Van Der Waals gap-rich BiOCl atomic layers realizing efficient, pure-water CO₂-to-CO photocatalysis

Photocatalytic CO₂ reduction (PCR) is able to convert solar energy into chemicals, fuels, and feedstocks, but limited by the deficiencies of photocatalysts in steering photon-to-electron conversion and activating CO₂, especially in pure water. Here we report an efficient, pure water CO₂-to-CO conversion photocatalyzed by sub-3-nm-thick BiOCl nanosheets with van der Waals gaps (VDWGs) on the two-dimensional facets, a graphene-analog motif distinct from the majority of previously reported nanosheets usually bearing VDWGs on the lateral facets. Compared with bulk BiOCl, the VDWGs-rich atomic layers possess a weaker excitonic confinement power to decrease exciton binding energy from 137 to 36 meV, consequently yielding a 50-fold enhancement in the bulk charge separation efficiency. Moreover, the VDWGs facilitate the formation of VDWG-Bi-V_O^••-Bi defect, a highly active site to accelerate the CO₂-to-CO transformation via the synchronous optimization of CO₂ activation, *COOH splitting, and *CO desorption. The improvements in both exciton-to-electron and CO₂-to-CO conversions result in a visible light PCR rate of 188.2 μmol g^-1 h^-1 in pure water without any co-catalysts, hole scavengers, or organic solvents. These results suggest that increasing VDWG exposure is a way for designing high-performance solar-fuel generation systems.