文献类型：期刊文献

英文题名：Regulation of Active Hydrogen and Nitrate Concentration: Pulsed Potential Strategies in Nitrate Electroreduction Microenvironments

作者：Gu, Lin[1];Song, Nan[2];Wu, Ziyang[1];Luo, Hongxia[1];Chen, Jun[3];Yang, Jianping[1]

机构：[1]Donghua Univ, Coll Mat Sci & Engn, State Key Lab Adv Fiber Mat, Shanghai 201620, Peoples R China;[2]East China Univ Sci & Technol, State Key Lab Chem Engn, Shanghai 200237, Peoples R China;[3]Univ Wollongong, Intelligent Polymer Res Inst, Innovat Campus,Squires Way, Wollongong, NSW 2500, Australia

年份：2026

卷号：65

期号：7

外文期刊名：ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

收录：;EI(收录号：20255219801403);WOS:【SCI-EXPANDED(收录号:WOS:001644815000001)】；

基金：This work was supported by National Natural ScienceFoundation of China (No. 52172291, No.52473294 andNo.52122312), the Fundamental Research Funds for theCentral Universities (CUSF-DH-D-2025001), and the StateKey Laboratory of Advanced Fiber Materials (DonghuaUniversity).

语种：英文

外文关键词：Active hydrogen; Electrocatalytic reduction of nitrate; High-rate conversion; Nitrogen gas

摘要：The electrochemical reduction of nitrate (eNO3RR) plays a significant role in the nitrogen cycle and environmental remediation. The dynamics of active hydrogen in the eNO3RR were studied in depth by varying the nitrate concentration and applying a pulsed-potential approach. The effect of both factors on regulation of the degree of hydrogenation of the intermediates and the product distribution was evaluated. Density functional theory (DFT) calculations indicated that elevated nitrate levels decrease the energy barrier for *NO to *ONNO conversion, enhancing the adsorption of *NO3. The experimental results indicate that under high nitrate concentrations, copper-palladium (CuPd) catalysts exhibit faster reaction kinetics and higher nitrogen selectivity. In situ characterizations illuminated the critical role of active hydrogen on reaction intermediates. The CuPd catalyst achieved 95% NO3-N conversion and 99% N2 selectivity at 1 M nitrate by pulse potential modulation of the active hydrogen concentration on the catalyst surface. Finite element analysis (FEA) and molecular dynamics (MD) simulations verified that pulsed potentials modulate the local nitrate and hydrogen ion concentrations. The present work brings the eNO3RR closer to practical applications, aiding in environmental protection and the balance of the nitrogen cycle.