Photothermal Conversion Boosted Photocatalytic CO2 Reduction over S-Scheme CeO2@Cu-TCPP: In Situ Experiments and DFT Calculations

Herein, interfacial and defect-engineering strategies synergistically promote photocatalytic properties. Because of the matching energy levels and the close interfacial contact, the CeO2@ Cu-TCPP S-scheme architecture is successfully constructed via the in situ wet chemistry route. Photothermal conversion assists abundant OVs on the CeO2 compartment. Strong evidence of an S-scheme charge transfer path is verified by density functional theory (DFT) calculations and in situ irradiated X-ray photoelectron spectroscopy (XPS). This S-scheme heterojunction system is more deep-seated in facilitating the separation and transfer of photo -generated carriers as well as acquiring strong photoredox ability. Meanwhile, the abundant OVs proved by XPS and electron paramagnetic resonance spectra (ESR) enhanced the light-harvesting capacity and conductivity and shortened the transfer route. As a result, this synergistic heterojunction could mostly promote photocatalytic CO2 activation. The typical 0.25CeO2@ Cu-NS exhibited the best photocatalytic CO2RR to form CO and CH4 (rate: 229.6 ??mol??g???1), which is even 45.8-and 1.5-folds higher than those of pristine LA-CeO2 (5.0 ??mol??g???1) and Cu-TCPP (152.2 ??mol??g???1), respectively, higher than those of other reported CeO2-based photocatalysts. This study presents a reinforcement and matrix prospect for domain charge behaviors to accelerate CO2 activation.