Atomic-precision Pt₆ nanoclusters for enhanced hydrogen electro-oxidation.

Area of Science:

• Materials Science
• Electrochemistry
• Nanotechnology

Background:

• Platinum (Pt) exhibits excellent electrocatalytic activity but is scarce, necessitating efficient utilization.
• Atomic-level engineering of Pt is crucial for minimizing dosage while maximizing performance in electrocatalysis.
• Existing platinum catalysts often lack tolerance to carbon monoxide (CO) poisoning.

Purpose of the Study:

• To design and synthesize ultrasmall platinum nanoclusters for enhanced electrocatalytic hydrogen oxidation.
• To investigate the structure-activity relationship of atomic-precision platinum catalysts.
• To explore the CO tolerance of novel platinum nanocluster electrocatalysts.

Main Methods:

• Synthesis of triphenylphosphine-stabilized Pt₆ nanoclusters.
• Electrocatalytic evaluation of hydrogen oxidation reaction in alkaline media.
• Comparative analysis with platinum single atoms and nanoparticles.
• Density Functional Theory (DFT) calculations to elucidate reaction mechanisms.

Main Results:

• Pt₆ nanoclusters demonstrated superior mass activity and stability compared to Pt single atoms and nanoparticles.
• The nanocluster catalyst exhibited significant tolerance to CO poisoning, a limitation of conventional Pt/C catalysts.
• Theoretical calculations confirmed ligand effects tuning nanocluster formation and shifting Pt d-band center for improved kinetics.

Conclusions:

• Ultrasmall, atomically precise Pt₆ nanoclusters represent a highly efficient electrocatalyst for hydrogen oxidation.
• An unexpected size optimization principle for platinum electrocatalysts was uncovered.
• Triphenylphosphine ligands play a dual role in stabilizing nanoclusters and optimizing electronic properties for enhanced catalysis.