Global Optimization of Molybdenum Subnanoclusters on Graphene: A Consistent Approach toward Catalytic Applications

Area of Science:

• Computational catalysis and materials science.
• Surface science and nanotechnology.

Background:

• Designing subnanometer cluster (SNC) catalysts requires precise control over size, shape, and surface deposition.
• Existing computational methods often fail to adequately sample complex energy landscapes, leading to unreliable predictions of structure-reactivity relationships.
• The experimental deposition process significantly influences SNC adsorption geometries and catalytic activity but is frequently omitted in theoretical studies.

Purpose of the Study:

• To develop a systematic computational approach for simulating SNC deposition and predicting catalytic reactivity.
• To address limitations in current methods by incorporating global search techniques for comprehensive energy landscape exploration.
• To establish a reliable procedure for the rational design of novel SNC catalysts.

Main Methods:

• Utilized particle swarm optimization (PSO), a global search technique, combined with ab initio calculations.
• Simulated all stages of beam experiments, from predicting SNC structures in the beam to their adsorption on a surface.
• Investigated the catalytic properties of Molybdenum (Mo) SNCs on graphene for CO molecule dissociation.

Main Results:

• Successfully predicted relevant Mo SNC structures on graphene and their catalytic reactivity.
• Provided insights into the complex energy landscape of Mo SNCs on graphene, demonstrating catalytic activity.
• Highlighted the importance of statistical sampling of configurations and modeling experimental deposition procedures.

Conclusions:

• The proposed systematic approach reliably predicts SNC structures, adsorption geometries, and reactivity.
• This method enables a more accurate understanding of structure-reactivity relationships for rational catalyst design.
• The findings underscore the significance of exploring diverse configurations and experimental deposition simulation for advanced catalyst development.