催化学报 ›› 2026, Vol. 89: 1-39.DOI: 10.1016/S1872-2067(26)65122-4

• 综述 •    下一篇

二氧化碳捕集与还原双功能材料的机理研究进展

杨春杰a,b, 魏娜a,*(), 王舒a, 张琪a, 刘曦阳a, 徐文超a, 侯克克b, 张宁强c, 李伶聪a,*(), 赵震a,b,*()   

  1. a沈阳师范大学化学化工学院,能源与环境催化研究所,辽宁沈阳 110034
    b中国石油大学(北京)理学院,重质油加工国家重点实验室,北京 102249
    c东北大学资源与土木工程学院,辽宁沈阳 110819
  • 收稿日期:2025-12-31 接受日期:2026-02-22 出版日期:2026-10-18 发布日期:2026-09-01
  • 通讯作者: *电子信箱: wwweina@126.com (魏娜),
    lilingcong@synu.edu.cn (李伶聪),
    zhenzhao@cup.edu.cn (赵震).
  • 基金资助:
    2025年沈阳师范大学博士点建设重点学科项目(099-52501002);辽宁省教育厅高等学校基本科研项目(LJ222510166005)

Progress in unraveling the mechanisms of dual functional materials for CO2 capture and reduction

Chunjie Yanga,b, Na Weia,*(), Shu Wanga, Qi Zhanga, Xiyang Liua, Wenchao Xua, Keke Houb, Ningqiang Zhangc, Lingcong Lia,*(), Zhen Zhaoa,b,*()   

  1. aInstitute of Catalysis for Energy and Environment, College of Chemistry and Chemical Engineering, Shenyang Normal University, Shenyang 110034, Liaoning, China
    bState Key Laboratory of Heavy Oil Processing, College of Science, China University of Petroleum, Beijing 102249, China
    cSchool of Resources and Civil Engineering, Northeastern University, Shenyang 110819, Liaoning, China
  • Received:2025-12-31 Accepted:2026-02-22 Online:2026-10-18 Published:2026-09-01
  • Contact: *E-mail:wwweina@126.com(N. Wei),lilingcong@synu.edu.cn(L. Li),zhenzhao@cup.edu.cn(Z. Zhao).
  • About author:Na Wei (College of Chemistry and Chemical Engineering, Shenyang Normal University) received her Ph.D. degree from Liaoning University in 2017. In the same year, she joined the Institute of Catalysis for Energy and Environment, College of Chemistry and Chemical Engineering, Shenyang Normal University as a faculty member. Her current research interests focus on novel materials, heterogeneous catalysis and thermocatalysis with emphasis on design of new MOFs and their derivative catalysts, and the control of their morphology and microstructure, together with the study of reaction mechanisms for the efficient capture and catalytic conversion of CO2.
    Lingcong Li (College of Chemistry and Chemical Engineering, Shenyang Normal University) received her Ph.D. degree from Beijing University of Technology in 2019. From September 2019 to May 2025, she carried out postdoctoral research at the Institute for Catalysis, Hokkaido University (Japan), during which she was awarded the JSPS Fellowship for Foreign Researchers. Since June 2025, she has joined the faculty of College of Chemistry and Chemical Engineering, Shenyang Normal University, as a Professor and Master Supervisor. Her research interests are focused on catalyst design and catalysis nature study for the environment and energy catalysis. Especially for CO₂ capture and conversion, CH4 conversion, and vehicle exhaust emission control. She has published more than 40 peer-reviewed papers.
    Zhen Zhao (College of Chemistry and Chemical Engineering, Shenyang Normal University) received his Ph.D. degree in 1996 from Changchun Institute of Applied Chemistry, Chinese Academy of Sciences. From 1997 to 2002, he conducted postdoctoral research at National Institute for Resources and Environment (AIST, Japan), National Institute of Industrial Technology (Osaka, Japan), and Lehigh University (USA). Now, he is a Distinguished Professor “Changjiang Scholars Program”, Second Class Professor and Doctoral Supervisor at China University of Petroleum (Beijing); Shenyang Normal University Special Professor Hired, Dean of the College of Chemistry and Chemical Engineering at Shenyang Normal University, and Director of Institute of Catalysis for Energy and Environment. His research interests are focused on catalyst design and catalysis nature study for the energy catalysis; environmental catalysis and rare earth catalysis, especially for diesel exhaust purification, petrochemical conversion of oil and gas, and CO2 conversion and utilization. He has published more than 600 peer-reviewed papers with over 26800 citations and an H-index of 85, and has been an Elsevier Highly Cited Chinese Researcher for 11 consecutive years with more than 60 authorized invention patents.
  • Supported by:
    Key Discipline Project for Doctoral Program Construction at Shenyang Normal University in 2025(099-52501002);Basic Scientific Research Project for Higher Education Institutions of Liaoning Provincial Department of Education(LJ222510166005)

摘要:

工业革命以来, 二氧化碳(CO2)大规模排放引发全球变暖, 严重威胁生态环境与可持续发展. 2024年全球能源相关CO2排放量达37.8 Gt, 尽管可再生能源实现了有效减排, 但化石燃料仍主导能源结构. CO2捕集与加氢还原(CCR)技术可将CO2转化为甲烷、甲醇等高附加值化学品, 是实现碳中和的关键路径. 传统CCR技术中捕集与转化分步进行, 存在设备成本高、能耗大等问题, 而双功能材料(DFMs)能在单一体系中同步完成CO2捕集与原位加氢, 为解决上述难题提供了新方向.

本文围绕DFMs在CCR反应中的催化机理与应用展开系统综述, 从反应路径、表征技术、催化剂分类进行全面梳理. 在反应路径方面, 详细解析了CO2加氢生成甲烷、一氧化碳、甲醇、乙醇及C2-C4低碳烯烃的关键路径与中间体演化规律, 明确了甲酸盐(*HCOO)和羰基(*CO)为核心中间体, 阐明了不同路径的热力学与动力学差异. 其中, 甲烷化反应存在甲酸盐和羰基两条竞争路径; 低碳烯烃合成则通过CO2改性费托合成或甲醇介导路径实现; 甲醇合成主要遵循甲酸盐路径与羧基路径; 而乙醇合成则涉及CO插入、CHx-CHxO耦合及CHx-HCOO耦合三种机制. 在表征技术上, 重点突出原位振动光谱、X-射线吸收光谱等原位/操作表征手段与密度泛函理论计算的协同作用, 这些技术为揭示金属与吸附剂协同效应、活性位点动态演化及反应机理提供了关键支撑. 另外, 根据活性金属类型系统评述了Ni, Ru, Cu和Fe基及其他类型DFMs的研究进展, 明确了各类DFMs核心协同规律. 其中, Ni基DFMs依赖双金属合金化与助剂调控实现高效甲烷化及稳定性提升, Ru基DFMs通过碱金属修饰与活性相调控强化低温甲烷化选择性, Cu基DFMs借助界面工程与多组分耦合适配多反应路径, Fe基DFMs通过相演变与助剂调控实现低碳烯烃高效合成的核心协同规律. 通过深入剖析活性金属、吸附剂、助剂与载体间的协同机制, 针对性的提出通过微结构设计、界面耦合、粒径调控等优化方案来解决烧结、失活等工业核心难题. 通过分析DFMs在等温和变温操作下的动力学匹配规律, 揭示了速率决定步骤的动态迁移特性, 给出适配的结构优化方案, 保障DFMs在不同反应条件下的高效稳定运行.

未来, DFMs的发展需聚焦结构稳定性提升、抗干扰能力强化、成本降低及量化机理模型构建等方向. 本文通过系统梳理DFMs的催化机理与协同关系, 为开发高效、低耗、工业化可行的CCR材料提供了重要理论指导, 助力推动碳中和技术的实际应用与发展.

关键词: 双功能材料, 二氧化碳甲烷化, 逆水煤气变换, 甲醇合成, 低碳烯烃合成

Abstract:

Carbon dioxide (CO2) capture and hydrogenation reduction (CCR) offers a promising route to reduce greenhouse gas emissions while converting CO2 into value-added chemicals, contributing to carbon-neutral strategies. Dual functional materials (DFMs), which could simultaneously achieve CO2 capture and in-situ hydrogenation conversion in a single material system, have therefore attracted growing attention. Nevertheless, the complex reaction pathways, multiple intermediates, and parallel networks involved in CO2 hydrogenation led to highly diverse and intricate catalytic mechanisms over DFMs. This review summarizes recent advances in DFMs for CCR, focusing on key hydrogenation pathways to CO, CH4, and CH3OH and the evolution of associated intermediates. Advanced in-situ/operando characterization techniques and density functional theory calculations are highlighted for their roles in elucidating reaction mechanisms and metal-adsorbent synergistic effects. DFMs are further classified by active metal type, with representative Ni-, Ru-, Cu-, and Fe-based systems critically reviewed to highlight synergistic interactions among active metals, adsorbents, promoters, and supports, as well as rational structural design strategies for mitigating sintering and deactivation. Overall, this review provides mechanistic insights and design principles to guide the development of efficient, low-energy, and industrially viable DFMs for CCR reactions.

Key words: Dual functional materials, CO2 methanation, Reverse water-gas shift, Methanol synthesis, Low-carbon olefin synthesis