We present a comprehensive review of complex heterogeneous catalysts for CO₂ hydrogenation, with a particular focus on dual‑site catalysts and three‑dimensional (3D) nanoreactors. Drawing on recent advances, this review analyzes how structural complexity, synergistic interactions, and spatial confinement can be leveraged to enhance catalytic activity, selectivity, and stability. The article systematically summarizes structure–property relationships and discusses key challenges and future opportunities for developing next‑generation catalysts for efficient CO₂ conversion.

Key Highlights

• Dual‑site catalyst design principles are outlined, emphasizing synergistic, electronic, and spacing effects that enable cooperative activation of CO₂ and H₂.
• Recent advances in homonuclear and heteronuclear dual‑atom catalysts, single‑atom–nanoparticle/nanoclusters hybrids, and dual‑site alloys and solid solutions are systematically reviewed.
• The role of 3D nanoreactors—including core–shell, yolk–shell, and hollow structures—in regulating mass transport, diffusion, and tandem reaction pathways is highlighted.
• Representative catalytic systems are summarized for producing CO, methane, methanol, formate, ethanol, higher alcohols, and light olefins from CO₂ hydrogenation.
• Comparative analysis of catalytic performance metrics provides structure–activity insights to guide rational catalyst design.

Significance

Thermo‑catalytic CO₂ hydrogenation is a key pathway for carbon capture and utilization, yet its efficiency is limited by the chemical inertness of CO₂ and the complexity of multi‑step reaction networks. This review highlights complex heterogeneous catalysts as an effective strategy to overcome these limitations. By integrating dual‑site cooperation with three‑dimensional spatial regulation, such catalysts enable selective activation of reactants, controlled transformation of intermediates, and suppression of undesired side reactions. The review further emphasizes the need for precise synthesis of complex active sites and advanced in‑situ and operando characterization techniques to achieve deeper mechanistic understanding and catalyst optimization.

Authors

Zijian Wang; Lingling Zhang; Yuou Li; Xiaomei Wang; Rui Zhang; Ke Wang; Jing Xu*; Meng Zhao; Xiao Wang*; Shuyan Song*; Hongjie Zhang*
Affiliations: Changchun Institute of Applied Chemistry, Chinese Academy of Sciences; University of Science and Technology of China; Tsinghua University.
Corresponding authors: xujing@ciac.ac.cn; wangxiao@ciac.ac.cn; songsy@ciac.ac.cn; hongjie@ciac.ac.cn

How to Cite

Wang Z., Zhang L., Li Y., et al. The application of complex heterogeneous catalysts in CO₂ hydrogenation. Catal, 2026, 2:2. DOI: 10.1007/s44422‑025‑00014‑6