文献类型：期刊文献

英文题名：CO Activation Using Nitrogen-Doped Carbon Nanotubes for Reductive Carbonylation of Nitroaromatics to Benzimidazolinone and Phenyl Urea

作者：Wu, Qiumin[1,2];Chen, Jinzhu[2];Liu, Zhen[1];Xu, Yisheng[1]

机构：[1]East China Univ Sci & Technol, State Key Lab Chem Engn, Int Joint Res Ctr Green Energy Chem Engn, Shanghai 200237, Peoples R China;[2]Jinan Univ, Dept Chem, Coll Chem & Mat Sci, Guangzhou 511443, Peoples R China

年份：2020

卷号：12

期号：43

起止页码：48700

外文期刊名：ACS APPLIED MATERIALS & INTERFACES

收录：;EI(收录号：20204709502358);WOS:【SCI-EXPANDED(收录号:WOS:000586868400046)】；

基金：This work was financially supported by the National Natural Science Foundation of China (U1810111, 22075104, and 21676089), Natural Science Foundation of Guangdong Province, China (2018B030311010), and Youth Science and Technology Innovation Talent of Guangdong TeZhi Plan (2019TQ05L111).

语种：英文

外文关键词：carbon catalysis; carbon monoxide; carbonylation; defect; nitrogen-doped carbon nanotubes

摘要：Carbonylation of nitroaromatics with CO is extensively investigated with efficient but precious group 8-10 metal-based catalysts for the productions of both industrially and academically important chemicals such as isocyanates, formamides, carbamates, ureas and several types of heterocyclic compounds. Herein, we report that rationally designed nitrogendoped carbon nanotubes (N-CNTs) exhibit catalytic activity toward CO activation for carbonylation of nitroaromatics to benzimidazolinones and ureas. Under the optimal conditions, N-CNT-promoted intramolecular carbonylation of 2-nitroaniline (1a) with CO leads to formation of 1,3-dihydro-2H-benzo[d]imidazol-2-one in 90% yield. Moreover, an intermolecular carbonylation of nitrobenzene and aniline with CO in the presence of the N-CNT gives 70% yield of N,N'-diphenylurea. The N-CNT is also applicable to various benzimidazolinones and phenyl ureas; moreover, it can be readily reused at least 9 times for the carbonylation. The theoretical investigation based on density functional theory calculations indicates that the graphitic N of the N-CNT plays a crucial step in the 1a reduction with CO. The correlation between the structural defect and catalytic performance of the N-CNT reveals an enhanced catalytic activity of the N-CNT with its increased structural defects. This research thus represents a major breakthrough in CO activation for nitroaromatic carbonylation with environmental-friendly, low-cost, and carbon-based catalysts as a potential alternative to expensive and scarce noble-metalbased catalysts.