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Competitive hydrogen evolution and multiple proton-coupled electron transfer reactions limit photoelectrochemical CO 2  reduction in aqueous electrolyte. Here, oxygen-terminated lightly boron-doped diamond (BDD L ) thin films were synthesized as a semiconductor electron source to accelerate CO 2  reduction. However, BDD L  alone could not stabilize the intermediates of CO 2  reduction, yielding a negligible amount of reduction products. Silver nanoparticles were then deposited on BDD L  because of their selective electrochemical CO 2  reduction ability. Excellent selectivity (estimated CO:H 2  mass ratio of 318:1) and recyclability (stable for five cycles of 3 h each) for photoelectrochemical CO 2  reduction were obtained for the optimum silver nanoparticle-modified BDD L  electrode at −1.1 V vs. RHE under 222-nm irradiation. The high efficiency and stability of this catalyst are ascribed to the  in situ  photoactivation of the BDD L  surface during the photoelectrochemical reaction. The present work reveals the potential of BDD L  as a high-energy electron source for use with co-catalysts in photochemical conversion.

Boron-doped diamond semiconductor electrodes: Efficient photoelectrochemical CO2 reduction through surface modification