Photoelectrochemical NADH Regeneration using Pt-Modified p-GaAs Semiconductor Electrodes

Cofactor regeneration in enzymatic reductions is crucial for the application of enzymes to both biological and energy-related catalysis. Specifically, regenerating NADH from NAD⁺ is of great interest, and using electrochemistry to achieve this end is considered a promising option. Here, we report the first example of photoelectrochemical NADH regeneration at the illuminated (λ>600 nm), metal-modified, p-type semiconductor electrode Pt/p-GaAs. Although bare p-GaAs electrodes produce only enzymatically inactive NAD₂, NADH was produced at the illuminated Pt-modified p-GaAs surface. At low overpotential (−0.75 V vs. Ag/AgCl), Pt/p-GaAs exhibited a seven-fold greater faradaic efficiency for the formation of NADH than Pt alone, with reduced competition from the hydrogen evolution reaction. Improved faradaic efficiency and low overpotential suggest the possible utility of Pt/p-GaAs in energy-related NADH-dependent enzymatic processes.