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Frontier-orbital modulation of rhodium single-atom catalysts for enhanced hydrogen evolution
Rouna Jia1,2, Zongyan Liu1,2, Yang Wang3,4
1State Key Laboratory of Tropic Ocean Engineering Materials and Materials Evaluation, School of Materials Science and Engineering, Hainan University, Haikou, China.
Researchers developed rhodium single-atom catalysts (SACs) on tunable MoSxSe2-x supports. Optimizing metal-support interactions via anion composition enhances hydrogen evolution reaction activity and stability.
Area of Science:
- Materials Science
- Catalysis
- Electrochemistry
Background:
- Single-atom catalysts (SACs) offer maximal atomic efficiency for reactions like hydrogen evolution.
- Controlling metal-support interactions is crucial for SAC activity and stability but remains challenging.
- Understanding frontier orbital interactions is key to designing advanced SACs.
Purpose of the Study:
- To systematically investigate the impact of anion composition in MoSxSe2-x supports on rhodium SACs.
- To elucidate the role of metal-support frontier orbital interactions in dictating catalyst performance.
- To establish a rational design strategy for highly active and stable SACs.
Main Methods:
- Fabrication of rhodium single-atom catalysts (RhSA) anchored on MoSxSe2-x supports with varying sulfur-selenium ratios.
- Characterization of electronic structures and frontier orbital interactions (HOMO-LUMO) between Rh atoms and supports.
- Electrochemical evaluation of hydrogen evolution reaction (HER) activity and long-term stability.
Main Results:
- Gradient modulation of metal-support frontier orbital interactions was achieved by tuning the anion composition of MoSxSe2-x supports.
- Elevated support LUMO levels and strengthened HOMO-LUMO hybridization enhanced catalyst stability.
- Optimized adsorption energies for hydroxide and hydrogen intermediates led to improved HER activity.
- The RhSA-MoSSe catalyst exhibited superior activity and stability.
Conclusions:
- Metal-support frontier orbital interactions significantly influence the performance of SACs.
- Systematic tuning of anion composition in MoSxSe2-x supports provides a viable strategy for optimizing SACs.
- This study offers fundamental insights and a design framework for developing robust and efficient electrocatalysts.
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