Adsorption and Activation of CO₂ on Small-Sized Cu-Zr Bimetallic Clusters

Adsorption and activation of CO₂ is a key step in any chemical reaction, which aims to convert it to other useful chemicals. Therefore, it is important to understand the factors that drive the activation process and also search for materials that promote the process. We employ the density functional theory to explore the possibility of using small-sized bimetallic Cu-Zr clusters, Cu_4-Zr, with n = 1-3 for the above-mentioned key step. Our results suggest that after adsorption, a CO₂ molecule preferably resides on Zr atoms or at the bridge and triangular faces formed by Zr atoms in bimetallic Cu-Zr clusters accompanied with its high degree of activation. Importantly, maximum activation occurs when CO₂ is adsorbed on the CuZr₃ cluster. Interestingly, we find that the adsorption energy of CO₂ can be tuned by varying the extent of the Zr atom in Cu-Zr clusters. We rationalize the high adsorption of CO₂ with the increase in the number of Zr atoms using the d-band center model and the concept of chemical hardness. The strong chemisorption and high activation of CO₂ are ascribed to charge migration between Cu-Zr clusters and the CO₂ molecule. We find an additional band in the infrared vibrational spectra of CO₂ chemisorbed on all of the clusters, which is absent in the case of free CO₂. We also observe that the energy barriers for the direct dissociation of the CO₂ molecule to CO and O decrease significantly on bimetallic Cu-Zr clusters as compared to that on pure Cu₄. In particular, the barrier heights are considerably small for Cu₃Zr and CuZr₃ clusters. This study demonstrates that Cu₃Zr and CuZr₃ clusters may serve as good candidates for activation and dissociation of the CO₂ molecule.