文献类型：期刊文献

英文题名：High Performance Polyoxometalate-Stabilizing Pt Nanocatalysts for Quinoline Hydrogenation with Water-Mediated Dynamic Hydrogen

作者：Wei, Xinjia[1];Jiang, Yongjun[2,3];Ma, Yuan[1];Liao, Huiying[1];Dai, Sheng[2,3];An, Pengfei[7];Wang, Zhi-Qiang[5,6];Gong, Xue-Qing[4];Hou, Zhenshan[1]

机构：[1]East China Univ Sci & Technol, Res Inst Ind Catalysis, Sch Chem & Mol Engn, State Key Lab Green Chem Engn & Ind Catalysis, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Inst Fine Chem, Sch Chem & Mol Engn, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[3]East China Univ Sci & Technol, Feringa Nobel Prize Scientist Joint Res Ctr, Shanghai 200237, Peoples R China;[4]Shanghai Jiao Tong Univ, Sch Chem & Chem Engn, Shanghai 200240, Peoples R China;[5]East China Univ Sci & Technol, Ctr Computat Chem, State Key Lab Green Chem Engn & Ind Catalysis, Sch Chem & Mol Engn, Shanghai 200237, Peoples R China;[6]East China Univ Sci & Technol, Res Inst Ind Catalysis, Shanghai 200237, Peoples R China;[7]Chinese Acad Sci, Inst High Energy Phys, Beijing Synchrotron Radiat Facil BSRF, Beijing 100049, Peoples R China

年份：2024

卷号：14

期号：7

起止页码：5344

外文期刊名：ACS CATALYSIS

收录：;EI(收录号：20241415838607);WOS:【SCI-EXPANDED(收录号:WOS:001191197500001)】；

基金：The authors acknowledge the support from the National Key Research and Development Program of China (2022YFA1504903, 2023YFA1508500, 2021YFA1500700), the National Natural Science Foundation of China (21773061, 21978095, 22203030), and State Key Laboratory of Petroleum Molecular & Process Engineering.

语种：英文

外文关键词：quinoline hydrogenation; polyoxometalates; Pt nanocluster; water; hydride

摘要：In this work, a Keggin-type platinum substituted polyoxometalate (POM) is constructed by the reaction of monolacunary phosphotungstate precursor [PW11O39](7-) with chloroplatinic acid. The as-obtained tetrabutylammonium salt (TBA-PWPt) demonstrates that the dimeric Pt2+ ions are incorporated into POM frameworks and linked by two monolacunary POM anions. Notably, once the Pt-substituted Keggin-type POM anion is reduced by H-2, the POM anion-stabilizing Pt nanocatalysts are generated, which greatly facilitates forming oxygen vacancies adjacent to Pt-0 species. The Pt nanocatalysts show superior catalytic activity and stability for the selective hydrogenation of quinoline into 1,2,3,4-tetrahydroquinoline in water. Detailed investigations elucidate that the stronger adsorption of quinoline on the Pt surface and the H-2 is activated by the adsorption at the POMs-Pt interface site. Moreover, density functional theory (DFT) calculations show that H2O is adsorbed at the interfacial oxygen vacancies and then undergoes homolytic dissociation to produce hydroxyl group (OH-) and hydride (H-) species. The H- species are transferred to the N-containing pyridine ring in quinoline hydrogenation, and the OH- species adsorbed on oxygen vacancies help to promote the H-2 heterolytic dissociation to produce H+ and H- species. Sequentially, the produced proton and hydroxyl groups generate H2O, and the reaction cycle is completed.