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Published on: April 6, 2017
Enhanced Electrochemical C-N Coupling for Glycine Synthesis via an Active Hydrogen Pump
Jiankang Liu1,2, Hengan Wang3,4, Zhonghua Wu2,4
1Institute of Rare and Scattered Elements, College of Chemistry, Liaoning University, Shenyang, P. R. China.
Abstract:
Direct electrochemical C-N coupling of abundant carbon and nitrogen feedstocks offers a sustainable route to glycine synthesis, yet achieving high efficiency remains challenging. Here, we develop an In-Bi catalyst by incorporating oxophilic indium (In) into a bismuth (Bi) matrix. During the co-reduction of oxalic acid and NO3 -, the In-Bi catalyst delivers an exceptional Faradaic efficiency toward glycine (FEGlycine) of 83.3% with an industrial-level current density of 361.3 mA cm-2, together with a glycine production rate of 4.3 mol h-1 gcat. -1. It outperforms pristine Bi and previously reported state-of-the-art catalysts. Large-scale glycine electrosynthesis is further demonstrated over a 10 cm2 In-Bi electrode, achieving a total current of 1.5 A with FEGlycine of 68.5% and yielding 1.4 g of glycine in 6 h. Mechanistically, oxalic acid and NO3 - first form glyoxylic acid oxime (GAO). Subsequently, In sites act as an "active hydrogen pump" to accelerate H2O dissociation, providing abundant surface-active hydrogen (*H) for efficient GAO hydrogenation to glycine. Meanwhile, the incorporation of In modulates the electronic structure of the Bi matrix, enhancing GAO adsorption and electron transfer. The synergistic regulation of *H supply and electronic structure accelerates the conversion of GAO to glycine, resulting in superior performance of In-Bi.
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