Pd3 cluster catalysis: Compelling evidence from in operando spectroscopic, kinetic, and density functional theory studies

作     者：Chunlin Lv Hao Cheng Wei He Muhammad Ishaq Ali Shah Congqiao Xu Xiangjian Meng Lei Jiao Shiqiang Wei Jun Li Lei Liu Yadong Li 

作者机构：Department of Chemistry and Collaborative Innovation Center for Nanomaterial Science and EngineeringTsinghua UniversityBeijing 100084China Tsinghua-Peking Center for Life SciencesTsinghua UniversityBeijing 100084China National Synchrotron Radiation Laboratory and Collaborative Innovation Center for Nanomaterial Science and EngineeringUniversity of Science and Technology of ChinaHefei 230029China 

出 版 物：《Nano Research》 (纳米研究（英文版）)

年 卷 期：2016年第9卷第9期

页      面：2544-2550页

核心收录：

学科分类：0808[工学-电气工程] 0809[工学-电子科学与技术（可授工学、理学学位）] 07[理学] 0805[工学-材料科学与工程（可授工学、理学学位）] 0703[理学-化学] 0702[理学-物理学] 

基　　金：We thank the financial supports by the National Natural Science Foundation of China (Nos.21221062 and 21521091) and the National Basic Research Program of China (973 program No.2013CB932800) 

主　　题：metal cluster catalysis operando studies active species cycloisomerization palladium 

摘      要：Identification of metal cluster catalysis is a topic that is being investigated since a long time. Here, we report a Pd3 metal cluster catalytic reaction investigated by means of operando studies. We discovered that atomically defined tri-nuclear palladium (Pd3) is a surprisingly active catalyst for the cycloisomerization of 2-phenylethynylaniline. Operando1H NMR spectroscopy and X-ray extended absorption fine structure (EXAFS) measurements have indicated that the structural integrity of such a catalyst remains intact throughout the reaction, which has also been confirmed by an ex situ X-ray photoelectron spectroscopy (XPS) study and catalyst recycling experiments. Kinetic data derived from operando IR spectroscopy measurements have shown that Pd3is the active catalytic species. Density functional theory calculations have revealed a reaction pathway consistent with the kinetic data, further supported by NMR titration and X-ray crystal structure studies. Overall, the present study presents a clear example of metal cluster catalysis. [Figure not available: see fulltext.] © 2016, Tsinghua University Press and Springer-Verlag Berlin Heidelberg.