Kaimeng Huang, Siyuan Chen, Changjiu Xia, Chenhao Li, Bin Zhu, Hongyi Gao, Xinxin Peng, Min Lin, Yibin Luo, Ge Wang, Xingtian Shu
State Key Laboratory of Catalytic Materials and Reaction Engineering, Research Institute of Petroleum Processing, SINOPEC 100083 Beijing The People's Republic of China
Beijing Advanced Innovation Center for Materials Genome Engineering, School of Materials Science and Engineering, University of Science and Technology Beijing Beijing 100083 The People's Republic of China
RSC Adv. 2020 Oct 1;10(59):36111-36118. doi: 10.1039/d0ra06367c. eCollection 2020 Sep 28.
The oxidative coupling of imines to ketazine with molecular oxygen is a green process towards the synthesis of hydrazine or hydrazine hydrate, which could efficiently address the economic and environmental issues of the traditional Raschig or peroxide-ketazine process. Herein, we developed an efficient heterogeneous base-free benzophenone imine oxidative coupling route with O catalyzed by Cu/CuO /carbon materials derived from MOFs under mild conditions. Under optimized conditions, the conversion of BI is up to 98.2% and the selectivity of ketamine is 94.9%. This catalyst has excellent structure stability, recycling, and regeneration performance, owing to the carbonization of organic ligands of MOF at high temperature. More importantly, it is confirmed that the metallic Cu core is essential to improve the catalytic performance of the CuO shell in the BI oxidative coupling reaction, due to the promotion of electron transfer in the CuO surface, making dissolved O molecules more easily insert oxygen vacancies. This strategy might open an avenue to the sustainable catalytic synthesis of hydrazine or hydrazine hydrate.
亚胺与分子氧氧化偶联生成酮连氮是合成肼或水合肼的绿色过程，这可以有效解决传统拉西希法或过氧化物 - 酮连氮法的经济和环境问题。在此，我们开发了一种高效的非均相无碱二苯甲酮亚胺氧化偶联路线，在温和条件下由源自金属有机框架（MOF）的Cu/CuO/碳材料催化O₂。在优化条件下，二苯甲酮亚胺（BI）的转化率高达98.2%，酮连氮的选择性为94.9%。由于MOF有机配体在高温下碳化，该催化剂具有优异的结构稳定性以及循环和再生性能。更重要的是，已证实金属Cu核对于提高CuO壳层在BI氧化偶联反应中的催化性能至关重要，这是因为它促进了CuO表面的电子转移，使溶解的O₂分子更容易插入氧空位。该策略可能为肼或水合肼的可持续催化合成开辟一条途径。
