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Updated: Aug 23, 2025

Synthesis of Metal Nanoparticles Supported on Carbon Nanotube with Doped Co and N Atoms and its Catalytic Applications in Hydrogen Production
Published on: December 6, 2021
Coverage-Dependent Rate-Driving Force Relationships: Hydrogen Transfer from Cerium Oxide Nanoparticle Colloids
Rishi G Agarwal1, James M Mayer1
1Department of Chemistry, Yale University, New Haven, Connecticut06520-8107, United States.
This study measured hydrogen atom transfer rates on nanoceria, revealing linear Brønsted-Evans-Polanyi relationships. The findings challenge assumptions about adsorbate coverage effects in catalysis and electrocatalysis.
Area of Science:
- Heterogeneous catalysis
- Nanomaterials science
- Surface chemistry
Background:
- Brønsted-Evans-Polanyi (BEP) relations are key for predicting catalyst performance.
- Current methods often assume constant adsorbate coverage effects, which may not hold true.
Purpose of the Study:
- To experimentally test assumptions about adsorbate coverage effects on reaction rates.
- To measure Brønsted-Evans-Polanyi relationships for hydrogen atom transfer on nanoceria.
Main Methods:
- Utilized UV-visible spectroscopy to measure reaction rates.
- Investigated hydrogen atom transfer from cerium oxide nanoparticles (nanoceria) to organic reagents.
- Varied surface CeO-H bond strengths and surface coverages.
Main Results:
- Observed a linear BEP relationship (Δlog(k) = αΔlog(Keq)) across different conditions.
- Found a low Brønsted slope (0.2) for CeO-H bond strength variations.
- Reported a Brønsted slope >1 when altering reaction driving force via organic reagent bond strength.
Conclusions:
- Rate constants are less sensitive to CeO-H bond strength than typically assumed for nanomaterials.
- The findings have implications for understanding reaction mechanisms (concerted vs. stepwise).
- These are the first solution-phase BEP measurements for hydrogen coverage on a nanomaterial.
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