Copper Vacancy and LSPR-Activated MXene Synergistically Enabling Selective Photoreduction CO2 to Acetate

Graphical A highly effective photocatalytic system (V Cu −CuInS 2 /MXene) was developed for transforming CO 2 into acetate under full spectrum irradiation. The incorporation of the LSPR effect and defect engineering leads to a highly selective system. Photocatalytic CO 2 conversion towards C 2+ fuels is a promising technology for simultaneously achieving carbon neutrality and alleviating the energy crisis. However, this strategy is inefficient due to the difficulty of both multi-electron transfer and C−C coupling during C 2+ formation. In this work, CuInS 2 /MXene heterostructure with Cu vacancy is rationally designed by in situ hydrothermal synthesis. The V Cu −CuInS 2 /MXene heterostructure has a suitable band structure and tight interface contact. Catalytic performances under different testing conditions, in situ spectroscopy, and COMSOL simulation reveal that LSPR-activated MXene promotes the formation of crucial intermediate CH 2 * and triggers the C−C coupling process under near-infrared light, as the key to acetate. Moreover, in situ XPS analysis, DFT calculations, and photoelectrochemical characterizations unveil that copper vacancy can promote charge transfer from CuInS 2 to MXene and boost local electron aggregation on the MXene, further enhancing the photocatalytic efficiency and selectivity of C 2 products. Contributing to the synergistic effect of copper vacancy and plasmonic MXene, V Cu −CuInS 2 /MXene achieved excellent CO 2 RR activity with an acetate evolution rate of 250.0 μmol/h/g and a selectivity of 97.5 % under the full spectrum irradiation, which is 38.8 and 3.3 times higher than that of V Cu −CuInS 2 and CuInS 2 /MXene, respectively.