CO₂ adsorption on gas-phase Cu_4-xPt_x (x = 0-4) clusters: a DFT study

Area of Science:

• Materials Science
• Computational Chemistry
• Catalysis

Background:

• Transition and noble metal clusters are promising novel materials for catalysis.
• These clusters offer potential advantages over conventional catalysts in processes like carbon dioxide transformation.
• Understanding CO2 adsorption on these clusters is key to developing efficient catalytic systems.

Purpose of the Study:

• To systematically study CO2 adsorption on gas-phase copper-platinum (Cu4-xPtx) clusters using computational methods.
• To identify ground-state and low-lying energy isomers of Cu4-xPtx clusters.
• To analyze the effect of cluster composition on CO2 adsorption and cluster stability.

Main Methods:

• Density functional theory (DFT) combined with basin-hopping global optimization was used to explore potential energy surfaces.
• Ground-state and low-lying energy isomers of Cu4-xPtx clusters were identified.
• CO2 adsorption energies and structural changes were analyzed for various cluster compositions.

Main Results:

• CO2 adsorption deforms the linear CO2 molecule, with bend angles ranging from 132° to 139°.
• Cluster geometries remained largely unchanged, except for Cu3Pt1 and Pt4 clusters where CO2 adsorption facilitated structural conversion.
• CO2 adsorption energies increased with platinum content, showing a volcano-type trend.

Conclusions:

• Platinum-rich Cu-Pt clusters exhibit enhanced CO2 adsorption capabilities.
• CO2 adsorption can influence the structural stability of certain Cu-Pt clusters.
• These findings provide insights into the design of advanced catalysts for CO2 conversion.