Methane Activation by Gas Phase Atomic Clusters.

The increasing supply of natural gas has created a strong demand for developing efficient catalytic processes to upgrade methane, the most stable alkane molecule, into value-added chemicals. Currently, methane conversion in laboratory and industry is mostly performed under high-temperature conditions. A lot of effort has been devoted to exploring chemical entities that are able to activate the C-H bond of methane at lower temperatures, preferably room temperature. Gas phase atomic clusters with limited numbers of atoms are ideal models of active sites on heterogeneous catalysts. The cluster systems are being actively studied to activate methane under room-temperature conditions. State-of-the-art mass spectrometry, photoelectron imaging spectroscopy, and quantum chemistry calculations have been combined in our laboratory to reveal the molecular-level mechanisms of methane activation by atomic clusters. In this Account, we summarize our recent progress on thermal methane activation by metal oxide clusters doped with noble-metal atoms (Au, Pt, and Rh) as well as by oxygen-free species including carbides and borides of base metals (V, Ta, Mo, and Fe). In contrast to the generations of CH3• free radicals in many of the previously reported cluster reactions with methane, the generations of stable products such as formaldehyde, acetylene, and syngas as well as closed-shell species AuCH3 and B3CH3 have been identified for the cluster reaction systems herein. Besides the well recognized mechanisms of methane activation by the O-• radicals through hydrogen atom abstraction and by metal atoms through oxidative addition, the new mechanisms of synergistic methane activation by Lewis acid-base pairs (such as Auδ+-Oδ- and Bδ+-Bδ-) and by dinuclear metal centers (such as Ta-Ta) have been recently revealed. In the reactions between methane and oxide clusters doped with noble-metal atoms, the oxide cluster "supports" can accept the H atoms and the CH x species delivered through the noble-metal atoms and then transform methane into stable oxygenated compounds. The product selectivity (such as formaldehyde versus syngas) can be controlled by different noble-metal atoms (such as Pt versus Rh). The electronic structures of base metal centers can be engineered through carburization so that the low-spin states can be accessible to reduce the C-H bond of methane. Such active base metal centers in low-spin states resemble related noble-metal atoms in methane activation. The boron clusters (such as B3 in VB3+) can be polarized by the metal cations to form the Lewis acid-base pair Bδ+-Bδ- to cleave the C-H bond of methane very easily. These molecular-level mechanisms may well be operative in related heterogeneous catalysis and can be a fundamental basis to design efficient catalysts for activation and conversion of methane under mild conditions.