催化作用
双金属片
活化能
化学
腈
物理化学
化学工程
有机化学
工程类
作者
Yunzhu Wang,Shinya Furukawa,Ning Yan
标识
DOI:10.1021/acscatal.9b00043
摘要
Development of heterogeneous catalysts for alcohol transformation into nitriles under oxidant-free conditions is a challenge. Considering the C–H activation on α-carbon of primary alcohols is the rate-determining step, decreasing the activation energy of C–H activation is critical in order to enhance the catalytic activity. Several NiM/Al2O3 bimetallic catalysts were synthesized and scrutinized in catalytic transformation of 1-butanol to butyronitrile. Ni–Cu was identified as a suitable combination with the optimized Ni0.5Cu0.5/Al2O3 catalyst exhibiting 10 times higher turnover frequency than Ni/Al2O3 catalyst. X-ray absorption spectroscopy (XAS) and high angle annular dark field scanning transmission electron microscopy (HAADF-STEM) revealed that the NiCu particles in the catalyst exist in the form of homogeneous alloys with an average size of 8.3 nm, providing an experimental foundation to build up a catalyst model for further density functional theory (DFT) calculations. Calculations were done over a series of NiM catalysts, and the experimentally observed activity trend could be rationalized by the Brønsted–Evans–Polanyi (BEP) principle, i.e., catalysts that afford reduced reaction energy also feature lower activation barriers. The calculated activation energy (Ea) for C–H activation with coadsorbed NH3 dropped from 63.4 kJ/mol on pure Ni catalyst to 49.9 kJ/mol on the most active NiCu-2 site in NiCu bimetallic catalyst, in good agreement with the experimentally measured activation energy values. The Ni0.5Cu0.5/Al2O3 catalyst was further employed to convert 11 primary alcohols into nitriles with high to near-quantitative yields, at a Ni loading 10 times less than that of the conventional Ni/Al2O3 catalyst.
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