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Although the performance of microbial fermentation in the MES system is closely related to the H<jats:sub>2<\/jats:sub> production rate, high\u2010performing metallic H<jats:sub>2<\/jats:sub>\u2010evolving catalysts (HEC) generate cytotoxic H<jats:sub>2<\/jats:sub>O<jats:sub>2<\/jats:sub> and metal cations from undesirable side reactions, severely damaging microorganisms. Herein, a novel design for self\u2010detoxifying metallic HEC, resulting in biologically benign H<jats:sub>2<\/jats:sub> production, is reported. Cu\/NiMo composite HEC suppresses H<jats:sub>2<\/jats:sub>O<jats:sub>2<\/jats:sub> evolution by altering the O<jats:sub>2<\/jats:sub> reduction kinetics to a four\u2010electron pathway and subsequently decomposes the inevitably generated H<jats:sub>2<\/jats:sub>O<jats:sub>2<\/jats:sub> in sequential catalytic and electrochemical pathways. Furthermore, in situ generated Cu\u2010rich 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 <jats:italic>Cupriavidus necator<\/jats:italic> H16, for the conversion of CO<jats:sub>2<\/jats:sub> to a biopolymer, poly(3\u2010hydroxybutyrate). This work successfully demonstrates the concept of self\u2010detoxification in designing biocompatible materials for bioelectrochemical applications as well as MES systems.<\/jats:p>","DOI":"10.1002\/advs.202309775","type":"journal-article","created":{"date-parts":[[2024,3,29]],"date-time":"2024-03-29T14:50:26Z","timestamp":1711723826000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":8,"title":["Biocompatible Cu\/NiMo Composite Electrocatalyst for Hydrogen Evolution Reaction in Microbial Electrosynthesis; Unveiling the Self\u2010Detoxification Effect of Cu"],"prefix":"10.1002","volume":"11","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-2927-9426","authenticated-orcid":false,"given":"Byeong Cheul","family":"Moon","sequence":"first","affiliation":[{"name":"Clean Energy Research Center Korea Institute of Science and Technology (KIST)  Seoul 02792 Republic of Korea"},{"name":"Center for Water Cycle Research Korea Institute 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Research Center Korea Institute of Science and Technology (KIST)  Seoul 02792 Republic of Korea"},{"name":"Division of Energy and Environment Technology KIST School University of Science and Technology  Seoul 02792 Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3740-0986","authenticated-orcid":false,"given":"Dong Ki","family":"Lee","sequence":"additional","affiliation":[{"name":"Clean Energy Research Center Korea Institute of Science and Technology (KIST)  Seoul 02792 Republic of Korea"},{"name":"Department of Chemical and Biomolecular Engineering Yonsei\u2010KIST Convergence Research Institute Yonsei University  Seoul 03722 Republic of Korea"},{"name":"Graduate School of Energy and Environment Korea University  Seoul 02841 Republic of 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