Interfacial Auδ−–OV–Ti Structure Promoted C–H Bond Activation for Selective Oxidation of Fatty Alcohols to Fatty Acids

化学 脂肪酸 有机化学 立体化学
作者
Yu Su,Rong Fan,Jiabao Li,Yangxi Liu,Ziyuan Zheng,Xin Zhou,Xiang Feng,Yibin Liu,Hui Zhao,Xiaobo Chen,Xingong Zhang,Chaohe Yang,Hao Yan
出处
期刊:Industrial & Engineering Chemistry Research [American Chemical Society]
卷期号:63 (30): 13115-13126 被引量:4
标识
DOI:10.1021/acs.iecr.4c00986
摘要

Oxidation of fatty alcohols to fatty acids is still challenging due to the sluggish activation of the C–H bond over Au supported on reducible oxides with a coordination-saturated structure. Herein, we constructed an efficient interfacial Auδ−–OV–Ti structure by tuning the crystal forms of TiO2. Compared with TiO2-rutile exposed by (110) and (111) crystal facets, TiO2-anatase can exploit the defect (101) crystal facet to obtain rich oxygen vacancies (OV), inducing electron migration from TiO2-anatase support to Au species to form electron-rich Auδ− species. Specifically, the synergistic catalytic effect between the OV–Ti and Auδ− species greatly enhances the adsorption of alcohol and thereby overcomes sluggish activation of the C–H bond caused by the electron pushing effect triggered by long carbon chains. Consequently, the Au/TiO2-anatase catalyst shows excellent isooctyl alcohol conversion (69.5%) and isocaprylic acid selectivity (67.9%) under base-free conditions. The catalytic system is further extended to the oxidation of other fatty alcohols to fatty acids with excellent catalytic performance.
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