A Nanobiocatalyst‐Driven Hybrid System for Efficient and Sustainable Hydrogen Production via Electron Flow Optimization

Abstract Biohydrogen production offers a promising pathway for developing clean and renewable energy sources. However, its practical application has been hindered by low efficiency and sustainability issues. Here, it is introduced an energy‐efficient and output‐sustainable hybrid system (LPBC/CH system) for biohydrogen production by integrating self‐assembling intermetallic ( L 1 0 ) FePt@polypyrrole nanobiocatalysts (LPBC) with Clostridium pasteurianum . The engineered LPBC, characterized by optimal atomic structures and defined electronic properties, demonstrates robust transcriptional enhancement efficiency and biocatalytic capability, leading to an ≈103% increase in hydrogen production rate and a 57% enhancement in hydrogen yield to the bare C. pasteurianum system. Within the LPBC/CH system, the nanobiocatalysts target NADH and [FeFe] hydrogenase, triggering efficient tandem biocatalytic reactions for proton reduction. Notably, the LPBC achieves sustained performance for at least 30 days – a benchmark unmatched by other reported nanobiocatalysts. This study not only advances the frontiers of biohydrogen production but also establishes a universal framework for constructing hybrid systems with superior efficiency and sustainability.