Electrosynthesis of hydroxylamine from nitrate reduction in water  

作　　者：Xianen Lan Chuanqi Cheng Chengying Guo Minghao Guo Tieliang Li Yongmeng Wu Yifu Yu Bin Zhang 

机构地区：[1]Institute of Molecular Plus,Department of Chemistry,School of Science,Tianjin University,Tianjin 300072,China [2]Institute of New Energy Materials,School of Materials Science and Engineering,Tianjin University,Tianjin 300072,China [3]Haihe Laboratory of Sustainable Chemical Transformations,Tianjin 300192,China

出　　处：《Science China Chemistry》2023年第6期1758-1762,共5页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China(22271213(B.Z.)and 22071173(Y.Y.));the Haihe Laboratory of Sustainable Chemical Transformations;the National Postdoctoral Science Foundation of China(2022M722357(Y.W.))。

摘　　要：Hydroxylamine(NH_(2)OH),a vital but unstable industrial feedstock,is presently prepared under harsh conditions that cause environmental and energy concerns.Here,we report an electrochemical method to prepare oximes,which serve as precursors for NH_(2)OH after facile hydrolysis.The carbon-supported amorphous Mn electrocatalyst delivers a current density of~100 mA cm^(-2) with a Faradaic efficiency of 40.92%and a yield rate of 0.251 mmol cm^(-2)h^(-1) for formaldoxime(CH_(2)NOH)generation by using nitrate and formaldehyde as reactants.Formaldoxime can be easily released to produce NH_(2)OH via hydrolysis.Impressively,this method exhibits an economic advantage over conventional manufacturing based on techno-economic analysis.A series of control experiments,in situ characterizations,and theoretical simulations unveil the reaction mechanism via the spontaneous reaction between an aldehyde and*NH_(2)OH intermediate derived from nitrate electroreduction.The high activity of Mn originates from its inhibitory effects on the further reduction of key*NH_(2)OH intermediate.This strategy opens a sustainable and green way for NH_(2)OH synthesis under mild conditions using renewable energy.

关 键 词：ELECTROSYNTHESIS HYDROXYLAMINE nitrate reduction amorphous Mn reaction pathway 

分 类 号：O623.7[理学—有机化学]