物理化学学报 >> 2025, Vol. 41 >> Issue (7): 100073.doi: 10.1016/j.actphy.2025.100073

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非均相催化CO2与烃类协同催化转化的最新进展

张红红1, 魏振1,*(), HaoDerek2, 敬林1, 刘雨溪1, 戴洪兴1, 魏伟钦3,*(), 邓积光1,*()   

  1. 1 北京工业大学材料科学与工程学院, 绿色催化与分离北京市重点实验室, 北京 100124
    2 Centre for Atomaterials and Nanomanufacturing (CAN), School of Science, RMIT University, Melbourne 3000, Australia
    3 北京大学化学与分子工程学院, 北京分子工程国家实验室, 北京 100871
  • 收稿日期:2025-01-08 修回日期:2025-02-05 录用日期:2025-02-25 发布日期:2025-05-22
  • 通讯作者: Email: xfwz522@126.com (魏振)2306388562@pku.edu.cn (魏伟钦)jgdeng@bjut.edu.cn (邓积光)
  • 基金资助:
    国家自然科学基金(22406009); 国家自然科学基金(U23A20120); 河北省自然科学基金重点项目(B2021208033); 北京市教委科技计划重点项目(KZ202210005011)

Recent advances in synergistic catalytic valorization of CO2 and hydrocarbons by heterogeneous catalysis

Honghong Zhang1, Zhen Wei1,*(), Derek Hao2, Lin Jing1, Yuxi Liu1, Hongxing Dai1, Weiqin Wei3,*(), Jiguang Deng1,*()   

  1. 1 Beijing Key Laboratory for Green Catalysis and Separation, College of Materials Science and Engineering, Beijing University of Technology, Beijing 100124, China
    2 Centre for Atomaterials and Nanomanufacturing (CAN), School of Science, RMIT University, Melbourne 3000, Australia
    3 Beijing National Laboratory for Molecular Engineering, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China
  • Received:2025-01-08 Revised:2025-02-05 Accepted:2025-02-25 Published:2025-05-22
  • Contact: Email: xfwz522@126.com (Zhen Wei)2306388562@pku.edu.cn (Weiqin Wei)jgdeng@bjut.edu.cn (Jiguang Deng)
  • Supported by:
    the National Natural Science Foundation of China(22406009); the National Natural Science Foundation of China(U23A20120); Natural Science Foundation of Hebei Province(B2021208033); R & D Program of Beijing Municipal Education Commission(KZ202210005011)

摘要:

在当今时代,全球极端天气事件呈现出愈发频繁的态势,过量温室气体排放是极为关键的诱因。二氧化碳(CO2)是最主要的温室气体之一,排放量逐年递增,迫使人们采取行之有效的行动以应对过量CO2排放的影响和威胁。全球各国都在探索脱碳技术以实现净零排放。从能源角度来说,CO2是一种丰富且低成本的碳资源,其可通过与烃类化合物(如烷烃、烯烃、芳香烃和聚烯烃等)协同转化为高值化学品。通过氢转移,CO2可被还原成CO,同时形成H2O。通过CO2和烃分子干重整,可转化为合成气(CO和H2)。此外,CO2还可以插入烃分子,引起碳链增长,生成醇类、羧酸和芳烃等物种。然而,由于CO2的热力学稳定性和动力学惰性,以及烃类中C―H键的键能较高和极性较小,CO2和烃类的协同转化极具挑战。本综述重点介绍在非均相催化剂上协同催化CO2和不同烃类增值转化的产物和反应效率的最新进展,探讨了CO2和烃类转化中涉及的相关反应动力学模型(Langmuir-Hinshelwood和Eley-Rideal)。此外,设计具有不同活性位点的双功能催化剂可分别活化这两种反应分子,以及调控酸碱性、构筑氧空位和优化界面位点是增强催化性能的有效策略。最后,提出了CO2与烃类共转化技术的未来发展方向,并对低碳发展战略提出了建议。

关键词: 二氧化碳, 烃类, 协同催化增值, 增值化学品, 非均相催化

Abstract:

The escalating frequency of extreme weather events globally has necessitated immediate action to mitigate the impacts and threats posed by excessive greenhouse gas emissions, particularly carbon dioxide (CO2). Consequently, reducing CO2 emissions has become imperative, with decarbonization techniques being extensively investigated worldwide to achieve net-zero emissions. From an energy perspective, CO2 represents an abundant and low-cost carbon resource that can be converted into high-value chemical products through reactions with hydrocarbons, including alkanes, alkenes, aromatic hydrocarbons, and polyolefins. Through hydrogen transfer, CO2 can be reduced to CO, accompanied by the formation of H2O. CO2 and hydrocarbons can also be transformed into syngas (CO and H2) via dry reforming. Furthermore, CO2 can be incorporated into hydrocarbon molecules, resulting in carbon chain growth, such as the production of alcohols, carboxylic acids, and aromatics. However, due to the thermodynamic stability and kinetic inertness of CO2, as well as the high bond energy and low polarity of hydrocarbon C―H bonds, the conversion of CO2 and hydrocarbons remains a highly challenging and demanding strategic objective. This review focuses on the synergistic catalytic valorization of CO2 and hydrocarbons using heterogeneous catalysts, summarizing recent advancements in coupling CO2 with various hydrocarbons. It also examines relevant kinetic models, including Langmuir-Hinshelwood and Eley-Rideal mechanisms. For catalyst design, bifunctional catalysts with distinct active sites can independently activate these two reactive molecules, and the modulation of acid-base properties, oxygen vacancies, and interfacial interactions represents an effective strategy to optimize catalytic performance. Finally, future directions for advancing CO2-hydrocarbon co-utilization technologies are proposed, along with recommendations for low-carbon development strategies.

Key words: CO2, Hydrocarbons, Synergistic catalytic valorization, Value-added chemicals, Heterogeneous catalysis