Highly dispersed molybdenum oxide supported on mesoporous silica SBA-15 has been prepared by anion exchange resulting in a series of catalysts with changing Mo densities (0.2-2.5 Mo atoms nm(-2) ). X-ray absorption, UV/Vis, Raman, and IR spectroscopy indicate that doubly anchored tetrahedral dioxo MoO4 units are the major surface species at all loadings. Higher reducibility at loadings close to the monolayer measured by temperature-programmed reduction and a steep increase in the catalytic activity observed in metathesis of propene and oxidative dehydrogenation of propane at 8 % of Mo loading are attributed to frustration of Mo oxide surface species and lateral interactions. Based on DFT calculations, NEXAFS spectra at the O-K-edge at high Mo loadings are explained by distorted MoO4 complexes. Limited availability of anchor silanol groups at high loadings forces the MoO4 groups to form more strained configurations. The occurrence of strain is linked to the increase in reactivity.
Mixed oxides composed of the four metals Mo, V, Te, and Nb are known to be efficient catalysts in selective oxidation of lower alkanes. The outstanding catalytic performance of such mixed oxides is attributed to the presence of the so-called M1 crystal phase that contains all four elements in the metal positions of the structure. In the present work, an M1 phase composed only of Mo and V has been prepared by hydrothermal synthesis. High crystallinity was achieved by applying a synthesis temperature of 200 °C. The phase-pure mixed MoV oxide was studied as catalyst in the oxidation of propane. In contrast to previous reports, the desirable oxidation product acrylic acid is formed over the Te-free M1 structure in significant amounts, implying that Te is not necessarily required as a component of the active ensemble responsible for selective oxygen insertion. The MoV M1 oxide is, however, less selective compared to that of the M1 structure composed of the four metals Mo, V, Te, and Nb. The reason has been determined by applying a combination of synchrotron-based single crystal structure analysis and near-ambient-pressure X-ray photoelectron spectroscopy. Determination of the crystal structure of MoV M1 oxide reveals partial occupation of sites in the hexagonal channels of the M1 structure by V, which are occupied by Te in MoVTeNb M1 oxide. Hydrolysis of the M-O bonds (M = V, Te) under reaction conditions leads to migration of the metal in the hexagonal channels to the surface. Accumulation of more than 50 at % V on the surface of the MoV M1 oxide most likely causes postcombustion of formed acrylic acid, whereas enrichment of Te at the surface of MoVTeNb M1 oxide results in dilution of surface V5+ species and, consequently, high selectivity
The “Seven Pillars” of oxidation catalysis proposed by Robert K. Grasselli represent an early example of phenomenological descriptors in the field of heterogeneous catalysis. Major advances in the theoretical description of catalytic reactions have been achieved in recent years and new catalysts are predicted today by using computational methods. To tackle the immense complexity of high-performance systems in reactions where selectivity is a major issue, analysis of scientific data by artificial intelligence and data science provides new opportunities for achieving improved understanding. Modern data analytics require data of highest quality and sufficient diversity. Existing data, however, frequently do not comply with these constraints. Therefore, new concepts of data generation and management are needed. Herein we present a basic approach in defining best practice procedures of measuring consistent data sets in heterogeneous catalysis using “handbooks”. Selective oxidation of short-chain alkanes over mixed metal oxide catalysts was selected as an example.
One of the main goals in catalysis is the characterization of solid/gas interfaces in a reaction environment. The electronic structure and chemical composition of surfaces become heavily influenced by the surrounding environment. However, the lack of surface sensitive techniques that are able to monitor these modifications under high pressure conditions hinders the understanding of such processes. This limitation is known throughout the community as the "pressure gap." We have developed a novel experimental setup that provides chemical information on a molecular level under atmospheric pressure and in presence of reactive gases and at elevated temperatures. This approach is based on separating the vacuum environment from the high-pressure environment by a silicon nitride grid-that contains an array of micrometer-sized holes-coated with a bilayer of graphene. Using this configuration, we have investigated the local electronic structure of catalysts by means of photoelectron spectroscopy and in presence of gases at 1 atm. The reaction products were monitored online by mass spectrometry and gas chromatography. The successful operation of this setup was demonstrated with three different examples: the oxidation/reduction reaction of iridium (noble metal) and copper (transition metal) nanoparticles and with the hydrogenation of propyne on Pd black catalyst (powder).
The crystal structure of perovskites can incorporate a wide variety of cations, which makes this class of materials so interesting for studies of links between solid-state chemistry and catalysis. Perovskites are known as typical total combustion catalysts in hydrocarbon oxidation reactions. The fundamental question that we investigate here is whether surface modifications of perovskites can lead to the formation of valuable reaction products in alkane oxidation. We studied the effect of segregated two-dimensional surface nanostructures on selectivity to propene in the oxidative dehydrogenation of propane. Manganese-based perovskites AMnO 3 (A = La, Sm) were prepared by combustion and hydrothermal synthesis. Bulk and surface structures were investigated by X-ray diffraction, temperature-programmed reduction, aberration-corrected scanning transmission electron microscopy (STEM), multiwavelength Raman, and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) in combination with near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Surface oxygen species responsible for C−H activation were distinguished by AP-XPS on the basis of a rigorous in situ analysis of the O 1s spectra recorded under a broad range of reaction conditions. Signals at 529.2, 530.1, 530.9, 531.2, and 531.8 eV were attributed to lattice O, defect-affected O, surface O, oxygen in carbonates, and hydroxyl groups, respectively. Operando AP-XPS revealed critical surface features, which occur under catalyst operation. The catalyst performance depends on the synthesis technique and the reaction conditions. In presence of a two-dimensional MnO x surface phase, addition of steam to the feed resulted in an increase in selectivity to the partial oxidation product propene to practically relevant values. The selectivity increase is related to the presence of Mn in a low oxidation state (2+/3+), an increased concentration of hydroxyl groups, and a higher abundance of adsorbed activated oxygen species on the catalyst surface. The surface analysis of a working catalyst highlights the importance of the termination layer of polycrystalline perovskites as a genuine property implemented by catalyst preparation. Such a termination layer controls the chemical properties and reactivity of perovskites. The information provides input for the development of realistic models that can be used by theory to predict functional properties.
The catalytic performance of 1) crystalline MoVTeNb oxide that exhibits the electronic properties of a n-type semiconductor, 2) submonolayer vanadium oxide supported on meso-structured silica (SBA-15) as an insulating support, and 3) surface-functionalized carbon nanotubes that contain neither a redox active metal nor bulk oxygen, but only surface oxygen species have been compared in the oxidative dehydrogenation of ethane and propane under equal reaction conditions. The catalytic results indicate similarities in the reaction network over all three catalysts within the range of the studied reaction conditions implying that differences in selectivity are a consequence of differences in the rate constants. Higher activity and selectivity to acrylic acid over MoVTeNb oxide as compared to the other two catalysts are attributed to the higher density of potential alkane adsorption sites on M1 and the specific electronic structure of the semiconducting bulk catalyst. Microcalorimetry has been used to determine and quantify different adsorption sites revealing a low Vsurface/C3H8 ads ratio of 4 on M1 and a much higher ratio of 150 on silica-supported vanadium oxide. On the latter catalyst less than one per cent of the vanadium atoms adsorb propane. Barriers of propane activation increase in the order P/oCNT (139 kJ mol−1)≤M1 (143 kJ mol−1)<6V/SBA-15 (162 kJ mol−1), which is in agreement with trends predicted by theory
Oxygen core excitations in different molecular molybdena silica models are evaluated using density-functional theory (DFT). These results can be compared with in situ X-ray absorption fine structure (NEXAFS) measurements near the O K-edge of molybdena model catalysts supported on SBA-15 silica, used for exploratory catalytic activity studies. The comparison allows an analysis of structural details of the molybdena species. The silica support is found to contribute to the NEXAFS spectrum in an energy range well above that of the molybdena units, allowing a clear separation between the corresponding contributions. Different types of oxygen species, O(1) in terminal MdO bonds, O(2) in interphase Mo—O—Si bridges and in Mo—O—Mo linkages, as well as O(2) in terminal Mo—O—H groups can be distinguished in the theoretical spectra of the molybdena species with molybdenum in tetrahedral (dioxo species), pentahedral (monooxo species), and octahedral coordination. The experimental NEXAFS spectra exhibit a pronounced double-peak structure in the O 1s to Mo 4dO 2p excitation range of 529 536 eV. Comparison with the present theoretical data gives clear indications that dioxo molybdena species with tetrahedral MoO4 units can explain the experimental spectrum. This does not fully exclude species with other Mo coordination, like pentahedral. However, the latter are believed to exist in the present samples in much smaller amounts. The experimental NEXAFS spectrum for the supported molybdena species differs substantially from that for MoO3 bulk material with octahedral MoO6 units where the observed asymmetric peak structure is also reproduced by the calculations
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.
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