Catalytic Activation of Carbon Dioxide on Metal Surfaces

The catalytic activation of carbon dioxide on metal surfaces encompasses the adsorption, charge transfer and bond‐cleavage processes that convert CO₂ into reactive intermediates for further chemical transformation. CO₂ is inherently inert due to its linear geometry and strong C=O bonds, requiring catalysts with specific electronic and structural properties to enable its activation. Metal surfaces provide sites for physisorption and chemisorption, where charge redistribution can induce bending of the CO₂ molecule and formation of surface‐bound species such as carbonyl or formate intermediates. The nature of the active sites, including crystal facets, oxygen vacancies and bimetallic ensembles, dictates the balance between adsorption strength and activation barrier. Techniques such as near‐ambient‐pressure X‐ray photoelectron spectroscopy and in situ infrared spectroscopy have elucidated the role of surface oxides, subnanometre clusters and interfacial metal–oxide sites in modulating reactivity. Practical applications range from the reverse water–gas shift reaction to hydrogenation towards methanol or methane, offering pathways to carbon‐neutral fuels. Advances in atomic‐level characterisation and computational modelling are unravelling mechanistic details, informing the rational design of sustainable catalysts with enhanced activity, selectivity and stability.

Research from Nature Portfolio

Recent studies have directly observed the initial dissociation of CO₂ on atomically flat Rh(111) at near‐ambient pressure, revealing that the linear molecule adopts a bent, chemisorbed configuration that facilitates non‐uniform charge transfer and O–C bond cleavage at room temperature. Ordered intermediates form a (2×2) structure, indicating a redox‐driven mechanism. In complementary work, in situ infrared spectroscopy with isotope labelling has identified bifunctional active sites in Cu/TiO₂ catalysts. Oxygen vacancies bind and activate CO molecules, while metallic copper sites drive CO₂ dissociation. Competitive adsorption of water and CO₂ influences migration between sites, demonstrating how interfacial synergy governs reaction pathways under hydrogenation conditions.

Catalytic Activation of Carbon Dioxide on Metal Surfaces publication trend

The graph below shows the total number of articles in catalytic activation of carbon dioxide on metal surfaces across all publications each year (not limited to Nature Index journals).

Technical terms

Adsorption: The adherence of molecules to a catalyst surface, including physisorption (weak forces) and chemisorption (strong chemical bonding).

Chemisorption: Strong binding of adsorbates via electron sharing or transfer, often resulting in activation of the molecule.

Formate intermediate: A surface‐bound species (HCOO*) formed by hydrogen‐assisted conversion of CO₂, crucial in hydrogenation pathways.

Oxygen vacancy: A defect site in metal oxides where an oxygen atom is missing, providing localised electrons that can activate CO₂.

Reverse water–gas shift reaction: The conversion of CO₂ and H₂ into CO and H₂O, serving as an entry point to synthesis of fuels and chemicals.

References

1. Correlating the Reverse Water–Gas Shift Reaction with Surface Chemistry: The Influence of Reactant Gas Exposure to Ni(100). ACS Catalysis (2023).
2. Influence of zinc oxide nanoparticles on the carbon accumulation on silver exposed to carbon dioxide hydrogenation reaction conditions. Nanoscale (2025).
3. How Rh surface breaks CO2 molecules under ambient pressure. Nature Communications (2020).
4. Probing active sites for carbon oxides hydrogenation on Cu/TiO2 using infrared spectroscopy. Communications Chemistry (2022).