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.

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.

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.

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.

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.

Adapting Aluminum-Doped Zinc Oxide for Electrically Conductive Membranes Fabricated by Atomic Layer Deposition.

The use of electrically conductive membranes has recently drawn great interest in water treatment as an approach to reduce biofouling. Most conductive membranes are made by binding nanoparticles (carbon nanotubes or graphene) to a polymeric membrane using additional polymers, but this method risks leaching these nanomaterials into the environment. A new approach was developed here based on producing an electrically conductive layer of aluminum-doped zinc oxide (AZO) by atomic layer deposition. The aqueous instability of AZO, which is a critical challenge for water applications, was solved by capping the AZO layer with an ultrathin (∼11 nm) TiO2 layer (AZO/TiO2). The combined film exhibited prolonged stability in water and had a low sheet resistance of 67 Ω/sq with a 120 nm-thick coating, while the noncapped AZO coating quickly deteriorated as shown by a large increase in membrane resistance. The AZO/TiO2 membranes had enhanced resistance to biofouling, with a 72% reduction in bacterial counts in the absence of an applied current due to its higher hydrophilicity than the bare polymeric membrane, and it achieved an additional 50% reduction in bacterial colonization with an applied voltage. The use of TiO2-capped AZO layers provides a new approach for producing conductive membranes using abundant materials, and it avoids the risk of releasing nanoparticles into the environment.

Balancing Water Dissociation and Current Densities To Enable Sustainable Hydrogen Production with Bipolar Membranes in Microbial Electrolysis Cells.

Hydrogen production using two-chamber microbial electrolysis cells (MECs) is usually adversely impacted by a rapid rise in catholyte pH because of proton consumption for the hydrogen evolution reaction. While using a bipolar membrane (BPM) will maintain a more constant electrolyte pH, the large voltage loss across this membrane reduces performance. To overcome these limitations, we used an acidic catholyte to compensate for the potential loss incurred by using a BPM. A hydrogen production rate of 1.2 ± 0.7 L-H2/L/d (jmax = 10 ± 0.4 A/m2) was obtained using a Pt cathode and BPM with a pH difference (ΔpH = 6.1) between the two chambers. This production rate was 2.8 times greater than that of a conventional MEC with an anion exchange membrane (AEM, 0.43 ± 0.1 L-H2/L/d, jmax = 6.5 ± 0.3 A/m2). The catholyte pH gradually increased to 11 ± 0.3 over 9 days using the BPM and Pt/C, which decreased current production (jmax = 2.5 ± 0.3 A/m2). However, this performance was much better than that obtained using an AEM as the catholyte pH increased to 10 ± 0.4 after just one day. The use of an activated carbon cathode with the BPM enabled stable performance over a longer period of 12 days, although it reduced the hydrogen production rate (0.45 ± 0.1 L-H2/L/d).

Impact of cleaning procedures on restoring cathode performance for microbial fuel cells treating domestic wastewater.

Degradation of cathode performance over time is one of the major drawbacks in applications of microbial fuel cells (MFCs) for wastewater treatment. Over a two month period the resistance of air cathodes (RCt) with a polyvinylidene fluoride (PVDF) diffusion layer increased of 111% from 70 ±â€¯10 mΩ m2 to 148 ±â€¯32 mΩ m2. Soaking the cathodes in hydrochloric acid (100 mM HCl) restored cathode performance to RCt = 74 ±â€¯17 mΩ m2. Steam, ethanol, or sodium hydroxide treatment produced only a small change in performance, and slightly increased RCt. With a polytetrafluoroethylene (PTFE) diffusion layer on the cathodes, RCt increased from 54 ±â€¯14 mΩ m2 to 342 ±â€¯142 mΩ m2 after two months of operation. The acid concentration was critical for effectiveness in cleaning, as HCl (100 mM) decreased RCt to 28 ±â€¯8 mΩ m2. A lower concentration of HCl (<1 mM) showed no improvement, and vinegar (5% acetic acid) produced 48 ±â€¯4 mΩ m2.

Applying the electrode potential slope method as a tool to quantitatively evaluate the performance of individual microbial electrolysis cell components.

Improving the design of microbial electrolysis cells (MECs) requires better identification of the specific factors that limit performance. The contributions of the electrodes, solution, and membrane to internal resistance were quantified here using the newly-developed electrode potential slope (EPS) method. The largest portion of total internal resistance (120 ±â€¯0 mΩ m2) was associated with the carbon felt anode (71 ±â€¯5 mΩ m2, 59% of total), likely due to substrate and ion mass transfer limitations arising from stagnant fluid conditions and placement of the electrode against the anion exchange membrane. The anode resistance was followed by the solution (25 mΩ m2) and cathode (18 ±â€¯2 mΩ m2) resistances, and a negligible membrane resistance. Wide adoption and application of the EPS method will enable direct comparison between the performance of the components of MECs with different solution characteristics, electrode size and spacing, reactor architecture, and operating conditions.

Electroactive microorganisms in bioelectrochemical systems.

A vast array of microorganisms from all three domains of life can produce electrical current and transfer electrons to the anodes of different types of bioelectrochemical systems. These exoelectrogens are typically iron-reducing bacteria, such as Geobacter sulfurreducens, that produce high power densities at moderate temperatures. With the right media and growth conditions, many other microorganisms ranging from common yeasts to extremophiles such as hyperthermophilic archaea can also generate high current densities. Electrotrophic microorganisms that grow by using electrons derived from the cathode are less diverse and have no common or prototypical traits, and current densities are usually well below those reported for model exoelectrogens. However, electrotrophic microorganisms can use diverse terminal electron acceptors for cell respiration, including carbon dioxide, enabling a variety of novel cathode-driven reactions. The impressive diversity of electroactive microorganisms and the conditions in which they function provide new opportunities for electrochemical devices, such as microbial fuel cells that generate electricity or microbial electrolysis cells that produce hydrogen or methane.

Evaluation of Electrode and Solution Area-Based Resistances Enables Quantitative Comparisons of Factors Impacting Microbial Fuel Cell Performance.

Direct comparisons of microbial fuel cells based on maximum power densities are hindered by different reactor and electrode sizes, solution conductivities, and materials. We propose an alternative method here, the electrode potential slope (EPS) analysis, to enable quantitative comparisons based on anode and cathode area-based resistances and operating potentials. Using EPS analysis, the brush anode resistance ( RAn = 10.6 ± 0.5 mΩ m2) was shown to be 28% lower than the resistance of a 70% porosity diffusion layer (70% DL) cathode ( RCat = 14.8 ± 0.9 mΩ m2) and 24% lower than the solution resistance ( RΩ = 14 mΩ m2) (acetate in a 50 mM phosphate buffer solution). Using a less porous cathode (30% DL) did not impact the cathode resistance but did reduce the cathode performance due to a lower operating potential. With low-conductivity domestic wastewater ( RΩ = 87 mΩ m2), both electrodes had higher resistances [ RAn = 75 ± 9 mΩ m2, and RCat = 54 ± 7 mΩ m2 (70% DL)]. Our analysis of the literature using EPS analysis shows how electrode resistances can easily be quantified to compare system performance when the electrode distances are changed or the sizes of the electrodes are different.

Evaluating a multi-panel air cathode through electrochemical and biotic tests.

To scale up microbial fuel cells (MFCs), larger cathodes need to be developed that can use air directly, rather than dissolved oxygen, and have good electrochemical performance. A new type of cathode design was examined here that uses a "window-pane" approach with fifteen smaller cathodes welded to a single conductive metal sheet to maintain good electrical conductivity across the cathode with an increase in total area. Abiotic electrochemical tests were conducted to evaluate the impact of the cathode size (exposed areas of 7 cm2, 33 cm2, and 6200 cm2) on performance for all cathodes having the same active catalyst material. Increasing the size of the exposed area of the electrodes to the electrolyte from 7 cm2 to 33 cm2 (a single cathode panel) decreased the cathode potential by 5%, and a further increase in size to 6200 cm2 using the multi-panel cathode reduced the electrode potential by 55% (at 0.6 A m-2), in a 50 mM phosphate buffer solution (PBS). In 85 L MFC tests with the largest cathode using wastewater as a fuel, the maximum power density based on polarization data was 0.083 ±â€¯0.006 W m-2 using 22 brush anodes to fully cover the cathode, and 0.061 ±â€¯0.003 W m-2 with 8 brush anodes (40% of cathode projected area) compared to 0.304 ±â€¯0.009 W m-2 obtained in the 28 mL MFC. Recovering power from large MFCs will therefore be challenging, but several approaches identified in this study can be pursued to maintain performance when increasing the size of the electrodes.

Impact of Ohmic Resistance on Measured Electrode Potentials and Maximum Power Production in Microbial Fuel Cells.

Low solution conductivity is known to adversely impact power generation in microbial fuel cells (MFCs), but its impact on measured electrode potentials has often been neglected in the reporting of electrode potentials. While errors in the working electrode (typically the anode) are usually small, larger errors can result in reported counter electrode potentials (typically the cathode) due to large distances between the reference and working electrodes or the use of whole cell voltages to calculate counter electrode potentials. As shown here, inaccurate electrode potentials impact conclusions concerning factors limiting power production in MFCs at higher current densities. To demonstrate how the electrochemical measurements should be adjusted using the solution conductivity, electrode potentials were estimated in MFCs with brush anodes placed close to the cathode (1 cm) or with flat felt anodes placed further from the cathode (3 cm) to avoid oxygen crossover to the anodes. The errors in the cathode potential for MFCs with brush anodes reached 94 mV using acetate in a 50 mM phosphate buffer solution. With a felt anode and acetate, cathode potential errors increased to 394 mV. While brush anode MFCs produced much higher power densities than flat anode MFCs under these conditions, this better performance was shown primarily to result from electrode spacing following correction of electrode potentials. Brush anode potentials corrected for solution conductivity were the same for brushes set 1 or 3 cm from the cathode, although the range of current produced was different due to ohmic losses with the larger distance. These results demonstrate the critical importance of using corrected electrode potentials to understand factors limiting power production in MFCs.

In situ biofilm removal from air cathodes in microbial fuel cells treating domestic wastewater.

One challenge in using microbial fuel cells (MFCs) for wastewater treatment is the reduction in performance over time due to cathode fouling. An in-situ technique was developed to clean air cathodes using magnets on either side of the electrode, with the air-side magnet moved to clean the water-side magnet by scraping off the biofilm. The power output of the magnet-cleaned cathodes after one month of operation was 132 ±â€¯7 mW m-2, which was 42% higher than the controls with no magnet (93 ±â€¯4 mW m-2) (no separator, NS), and 110% higher (116 ±â€¯4 mW m-2) than controls with separators (Sp, 55 ±â€¯7 mW m-2). Cleaning cathodes using magnets reduced the biofilm by 75% (NS) and 28% (Sp). The in-situ cleaning technique thus improved the performance of the MFC over time by reducing biofouling due to biofilm formation on the air cathodes.

Mitigating external and internal cathode fouling using a polymer bonded separator in microbial fuel cells.

Microbial fuel cell (MFC) cathodes rapidly foul when treating domestic wastewater, substantially reducing power production over time. Here a wipe separator was chemically bonded to an activated carbon air cathode using polyvinylidene fluoride (PVDF) to mitigate cathode fouling and extend cathode performance over time. MFCs with separator-bonded cathodes produced a maximum power density of 190 ±â€¯30 mW m-2 after 2 months of operation using domestic wastewater, which was ∼220% higher than controls (60 ±â€¯50 mW m-2) with separators that were not chemically bonded to the cathode. Less biomass (protein) was measured on the bonded separator surface than the non-bonded separator, indicating chemical bonding reduced external bio-fouling. Salt precipitation that contributed to internal fouling was also reduced using separator-bonded cathodes. Overall, the separator-bonded cathodes showed better performance over time by mitigating both external bio-fouling and internal salt fouling.