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Integrating Hydrogen Production and Transfer Hydrogenation with Selenite Promoted Electrooxidation of α‐Nitrotoluenes to E ‐Nitroethenes
Author(s) -
Chong Xiaodan,
Liu Cuibo,
Wang Changhong,
Yang Rong,
Zhang Bin
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202108666
Subject(s) - electrochemistry , chemistry , adsorption , bifunctional , inorganic chemistry , anode , hydrogen , oxygen evolution , hydrogen production , leaching (pedology) , faraday efficiency , glassy carbon , electrode , catalysis , organic chemistry , cyclic voltammetry , environmental science , soil science , soil water
Developing an electrochemical carbon‐added reaction with accelerated kinetics to replace the low‐value and sluggish oxygen evolution reaction (OER) is markedly significant to pure hydrogen production. Regulating the critical steps to precisely design electrode materials to selectively synthesize targeted compounds is highly desirable. Here, inspired by the surfaced adsorbed SeO x 2− promoting OER, NiSe is demonstrated to be an efficient anode enabling α‐nitrotoluene electrooxidation to E‐nitroethene with up to 99 % E selectivity, 89 % Faradaic efficiency, and the reaction rate of 0.25 mmol cm −2 h −1 via inhibiting side reactions for energy‐saving hydrogen generation. The high performance can be associated with its in situ formed NiOOH surface layer and absorbed SeO x 2− via Se leaching‐oxidation during electrooxidation, and the preferential adsorption of two ‐NO 2 groups of intermediate on NiOOH. A self‐coupling of α‐carbon radicals and subsequent elimination of a nitrite molecule pathway is proposed. Wide substrate scope, scale‐up synthesis of E‐nitroethene, and paired productions of E‐nitroethene and hydrogen or N‐protected aminoarenes over a bifunctional NiSe electrode highlight the promising potential. Gold also displays a similar promoting effect for α‐nitrotoluene transformation like SeO x 2− , rationalizing the strategy of designing materials to suppress side reactions.