RCT), diffusion (Rd) and total anode resistance (RAn). Electrochemical impedance spectroscopy (EIS) was used to quantify anode impedance at different set potentials. Reducing Rext from 50 Ω to 20 Ω during acclimation reduced RCT by 31% (from 6.12 ± 0.09 mΩ m2 to 4.21 ± 0.03 mΩ m2) and Rd by 18% (from 3.4 ± 0.2 mΩ m2 to 2.8 ± 0.1 mΩ m2) at a set anode potential of -115 mV during EIS. Overall RAn decreased by 27%, to 5.13 ± 0.02 mΩ m2 for acclimation at 20 Ω, enabling the anode to achieve 38% higher current densities of 29 ± 1 A m-2. The results show a clear dependence of acclimation procedures and external resistance on kinetic and diffusion components of anode impedance that can impact overall bioelectrochemical performance.