Enhancing CO2-reduction methanogenesis in microbial electrosynthesis: Role of oxygen-containing groups on carbon-based cathodes.

Microbial electrosynthesis is a promising technology that recovers energy from wastewater while converting CO2 into CH4. Constructing a biocathode with both strong H2-mediated and direct electron transfer capacities is crucial for efficient startup and long-term stable CH4 production. This study found that introducing carboxyl groups onto the cathode effectively enhanced both electron transfer pathways, improving the reduction rate and coulombic efficiency of CH4 production and increasing the CH4 yield by 2-3 times. Carboxyl groups decreased the overpotential for H2 evolution and increased current density, thereby enhancing H2-mediated electron transfer. Additionally, carboxyl groups increased the relative abundance of Methanosaeta by 3%-10%, doubled the protein content in extracellular polymeric substances, and boosted the expression of cytochrome c-related genes, thereby enhancing direct electron transfer capacity. These findings present a novel and efficient approach for constructing a stable, high-performance biocathode, contributing to energy recovery and CO2 fixation.