Using a non-precious metal catalyst for long-term enhancement of methane production in a zero-gap microbial electrosynthesis cell

Microbial electrosynthesis (MES) cells exploit the ability of microbes to convert CO₂ into valuable chemical products such as methane and acetate, but high rates of chemical production may need to be mediated by hydrogen and thus require a catalyst for the hydrogen evolution reaction (HER). To avoid the usage of precious metal catalysts and examine the impact of the catalyst on the rate of methane generation by microbes on the electrode, we used a carbon felt cathode coated with NiMo/C and compared performance to a bare carbon felt or a Pt/C-deposited cathode. A zero-gap configuration containing a cation exchange membrane was developed to produce a low internal resistance, limit pH changes, and enhance direct transport of H₂ to microorganisms on the biocathode. At a fixed cathode potential of –1 V vs Ag/AgCl, the NiMo/C biocathode enabled a current density of 23 ± 4 A/m² and a high methane production rate of 4.7 ± 1.0 L/L-d. This performance was comparable to that using a precious metal catalyst (Pt/C, 23 ± 6 A/m², 5.4 ± 2.8 L/L-d), and 3–5 times higher than plain carbon cathodes (8 ± 3 A/m², 1.0 ± 0.4 L/L-d). The NiMo/C biocathode was operated for over 120 days without observable decay or severe cathode catalyst leaching, reaching an average columbic efficiency of 53 ± 9 % based on methane production under steady state conditions. Analysis of microbial community on the biocathode revealed the dominance of the hydrogenotrophic genus Methanobacterium (∼40 %), with no significant difference found for biocathodes with different materials. These results demonstrated that HER catalysts improved rates of methane generation through facilitating hydrogen gas evolution to an attached biofilm, and that the long-term enhancement of methane production in MES was feasible using a non-precious metal catalyst and a zero-gap cell design.