Boosting primary amines renewable tandem synthesis via defect engineering of NiCo alloy

• Published in: AIChE journal 2024-07, Vol.70 (7), p.n/a
• Main Authors: Zhao, Yang, Wang, Qian, Wu, Huifang, Zheng, Lirong, Gao, Zhexi, Guo, Xuanlin, Cao, Xingzhong, Li, Dianqing, Feng, Junting
• Format: Article
• Language: English
• Subjects: 5‐HMF; adsorption configuration; Aldehydes; Amination; Amines; Catalysts; Chemical synthesis; Clusters; Configurations; Crystal defects; Crystallization; Density functional theory; Electron transfer; Fourier transforms; Infrared spectroscopy; Intermediates; Intermetallic compounds; metal defects; reductive amination
• ISSN: 0001-1541; 1547-5905
• DOI: 10.1002/aic.18446

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 NiCo electron transfer, which strengthened electronic coupling between secondary imine with catalyst, resulting in a flat configuration that was conducive to CN 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.