Dynamic dissolution-reorganization of molybdenum triggers synergistic electrocatalysis on copper for efficient nitrate-to-ammonia conversion

IF 19.7 1区化学 Q1 CHEMISTRY, PHYSICAL

Applied Catalysis B: Environmental Pub Date : 2025-11-11 DOI:10.1016/j.apcatb.2025.126187

Xuran Mao, Yanbing Huang, Yue Xiao, Xun Liu, Yan Pei, Qianwen Chen, X.H. Wang, Wen Guo, Hong‐Bing Yang, Fuxi Bao

{"title":"Dynamic dissolution-reorganization of molybdenum triggers synergistic electrocatalysis on copper for efficient nitrate-to-ammonia conversion","authors":"Xuran Mao, Yanbing Huang, Yue Xiao, Xun Liu, Yan Pei, Qianwen Chen, X.H. Wang, Wen Guo, Hong‐Bing Yang, Fuxi Bao","doi":"10.1016/j.apcatb.2025.126187","DOIUrl":null,"url":null,"abstract":"Developing highly efficient and robust electrocatalysts to enhance the kinetics of electrochemical nitrate reduction reaction (NO 3 RR) to ammonia is crucial for realizing the conversion and storage of green electrochemical ammonia energy. Herein, we constructed a molybdenum-doped metallic copper electrocatalyst (Cu-Mo 0.2 /NF) and systematically investigated the pivotal role of molybdenum dynamic recombination in enhancing the kinetics of the NO 3 RR. In situ Raman spectroscopy, XPS and ICP-OES reveals that Mo dissolves during the NO 3 RR process and recombines into Mo 2 O 7 2- species, which are adsorbed onto the surface of the electrocatalyst. The experimental results combined with DFT calculations indicates that this dynamic dissolution, reorganization, and adsorption process of Mo significantly activates *NO 3 , thereby greatly enhancing the kinetics of *NO 3 reduction to *NO 2 . Furthermore, Differential electrochemical mass spectrometry (DEMS) and in situ attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) elucidate the NO 3 RR pathway: *NO 3 → *NO 2 → *NO → *NOH → *N → *NH → *NH 2 → *NH 3 . This reaction mechanism, which circumvents high-energy-barrier step (NO → N 2 O), endows the electrocatalyst with superior kinetics and high selectivity. Benefiting from the dynamic dissolution and redeposition of Mo and the advantages of the reaction pathway, the electrocatalyst achieves a record ammonia yield ( 1.55 mmol h -1 cm -2 ) with near-unity Faradaic efficiency ( 98.99% ), and 30 h stability. The Mo-doped metallic copper electrocatalyst supported on nickel foam (Cu-Mo 0.2 /NF) was designed. During the NO 3 RR process in alkaline media, Mo dissolves into the electrolyte and is subsequently transformed into adsorbed Mo 2 O 7 2- species on the electrocatalyst surface. The dynamic reconstruction of Mo 2 O 7 2- accelerates * NO 3 →* NO 2 kinetics for NO 3 RR, achieving a record ammonia yield of 1.55 mmol h -1 cm -2 with 98.99% Faraday efficiency. • The Cu-Mo 0.2 /NF was fabricated via a one-step electrodeposition method. • In situ Raman spectroscopy revealed the dissolution-redeposition mechanism of Mo. • The formed Mo 2 O 7 2- species can accelerate the * NO 3 → * NO 2 kinetics. • The electrocatalyst achieves an NH 3 yield of 1.55 mmol h -1 cm -2 with 98.99% FE. • In situ experiments (DEMS and ATR-FTIR) revealed the NO 3 RR pathway.","PeriodicalId":244,"journal":{"name":"Applied Catalysis B: Environmental","volume":"384 1","pages":"126187-126187"},"PeriodicalIF":19.7000,"publicationDate":"2025-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"1","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Applied Catalysis B: Environmental","FirstCategoryId":"0","ListUrlMain":"https://doi.org/10.1016/j.apcatb.2025.126187","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}

引用次数: 1

Abstract

Developing highly efficient and robust electrocatalysts to enhance the kinetics of electrochemical nitrate reduction reaction (NO 3 RR) to ammonia is crucial for realizing the conversion and storage of green electrochemical ammonia energy. Herein, we constructed a molybdenum-doped metallic copper electrocatalyst (Cu-Mo 0.2 /NF) and systematically investigated the pivotal role of molybdenum dynamic recombination in enhancing the kinetics of the NO 3 RR. In situ Raman spectroscopy, XPS and ICP-OES reveals that Mo dissolves during the NO 3 RR process and recombines into Mo 2 O 7 2- species, which are adsorbed onto the surface of the electrocatalyst. The experimental results combined with DFT calculations indicates that this dynamic dissolution, reorganization, and adsorption process of Mo significantly activates *NO 3 , thereby greatly enhancing the kinetics of *NO 3 reduction to *NO 2 . Furthermore, Differential electrochemical mass spectrometry (DEMS) and in situ attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) elucidate the NO 3 RR pathway: *NO 3 → *NO 2 → *NO → *NOH → *N → *NH → *NH 2 → *NH 3 . This reaction mechanism, which circumvents high-energy-barrier step (NO → N 2 O), endows the electrocatalyst with superior kinetics and high selectivity. Benefiting from the dynamic dissolution and redeposition of Mo and the advantages of the reaction pathway, the electrocatalyst achieves a record ammonia yield ( 1.55 mmol h -1 cm -2 ) with near-unity Faradaic efficiency ( 98.99% ), and 30 h stability. The Mo-doped metallic copper electrocatalyst supported on nickel foam (Cu-Mo 0.2 /NF) was designed. During the NO 3 RR process in alkaline media, Mo dissolves into the electrolyte and is subsequently transformed into adsorbed Mo 2 O 7 2- species on the electrocatalyst surface. The dynamic reconstruction of Mo 2 O 7 2- accelerates * NO 3 →* NO 2 kinetics for NO 3 RR, achieving a record ammonia yield of 1.55 mmol h -1 cm -2 with 98.99% Faraday efficiency. • The Cu-Mo 0.2 /NF was fabricated via a one-step electrodeposition method. • In situ Raman spectroscopy revealed the dissolution-redeposition mechanism of Mo. • The formed Mo 2 O 7 2- species can accelerate the * NO 3 → * NO 2 kinetics. • The electrocatalyst achieves an NH 3 yield of 1.55 mmol h -1 cm -2 with 98.99% FE. • In situ experiments (DEMS and ATR-FTIR) revealed the NO 3 RR pathway.

查看原文本刊更多论文

钼的动态溶解重组触发铜的协同电催化以实现硝酸盐到氨的高效转化

开发高效、稳健的电催化剂，提高硝酸还原反应（NO 3 RR）制氨动力学，是实现绿色电化学氨能转化和储存的关键。本文构建了一种掺杂钼的金属铜电催化剂（Cu-Mo 0.2 /NF），系统地研究了钼动态复合在提高NO 3 RR动力学中的关键作用。原位拉曼光谱、XPS和ICP-OES分析表明，Mo在no3rr过程中溶解并重组为mo2o3 -，并吸附在电催化剂表面。实验结果结合DFT计算表明，Mo的动态溶解、重组和吸附过程显著激活了*NO 3，从而大大增强了*NO 3还原为*NO 2的动力学。此外，差分电化学质谱（DEMS）和原位衰减全反射-傅里叶变换红外光谱（ATR-FTIR）阐明了NO 3的RR途径：*NO 3→*NO 2→*NO→*NOH→*N→*NH→*NH 2→*NH 3。该反应机制绕过了NO→n2这一高能量势垒步骤，使得电催化剂具有优异的动力学和高选择性。利用Mo的动态溶解和再沉积以及反应途径的优势，电催化剂获得了创纪录的氨产率（1.55 mmol h -1 cm -2）、接近统一的法拉第效率（98.99%）和30 h稳定性。设计了泡沫镍负载的掺钼金属铜电催化剂（Cu-Mo 0.2 /NF）。在碱性介质中的no3rr过程中，Mo溶解到电解液中，随后转化为吸附在电催化剂表面的mo2o3 -。mo2o3 -的动态重构加速了no3 RR的* no3→* no2动力学，实现了创纪录的1.55 mmol h -1 cm -2的氨收率和98.99%的法拉第效率。•采用一步电沉积法制备Cu-Mo 0.2 /NF。•原位拉曼光谱揭示了Mo的溶解-再沉积机理。•形成的mo2o3 -可以加速* no3→* no2动力学。•电催化剂的nh3产率为1.55 mmol h -1 cm -2， FE为98.99%。•原位实验（dem和ATR-FTIR）揭示了NO 3 RR通路。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

来源期刊

Applied Catalysis B: Environmental 环境科学-工程：化工

CiteScore

38.60

自引率

6.30%

发文量

1117

审稿时长

24 days

期刊介绍： Applied Catalysis B: Environment and Energy (formerly Applied Catalysis B: Environmental) is a journal that focuses on the transition towards cleaner and more sustainable energy sources. The journal's publications cover a wide range of topics, including: 1.Catalytic elimination of environmental pollutants such as nitrogen oxides, carbon monoxide, sulfur compounds, chlorinated and other organic compounds, and soot emitted from stationary or mobile sources. 2.Basic understanding of catalysts used in environmental pollution abatement, particularly in industrial processes. 3.All aspects of preparation, characterization, activation, deactivation, and regeneration of novel and commercially applicable environmental catalysts. 4.New catalytic routes and processes for the production of clean energy, such as hydrogen generation via catalytic fuel processing, and new catalysts and electrocatalysts for fuel cells. 5.Catalytic reactions that convert wastes into useful products. 6.Clean manufacturing techniques that replace toxic chemicals with environmentally friendly catalysts. 7.Scientific aspects of photocatalytic processes and a basic understanding of photocatalysts as applied to environmental problems. 8.New catalytic combustion technologies and catalysts. 9.New catalytic non-enzymatic transformations of biomass components. The journal is abstracted and indexed in API Abstracts, Research Alert, Chemical Abstracts, Web of Science, Theoretical Chemical Engineering Abstracts, Engineering, Technology & Applied Sciences, and others.