A Bio-Photo/Electro Hybrid Catalytic Cell for Biomass Valorization Coupled with NADH-Driven Enzymatic Synthesis

Biomass valorization and NADH-driven enzymatic synthesis are both central to the development of electrified chemical manufacturing. Here, we present a bio-photo/electro hybrid catalytic cell that simultaneously enables biomass valorization and NADH-driven enzymatic synthesis. This platform couples efficient glucose oxidation into value-added organic acids with highly efficient NADH regeneration, and the in situ regenerated cofactor further supports diverse NADH-dependent enzymatic transformations. Guided by experimental evidence and density functional theory calculations, we proposed the detailed reaction pathway of anodic glucose oxidation and demonstrated the better performance of Cu catalysts for cathodic NADH regeneration compared with Pt and Ni. Techno-economic analysis reveals that achieving a higher current density and prolonged enzyme stability are essential for the economic viability of this hybrid system. Together, these findings establish a bifunctional bio-photo/electro hybrid catalytic strategy that leverages renewable biomass feedstocks and expands the industrial potential of enzymatic synthesis for chemical production.