数字农科院2.0

Enhanced hole-proton-coupled electron transfer of spin polarized photocatalyst via Mo-S4 coordination for sequential activation of C (sp3)-H and O-H bonds

文献类型： 外文期刊

作者： Wang, Xiaoping;Yang, Bowen;Wang, Haoye;Guo, Haixin;Smith, Richard Lee;Su, Yaqiong;Qi, Xinhua

作者机构：

关键词： Photooxidation;Mo-Vs-ZIS;Spin polarization;Proton-coupled electron transfer;C(sp3)-H activation

期刊名称： JOURNAL OF ENERGY CHEMISTRY

ISSN： 2095-4956

年卷期： 2025 年 115 卷

页码：

收录情况： SCIE（2025版） ; ; EI（2025版） ; ; CSCD（2025-2026年度） ; ; 科技核心（2024版）

摘要： Photocatalytic oxidative dehydrogenation of biomass feedstocks offers the possibility for synthesizing value-added chemicals, but the sluggish transport kinetics and rapid recombination of photogenerated charge carriers constrain photocatalysis efficiency. Spin-polarized photocatalysts, by accelerating the separation of photogenerated electrons and holes, offer a promising strategy for selective biomass valorization. Herein, polarization unit Mo was incorporated into ZnIn2S4 (ZIS) with S-vacancy through Mo-S4 coordination (Mo-Vs-ZIS) to enhance hole and proton-coupled electron transfer (PCET). Mo-Vs-ZIS spin polarized photocatalyst applied to 5-hydroxymethylfurfural (HMF) afforded a 2,5-diformylfuran (DFF) selectivity of 92.3 % at a production rate of 1105.3 lmol gcat-1 h-1, attributed to carrier transport and reaction processes. The Mo-Vs-ZIS photocatalyst efficiently (100 min) converted benzyl and furfuryl alcohols, aromatic alcohols bearing electron-rich substituents, and halogen-substituted aromatic alcohols into their corresponding aldehydes. Piezoelectric force microscopy (PFM) and Kelvin probe force microscopy analyses (KPFM) revealed that the full-space polarized electric field was formed to drive directional transfer of photogenerated carriers, facilitating bulk-to-surface charge separation. Moreover, Mo-Vs-ZIS showed high Bader charge transfer to O2, where Mo atomic sites functioned as an electron reservoir, driving the activation of O2 to form center dot O2-, a kinetically favorable step for HMF oxidation and induced transfer of holes to activate C(sp3)-H bonds, which is a rate-determining step. Then, the critical step of PCET (center dot O2-+ H+ -> center dot OOH) over Mo-Vs-ZIS gave center dot OOH for O-H activation to complete the reaction sequence. This spin-polarized modification strategy featuring atomic-level catalytic sites enables its application to other semiconductor photocatalysts for biomass conversion. (c) 2025 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights are reserved, including those for text and data mining, AI training, and similar technologies.

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