Efficient photoelectrochemical CO₂ conversion for selective acetic acid production

Amidst the development of photoelectrochemical (PEC) CO₂ conversion toward practical application, the production of high-value chemicals beyond C₁ compounds under mild conditions is greatly desired yet challenging. Here, through rational PEC device design by combining Au-loaded and N-doped TiO₂ plate nanoarray photoanode with Zn-doped Cu₂O dark cathode, efficient conversion of CO₂ to CH₃COOH has been achieved with an outstanding Faradaic efficiency up to 58.1% (91.5% carbon selectivity) at 0.5 V vs. Ag/AgCl. Temperature programmed desorption and in situ Raman spectra reveal that the Zn-dopant in Cu₂O plays multiple roles in selective catalytic CO₂ conversion, including local electronic structure manipulation and active site modification, which together promote the formation of intermediate *CH₂/*CH₃ for C-C coupling. Apart from that, it is also unveiled that the sufficient electron density provided by the Au-loaded and N-doped TiO₂ plate nanoarray photoanode plays an equally important role by initiating multi-electron CO₂ reduction. This work provides fresh insights into the PEC system design to reach the multi-electron reduction reaction and facilitate the C-C coupling reaction toward high-value multicarbon (C₂₊) chemical production via CO₂ conversion.