Boosting primary amines renewable tandem synthesis via defect engineering of <scp>NiCo</scp> alloy
Yang Zhao, Qian Wang, Huifang Wu, Lirong Zheng, Zhexi Gao, Xuanlin Guo, Xingzhong Cao, Dianqing Li, Junting Feng
Abstract
Abstract Reductive amination of biomass aldehydes is a vital process to synthesize chemical intermediates primary amine, but the selectivity is severely compromised by the self‐condensation of highly reactive imine intermediates. Herein, we proposed a solution by manipulating the adsorption configuration of secondary imine via defect engineering. Specifically, a gradient reduction strategy was used to adjust the driving force of NiCo alloy crystallization, thus motivating the formation of metal vacancy clusters. The primary amine selectivity was raised from 70.9% to 95.1% with defect concentration increased from 36.1% to 42.5% on catalysts. In situ fourier transform infrared spectroscopy (FTIR) and density functional theory demonstrated metal vacancy clusters induced remarkable NiCo electron transfer, which strengthened electronic coupling between secondary imine with catalyst, resulting in a flat configuration that was conducive to CN bond breakage to guarantee smooth conversion into primary amines. This catalyst exhibited potential real‐life application prospects for its low cost, universality in reductive amination of various aldehydes, and long‐life reusability.