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Size-Selective CO2 Activation at Rhodium Cluster Anions
Christian T Haakansson1, David J Vesty1, Peter T Rubli1
1Department of Chemistry, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA, United Kingdom.
Researchers studied carbon dioxide (CO2) adsorption on rhodium clusters. CO2 binding and activation varied with cluster size, offering insights into catalysis for climate change mitigation.
Area of Science:
- Materials Science
- Chemical Catalysis
- Surface Science
Background:
- Carbon dioxide (CO2) fixation and activation are critical for mitigating climate change.
- Vibrational spectroscopy offers insights into CO2 binding and activation on catalysts.
Purpose of the Study:
- Investigate CO2 adsorption on rhodium cluster anions (Rhn-, n=3-12).
- Determine the effect of cluster size on CO2 binding and activation.
Main Methods:
- Infrared free-electron laser spectroscopy.
- Quantum chemical calculations.
Main Results:
- Observed a clear cluster-size dependence in CO2 adsorption.
- Small clusters (n≤4) showed dissociative adsorption (carbonyl stretch at 1880 cm-1).
- Larger clusters (n≥7) exhibited activated molecular binding, with intermediate sizes (n=5,6) showing both motifs.
Conclusions:
- Spectroscopic analysis revealed distinct CO2 binding modes based on rhodium cluster size.
- CO2 activation is linked to binding at Rh-Rh bridge sites and electron transfer.
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