Regulating the selectivity of reaction pathways to desirable products via controlling adsorption/activation behaviors towards reactants is significant for the design of excellent catalysts for selective hydrogenation but remains challenging. Exemplified with dimethyl oxalate (DMO) hydrogenation, we herein propose an exsolution strategy for constructing interfacial Ni/Ni sites by using pre-synthesized Ni phyllosilicate as the precursor to control the reaction pathways of selective hydrogenation. Structural characterizations, including spectroscopic and isotopic studies, and theoretical calculations elucidate that the interfacial Ni/Ni sites can selectively activate monoester group of DMO via a tilted adsorption configuration and hence boost hydrogen dissociation. With such activation behaviors the reaction pathway is steered to methyl glycolate, other than the pathway to ethylene glycol on the reference active sites where both ester groups are activated and methyl formate is formed via breaking the C–C bond of DMO.

中文翻译：

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原位脱溶制备界面 Ni0/Niδ+ 位点以调节加氢反应路径


通过控制对反应物的吸附/活化行为来调节反应途径对所需产物的选择性对于设计用于选择性加氢的优异催化剂具有重要意义，但仍然具有挑战性。以草酸二甲酯（DMO）氢化为例，我们提出了一种通过使用预合成的镍层状硅酸盐作为前体来构建界面Ni/Ni位点的溶出策略，以控制选择性氢化的反应途径。结构表征（包括光谱和同位素研究）以及理论计算表明，界面 Ni/Ni 位点可以通过倾斜吸附构型选择性激活 DMO 的单酯基团，从而促进氢解离。通过这种激活行为，反应途径转向乙醇酸甲酯，而不是参考活性位点上的乙二醇途径，其中两个酯基都被激活，并且通过破坏 DMO 的 C-C 键形成甲酸甲酯。