Regulating Ni site in NiV LDH for efficient electrocatalytic production of formate and hydrogen by glycerol electrolysis

作     者：Lin Dong Guan-Ru Chang Yi Feng Xian-Zhi Yao Xin-Yao Yu Lin Dong;Guan-Ru Chang;Yi Feng;Xian-Zhi Yao;Xin-Yao Yu

作者机构：Key Laboratory of Structure and Functional Regulation of Hybrid MaterialsInstitutes of Physical Science and Information TechnologyAnhui UniversityMinistry of Education.Hefei 230601China School of Chemistry and Chemical EngineeringHuangshan UniversityHuangshan 245041China Department of Polymer Materials and EngineeringAcademy of Chemical EngineeringHebei University of TechnologyTianjin 300130China Ningbo Research Institute of Ecological and Environmental SciencesNingbo 315000China Energy Materials and Devices Key Laboratory of Anhui Province for Photoelectric ConversionAnhui UniversityHefei 230601China 

出 版 物：《Rare Metals》 (稀有金属（英文版）)

年 卷 期：2022年第41卷第5期

页      面：1583-1594页

核心收录：

学科分类：081702[工学-化学工艺] 081705[工学-工业催化] 0806[工学-冶金工程] 08[工学] 0817[工学-化学工程与技术] 0805[工学-材料科学与工程（可授工学、理学学位）] 080502[工学-材料学] 

基　　金：the National Science Foundation of China(No.12075002) the Outstanding Youth Fund of Anhui Province(No.2008085J21) Anhui Provincial Supporting Program for Excellent Young Talents in Universities(No.gxyqZD2019005) the Innovation and Entrepreneurship Project of Overseas Returnees in Anhui Province(No.2019LCX018) 

主　　题：Glycerol electrolysis Glycerol oxidation reaction Hydrogen evolution reaction NiV LDH Formate 

摘      要：Energy-saving glycerol electrolysis with lower potential than water spitting endows a promising way for the concurrent production of value-added formate and high-purity hydrogen. However, there is still lack of efficient electrocatalysts at both anode and cathode for glycerol electrolysis. Herein, we report the activation of Ni site in NiV layered double hydroxide(LDH) by electrochemical and N_(2)/H_(2) plasma regulations for boosting the activity of glycerol oxidation reaction(GOR) and hydrogen evolution reaction(HER), respectively. Specifically, boosted GOR performance with a low overpotential(1.23 V at 10 mA·cm^(-2)) and a high Faradic efficiency(94%) is demonstrated by electrochemically regulated NiV LDH(ENiV LDH) with elevated valence state of Ni site. In situ Raman spectrum reveals the generation of Ni(Ⅲ) species by electrochemical regulation, and the highly active Ni(Ⅲ)can be regenerated with the process of electrochemical oxidation. Additionally, the possible reaction pathway is speculated based on the in situ Fourier transform infrared spectroscopy(FTIR) and high-performance liquid chromatography results. The plasma-regulated NiV LDH(PNiV LDH) with lower valence state of Ni site exhibits outstanding HER activity, displaying a low overpotential of 45 m V to deliver 10 mA·cm^(-2).When employing E-NiV LDH and P-NiV LDH as anode and cathode electrocatalyst, respectively, the assembled electrolyzer merely needs 1.25 V to achieve 10 m A·cm^(-2) for simultaneous production of formate and hydrogen, demonstrating remarkable 320 mV of lower potential than water electrolysis.