| Abstract | This study investigates the impacts of bismuth and tin on the production of CH₄ and volatile fatty acids in a microbial electrosynthesis cell with a continuous CO₂ supply. First, the impact of several transition metal ions (Ni²⁺, Fe²⁺, Cu²⁺, Sn²⁺, Mn²⁺, MoO₄²⁻, and Bi³⁺) on hydrogenotrophic and acetoclastic methanogenic microbial activity was evaluated in a series of batch bottle tests incubated with anaerobic sludge and a pre-defined concentration of dissolved transition metals. While Cu is considered a promising catalyst for the electrocatalytic conversion of CO₂ to short chain fatty acids such as acetate, its presence as a Cu²⁺ ion was demonstrated to significantly inhibit the microbial production of CH₄ and acetate. At the same time, CH₄ production increased in the presence of Bi³⁺ (0.1 g L⁻¹) and remained unchanged at the same concentration of Sn²⁺. Since Sn is of interest due to its catalytic properties in the electrochemical CO₂ conversion, Bi and Sn were added to the cathode compartment of a laboratory-scale microbial electrosynthesis cell (MESC) to achieve an initial concentration of 0.1 g L⁻¹. While an initial increase in CH₄ (and acetate for Sn²⁺) production was observed after the first injection of the metal ions, after the second injection, CH₄ production declined. Acetate accumulation was indicative of the reduced activity of acetoclastic methanogens, likely due to the high partial pressure of H₂. The modification of a carbon-felt electrode by the electrodeposition of Sn metal on its surface prior to cathode inoculation with anaerobic sludge showed a doubling of CH₄ production in the MESC and a lower concentration of acetate, while the electrodeposition of Bi resulted in a decreased CH₄ production. |
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