A red-light-powered silicon nanowire biophotochemical diode for simultaneous CO₂ reduction and glycerol valorization

A bias-free photochemical diode, in which a p-type photocathode is connected to an n-type photoanode to harness light for driving photoelectrochemical reduction and oxidation pairs, serves as a platform for realizing light-driven fuel generation from CO₂. However, the conventional design, in which cathodic CO₂ reduction is coupled with the anodic oxygen evolution reaction (OER), requires substantial energy input. Here we present a photochemical diode device that harnesses red light (740 nm) to simultaneously drive biophotocathodic CO₂-to-multicarbon conversion and photoanodic glycerol oxidation as an alternative to the OER to overcome the above thermodynamic limitation. The device consists of an efficient CO₂-fixing microorganism, Sporomusa ovata, interfaced with a silicon nanowire photocathode and a Pt–Au-loaded silicon nanowire photoanode. This photochemical diode operates bias-free under low-intensity (20 mW cm⁻²) red light irradiation with ~80% Faradaic efficiency for both the cathodic and anodic products. This work provides an alternative photosynthetic route to mitigate excessive CO₂ emissions and efficiently generate value-added chemicals from CO₂ and glycerol.