Selective oxidation of primary carbon-hydrogen bonds with oxygen is of crucial importance for the sustainable exploitation of available feedstocks. To date, heterogeneous catalysts have either shown low activity and/or selectivity or have required activated oxygen donors. We report here that supported gold-palladium (Au-Pd) nanoparticles on carbon or TiO(2) are active for the oxidation of the primary carbon-hydrogen bonds in toluene and related molecules, giving high selectivities to benzyl benzoate under mild solvent-free conditions. Differences between the catalytic activity of the Au-Pd nanoparticles on carbon and TiO(2) supports are rationalized in terms of the particle/support wetting behavior and the availability of exposed corner/edge sites.

Iron copper zeolite (Fe‐Cu‐ZSM‐5) with aqueous hydrogen peroxide is active for the selective oxidation of methane to methanol. Iron is involved in the activation of the carbon–hydrogen bond, while copper allows methanol to form as the major product. The catalyst is stable, re‐usable and activates methane giving >90 % methanol selectivity and 10 % conversion in a closed catalytic cycle (see scheme).

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The development of a catalytic, one-step route for the oxidation of methane to methanol remains one of the greatest challenges within catalysis. Of particular importance is the need to develop an efficient route that proceeds under mild reaction conditions so as to avoid deeper oxidation and the economic limitations of the currently practiced syngas route. Recently, it was demonstrated that a copper-and ironcontaining zeolite is an efficient catalyst for such a one-step process. The catalyst in question (Cu−Fe−ZSM-5) is capable of selectively transforming methane to methanol in an aqueous medium with hydrogen peroxide as the terminal oxidant. Nevertheless, despite its high activity and unparalleled methanol selectivity, the origin of its activity and the precise nature of its active species are not yet fully understood. Through a combination of catalytic and spectroscopic studies, we hereby demonstrate that extraframework Fe species are the active component of the catalyst for methane oxidation, although the speciation of these sites from synthesis to catalysis significantly alters the observed activity and selectivity. The analogies and differences between this system and other iron-containing zeolite-catalyzed processes, such as N 2 O-mediated benzene hydroxylation, are also considered.

The partial oxidation of methane to methanol presents one of the most challenging targets in catalysis. Although this is the focus of much research, until recently, approaches had proceeded at low catalytic rates (<10 h(-1)), not resulted in a closed catalytic cycle, or were unable to produce methanol with a reasonable selectivity. Recent research has demonstrated, however, that a system composed of an iron- and copper-containing zeolite is able to catalytically convert methane to methanol with turnover frequencies (TOFs) of over 14,000 h(-1) by using H(2)O(2) as terminal oxidant. However, the precise roles of the catalyst and the full mechanistic cycle remain unclear. We hereby report a systematic study of the kinetic parameters and mechanistic features of the process, and present a reaction network consisting of the activation of methane, the formation of an activated hydroperoxy species, and the by-production of hydroxyl radicals. The catalytic system in question results in a low-energy methane activation route, and allows selective C(1)-oxidation to proceed under intrinsically mild reaction conditions.

The reaction of glycerol with urea to form glycerol carbonate is mostly reported in the patent literature and to date there have been very few fundamental studies of the reaction mechanism. Furthermore, most previous studies have involved homogeneous catalysts whereas the identification of heterogeneous catalysts for this reaction would be highly beneficial. This is a very attractive reaction that utilises two inexpensive and readily available raw materials in a chemical cycle that overall, results in the chemical fixation of CO(2). This reaction also provides a route to up-grade waste glycerol produced in large quantities during the production of biodiesel. Previous reports are largely based on the utilisation of high concentrations of metal sulfates or oxides, which suffer from low intrinsic activity and selectivity. We have identified heterogeneous catalysts based on gallium, zinc, and gold supported on a range of oxides and the zeolite ZSM-5, which facilitate this reaction. The addition of each component to ZSM-5 leads to an increase in the reaction yield towards glycerol carbonate, but supported gold catalysts display the highest activity. For gold-based catalysts, MgO is the support of choice. Catalysts have been characterised by XRD, TEM, STEM and XPS, and the reaction has been studied with time-on-line analysis of products via a combination of FT-IR spectroscopy, HPLC, (13)C NMR and GC-MS analysis to evaluate the reaction pathway. Our proposed mechanism suggests that glycerol carbonate forms via the cyclization of a 2,3-dihydroxypropyl carbamate and that a subsequent reaction of glycerol carbonate with urea yields the carbamate of glycerol carbonate. Stability and reactivity studies indicate that consecutive reactions of glycerol carbonate can limit the selectivity achieved and reaction conditions can be selected to avoid this. The effect of the catalyst in the proposed mechanism is discussed.

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