Asymmetric Zn-Sn Dual-Atom Sites with Sulfur Doping for Efficient Oxygen Reduction Reaction: Insights from...

Area of Science:

• Materials Science
• Electrochemistry
• Computational Chemistry

Background:

• The oxygen reduction reaction (ORR) is crucial for energy conversion technologies.
• Catalyst design for efficient ORR often relies on understanding heteroatom coordination and orbital interactions.
• Developing cost-effective and high-performance ORR electrocatalysts remains a significant challenge.

Purpose of the Study:

• To design and theoretically investigate asymmetric dual-atom sites for enhanced ORR catalysis.
• To elucidate the role of p-d orbital hybridization in governing ORR activity.
• To provide theoretical guidance for creating novel multiheteroatomic electrocatalysts.

Main Methods:

• Computational modeling and simulation.
• Density Functional Theory (DFT) calculations.
• Analysis of projected density of states (PDOS) and charge density differences.

Main Results:

• Construction of asymmetric Zn-Sn dual-atom sites (ZnSnS-NC) within a N,S-codoped carbon matrix.
• ZnSnS-NC demonstrated outstanding ORR catalytic performance with a theoretical overpotential of 0.51 V.
• The asymmetric coordination environment facilitated efficient p-d orbital hybridization, promoting O2 activation and optimizing OH adsorption/desorption.

Conclusions:

• Asymmetric p-d orbital interactions are key to regulating ORR kinetics.
• The synergistic coupling between Zn-3d and Sn-5p orbitals enhances catalytic activity.
• This work offers valuable theoretical insights for designing advanced multiheteroatomic synergistic electrocatalysts.