Correlation between Heteroatom Coordination and Hydrogen Evolution for Single-site Pt on Carbon-based Nanocages

Area of Science:

• Materials Science
• Electrochemistry
• Catalysis

Background:

• Single-site catalysts (SSCs) performance depends on metal atom electronic structure.
• Heteroatom doping of supports influences SSCs' electrocatalytic properties.

Purpose of the Study:

• To construct and evaluate platinum SSCs on heteroatom-doped carbon nanocages for hydrogen evolution reaction (HER).
• To elucidate the structure-activity relationship governing HER on Pt SSCs.

Main Methods:

• Synthesis of platinum SSCs on S-, P-, N-doped, and undoped hierarchical carbon nanocages.
• Electrocatalytic testing for HER activity.
• Theoretical simulations (e.g., DFT) to analyze electronic structure and adsorption processes.

Main Results:

• HER activity increased in the order: S-doped < P-doped < undoped < N-doped supports.
• Theoretical analysis revealed a multi-hydrogen atom adsorption process on Pt SSCs.
• N-coordinated Pt exhibited higher HER activity due to electron transfer from N to Pt, enhancing proton capture.

Conclusions:

• The electronic structure, particularly N-coordination, is crucial for Pt SSCs' HER performance.
• Rational design of Pt SSCs can be achieved by optimizing heteroatom doping on carbon supports.
• This work provides insights for developing advanced platinum-based electrocatalysts.