Direct electro-synthesis of valuable C=N compound from NO

被引:40
作者
Zhang, Xianhao [1 ]
Jing, Huijuan [1 ,2 ]
Chen, Shiming [1 ]
Liu, Bing [1 ]
Yu, Liang [1 ,2 ]
Xiao, Jianping [1 ,2 ]
Deng, Dehui [1 ,2 ]
机构
[1] Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Catalysis, Dalian 116023, Peoples R China
[2] Univ Chinese Acad Sci, Beijing 100049, Peoples R China
来源
CHEM CATALYSIS | 2022年 / 2卷 / 07期
基金
中国国家自然科学基金;
关键词
SELECTIVE CATALYTIC-REDUCTION; TOTAL-ENERGY CALCULATIONS; EPSILON-CAPROLACTAM; OXYGEN REDUCTION; NITRIC-OXIDE; ONE-STEP; ELECTROREDUCTION; EFFICIENCY; PLATINUM; INSIGHTS;
D O I
10.1016/j.checat.2022.06.003
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Cyclohexanone oxime ( CHO), a key C=N organic compound in the manufacture of nylon 6, is conventionally synthesized via amultistep process that consumes expensive NH3 and H-2 under harsh conditions. Herein, we report the direct electro-synthesis of CHO from low-cost NO, H2O, and cyclohexanone over a carbon catalyst under ambient conditions. A high Faradaic efficiency of 44.8% and a formation rate of 10.7 mg cm(-2) h(-1) for CHO were achieved at -0.4 V versus the reversible hydrogen electrode through optimizing the surface hydrophobicity of the catalyst to facilitate diffusion of reactants. Controlled experiments and 15N- labeling tests verified that the nitrogen in the CHO product originates from NO. Density functional theory calculations showed that the armchair edge of carbon could be the active site with a reaction mechanism following NO/ NO*/ HNO*/ HNOH*/ NH2OH/ CHO. This work suggests a direct, green, and low-cost synthesis strategy for high- value CHO from pollutant NO.
引用
收藏
页码:1807 / 1818
页数:12
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