Computational Design of Ni₆@Pt₁M₃₁ Clusters for Multifunctional Electrocatalysts

Area of Science:

• Materials Science
• Electrochemistry
• Computational Chemistry

Background:

• High-efficiency and low-cost multifunctional electrocatalysts are crucial for regenerative fuel cells, particularly for hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR).
• Developing novel catalyst structures is essential to meet the demands of advanced energy storage and conversion technologies.

Purpose of the Study:

• To investigate the activity trends of core-shell Ni₆@M₃₂ and Ni₆@Pt₁M₃₁ (M = Pt, Pd, Cu, Ag, Au) electrocatalysts using density functional theory (DFT).
• To identify promising multifunctional electrocatalysts for HER, OER, and ORR applications.

Main Methods:

• Density Functional Theory (DFT) calculations were employed to study the electronic structure and catalytic activity of various core-shell nanoclusters.
• Kinetic analysis and rate constant calculations were performed to determine favorable reaction pathways and mechanisms for HER, OER, and ORR.

Main Results:

• Ni₆@Pt₁Ag₃₁ demonstrated high efficiency as a HER catalyst, with the Volmer-Tafel process being the kinetically favorable pathway for Ni₆@Pt₁M₃₁ structures.
• The incorporation of a single platinum atom significantly reduced energy barriers and altered reaction mechanisms.
• Ni₆@Pt₁Ag₃₁ exhibited low overpotentials for ORR (0.12 V) and OER (0.33 V), indicating its potential as a multifunctional electrocatalyst.
• These core-shell clusters offer abundant active sites with moderate adsorption strengths for key reaction intermediates (*H, *O, *OH, *OOH).

Conclusions:

• Embedding a single platinum atom onto a Ni@M core-shell cluster is an effective strategy for designing advanced multifunctional electrocatalysts.
• The Ni₆@Pt₁Ag₃₁ nanocluster shows significant promise for applications in regenerative fuel cells due to its excellent catalytic performance across multiple reactions.
• The findings provide valuable insights into rational catalyst design for efficient energy conversion technologies.