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

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 (L1₀) 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.