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Water-involving transfer hydrogenation and dehydrogenation of N-heterocycles over a bifunctional MoNi4 electrode
Chinese Journal of Catalysis ( IF 15.7 ) Pub Date : 2021-08-30 , DOI: 10.1016/s1872-2067(21)63834-2
Mengyang Li 1, 2 , Cuibo Liu 1 , Yi Huang 1 , Shuyan Han 1 , Bin Zhang 1, 3
Affiliation  

A room-temperature electrochemical strategy for hydrogenation (deuteration) and reverse dehydrogenation of N-heterocycles over a bifunctional MoNi4 electrode is developed, which includes the hydrogenation of quinoxaline using H2O as the hydrogen source with 80% Faradaic efficiency and the reverse dehydrogenation of hydrogen-rich 1,2,3,4-tetrahydroquinoxaline with up to 99% yield and selectivity. The in situ generated active hydrogen atom (H*) is plausibly involved in the hydrogenation of quinoxaline, where a consecutive hydrogen radical coupled electron transfer pathway is proposed. Notably, the MoNi4 alloy exhibits efficient quinoxaline hydrogenation at an overpotential of only 50 mV, owing to its superior water dissociation ability to provide H* in alkaline media. In situ Raman tests indicate that the NiII/NiIII redox couple can promote the dehydrogenation process, representing a promising anodic alternative to low-value oxygen evolution. Impressively, electrocatalytic deuteration is easily achieved with up to 99% deuteration ratios using D2O. This method is capable of producing a series of functionalized hydrogenated and deuterated quinoxalines.



中文翻译:

双功能MoNi4电极上N-杂环的涉及水的转移氢化和脱氢

开发了一种在双功能 MoNi 4电极上对N-杂环进行加氢(氘化)和反向脱氢的室温电化学策略,其中包括使用 H 2 O 作为氢源的喹喔啉加氢(法拉第效率为 80%)和反向脱氢富氢 1,2,3,4-四氢喹喔啉的产率和选择性高达 99%。该原位生成的活性氢原子(H *)的振振有词涉及喹喔啉,其中提出了一种连续氢自由基偶联的电子传递路径的氢化。值得注意的是,MoNi 4合金在仅 50 mV 的过电位下表现出有效的喹喔啉氢化,因为它具有在碱性介质中提供 H* 的优异水离解能力。原位拉曼测试表明,Ni II / Ni III氧化还原对可以促进脱氢过程,是低值析氧的有前途的阳极替代品。令人印象深刻的是,使用 D 2 O可以轻松实现高达 99% 的氘化率的电催化氘化。该方法能够生产一系列功能化的氢化和氘化喹喔啉。

更新日期:2021-08-30
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