Speciation and Reactivity Control of Cu-Oxo Clusters via Extraframework Al in Mordenite for Methane Oxidation.

The stoichiometric conversion of methane to methanol by Cu-exchanged zeolites can be brought to highest yields by the presence of extraframework Al and high CH chemical potentials. Combining theory and experiments, the differences in chemical reactivity of monometallic Cu-oxo and bimetallic Cu-Al-oxo nanoclusters stabilized in zeolite mordenite (MOR) are investigated. Cu-L edge X-ray absorption near-edge structure (XANES), infrared (IR), and ultraviolet-visible (UV-vis) spectroscopies, in combination with CH oxidation activity tests, support the presence of two types of active clusters in MOR and allow quantification of the relative proportions of each type in dependence of the Cu concentration.

Structural evolution after oxidative pretreatment and CO oxidation of Au nanoclusters with different ligand shell composition: a view on the Au core.

The reactivity of supported monolayer protected Au nanoclusters is directly affected by their structural dynamics under pretreatment and reaction conditions. The effect of different types of ligands of Au clusters supported on CeO on their core structure evolution, under oxidative pretreatment and CO oxidation reaction, was investigated. X-ray absorption and X-ray photoelectron spectroscopy studies revealed that the clusters evolve to a similar core structure above 250 °C in all the cases, indicating the active role of the ligand-support interaction in the reaction.

Mechanistic differences between methanol and dimethyl ether in zeolite-catalyzed hydrocarbon synthesis.

Water influences critically the kinetics of the autocatalytic conversion of methanol to hydrocarbons in acid zeolites. At very low conversions but otherwise typical reaction conditions, the initiation of the reaction is delayed in presence of HO. In absence of hydrocarbons, the main reactions are the methanol and dimethyl ether (DME) interconversion and the formation of a C reactive mixture-which in turn initiates the formation of first hydrocarbons in the zeolite pores.

Importance of Methane Chemical Potential for Its Conversion to Methanol on Cu-exchanged Mordenite.

Invited for the cover of this issue is the collaborative team of researchers from TU Munich, PNNL and TU Delft. Read the full text of the article at 10.1002/chem.

Importance of Methane Chemical Potential for Its Conversion to Methanol on Cu-Exchanged Mordenite.

Copper-oxo clusters exchanged in zeolite mordenite are active in the stoichiometric conversion of methane to methanol at low temperatures. Here, we show an unprecedented methanol yield per Cu of 0.6, with a 90-95 % selectivity, on a MOR solely containing [Cu (μ-O) ] active sites.

Design and synthesis of highly active MoVTeNb-oxides for ethane oxidative dehydrogenation.

Ethane oxidative dehydrogenation (ODH) is an alternative route for ethene production. Crystalline M1 phase of Mo-V mixed metal oxide is an excellent catalyst for this reaction. Here we show a hydrothermal synthesis method that generates M1 phases with high surface areas starting from poorly soluble metal oxides.

Critical role of formaldehyde during methanol conversion to hydrocarbons.

Formaldehyde is an important intermediate product in the catalytic conversion of methanol to olefins (MTO). Here we show that formaldehyde is present during MTO with an average concentration of ~0.2 C% across the ZSM-5 catalyst bed up to a MeOH conversion of 70%.

Formation of Oxygen Radical Sites on MoVNbTeOx by Cooperative Electron Redistribution.

A novel pathway of increasing the surface density of catalytically active oxygen radical sites on a MoVTeNb oxide (M1 phase) catalyst during alkane oxidative dehydrogenation is reported. The novel sites form when a fraction of Te is reduced and emitted from the M1 crystals under catalytic operating conditions, without compromising structural integrity of the catalyst framework. Density functional theory calculations show this Te reduction induces multiple inter-related electron transfers, and the associated cooperative effects lead to the formation of O radicals.

Methane Oxidation to Methanol Catalyzed by Cu-Oxo Clusters Stabilized in NU-1000 Metal-Organic Framework.

Copper oxide clusters synthesized via atomic layer deposition on the nodes of the metal-organic framework (MOF) NU-1000 are active for oxidation of methane to methanol under mild reaction conditions. Analysis of chemical reactivity, in situ X-ray absorption spectroscopy, and density functional theory calculations are used to determine structure/activity relations in the Cu-NU-1000 catalytic system. The Cu-loaded MOF contained Cu-oxo clusters of a few Cu atoms.

Role of Spatial Constraints of Brønsted Acid Sites for Adsorption and Surface Reactions of Linear Pentenes.

The Brønsted acid sites of H-ZSM-5 and ferrierite reversibly adsborb linear pentenes via hydrogen bonding, rapidly isomerizing the double bond. On H-ZSM-5, dimerization of adsorbed pentenes occurs at a slower rate and leads to pentyl ester covalently bound to the surface. Pentene adsorbed on zeolites with narrower pores, such as ferrierite, remained stable in a hydrogen-bonded state even up to 423 K.

Hydrogen Transfer Pathways during Zeolite Catalyzed Methanol Conversion to Hydrocarbons.

Hydrogen transfer is the major route in catalytic conversion of methanol to olefins (MTO) for the formation of nonolefinic byproducts, including alkanes and aromatics. Two separate, noninterlinked hydrogen transfer pathways have been identified. In the absence of methanol, hydrogen transfer occurs between olefins and naphthenes via protonation of the olefin and the transfer of the hydride to the carbenium ion.

Formation Mechanism of the First Carbon-Carbon Bond and the First Olefin in the Methanol Conversion into Hydrocarbons.

The elementary reactions leading to the formation of the first carbon-carbon bond during early stages of the zeolite-catalyzed methanol conversion into hydrocarbons were identified by combining kinetics, spectroscopy, and DFT calculations. The first intermediates containing a C-C bond are acetic acid and methyl acetate, which are formed through carbonylation of methanol or dimethyl ether even in presence of water. A series of acid-catalyzed reactions including acetylation, decarboxylation, aldol condensation, and cracking convert those intermediates into a mixture of surface bounded hydrocarbons, the hydrocarbon pool, as well as into the first olefin leaving the catalyst.

Atomic-Scale Determination of Active Facets on the MoVTeNb Oxide M1 Phase and Their Intrinsic Catalytic Activity for Ethane Oxidative Dehydrogenation.

Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) has been used to image the basal {001} plane of the catalytically relevant M1 phase in MoVTeNb complex oxides. Facets {010}, {120}, and {210} are identified as the most frequent lateral termination planes of the crystals. Combination of STEM with He ion microscopy (HIM) images, Rietveld analysis, and kinetic tests reveals that the activation of ethane is correlated to the availability of facets {001}, {120}, and {210} at the surface of M1 crystals.

Single-site trinuclear copper oxygen clusters in mordenite for selective conversion of methane to methanol.

Copper-exchanged zeolites with mordenite structure mimic the nuclearity and reactivity of active sites in particulate methane monooxygenase, which are enzymes able to selectively oxidize methane to methanol. Here we show that the mordenite micropores provide a perfect confined environment for the highly selective stabilization of trinuclear copper-oxo clusters that exhibit a high reactivity towards activation of carbon-hydrogen bonds in methane and its subsequent transformation to methanol. The similarity with the enzymatic systems is also implied from the similarity of the reversible rearrangements of the trinuclear clusters occurring during the selective transformations of methane along the reaction path towards methanol, in both the enzyme system and copper-exchanged mordenite.

Aiding the self-assembly of supramolecular polyoxometalates under hydrothermal conditions to give precursors of complex functional oxides.

In situ Raman spectroscopy allows insight into molecular processes under hydrothermal conditions during synthesis of complex nanostructured MoVTeNb oxides (see picture: Nb yellow, Mo blue, V/Mo pale blue, Te red). Based on the knowledge acquired, the synthesis can be more efficiently directed towards the desired product with improved functionality.