Integrating Hydrogen Production and Transfer Hydrogenation with Selenite Promoted Electrooxidation of α-Nitrotoluenes to E-Nitroethenes.

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 SeOx 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 SeOx 2- via Se leaching-oxidation during electrooxidation, and the preferential adsorption of two -NO2 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 SeOx 2- , rationalizing the strategy of designing materials to suppress side reactions.