Water activation by small free ruthenium oxide clusters

Area of Science:

• Inorganic Chemistry
• Catalysis
• Surface Science

Background:

• Ruthenium clusters and their oxides are studied for catalytic applications.
• Understanding metal-cluster interactions with water is crucial for catalysis.

Purpose of the Study:

• Investigate reactions of ruthenium (Rux+) and ruthenium oxide (RuxOy+) clusters with water.
• Determine the factors influencing reaction efficiency and mechanisms.

Main Methods:

• Gas phase ion trap mass spectrometry for experimental analysis.
• First-principle density functional calculations for theoretical insights.
• (16)O/(18)O isotope exchange experiments for mechanistic confirmation.

Main Results:

• Ruthenium oxide clusters exhibit significantly higher reactivity with water compared to pure ruthenium clusters.
• Water activation and efficient hydrogen transfer to ruthenium oxide clusters were observed.
• Isotope exchange experiments confirmed the theoretical prediction of hydrogen shift reactions.

Conclusions:

• Ruthenium oxide clusters facilitate water activation through hydrogen transfer mechanisms.
• Low energy barriers for hydrogen atom transfer via [1,3] shifts enable oxygen isotope exchange.
• Findings suggest potential for ruthenium oxide clusters in driving water oxidation reactions.