The photochemical generation of nicotinamide cofactor 1,4-NADH, facilitated by inorganic photosensitizers, emerges as a promising model system for investigating charge transfer phenomena at the interface of semiconductors and bacteria, with implications for enhancing photosynthetic biohybrid systems (PBSs). However, extant semiconductor nanocrystal model systems suffer from achieving optimal conversion efficiency under visible light. This study investigates quasi-one-dimensional CdS nanorods as superior light absorbers, surface modified with catalyst Cp*Rh(4,4'-COOH-bpy)Cl₂ to produce enzymatically active NADH. This model subsystem facilitates easy product isolation and achieves a turnover frequency (TOF) of 175 h^-1, one of the highest efficiencies reported for inorganic photosensitizer-based nicotinamide cofactor generation. Charge transfer kinetics, fundamental for catalytic solar energy conversion, range from 10⁶ to 10⁸ s^-1 for this system highlighting the superior electron transfer capabilities of NRs. This model ensures efficient cofactor production and offers critical insights into advancing systems that mimic natural photosynthesis for sustainable solar-to-chemical synthesis.

Photocathodic conversion of NAD⁺ to NADH cofactor is a promising platform for activating redox biological catalysts and enzymatic synthesis using renewable solar energy. However, many photocathodes suffer from low photovoltage, consequently requiring a high cathodic bias for NADH production. Here, we report an n⁺p-type silicon nanowire (n⁺p-SiNW) photocathode having a photovoltage of 435 mV to drive energy-efficient NADH production. The enhanced band bending at the n⁺/p interface accounts for the high photovoltage, which conduces to a benchmark onset potential [0.393 V vs the reversible hydrogen electrode (V_RHE)] for SiNW-based photocathodic NADH generation. In addition, the n⁺p-SiNW nanomaterial exhibits a Faradaic efficiency of 84.7% and a conversion rate of 1.63 μmol h^-1 cm^-1 at 0.2 V_RHE, which is the lowest cathodic potential to achieve the maximum productivity among SiNW-sensitized cofactor production.