A comprehensive comparison of five different carbon-based cathode materials in CO₂ electromethanogenesis: Long-term performance, cell-electrode contact behaviors and extracellular electron transfer pathways

Each carbon-based material, due to the discrepancy in critical properties, has distinct capability to enrich electroactive microbes able to electrosynthesize methane from CO₂. To optimize electromethanogenesis process, this study physically prepared and examined several carbon-based cathode materials: carbon stick (CS), CS twined by Ti wire (CS-Ti) or covered with carbon fiber (CS-CF), graphite felt (CS-GF) and carbon cloth (CS-CC). CS-GF electrode had constantly stable methane production (75.8 mL/L/d at −0.9 V vs. Ag/AgCl) while CS-CC showed a suppressed performance over time caused by the desposition of inorganic shell. Electrode material properties affected biofilms growth, cell-electrode contact behaviors and electron exchange. Methane formation with CS-CC biocathode was H₂-concnetration dependent; CS-GF cathode possessed high antifouling properties and extensive space, enriching the microorganisms capable of catalyzing electromethanogenesis through more efficient non-H₂ route. This study re-interpreted the application potentials of carbon-based materials in CO₂ electroreduction and electrofuel recovery, providing valuable guidance for materials’ selection.