Electronic Modulation Caused by Interfacial Ni-O-M (M=Ru, Ir, Pd) Bonding for Accelerating Hydrogen Evolution...

Area of Science:

• Materials Science
• Catalysis
• Nanotechnology

Background:

• Optimizing noble metal catalyst activity often relies on controlling metal-support interactions.
• Designing stable and effective interfacial bonds between metals and supports remains a significant challenge in catalysis.

Purpose of the Study:

• To develop quantum-sized metal nanoparticles (NPs) anchored on nickel metal-organic framework nanohybrids (M@Ni-MOF) with precisely engineered metal-support interfaces.
• To investigate the impact of these interfacial bonds on the electronic structure and catalytic activity, particularly for the hydrogen evolution reaction (HER).

Main Methods:

• A spontaneous redox strategy was employed to synthesize M@Ni-MOF nanohybrids (M=Ru, Ir, Pd).
• Characterization of structural stability, active site exposure, and interfacial electronic properties.
• Electrochemical testing for hydrogen evolution reaction (HER) activity across various pH conditions.
• Density functional theory (DFT) calculations to elucidate the reaction mechanism and electronic effects.

Main Results:

• The synthesized M@Ni-MOF nanohybrids exhibited robust structural stability with well-exposed active sites due to metal-oxygen bonds.
• The interfacial metal-oxygen-metal (Ni-O-M) bridge facilitated charge transfer, modulating the electronic structure and enhancing reaction kinetics.
• The Ru@Ni-MOF catalyst demonstrated exceptional HER activity across all pH values, surpassing commercial Pt/C and other noble metal catalysts.
• Theoretical calculations confirmed that interfacial bond-induced electron redistribution optimizes adsorption energies for water and hydrogen intermediates.

Conclusions:

• Precisely designed metal-support interfacial bonds are crucial for enhancing the intrinsic activity of noble metal catalysts.
• The M@Ni-MOF nanohybrid architecture, particularly Ru@Ni-MOF, offers a promising platform for highly efficient and stable electrocatalysis.
• The study provides a mechanistic understanding of how interfacial engineering boosts catalytic performance for the hydrogen evolution reaction.