July 2017 | Shyam Kattel, Ping Liu, and Jingguang G. Chen
The chemical transformation of CO₂ is a promising approach to mitigate anthropogenic CO₂ emissions and produce carbon compounds for fuels and chemicals. This review discusses recent advances in understanding the mechanisms of CO₂ hydrogenation to C1 compounds (CO, CH₃OH, and CH₄) on metal/oxide catalysts. The metal/oxide interface plays a critical role in controlling reaction pathways and selectivity through synergistic interactions between metal nanoparticles and oxide supports. The binding strength of reaction intermediates at the interface determines the activity and selectivity of the catalysts. Key descriptors, such as the binding energy of intermediates, influence the conversion of CO₂ to specific products.
For CO₂ hydrogenation to CO, various metals (e.g., Cu, Pt, Rh) and oxides (e.g., ZnO, CeO₂, TiO₂) have been studied. The activity and selectivity depend on the metal/oxide interface, with factors such as particle size, oxide reducibility, and metal/oxide interactions influencing the reaction. For example, Cu/ZnO/Al₂O₃ is an industrial catalyst for CO₂ to CH₃OH conversion, but CO remains the major product. The synergy between Cu and ZnO in Cu/ZnO/Al₂O₃ enhances methanol production through the formation of CuZn alloys.
For CO₂ hydrogenation to CH₃OH, the metal/oxide interface is crucial for stabilizing intermediates and promoting the reaction. The Formate pathway and RWGS + CO-Hydro pathway are two main mechanisms. The selectivity is influenced by the binding strength of intermediates, with the Formate pathway being preferred in some cases. The binding of *HCOO is critical for the reaction, and its stabilization can lead to surface poisoning.
For CO₂ hydrogenation to CH₄, the Direct C-O bond cleavage, RWGS + CO-Hydro, and Formate pathways are possible. The selectivity is determined by the competition between C-O bond scission and hydrogenation of intermediates. Ni and Ru-based catalysts are effective for CH₄ production, with the addition of secondary components enhancing selectivity.
The review highlights the importance of understanding reaction mechanisms, identifying key descriptors, and optimizing metal/oxide interfaces for selective CO₂ conversion. Challenges include the complexity of reaction networks and the need for experimental and theoretical studies to identify active intermediates and reaction pathways. Future research should focus on developing catalysts with optimized interfaces, using promoters, and improving the stability of catalysts under reaction conditions. The goal is to achieve high activity and selectivity for CO₂ conversion to C1 compounds.The chemical transformation of CO₂ is a promising approach to mitigate anthropogenic CO₂ emissions and produce carbon compounds for fuels and chemicals. This review discusses recent advances in understanding the mechanisms of CO₂ hydrogenation to C1 compounds (CO, CH₃OH, and CH₄) on metal/oxide catalysts. The metal/oxide interface plays a critical role in controlling reaction pathways and selectivity through synergistic interactions between metal nanoparticles and oxide supports. The binding strength of reaction intermediates at the interface determines the activity and selectivity of the catalysts. Key descriptors, such as the binding energy of intermediates, influence the conversion of CO₂ to specific products.
For CO₂ hydrogenation to CO, various metals (e.g., Cu, Pt, Rh) and oxides (e.g., ZnO, CeO₂, TiO₂) have been studied. The activity and selectivity depend on the metal/oxide interface, with factors such as particle size, oxide reducibility, and metal/oxide interactions influencing the reaction. For example, Cu/ZnO/Al₂O₃ is an industrial catalyst for CO₂ to CH₃OH conversion, but CO remains the major product. The synergy between Cu and ZnO in Cu/ZnO/Al₂O₃ enhances methanol production through the formation of CuZn alloys.
For CO₂ hydrogenation to CH₃OH, the metal/oxide interface is crucial for stabilizing intermediates and promoting the reaction. The Formate pathway and RWGS + CO-Hydro pathway are two main mechanisms. The selectivity is influenced by the binding strength of intermediates, with the Formate pathway being preferred in some cases. The binding of *HCOO is critical for the reaction, and its stabilization can lead to surface poisoning.
For CO₂ hydrogenation to CH₄, the Direct C-O bond cleavage, RWGS + CO-Hydro, and Formate pathways are possible. The selectivity is determined by the competition between C-O bond scission and hydrogenation of intermediates. Ni and Ru-based catalysts are effective for CH₄ production, with the addition of secondary components enhancing selectivity.
The review highlights the importance of understanding reaction mechanisms, identifying key descriptors, and optimizing metal/oxide interfaces for selective CO₂ conversion. Challenges include the complexity of reaction networks and the need for experimental and theoretical studies to identify active intermediates and reaction pathways. Future research should focus on developing catalysts with optimized interfaces, using promoters, and improving the stability of catalysts under reaction conditions. The goal is to achieve high activity and selectivity for CO₂ conversion to C1 compounds.