Abstract

Abstract Heterojunction engineering, especially 2D/2D heterojunctions, is regarded as a quite promising strategy to manipulate the photocatalytic performance of semiconductor catalysts. In this manuscript, a direct Z‐scheme 2D/2D heterojunction of CsPbBr 3 /Bi 2 WO 6 is designed and fabricated by a simple electrostatic self‐assembly process. By using ultrathin nanosheets with several atomic layers as the building blocks, a close CsPbBr 3 /Bi 2 WO 6 heterointerface over large area with quite a short charge transport distance is obtained, which enables a valid Z‐scheme interfacial charge transfer between Bi 2 WO 6 and CsPbBr 3 and thus boosts charge separation. The CsPbBr 3 /Bi 2 WO 6 heterojunction exhibits a superior photocatalytic performance toward CO 2 reduction. By incorporating Pt nanoparticles as the cocatalyst, a high photoelectron consumption rate of 324.0 µmol g −1 h −1 under AM 1.5G irradiation (150 mW cm −2 ) is obtained, which is 12.2 fold higher than that of CsPbBr 3 nanosheets. Moreover, a stable product yield of up to 1582.0 µ mol g −1 and electron consumption yield of 8603.0 µ mol g −1 for photocatalytic CO 2 reduction to CO (11.4%) and CH 4 (84.3%) can be achieved after 30 h of continuous catalytic reaction. The accelerated photogenerated charge transfer and spatial charge separation are investigated in detail by ultrafast spectra, photoelectrochemical test, and Kelvin probe force microscopy.