Synergistic Coupling of Photocatalysis and Thermocatalysis for Efficient CO2 Conversion by Direct Z‐Scheme WO3/WS2

Abstract Photothermal CO 2 reduction using H 2 O combined with photocatalysis‐driven H 2 O splitting combined with thermal catalysis‐supported CO 2 reduction has attracted rapid interest in artificial synthesis of solar fuel. With respect to extremely efficient photothermal catalysis, the photothermal impact of TMDCs (Transition Metal Dichalcogenides) facilitates CO 2 reduction by activating lattice oxygen in oxide to enhance H 2 O oxidation. However, the fixed band gap of single photocatalyst is limited. The purpose of this work is to expand the band gap and improve the redox capacity. Hollow boxwood ball‐like WO 3 /WS 2 Z‐scheme heterojunctions were prepared and used for photothermal catalytic CO 2 reduction. DFT calculations and UV‐Vis spectra show LSPR effect in WOS heterojunctions, and the optical response extends to near infrared region. By comparison, the photothermal catalytic reduction of WO 3 /WS 2 (9.717 μmol) by CO 2 at 513 K is higher than that at 298 K (1.198 μmol) by a factor of 8. The formation of Z‐scheme heterojunction promotes rapid carrier transfer and lowers the reaction energy barrier. As well as the hollow structure improves light utilization and increases the interfacial area and number of active sites. In addition, the WO 3 /WS 2 heterostructure utilizes its unique LSPR effect to generate heat through the photothermal effect, which can also promote molecular activation. This work reveals the important role of the LSPR effect in photothermal catalysis and demonstrates a TMDCs‐based photothermal‐driven catalysts, which presents a promising approach for designing of photothermal catalytic CO 2 reduction.