Biocompatible Cu/NiMo Composite Electrocatalyst for Hydrogen Evolution Reaction in Microbial Electrosynthesis; Unveiling the Self‐Detoxification Effect of Cu

Abstract H₂‐driven microbial electrosynthesis (MES) is an emerging bioelectrochemical technology that enables the production of complex compounds from CO₂. Although the performance of microbial fermentation in the MES system is closely related to the H₂ production rate, high‐performing metallic H₂‐evolving catalysts (HEC) generate cytotoxic H₂O₂ and metal cations from undesirable side reactions, severely damaging microorganisms. Herein, a novel design for self‐detoxifying metallic HEC, resulting in biologically benign H₂ production, is reported. Cu/NiMo composite HEC suppresses H₂O₂ evolution by altering the O₂ reduction kinetics to a four‐electron pathway and subsequently decomposes the inevitably generated H₂O₂ in sequential catalytic and electrochemical pathways. Furthermore, in situ generated Cu‐rich layer at the surface prevents NiMo from corroding and releasing cytotoxic Ni cations. Consequently, the Cu/NiMo composite HEC in the MES system registers a 50% increase in the performance of lithoautotrophic bacterium Cupriavidus necator H16, for the conversion of CO₂ to a biopolymer, poly(3‐hydroxybutyrate). This work successfully demonstrates the concept of self‐detoxification in designing biocompatible materials for bioelectrochemical applications as well as MES systems.