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.
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.
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).
