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Updated: Jun 5, 2025
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Published on: July 27, 2022
Do Rh-Hydride Phases Contribute to the Catalytic Activity of Rh Catalysts under Reductive Conditions?
Ke-Xiang Zhang1, Lin Chen1, Zhi-Pan Liu1,2
1Collaborative Innovation Center of Chemistry for Energy Material, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Key Laboratory of Computational Physical Science, Department of Chemistry, Fudan University, Shanghai 200433, China.
Abstract:
Rh-hydride phases were believed to be key causes of the exceptional catalytic ability of Rh catalysts under H2 reductive conditions. Here, we utilize the large-scale machine-learning-based global optimization to explore millions of Rh bulk, surface, and nanoparticle structures in contact with H2, which rules out the presence of subsurface/interstitial H in Rh and Rh-hydride phases as thermodynamically stable phases under ambient conditions. Instead, an exceptional Rh-H affinity is identified for surface Rh atoms in Rh nanoparticles that can accommodate a high concentration of adsorbed H, with the surface Rh to H ratio reaching ∼2.5, featuring stable six-H-coordinated Rh, [RhH6]. Such [RhH6] species forming at edged Rh sites are found to be the key intermediates in the electrochemical hydrogen evolution reaction (HER) on Rh. Guided by theory, our synthesized Rh concave nanocubes with a high density of edged Rh sites achieve a Tafel slope of 28.4 mV dec-1 and a low overpotential of 36.1 mV at jECSA = 1 mA cm-2, which outperforms commercial Pt/C and other morphologies of Rh catalysts. Our results clarify the active phase in Rh-H nanosystems and guide the catalyst design by precise morphology control of nanocatalysts.
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