Maleimide‐Functionalized Conjugated Polymers Enable Covalent Biotic–Abiotic Integration to Boost Microbial Electrosynthesis

ABSTRACT

Integrating advanced conductive materials into microbial electrosynthesis systems is a powerful paradigm for merging abiotic performance with biotic specificity, facilitating sustainable transformation of organic waste and carbon dioxide into value‐added chemicals. The regulation of biotic‐abiotic hybrid interfaces in biohybrids is crucial for improving surface microbial abundance, enhancing electron injection, and increasing electrosynthesis production. Herein, maleimide‐functionalized conjugated polymers (p(mNDI‐gT2)) were employed to construct robust, covalent bio‐interfaces via in situ click reactions with cytochrome thiol groups of Shewanella oneidensis , resulting in a doubling of bacterial adhesion. Moreover, intimate contact and binding interactions drastically reduce interfacial resistance and boost electron injection. As a direct consequence of this optimized architecture, the system achieved a 23‐fold increase in electron transfer and a 6‐fold improvement in electrochemical reduction relative to bare S. oneidensis . Furthermore, it obviously outperformed the non‐covalent group, yielding a 2‐fold enhancement in total charge output and a 2‐fold increase in succinate yield. Molecular docking simulations and proteomic analysis collectively reveal that p(mNDI‐gT2) not only facilitates efficient charge transfer but also predominantly upregulates the expression of key respiratory and bio‐interface protein complexes. Fundamentally, this covalent biotic–abiotic interface transcends traditional bulk‐adsorption methods, shifting the paradigm from simple microbial coating to molecular‐level interface engineering.