C=C bond cleavage on neutral VO3(V2O5)n clusters.

Area of Science:

• Surface Science and Catalysis
• Inorganic Chemistry
• Physical Chemistry

Background:

• Vanadium oxide clusters are crucial in catalysis, but their reactions with unsaturated hydrocarbons are not fully understood.
• Investigating the reactivity of neutral clusters provides fundamental insights into catalytic mechanisms.

Purpose of the Study:

• To investigate the reactions of neutral vanadium oxide clusters with various alkenes.
• To elucidate the reaction mechanisms using experimental and theoretical (DFT) approaches.
• To propose a catalytic cycle for alkene oxidation based on the findings.

Main Methods:

• Experimental investigation using single-photon ionization with extreme ultraviolet (EUV) radiation to detect neutral species.
• Density Functional Theory (DFT) calculations to determine reaction pathways, thermodynamics, and kinetics.
• Analysis of reaction products formed from vanadium oxide clusters and alkenes (e.g., ethylene, propylene, butenes, butadiene).

Main Results:

• Observed formation of specific products indicating C=C bond cleavage in alkenes by oxygen-rich vanadium oxide clusters.
• DFT calculations confirmed a thermodynamically favorable and barrierless reaction for VO(3) + C(3)H(6).
• Reactions with benzene yielded dehydration products, while tetrafluoroethylene showed no reaction.

Conclusions:

• Neutral vanadium oxide clusters effectively break C=C bonds in alkenes, suggesting potential catalytic applications.
• A mechanistic understanding of alkene oxidation on these clusters was established through combined experimental and theoretical studies.
• A catalytic cycle for alkene oxidation on vanadium oxide clusters is proposed.