Hydrogen production rates with closely-spaced felt anodes and cathodes compared to brush anodes in two-chamber microbial electrolysis cells

Flat anodes placed close to the cathode or membrane to reduce distances between electrodes in microbial electrolysis cells (MECs) could be used to develop compact reactors, in contrast to microbial fuel cells (MFCs) where electrodes cannot be too close due to oxygen crossover from the cathode to the anode that reduces performance. Graphite fiber brush anodes are often used in MECs due to their proven performance in MFCs. However, brush anodes have not been directly compared to flat anodes in MECs, which are completely anaerobic, and therefore oxygen crossover is not a factor for felt or brush anodes. MEC performance was compared using flat felt or brush anodes in two-chamber, cubic type MECs operated in fed-batch mode, using acetate in a 50 mM phosphate buffer. Despite placement of felt anodes next to the membrane, MECs with felt anodes had a lower hydrogen gas production rate of 0.32 ± 0.02 m³-H₂/m³-d than brush anodes (0.38 ± 0.02 m³-H₂/m³-d). The main reason for the reduced performance was substrate-limited mass transfer to the felt anodes. To reduce mass transfer limitations, the felt anode electrolyte was stirred, which increased the hydrogen gas production rate to 0.41 ± 0.04 m³-H₂/m³-d. These results demonstrate brush electrodes can improve performance of bioelectrochemical reactors even under fully anaerobic conditions.     

Influence of catholyte pH and temperature on hydrogen production from acetate using a two chamber concentric tubular microbial electrolysis cell

Microbial electrolysis cells (MECs) could be integrated with dark fermentative hydrogen production to increase the overall system yield of hydrogen. The influence of catholyte pH on hydrogen production from MECs and associated parameters such as electrode potentials (vs Ag/AgCl), COD reduction, current density and quantity of acid needed to control pH in the cathode of an MEC were investigated. Acetate (10 mM, HRT 9 h, 24 °C, pH 7) was used as the substrate in a two chamber MEC operated at 600 mV and 850 mV applied voltage. The effect of catholyte pH on current density was more significant at an applied voltage of 600 mV than at 850 mV. The highest hydrogen production rate was obtained at 850 mV, pH 5 amounting to 200 cm³_stp/l_anode/day (coulombic efficiency 60%, cathodic hydrogen recovery 45%, H₂ yield 1.1 mol/mol acetate converted and a COD reduction of 30.5%). Within the range (18.5–49.4 °C) of temperatures tested, 30 °C was found to be optimal for hydrogen production in the system tested, with the performance of the reactor being reduced at higher temperatures. These results show that an optimum temperature (approximately 30 °C) exists for MEC and that lower pH in the cathode chamber improves hydrogen production and may be needed if potentials applied to MECs are to be minimised.     

Electrochemical evaluation of molybdenum disulfide as a catalyst for hydrogen evolution in microbial electrolysis cells

There is great interest in hydrogen evolution in bioelectrochemical systems, such as microbial electrolysis cells (MECs), but these systems require non-optimal near-neutral pH conditions and the use of low-cost, non-precious metal catalysts. Here we show that molybdenum disulfide (MoS₂) composite cathodes have electrochemical performance superior to stainless steel (SS) (currently the most promising low-cost, non-precious metal MEC catalyst) or Pt-based cathodes in phosphate or perchlorate electrolytes, yet they cost ∼4.5 times less than Pt-based composite cathodes. At current densities typical of many MECs (2-5 A/m²), the optimal surface density with MoS₂ particles on carbon cloth was 25 g/m², achieving 31 mV less hydrogen evolution overpotential than similarly constructed Pt cathodes in galvanostatic tests with a phosphate buffer. At higher current densities (8-10 A/m²) the MoS₂ catalyst had 82 mV less hydrogen evolution overpotential than the Pt-based catalyst. MoS₂ composite cathodes performed similarly to Pt cathodes in terms of current densities, hydrogen production rates and COD removal over several batch cycles in MEC reactors. These results show that MoS₂ can be used to substantially reduce the cost of cathodes used in MECs for hydrogen gas production.     

Multi-electrode continuous flow microbial electrolysis cell for biogas production from acetate

Most microbial electrolysis cells (MECs) contain only a single set of electrodes. In order to examine the scalability of a multiple-electrode design, we constructed a 2.5 L MEC containing 8 separate electrode pairs made of graphite fiber brush anodes pre-acclimated for current generation using acetate, and 304 stainless steel mesh cathodes (64 m²/m³). Under continuous flow conditions and a one day hydraulic retention time, the maximum current was 181 mA (1.18 A/m², cathode surface area; 74 A/m³) within three days of operation. The maximum hydrogen production (day 3) was 0.53 L/L-d, reaching an energy efficiency relative to electrical energy input of η_E = 144%. Current production remained relatively steady (days 3–18), but the gas composition dramatically shifted over time. By day 16, there was little H₂ gas recovered and methane production increased from 0.049 L/L-d (day 3) to 0.118 L/L-d. When considering the energy value of both hydrogen and methane, efficiency relative to electrical input remained above 100% until near the end of the experiment (day 17) when only methane gas was being produced. Our results show that MECs can be scaled up primarily based on cathode surface area, but that hydrogen can be completely consumed in a continuous flow system unless methanogens can be completely eliminated from the system.     

Estimating microbial electrolysis cell (MEC) investment costs in wastewater treatment plants: Case study

Microbial electrolysis represents a new approach for harnessing the energy contained in the organic matter of wastewater. However, before this approach can be implemented on a practical basis, a cost-effective manufacturing process for microbial electrolysis cells (MECs) must be developed. The objective of this study is to estimate an acceptable purchase cost of an MEC reactor for a domestic wastewater treatment plant. We estimate that for a full-scale MEC operating at a current density of 5 A m_a⁻² (amperes per square meter of anode) and an energy consumption of 0.9 kWh kg-COD⁻¹ (kilowatt-hour per kg of removed chemical oxygen demand (COD)), a cost of €1220 m_a⁻³ (euro per m³ of anodic chamber) can be established as a target purchase cost at which a break-even point is reached after 7 years.     

The use and optimization of stainless steel mesh cathodes in microbial electrolysis cells

Microbial electrolysis cells (MECs) provide a high-yield method for producing hydrogen from renewable biomass. One challenge for commercialization of the technology is a low-cost and highly efficient cathode. Stainless steel (SS) is very inexpensive, and cathodes made of this material with high specific surface areas can achieve performance similar to carbon cathodes containing a platinum catalyst in MECs. SS mesh cathodes were examined here as a method to provide a higher surface area material than flat plate electrodes. Cyclic voltammetry tests showed that the electrochemically active surface area of certain sized mesh could be three times larger than a flat sheet. The relative performance of SS mesh in linear sweep voltammetry at low bubble coverages (low current densities) was also consistent with performance on this basis in MEC tests. The best SS mesh size (#60) in MEC tests had a relatively thick wire size (0.02 cm), a medium pore size (0.02 cm), and a specific surface area of 66 m²/m³. An applied voltage of 0.9 V produced a high hydrogen recovery (98 ± 4%) and overall energy efficiency (74 ± 4%), with a hydrogen production rate of 2.1 ± 0.3 m³H₂/m³d (current density of 8.08 A/m², volumetric current density of 188 ± 19 A/m³). These studies show that SS in mesh format shows great promise for the development of lower cost MEC systems for hydrogen production.     

Hydrogen gas production with Ni,Ni–Co and Ni–Co–P electrodeposits as potential cathode catalyst by microbial electrolysis cells

The development of efficient and economical cathode, operating at ambient temperature and neutral pH is a crucial challenge for microbial electrolysis cell (MEC) to become commercialize hydrogen production technology. In the present work, eight different electrodes are prepared by the electroplating of Ni, Ni–Co and Ni–Co–P on two base metals i.e., Stainless Steel 316 and Copper separately to use as cathode in MEC. Electrodeposited cathode materials have been characterized by XRD, XPS, FESEM, EDX and linear voltammetry. The fabricated cathodes show higher corrosion stability with improved electro-catalytic performance for the hydrogen production in the MECs as compared to the bare cathodes (SS316 and Cu). Data obtained from linear voltammetry and MEC experiments show that developed cathode possess four times higher intrinsic catalytic activity in comparison to bare cathode. Electrodeposited cathodes are intensively examined in membrane-less MEC, operating under applied voltage of 0.6 V in batch mode at 30 ± 2 °C temperature, in neutral pH with acetate as substrate and activated sludge as inoculum. Ni–Co–P electrodeposit on Stainless Steel 316 cathode gives maximum hydrogen production rate of 4.2 ± 0.5 m³(H₂)m⁻³d⁻¹, columbic efficiencies 96.9 ± 2%, overall hydrogen recovery 90.3 ± 4%, overall energy efficiency 241.2 ± 5%, volumetric current density 310 ± 5 Am⁻³. The net energy recovery and COD removal are 4.25 kJ/gCOD and 61%, respectively. Prepared cathodes show stable performance for continuous 5 batch cycle operations in MEC.     

Optimization of catholyte concentration and anolyte pHs in two chamber microbial electrolysis cells

The hydrogen production rate in a microbial electrolysis cell (MEC) using a non-buffered saline catholyte (NaCl) can be optimized through proper control of the initial anolyte pH and catholyte NaCl concentration. The highest hydrogen yield of 3.3 ± 0.4 mol H₂/mole acetate and gas production rate of 2.2 ± 0.2 m³ H₂/m³/d were achieved here with an initial anolyte pH = 9 and catholyte NaCl concentration of 98 mM. Further increases in the salt concentration substantially reduced the anolyte pH to as low as 4.6, resulting in reduced MEC performance due to pH inhibition of exoelectrogens. Cathodic hydrogen recovery was high (r_cat > 90%) as hydrogen consumption by hydrogenotrophic methanogens was prevented by separating the anode and cathode chambers using a membrane. These results show that the MEC can be optimized for hydrogen production through proper choices in the concentration of a non-buffered saline catholyte and initial anolyte pH in two chamber MECs.     

Assessment of biotic and abiotic graphite cathodes for hydrogen production in microbial electrolysis cells

Hydrogen represents a promising clean fuel for future applications. The biocathode of a two-chambered microbial electrolysis cell (biotic MEC) was studied and compared with an abiotic cathode (abiotic MEC) in order to assess the influence of naturally selected microorganisms for hydrogen production in a wide range of cathode potentials (from −400 to −1800 mV vs SHE). Hydrogen production in both MECs increased when cathode potential was decreased. Microorganisms present in the biotic MEC were identified as Hoeflea sp. and Aquiflexum sp. Supplied energy was utilized more efficiently in the biotic MEC than in the abiotic, obtaining higher hydrogen production respect to energy consumption. At −1000 mV biotic MEC produced 0.89 ± 0.10 m³ H₂ d⁻¹ m⁻³NCC (Net Cathodic Compartment) at a minimum operational cost of 3.2 USD kg⁻¹ H₂. This cost is lower than the estimated market value for hydrogen (6 USD kg⁻¹ H₂).     

Methanogenesis control by electrolytic oxygen production in microbial electrolysis cells

High purity H₂ production using microbial electrolysis cells (MECs) is often limited by methanogenesis. Here methanogenesis was effectively controlled by electrolytic oxygen production. Oxygen production was induced intermittently using two stainless steel electrodes, which were used as the MEC cathode during Normal operation. It was found that oxygen should be produced every 12 h or more frequently because of rapid hydrogenotrophic methanogen growth with available pure H₂. This method was also effective in an initially methanogen-dominated MEC. However, the growth of aerobic biofilms in MECs weakened methanogen control. Residual oxygen after fed-batch cycles was found to be the key indicator for effective methane control. Methane content was consistently smaller than 10% at the threshold residual oxygen volume (3 mL) or greater. MEC operation at such threshold conditions will allow high purity H₂ production, low energy consumption for O₂ production and minimal O₂ exposure on bioanodes, enabling sustainable wastewater treatment and energy recovery using MECs.     

Source of methane and methods to control its formation in single chamber microbial electrolysis cells

Methane production occurs during hydrogen gas generation in microbial electrolysis cells (MECs), particularly when single chamber systems are used which do not keep gases, generated at the cathode, separate from the anode. Few studies have examined the factors contributing to methane gas generation or the main pathway in MECs. It is shown here that methane generation is primarily associated with current generation and hydrogenotrophic methanogenesis and not substrate (acetate). Little methane gas was generated in the initial reaction time (<12 h) in a fed batch MEC when acetate concentrations were high. Most methane was produced at the end of a batch cycle when hydrogen and carbon dioxide gases were present at the greatest concentrations. Increasing the cycle time from 24 to 72 h resulted in complete consumption of hydrogen gas in the headspace (applied voltage of 0.7 V) with methane production. High applied voltages reduced methane production. Little methane (<4%) accumulated in the gas phase at an applied voltage of 0.6–0.9 V over a typical 24 h cycle. However, when the applied voltage was decreased to 0.4 V, there was a greater production of methane than hydrogen gas due to low current densities and long cycle times. The lack of significant hydrogen production from acetate was also supported by Coulombic efficiencies that were all around 90%, indicating electron flow was not altered by changes in methane production. These results demonstrate that methane production in single chamber MECs is primarily associated with current generation and hydrogen gas production, and not acetoclastic methanogenesis. Methane generation will therefore be difficult to control in mixed culture MECs that produce high concentrations of hydrogen gas. By keeping cycle times short, and using higher applied voltages (≥0.6 V), it is possible to reduce methane gas concentrations (<4%) but not eliminate methanogenesis in MECs.     

Simultaneous biohydrogen production with distillery wastewater treatment using modified microbial electrolysis cell

The objective of the present study was to construct a compact retrofit design of Microbial Electrolysis Cell (MEC) within an anaerobic digester. In this design, the cathode chamber is inserted in the anodic chamber for compactness, improved hydrogen production and wastewater treatment efficiency. The performance of the new design is compared with that of a conventional (dual chamber) MEC. A cumulative hydrogen of 40.05 ± 0.5 mL and 30.12 ± 0.5 mL were produced at the current density of 811.7 ± 20 and 908.3 ± 25 mA/m² respectively for conventional and modified MEC system. The cathodic hydrogen recovery (CHR) defined as the recovery of electrons as hydrogen which was observed a maximum of 46.5 ± 0.8 and 38.8 ± 0.5% in conventional and modified MEC. The Coulombic efficiency (CE) defined as the recovery of total electrons in acetate as current was observed as 17.25 ± 0.15 and 16.82 ± 0.1% for conventional and modified MEC. In addition, the wastewater COD removal efficiency was observed to be 77.5 ± 1.0% and 75.6 ± 1.5 in 70 h for conventional and modified MEC designs. As shown in the work below, the modified compact design worked effectively to produce hydrogen under different COD concentrations; anolyte and catholyte concentrations; and applied potentials. Thus the modified compact MEC which is also a retrofit to an existing anaerobic digester can extend the use of anaerobic digesters and improve their economics in waste water treatment.     

Reduced internal resistance of microbial electrolysis cell (MEC) as factors of configuration and stuffing with granular activated carbon

With limited external applied voltage, the microbial electrolysis cell (MEC) could produce hydrogen by exoelectrogenic microorganisms. The present study revealed that a cubiod-shaped chamber effectively reduces the distance between electrodes and thereby reduces the internal resistance of the entire cell. With 0.6 V of applied voltage, the cuboid MEC had a columbic efficiency of 33.7%, much higher than that achieved in the H-shaped MEC test (ca. 15%) of comparable size. Filling the anode chamber with granular activated carbon further enhanced the columbic efficiency to 45%. The corresponding hydrogen conversion rate could reach 35%.     

Ni foam cathode enables high volumetric H2 production in a microbial electrolysis cell

Valuable, “green” H₂ can be produced with a microbial electrolysis cell (MEC). To achieve a high volumetric production rate of high purity H₂, a continuous flow MEC with an anion exchange membrane, a flow through bioanode and a flow through Ni foam cathode was constructed. At an electrical energy input of 2.6 kWh m⁻³ H₂ (applied cell voltage: 1.00 V), this MEC was able to produce over 50 m³ H₂ m⁻³ MEC d⁻¹ (22.8 ± 0.1 A m⁻²). The MEC had a low cathode overpotential compared to an MEC with Pt-based cathode, because of the high specific surface area of Ni foam (128 m² m⁻² projected area). The MEC performance however, decreased during 32 days of operation due to an increase in anode and cathode overpotentials. Scaling likely caused the increase in anode overpotential, but it remained unclear what caused the increase in cathode overpotential.     

Sugar industry waste-derived anode for enhanced biohydrogen production from rice mill wastewater using artificial photo-assisted microbial electrolysis cell

Microbial Electrolysis Cell (MEC) is a promising green technology for energy production from wastewater. This study attempts to investigate the biohydrogen production from rice mill wastewater using artificial photo-assisted microbial electrolysis cell (APAMEC) with an inexpensive anode prepared from carbonaceous material disposed by sugar industry. The X-ray diffraction (XRD) and scanning electron microscopic (SEM) analyses confirmed the presence of carbon on the electrode surface. Cyclic Voltammogram analysis indicated that the carbonaceous anode has higher reduction peak at 0.7 V compared to control (plain carbon cloth) electrode. The experimental results showed a maximum hydrogen production of 220 mL on 5th day of fermentation and the production rate observed was 3.6 ± 0.4 mL/l/h. The effect of pH and acid concentration used in the acid hydrolysis of rice mill wastewater and the effect of artificial light on biohydrogen production were investigated. The optimum pH and acid concentration of 6 and 1.5%, respectively, gave better biohydrogen production and COD removal. The results demonstrated that the development of inexpensive anode from the waste disposed by sugar industry would pave the path to scale-up MECs.     

Key factors affecting microbial anode potential in a microbial electrolysis cell for H2 production

In order to optimize operations of microbial electrolysis cell (MEC) for hydrogen production, microbial anode potential (MAP) was analyzed as a function of factors in biofilm anode system, including pH, substrate and applied voltage. The results in “H” shape reactor showed that MAP reflected the information when any factor became limiting for hydrogen production. Commonly, hydrogen generation started around anode potential of −250 mV to −300 mV. While, higher current density and higher hydrogen rate were obtained when MAP went down to −400 mV or even lower in this study. Biofilm anode could work normally between pH 6.5 and 7.0, while the lowest anode potential appeared around 6.8–7.0. However, when pH was lower 6.0 or substrate concentration was less than 50 mg L⁻¹ in anode chamber, MAP went up to −300 mV or above, leading to hydrogen reduction. Applied voltage did not affect MAP much during the process of hydrogen production. Anode potential analysis also showed that planktonic bacteria in suspended solution presented positive effects on biofilm anode system and they contributed to enhance electron transfer by reducing internal resistance and lowering minimum voltage needed for hydrogen production to some extent.     

Highly durable,Pt free and large-area Ni–B film synthesized by SILAR as a bifunctional electrode for electrochemical water splitting

A search for efficient, durable, large-area, and economic catalyst material for low-cost production of hydrogen and oxygen is currently a high priority in the field of electrocatalysis (EC). In view of this, a cost-effective, earth abundant, highly stable, Pt free, and large-area (8 cm × 8 cm) bifunctional Ni–B electrocatalyst is reported via simple and economic SILAR method. A highly porous surface of Ni–B film with high surface wettability indicated better electrochemical water-splitting properties for the films and is obtained at 100 cycles. A Low over-potential value to obtain HER (49 mV) and OER (340 mV) at 10 mA/cm² current suggested that they are comparable to the well-known Pt and RuO electrodes in alkaline medium (1M KOH), respectively. In actual water-splitting setup having Ni–B film (as cathode) and stainless steel (as anode), the hydrogen production of 612 ml/h is obtained at constant potential, which was enhanced by 18% i.e., 726 ml/h when a Ni–B film as both cathode and anode electrode was used. Both the electrodes are highly stable for over 15 days and interestingly they showed 7% increment in the EC performance.     

Clean hydrogen production in a full biological microbial electrolysis cell

The recent interest in microbial electrolysis cell (MEC) technology has led the research platform to develop full biological MECs (bioanode-biocathode, FB-MEC). This study focused on biohydrogen production from a biologically catalyzed MEC. A bioanode and a biocathode were initially enriched in a half biological MFC (bioanode-abiocathode, HB-MFC) and a half biological MEC (abioanode-biocathode, HB-MEC), respectively. The FB-MEC was established by transferring the biocathode of the HB-MEC and the bioanode of the HB-MFC to a two-chamber MEC. The FB-MEC was operated under batch (FB-MEC-B) and recirculation batch (FB-MEC-RB) modes of operation in the anodic chamber. The FB-MEC-B reached a maximum current density of 1.5 A/m² and the FB-MEC-RB reached a maximum current density of 2.5 A/m² at a similar applied voltage while the abiotic control system showed the maximum of 0.2 A/m². Hydrogen production rate decreased in the FB-MEC compared to that of the HB-MEC. However, the cathodic hydrogen recovery increased from 42% obtained in the HB-MEC to 56% in the FB-MEC-B and 65% in the FB-MEC-RB, suggesting the efficient oxidation and reduction rates in the FB-MEC compared to the HB-MEC. The onset potential for hydrogen evolution reaction detected by linear sweep voltammetry analysis were −0.780 and −0.860 V vs Ag/AgCl for the FB-MEC-RB and the FB-MEC-B (−1.26 for the abiotic control MEC), respectively. Moreover, the results suggested that the FB-MEC worked more efficiently when the biocathode and the bioanode were enriched initially in half biological systems before transferring to the FB-MEC compared to that of the simultaneously enriched in one system.     

Novel nanostructured electrocatalysts for hydrogen evolution reaction in neutral and weak acidic solutions

Microbial electrolysis cells (MECs) provide an innovative bioelectrochemical approach for hydrogen production using microorganisms as biocatalysts. The development of cost-effective cathodes for near-neutral pH and ambient temperature conditions is the most critical challenge for the practical application of MEC technology. In this study, the electrocatalytic properties of electrodeposited onto carbon felt NiFe-, NiFeP- and NiFeCoP-nanostructures towards HER in neutral and weak acidic solutions were investigated. The voltage needed to initiate hydrogen production and the current production rates were estimated from obtained linear voltammograms. The developed composite materials possess much higher catalytic activity than bare carbon felt. The highest current production rate corresponding to 1.7 ± 0.1 m³H₂/day/m² was achieved with NiFeCoP/carbon felt electrodes. In addition, the applied modifications result in improvement of the corrosion resistance. The obtained results demonstrate that Ni-based nanomodified materials are promising electrocatalysts for HER in near-neutral electrolytes and could be applied as cathodes in MECs.     

Comparison of microbial electrolysis cells operated with added voltage or by setting the anode potential

Hydrogen production in a microbial electrolysis cell (MEC) can be achieved by either setting the anode potential with a potentiostat, or by adding voltage to the circuit with a power source. In batch tests the largest total gas production (46 ± 3 mL), lowest energy input (2.3 ± 0.3 kWh/m³ of H₂ generated), and best overall energy recovery (?_E+S = 58 ± 6%) was achieved at a set anode potential of E_An = −0.2 V (vs Ag/AgCl), compared to set potentials of −0.4 V, 0 V and 0.2 V, or an added voltage of E_ap = 0.6 V. Gas production was 1.4 times higher with E_An = −0.2 V than with E_ap = 0.6 V. Methane production was also reduced at set anode potentials of −0.2 V and higher than the other operating conditions. Continuous flow operation of the MECs at the optimum condition of E_An = −0.2 V initially maintained stable hydrogen gas production, with 68% H₂ and 21% CH₄, but after 39 days the gas composition shifted to 55% H₂ and 34% CH₄. Methane production was not primarily anode-associated, as methane was reduced to low levels by placing the anode into a new MEC housing. These results suggest that MEC performance can be optimized in terms of hydrogen production rates and gas composition by setting an anode potential of −0.2 V, but that methanogen proliferation must be better controlled on non-anodic surfaces.