Defect engineering is an effective strategy to enhance the photocatalytic performance of ZnIn2S4 (ZIS), but it remains a formidable challenge to manipulate the cationic defects in the catalyst because of their high formation energies. Herein, dual Zn and In defects have been successfully created in the ZnIn2S4 (ZIS-5) with a facile cetyltrimethylammonium chloride (CTAC)-assisted hydrothermal method. The resulting ZIS-5, rich in cation vacancies, achieved a 3.6-fold higher 2,5-diformylfuran (DFF) yield (92.0%) than the pristine ZIS (25.8%) for the visible-light-driven photocatalytic air-oxidation of 5-hydroxymethylfurfural (HMF). Especially, ZIS-5 delivers a high DFF productivity of 1600 μmol g–1 h–1, significantly surpassing the previously reported catalysts (75–953 μmol g–1 h–1) for the photocatalytic oxidation of HMF to DFF in air. Density functional theory (DFT) simulations revealed that the presence of dual Zn and In defects endows the catalyst with defect states that intersect the Fermi level and lower work function. These enhance the migration and separation of photogenerated carriers in ZIS-5, significantly promoting O2 activation and resulting in the generation of more reactive oxygen species (·O2– and 1O2) for the catalytic oxidation of HMF. This study offers valuable insights for guiding the design of photoredox reaction systems through cationic-defect-engineering strategies, enabling the efficient valorization of biomass-derived platform chemicals.
Electrochemical CO 2 -to-ethanol conversion is challenged by sluggish C-C coupling kinetics and wide products distribution. Although Cu + has been demonstrated to enhance multi-carbon (C 2+ ) formation, the stabilization of Cu + under reduction conditions is difficult. Here, we report a hydrogen-ethanol pretreatment strategy to obtain Cu nanoparticles covered by highly dispersed and disordered ZnO 1- x clusters. Ethanol-induced ZnO 1- x redispersion gives rise to abundant Cu + on the subsurface. The optimal catalyst delivers a 73.0% ethanol Faradaic efficiency (FE) and 86.0% total C 2+ FE at −0.9 V, with a 2.3 mmol cm −2 h −1 ethanol formation rate and single-pass ethanol yield of 18.0%. The catalyst also exhibits stability beyond 500 h, attributed to the stabilization of Cu + by the ZnO 1- x shield that requires a high energy barrier for lattice oxygen removal. In situ X-ray spectroscopy and calculations reveal a volcano relationship between Cu + ratio in Cu species and ethanol FE. Optimal Cu + density not only facilitates *OC-COH coupling but also optimizes the adsorption energy of *CH 2 CH 2 O on catalyst for ethanol electrosynthesis.
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