Co-NC@Co-NP hierarchical nanoforest steering charge exchange efficiency at biotic-abiotic interface for microbial electrochemical carbon reduction.

Converting anthropogenic carbon dioxide (CO2) to value-added products using bio-electrochemical conversions represents a promising strategy for producing sustainable fuel. However, the reaction kinetics are hindered by insufficient attachment of microorganisms and limited charge extraction at the bioinorganic interface. A hierarchical nanoforest with doped cobalt‑nitrogen-doped carbon covering cobalt nanoparticle (Co-NC@Co-NP) was integrated with a CO2-to-CH4 conversion microbiome for methane production to address these shortcomings. In-situ nanoforests were developed on the nanosheet by chemical vapor deposition with Co nanoparticles catalyzed. The bio-nanowire-like carbon nanotubes enhanced the electrostatic force for microbe enrichment via the tip effect, providing a maximum of 3.6-fold electron-receiving microbes to utilize reducing equivalents. The Co-NC@Co-NP enhanced the direct electron transfer between microbes and electrodes, reducing the adoption of energy barriers for heme-like proteins. Thus, the optimized electron transfer pathway improved selectivity by a factor of 2.0 compared to the pristine nanosheet biohybrid. Furthermore, the adjusted microbial community structure provided sufficient methanogenesis genes to match the strong electron flow, achieving maximal methane production rates (311.1 mmol/m2/day at -0.9 V vs. Ag/AgCl), 8.62 times higher than those of the counterpart nanosheet biohybrid (36.06 mmol/m2/day). This work demonstrates a comprehensive assessment of biotic-abiotic energy transfer, which may serve as a guiding principle for designing efficient bio-electrochemical systems.