文献类型：期刊文献

英文题名：Pulse electrodeposited CuCo catalyst for ultrahigh mass activity and selectivity of ammonia production from nitrate electroreduction

作者：Shamim, Hossain Md[1];Zhou, Linfeng[1];Li, Hong-Shuang[1];Qiu, Kaipei[1,2,3,4]

机构：[1]East China Univ Sci & Technol, Sch Resources & Environm Engn, Key Lab Environm Risk Assessment & Control Chem Pr, Minist Ecol & Environm, Shanghai 200237, Peoples R China;[2]State Key Lab Coal Liquificat Gasificat & Utilizat High Efficiency & Low Carbon, Shanghai 200237, Peoples R China;[3]Shanghai Inst Pollut Control & Ecol Secur, Shanghai 200292, Peoples R China;[4]Shanghai Environm Protect Key Lab Environm Stand & Risk Management Chem Pollutants, Shanghai 200237, Peoples R China

年份：2026

卷号：559

外文期刊名：ELECTROCHIMICA ACTA

收录：;EI(收录号：20261120262283);WOS:【SCI-EXPANDED(收录号:WOS:001735502900001)】；

基金：This study was supported by the National Key R&D Program of China (2023YFC3008803) , the National Natural Science Foundation of China (21972041 and 22006037) , the Natural Science Foundation of Shanghai Municipality (23ZR1416300) , and the Fundamental Research Funds for the Central Universities.

语种：英文

外文关键词：Nitrate reduction; Electrocatalysis; Bimetallic; Electrodeposition; Pulse reverse current

摘要：The increasing demand of high-concentration nitrate (NO3-N) wastewater treatment has driven the development of electrochemical nitrate reduction (NO3RR) due to its mild and controllable conditions, environmental friendliness, suitability for resource recovery. Copper (Cu)-based catalysts are commonly considered in NO3RR for their low cost, medium efficiency and ease of fabrication; however, the large-scale application is hindered by poor selectivity and low mass activity. To solve this challenge, we developed a copper-cobalt (CuCo) bimetallic catalyst using pulse electrodeposition. To start with, the direct current (DC) deposition method was employed to enhance product selectivity, with cobalt impregnation and sodium citrate (Na3C6H5O7) as a complexing agent. The obtained DC-CuCo catalyst demonstrated a significantly reduced nitrite (NO2-N) byproduct peak (3.7 %) and high NO3-N removal rate (93 %) within one hour, as well as an overall Faradaic efficiency of 87.8 % for ammonia (NH3) production. To further increase mass-specific activity, a pulse reverses current deposition (PRC) was adopted and optimized to remove less efficient and unstable active sites. The resulting PRC-CuCo catalyst exhibited a substantially greater electrochemical surface area and lower charge transfer resistance, leading to a significantly enhanced NH3 generation rate of 0.359 mmolh-1 mg-1, which almost doubled the performance of DC-CuCo catalyst, along with a further improved NO3-N removal rate of 96 % and a NO2-N byproduct peak at 3.16 %. Structural characterizations combined with NO2-reduction analysis confirmed the synergistic "tandem catalysis" mechanism, in which the Cu active site primarily facilitated the initial NO3-adsorption and NO2-conversion, while the Co active sites accelerated the subsequent hydrogenation, suppressing intermediate accumulation thereby mitigating the NO2-accumulation in "NO3--* NO2--* NH3" pathway. Overall, this works demonstrates that PRC electrodeposition is a simple yet effective strategy for designing high performance Cu-based bimetallic catalysts with enhanced mass activity, selectivity and stability for NO3RR.