摘要
Tandem water electrolysis for the transformation of universal feedstock to value-added chemicals integrated with hydrogen generation and in situ utilization is a promising approach to address the economic challenges of electrochemical hydrogen evolution and storage.Herein,we present the controllable electrocatalytic deuteration of halides using inexpensive and reusable heavy water(D2 O)as a D-source for the preparation of valuable D-labelled chemicals and pharmaceuticals under mild conditions.This electrochemical deuteration method with high efficiency and selectivity furnishes a series of D-labelled chemicals and pharmaceuticals in high yields with excellent D-incorporation.The reaction efficiency and selectivity,that is,the precise substitution of deuterium atoms at different halogen positions,can be tuned by varying the applied voltages.The results show the great potential of green and economical electrocatalytic methods for producing value-added fine chemicals in addition to hydrogen evolution.
利用电解水原位产生活性氢(氘)物种参与后续催化加氢反应可以实现低值化学品向高附加值产品转化,从而解决电解水析氢领域面临的氢气附加值不高以及存储过程的安全问题.本文以氘水为廉价、温和氘源,通过原位电解氘水与钯催化脱卤加氘反应串联设计,发展了温和条件下重水为氘源的转化氘化反应,实现了氘代化合物和氘代药物的绿色制造.该策略具有条件温和、氘代率高、易放大生产等优势,并可通过反应电压窗口来调控和优化反应电压,从而提供与反应物匹配的氧化还原环境,实现对不同卤代物以及不同反应位点的选择性脱卤氘代,具有高选择性、高产率和高法拉第效率特点.电解水产氢(氘)、用氢(氘)技术的创新发展将为以水资源为安全氢(氘)源的转移氢(氘)化反应的发展提供新的契机,具有潜在的工业应用前景.
作者
Bing Zhang
Chuntian Qiu
Shan Wang
Hua Gao
Kunyi Yu
Zhaofei Zhang
Xiang Ling
Wei Ou
Chenliang Su
张兵;邱春天;王山;高华;余坤益;张钊飞;凌祥;欧伟;苏陈良(International Collaborative Laboratory of 2D Materials for Optoelectronics Science and Technology of Ministry of Education,Institute of Microscale Optoelectronics,Shenzhen University,Shenzhen 518060,China;College of Materials Science and Engineering,Shenzhen University,Shenzhen 518060,China;School of Materials Science and Engineering,Ocean University of China,Qingdao 266100,China;Department of Chemistry,Tsinghua University,Beijing 100084,China)
基金
supported by the National Natural Science Foundation of China(21972094,21902105)
the National Postdoctoral Program for Innovative Talents(BX20180203)
China Postdoctoral Science Foundation(2018M643176)
Guangdong Special Support Program
Pengcheng Scholar program
Shenzhen Peacock Plan(KQJSCX20170727100802505 and KQTD2016053112042971)
Foundation for Distinguished Young Talents in Higher Education of Guangdong(2018KQNCX221)。
