High-temperature reactivity of vanadium oxide clusters in methane activation: Vibrational degrees of freedom matter

Abstract

Understanding the properties of small particles working under high-temperature conditions at the atomistic scale is imperative for exact control of related processes, but it is quite challenging to achieve experimentally. Herein, benefitting from state-of-the-art mass spectrometry and by using our newly designed high-temperature reactor, the activity of atomically precise particles of negatively charged vanadium oxide clusters toward hydrogen atom abstraction (HAA) from methane, the most stable alkane molecule, has been measured at elevated temperatures up to 873 K. We discovered the positive correlation between the reaction rate and cluster size that larger clusters possessing greater vibrational degrees of freedom can carry more vibrational energies to enhance the HAA reactivity at high temperature, in contrast with the electronic and geometric issues that control the activity at room temperature. This finding opens up a new dimension, vibrational degrees of freedom, for the simulation or design of particle reactions under high-temperature conditions.

Graphene-Supported Single-Atom Ni as High-Performance Catalyst for Direct Methane-to-Methanol Conversion

“…The above conclusion is consistent with previous gas-phase studies of MO + catalyzing CH 4 to CH 3 OH that M = Ni affords the best reactivity and selectivity among M = Ni, Pd, and Pt. − This inspiring agreement indicates that gas-phase studies on simple molecules/ions are powerful to predict the catalytic behavior of heterogeneous catalysts that bear the same functional units. − …”