A Pd@Zeolite Catalyst for Nitroarene Hydrogenation with High Product Selectivity by Sterically Controlled Adsorption in the Zeolite Micropores.
A Pd@Zeolite Catalyst for Nitroarene Hydrogenation with High Product Selectivity by Sterically Controlled Adsorption in the Zeolite Micropores.
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DOI：
10.1002/anie.201703938
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发表时间：
2017-05
影响因子：
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通讯作者：
Jian Zhang;Liang Wang;Y. Shao;Yanqin Wang;B. Gates;F. Xiao
中科院分区：
文献类型：
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作者：
Jian Zhang;Liang Wang;Y. Shao;Yanqin Wang;B. Gates;F. Xiao
分子在金属纳米颗粒上的吸附可以通过沸石晶体进行空间控制，从而提高了含有一个以上可还原基团的反应物加氢反应的产物选择性。这一成功的关键是将Pd纳米颗粒固定在Beta沸石晶体中形成定义的结构(Pd@Beta)。以多个可还原基团取代的硝基取代芳烃的加氢反应为模型反应，Pd@Beta催化剂对硝基加氢表现出了良好的选择性，其性能优于传统的负载于沸石晶体上的Pd纳米粒子和工业Pd/C催化剂。竞争吸附和吸附置换实验表明，Pd@Beta的超高选择性是由于分子筛微孔控制的Pd纳米粒子对硝基芳烃的空间选择性吸附。重要的是，这一策略是通用的，并被扩展到通过固定在贝塔和丝光沸石分子筛中合成选择性铂和Ru催化剂。
The adsorption of molecules on metal nanoparticles can be sterically controlled through the use of zeolite crystals, which enhances the product selectivity in hydrogenations of reactants with more than one reducible group. Key to this success was the fixation of Pd nanoparticles inside Beta zeolite crystals to form a defined structure (Pd@Beta). In the hydrogenation of substituted nitroarenes with multiple reducible groups as a model reaction, the Pd@Beta catalyst exhibited superior selectivity for hydrogenation of the nitro group, outperforming both conventional Pd nanoparticles supported on zeolite crystals and a commercial Pd/C catalyst. The extraordinary selectivity of Pd@Beta was attributed to the sterically selective adsorption of the nitroarenes on the Pd nanoparticles controlled by the zeolite micropores, as elucidated by competitive adsorption and adsorbate displacement tests. Importantly, this strategy is general and was extended to the synthesis of selective Pt and Ru catalysts by fixation inside Beta and mordenite zeolites.