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An Interstitial Boron Inserted Metastable Hexagonal Rh Nanocrystal for Efficient Hydrogen Oxidation Electrocatalysis.

Pengyu Han¹, Liqing Wu¹, Yu Zhang¹

¹College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, Hubei, 430072, P.R. China.

Angewandte Chemie (International Ed. in English)

|November 22, 2024

Summary

Researchers synthesized a novel metastable hexagonal rhodium nanocrystal catalyst by inserting boron atoms. This boron-doped catalyst demonstrates superior performance in the alkaline hydrogen oxidation reaction (HOR).

Keywords:

hexagonal Rh hydrogen binding energy hydrogen oxidation reaction hydroxyl binding energy phase transition

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Area of Science:

Materials Science
Nanotechnology
Catalysis

Background:

Constructing metastable phases in nanocrystals is crucial for enhancing catalytic performance.
Synthesizing metastable metallic nanocrystals is challenging due to their inherent thermodynamic instability.

Purpose of the Study:

To develop a novel synthesis method for metastable hexagonal rhodium nanocrystals.
To investigate the catalytic activity of these nanocrystals in the hydrogen oxidation reaction (HOR).

Main Methods:

Interstitial boron insertion into cubic rhodium (Rh) lattice to induce a phase transition to hexagonal close-packed (hcp).
Characterization using in situ surface-enhanced infrared absorption spectroscopy (SEIRAS).
Computational analysis using density functional theory (DFT) calculations.

Main Results:

Successful synthesis of metastable hexagonal rhodium nanocrystals (B_int-Rh_hcp/C) via boron insertion.
Achieved a high mass activity of 1.413 mA μg_PGM^-1 for the hydrogen oxidation reaction in alkaline media.
Identified strengthened hydroxyl adsorption and altered interfacial water structure as key factors for enhanced HOR.

Conclusions:

Interstitial boron doping effectively stabilizes the hexagonal rhodium phase.
The unique electronic and structural properties of B_int-Rh_hcp/C significantly boost alkaline HOR efficiency.
This work provides a new strategy for designing advanced nanocatalysts through phase engineering and doping.