催化学报 ›› 2026, Vol. 86: 201-211.DOI: 10.1016/S1872-2067(26)65046-2

• 论文 • 上一篇    下一篇

透散电极原位重构AgZn3用于安培级CO2电还原

刘小虎a,1, 李守杰a,1, 毛佳宁a,c,1, 陈奥辉a, 董笑a,*(), 韦懿恒a, 夏嘉雨a,b, 朱桓毅a,b, 王晓童a,b, 徐子然a,b,c, 李桂花a, 宋艳芳a, 魏伟a,b,*(), 陈为a,b,*()   

  1. a 中国科学院上海高等研究院, 低碳转化科学与工程中心, 上海 201210
    b 中国科学院大学, 北京 100049
    c 中国科学院上海应用物理研究所, 上海 201204
  • 收稿日期:2025-10-30 接受日期:2025-12-18 出版日期:2026-07-05 发布日期:2026-06-12
  • 通讯作者: *电子信箱: dongx@sari.ac.cn (董笑),
    weiwei@sari.ac.cn (魏伟),
    chenw@sari.ac.cn (陈为).
  • 作者简介:第一联系人:1共同第一作者.
  • 基金资助:
    中国科学院前瞻战略科技先导专项(XDB1500302);中国科学院前瞻战略科技先导专项(XDA0390402);国家重点研发项目(2022YFA1504604);国家自然科学基金(22478408);国家自然科学基金(22479156);国家自然科学基金(22302223);内蒙古自治区科技重大专项项目(2021ZD0020);河北省现代钢铁产业创新专项(252G4001D);上海市科委科技创新计划(23DZ1202600);上海市科委科技创新计划(23DZ1201804);上海市学术/科技研究带头人计划(23XD1404400);上海扬帆计划(23YF1453300);中国科学院青年创新促进会(E224301401);中国科学院上海分院优秀青年人才计划(E254991ZZ1)

Engineering substitutional AgZn3 on penetration electrodes via in-situ reconstruction for ampere-level CO2 electroreduction

Xiaohu Liua,1, Shoujie Lia,1, Jianing Maoa,c,1, Aohui Chena, Xiao Donga,*(), Yiheng Weia, Jiayu Xiaa,b, Huanyi Zhua,b, Xiaotong Wanga,b, Ziran Xua,b,c, Guihua Lia, Yanfang Songa, Wei Weia,b,*(), Wei Chena,b,*()   

  1. a Low-Carbon Conversion Science and Engineering Center, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210, China
    b University of Chinese Academy of Sciences, Beijing 100049, China
    c Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201204, China
  • Received:2025-10-30 Accepted:2025-12-18 Online:2026-07-05 Published:2026-06-12
  • About author:First author contact:1Contributed equally to this work.
  • Supported by:
    Strategic Priority Research Program of the Chinese Academy of Sciences(XDB1500302);Strategic Priority Research Program of the Chinese Academy of Sciences(XDA0390402);National Key R&D Program of China(2022YFA1504604);National Natural Science Foundation of China(22478408);National Natural Science Foundation of China(22479156);National Natural Science Foundation of China(22302223);Major Project of the Science and Technology Department of Inner Mongolia(2021ZD0020);Special Project for Innovation in Modern Steel Industry of Hebei Province(252G4001D);Science and Technology Innovation Plan of Shanghai Science and Technology Commission(23DZ1202600);Science and Technology Innovation Plan of Shanghai Science and Technology Commission(23DZ1201804);Program of Shanghai Academic/Technology Research Leader(23XD1404400);Shanghai Sailing Program(23YF1453300);Youth Innovation Promotion Association of Chinese Academy of Sciences(E224301401);Outstanding Young Talent Project of Shanghai Advanced Research Institute, Chinese Academy of Sciences(E254991ZZ1)

摘要:

电化学还原二氧化碳(eCO2RR)为高附加值化学品(如CO)是缓解碳排放和实现碳循环经济的重要途径. 然而, eCO2RR面临高过电位、竞争性析氢反应(HER)以及工业级电流密度下催化剂稳定性不足等关键挑战. 贵金属(如Ag)对CO选择性高, 但成本昂贵, 而储量丰富的锌(Zn)催化剂的本征活性有限, 因此可以通过将痕量Ag与Zn合金化的策略以调节电子结构、优化反应能垒并平衡成本与性能. 本研究提出通过电化学诱导的原位重构策略, 在具有独特传质优势的透散电极上构筑高分散的合金活性界面, 旨在协同优化反应物的传质过程.

本文通过化学置换、氧化烧结及电化学还原结合的方法, 设计并制备了一种表面合金化的银锌中空纤维透散电极(Ag-Zn HPE), 无需传统的高温合金化过程. 首先在Zn中空纤维粗胚上引入微量银物种, 经烧结形成Ag-ZnO中空纤维前驱体. 随后在电化学还原过程中, 电场驱动下原本与氧化锌基底相分离的银物种发生结构重构, 与Zn基底合金化形成高度分散的AgZn3合金相. 多种结构表征表明, 电化学重构使原本团聚的Ag2O/Ag纳米团簇均匀分散并嵌入Zn晶格, 形成了Ag-Zn合金活性位点, 同时电极仍然保持了中空纤维的多孔透散结构. 在3.0 mol L−1 KCl电解液中, 该Ag-Zn合金透散电极表现出优异的CO2电还原性能, 在1.2 A cm−2的高电流密度下CO法拉第效率保持在91%以上, 并稳定运行超过150 h. 对比纯Zn透散电极, 合金电极在宽电位范围内显示出更低的过电位, 其CO分电流密度在−1.20 V vs. RHE时可达1.39 A cm−2, 技术经济分析进一步表明其CO生产成本更低, 展现出良好的工业化应用前景. 此外, 透散效应的理论电流密度和电化学表征表明, 独特的中空纤维结构可强制CO2气体直接穿透表面合金化的多孔壁到达活性位点, 有效克服了传统扩散模式下因CO2低溶解度带来的传质限制, 使电催化在较高电流下仍由eCO2RR主导. 理论计算表明, 合金化调控了Zn的电子结构, 使其d带中心上移, 优化了关键中间体*COOH的吸附和*CO的脱附能垒, 同时有效抑制了HER副反应.

综上, 本工作通过电化学原位重构策略, 在具有高效传质结构的中空纤维透散电极上构筑高活性AgZn3合金位点, 实现了CO2在高电流密度下向CO的高效转化, 阐明了合金化和透散效应对反应动力学的调控机制, 为面向工业应用的电极设计提供了新思路.

关键词: CO2电还原, 结构重构, 电催化剂, 中空纤维透散电极, 银锌合金

Abstract:

The electrochemical reduction of CO2 to CO offers a promising route for mitigating carbon emissions and producing sustainable feedstocks. Although noble metals like Ag exhibit high CO selectivity, their high cost and scarcity hinder scalability. Earth-abundant Zn catalysts suffer from intrinsic activity limitations, while alloying with trace Ag would modulate electronic structures for tuning its CO2 electroreduction activity. Herein, a surface-alloyed Ag-Zn hollow-fiber penetration electrode (HPE) is constructed via an electrochemically induced reconfiguration process that transforms the initial phase-separated Ag clusters on ZnO substrate into a homogeneously dispersed Ag-Zn alloy (AgZn3). The resulting Ag-Zn HPE achieves 91% faradaic efficiency for CO at 1.2 A cm−2 and demonstrates long-term electrolysis over 150 hours, as well as promising cost-effectiveness for industrial applications. Combined with the penetration effect that effectively mitigates CO2 mass transport limitations, the HPE enables high-rate CO production even at large current densities. Mechanistic investigations reveal that alloying modifies the d-band center of Zn, strengthens *COOH adsorption and facilitates *CO desorption to boost CO formation while suppressing hydrogen evolution reaction. This work provides fundamental insights into the role of surface alloying in enhancing CO2 reduction kinetics and presents a scalable electrode architecture with significant potential for sustainable CO2 conversion.

Key words: CO2 electroreduction, Structural reconfiguration, Electrocatalyst, Hollow-fiber penetration electrode, Ag-Zn alloy