期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 140, 期 26, 页码 8206-8217出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.8b03505
关键词
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资金
- MATsynCELL project through Rontgen-Angstrom Cluster - Swedish Research Council (VR)
- German Federal Ministry of Education and Research (BMBF)
- Knut and Alice Wallenberg Foundation (KAW)
- KAW
The mechanism of the Heck C-C coupling reaction catalyzed by Pd@MOFs has been investigated using operando X-ray absorption spectroscopy (XAS) and powder X-ray diffraction (PXRD) combined with transmission electron microscopy (TEM) analysis and nuclear magnetic resonance (H-1 NMR) kinetic studies. A custom-made reaction cell was used, allowing operando PXRD and XAS data collection using high-energy synchrotron radiation. By analyzing the XAS data in combination with ex situ studies, the evolution of the palladium species is followed from the as-synthesized to its deactivated form. An adaptive reaction mechanism is proposed. Mononuclear Pd(II) complexes are found to be the dominant active species at the beginning of the reaction, which then gradually transform into Pd nanoclusters with 13-20 Pd atoms on average in later catalytic turnovers. Consumption of available reagent and substrate leads to coordination of Cl- ions to their surfaces, which causes the poisoning of the active sites. By understanding the deactivation process, it was possible to tune the reaction conditions and prolong the lifetime of the catalyst.
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