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The catalytic partial oxidation of methane is achieved at low temperatures (90% at ∼35% methane conversion at approximately 6 turnovers. Under our catalytic methane oxidation reaction conditions, MeTFA is stable against overoxidation, which explains the likely high selectivity at conversions >15%. Using combined experimental studies and DFT calculations, a mechanism involving soluble and molecular Mn species in the catalytic cycle is proposed. The proposed reaction pathway involves initial activation of Mnᴵᴵ by dioxygen, cleavage of a methane C–H bond by a Mnᴵᴵᴵ hydroxo intermediate, rebound of the methyl radical to generate MeTFA, and finally regeneration of the starting MnII complex. Also, this process is shown to be applicable to the oxidation of ethane, favoring the mono-oxidized product ethyl trifluoroacetate (EtTFA) and reaching ∼46% conversion.

Ceria has been used as a hydrogenation catalyst especially in selective alkyne hydrogenation, but the reaction mechanism regarding the role of different surface hydrogen species remains unclear. In...

The kinetics and mechanism of methanol dehydration, redox, and oxidative coupling were investigated at 300 °C under dilute oxygen concentration over anatase TiO2 nanoplates and truncated-bipyramidal nanocrystals in order to understand the surface structure effect of TiO2. The two TiO2 nanoshapes displayed both (001) and (101) facets, with a higher fraction of the (001) facet exposed on the nanoplates, while truncated-bipyramidal nanocrystals were dominated by the (101) facet. A kinetic study using in situ titration with ammonia shows that the active sites for methanol dehydration are acidic and nonequivalent in comparison to redox and oxidative coupling. In situ FTIR spectroscopy reveals that adsorbed methoxy is the dominant surface species for all reactions, while the observed methanol dimer is found to be a spectator species through isotopic methanol exchange, supporting the dissociative mechanism for methanol dehydration via surface methoxy over TiO2 surfaces. Density functional theory calculations sho...

An ultrastable Au nanocatalyst based on a heterostructured perovskite support with high surface area and uniform LaFeO3 nanocoatings was successfully synthesized and tested for CO oxidation. Strikingly, small Au nanoparticles (4–6 nm) are obtained after calcination in air at 700 °C and under reaction conditions. The designed Au catalyst not only possessed extreme sintering resistance but also showed high catalytic activity and stability because of the strong interfacial interaction between Au and the heterostructured perovskite support.

Methanol has been considered as a “smart” molecule in studying the surface sites of metal oxide catalysts. In this work, methanol was utilized to probe the nature of surface sites of ceria nanocrystals with defined surface planes (nanoshapes), including rods (containing {110}), cubes ({100}), and octahedra ({111}). The adsorption and desorption of methanol were followed by in situ IR and Raman spectroscopy as well as mass spectrometry. Upon methanol adsorption at room temperature, on-top, bridging and three-coordinate methoxy species are formed on the surface of rods and cubes, whereas only on-top methoxy is present on the octahedra surface. The distribution of the methoxy species is believed to be determined not only by the coordination status of surface Ce cations but also by the number of defect sites on the three nanoshapes. During the desorption process, the methoxy species are gradually dehydrogenated into H2 and CO via formate species as intermediates on the three ceria surfaces. A second intermedi...

This paper reports the synthesis of 2.5 nm gold clusters on the oxygen free and chemically labile support carbon nitride (C3N4). Despite having small particle sizes and high enough water partial pressure these Au/C3N4 catalysts are inactive for the gas phase and liquid phase oxidation of carbon monoxide. The reason for the lack of activity is attributed to the lack of surface −OH groups on the C3N4. These OH groups are argued to be responsible for the activation of CO in the oxidation of CO. The importance of basic −OH groups explains the well documented dependence of support isoelectric point versus catalytic activity.