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Solid-phase Synthesis of [4.4] Spirocyclic Oximes
Published on: February 6, 2019
From Mechanism to Catalyst: Integrated Catalysts for Direct Electrosynthesis of Glycine Through an Oxime Pathway
Ying Zhou1,2, Chaofan Wan3, Qizhi Min1,2
1State Key Laboratory of Precision and Intelligent Chemistry, University of Science and Technology of China, Hefei, Anhui, China.
Abstract:
The electrocatalytic synthesis of glycine from oxalic acid (H2C2O4) and hydroxylamine (NH2OH) involves a complex multi-step pathway comprising C-N coupling and multi-step selective protonation, making rational catalyst design a major challenge. In this work, by combining constant-potential density functional theory (DFT), the reaction mechanisms for the formation of glyoxylic oxime (GAO) from H2C2O4 and NH2OH on Pb surfaces, and its subsequent reduction to glycine on Cu surfaces are revealed. Guided by these mechanistic insights, we propose a set of criteria for designing integrated dual-site catalysts capable of catalyzing both GAO formation and selective protonation to glycine. Among the theoretically screened out integrated Pt1(Ir1, Ru1)/Pb(100) single atom catalysts, Pt1/Pb catalyst is synthesized experimentally, demonstrating high activity for glycine production. This study bridges fundamental mechanistic understanding with practical catalyst development for complex multi-step electrosynthesis.
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