Mechanism of Catalytic CO₂ Hydrogenation to Methane and Methanol Using a Bimetallic Cu₃Pd Cluster at a Zirconia Support

For very small nanocluster-based catalysts, the exploration of the influence of the particle size, composition, and support offers precisely variable parameters in a wide material search space to control catalysts’ performance. We present the mechanism of the CO₂ methanation reaction on the oxidized bimetallic Cu₃Pd tetramer (Cu₃PdO₂) supported on a zirconia model support represented by Zr₁₂O₂₄ based on the energy profile obtained from density functional theory calculations on the reaction of CO₂ and H₂. In order to determine the role of the Pd atom, the performance of Cu₃PdO₂ with monometallic Cu₄O₂ at the same support has been compared. Parallel to methane formation, the alternative path of methanol formation at this catalyst has also been investigated. The results show that the exchange of a single atom in Cu₄ with a single Pd atom improves catalyst/s performance via lowering the barriers associated with hydrogen dissociation steps that occur on the Pd atom. The above-mentioned results suggest that the doping strategy at the level of single atoms can offer a precise control knob for designing new catalysts with desired performance.