Molybdenum Oxycarbide Supported Rh-Clusters with Modulated Interstitial C-O Microenvironments for Promoting Hydrogen...

Area of Science:

• Materials Science
• Electrochemistry
• Catalysis

Background:

• Optimizing catalytic kinetics requires tuning the microenvironment and electronic structure of support materials for efficient electron transfer.
• Electron transfer between supports and active centers is crucial for enhancing catalytic performance.

Purpose of the Study:

• To synthesize molybdenum oxycarbide supported Rh-clusters (Rh/MoOC) with modulated interstitial C-O microenvironments.
• To promote efficient hydrogen evolution in water splitting through optimized electronic structure and charge transfer.

Main Methods:

• Synthesis of Rh/MoOC catalysts with specific interstitial C-O microenvironments.
• Electronic structure characterizations (e.g., XPS, DFT calculations).
• Electrochemical measurements to evaluate hydrogen evolution activity.

Main Results:

• Apparent charge transfer from Rh to MoOC was observed, optimizing d-band center, H2O adsorption, and hydrogen binding energies.
• The presence of interstitial C and O atoms in MoOC supports is vital for water dissociation.
• Rh/MoOC exhibited exceptional turnover and mass activities, significantly outperforming commercial Rh/C catalysts (over 40 times higher).

Conclusions:

• Tuning the support material's microenvironment and electronic structure is key for efficient hydrogen evolution.
• Rh/MoOC catalysts demonstrate superior performance in water splitting, offering a promising alternative to existing materials.
• This study provides insights into designing advanced water dissociation catalysts.