Small Clusters Research Articles

Highly Active Oxidation Catalysts through Confining Pd Clusters on CeO2 Nano‐Islands

AbstractCeO2‐supported noble metal clusters are attractive catalytic materials for several applications. However, their atomic dispersion under oxidizing reaction conditions often leads to catalyst deactivation. In this study, the noble metal cluster formation threshold is rationally adjusted by using a mixed CeO2‐Al2O3 support. The preferential location of Pd on CeO2 islands leads to a high local surface noble metal concentration and promotes the in situ formation of small Pd clusters at a rather low noble metal loading (0.5 wt %), which are shown to be the active species for CO conversion at low temperatures. As elucidated by complementary in situ/operando techniques, the spatial separation of CeO2 islands on Al2O3 confines the mobility of Pd, preventing the full redispersion or the formation of larger noble metal particles and maintaining a high CO oxidation activity at low temperatures. In a broader perspective, this approach to more efficiently use the noble metal can be transferred to further systems and reactions in heterogeneous catalysis.

NANOSCALE PATTERN FORMATION ON SURFACES BY CLUSTER ION BEAM IRRADIATION

Abstract Ion beam sputtering is a solid-surface nanostructuring procedure applicable to any type of material. In this study, we are interested in the bombardment of a metallic surface, specifically, of a Co(110) surface bombarded with Ar clusters at oblique incidence. The bombardment with clusters accentuates the effect of surface ripple formation. Sputter erosion and surface atomic redistribution are the processes that determine the morphological evolution of the surface from the collisional point of view. The importance of these processes was analyzed for different angles of incidence in the bombardment with very small clusters and atoms while always maintaining the same fluence. The sputter yield increases with the number of atoms in the cluster for angles greater than 50º; while for the rest, it barely experiences any increase. Unlike sputtering, displacements increase as the cluster size increases above the critical angle. Moreover, horizontal displacement only shows some sign of saturation for angles close to the normal. An analysis of redistributed volumes and previous data suggest that sputtering drives the ripple effect for grazing angles and ones close to these. It is also responsible for the enhancement effect in the cluster bombardment. For the rest of the angles, the weight of the redistribution is decisive. There is a proportional relationship between the emptied volume and the horizontal displacement.

SUPPORTED COBALT OXIDE NANOPARTICLES: THE INFLUENCE OF MESOPOROUS MATERIALS AND THEIR ROLE IMETHYL PHENYL SULFIDE OXIDATION REACTIONS.

The effect of the support in the incorporation of cobalt oxide nanoparticles on mesoporous materials (SBA‐15) and mesoporous cellular foam (MCF) was investigated. The materials were characterized using various techniques. The XRD diffraction patterns showed that the porous structures remained after cobalt incorporation, while high‐angle XRD of the MCF showed CoO peaks, in contrast to Co‐SBA‐15 which exhibited Co3O4. This was confirmed by XPS technique. The SEM‐EDS and HRTEM‐STEM microscopy indicate a distribution of cobalt oxides uniform in the samples synthesized and the average size of the particles is 1.88 nm. H2‐TPR analysis highlighted the interaction between the support surfaces and the metal oxide (SMSI). It was observed that in the SBA‐15 structure, small clusters of cobalt oxide formed with a strong interaction with silica, leading to high reduction temperatures. The catalysts activity was characterized in oxidation reactions of Methyl Phenyl Sulfide and a correlation was observed between the characterization results and the enhanced selectivity and yield towards sulfone exhibited by Co‐MCF.

Master equation modeling of water dissociation in small ionic water clusters: Ag+(H2O) n , n = 4-6.

We model temperature-dependent blackbody infrared radiative dissociation (BIRD) rate coefficients of Ag+(H2O) n , n = 4-6, a system with loosely bound water molecules. We employ a master equation modeling (MEM) approach with consideration of absorption and emission of blackbody radiation, comparing single and multiple-well descriptions. The unimolecular dissociation rate coefficients are obtained using the Rice-Ramsperger-Kassel-Marcus (RRKM) theory, employing two approaches to model the sum of states in the transition state, the rigid activated complex (RAC) and the phase space limit (PSL) approach. A genetic algorithm is used to find structures of low-lying isomers for the kinetic modeling. We show that the multiple-well MEM approach with PSL RRKM in the All Wells and Transition States Are Relevant (AWATAR) variant provides a reliable description of Ag+(H2O) n BIRD, in agreement with previously published experimental data. Higher-lying isomers contribute significantly to the overall dissociation rate coefficient, underlying the importance of the multiple-well ansatz in which all isomers are treated on the same footing.

Radio Observations of Tidal Disruption Events Around Direct Collapse Black Holes at Cosmic Dawn

Primordial haloes immersed within intermediate Lyman-Werner (LW) UV backgrounds are theorisedto be the seeds of supermassive primordial stars (SMSs) that could be the origin of the first quasars in our universe. Only extreme levels of LW fluxes however will destroy the molecular hydrogen H2 in these haloes, resulting in much less massive stars in the early stages of our universe. This investigation considers the collapse in haloes within weaker LW background that were much more common in the primordial universe, and allowed for the survival of some H2 within these haloes. The survival of H2 along with Tvir ∼ 104 K allows the atomic cooling of H2 to begin, triggering the baryonic collapse within these haloes. These flows are predicted to result in SMSs on the order of a few × 105 M⊙ before collapsing to a DCBH due to general relativistic instabilities within their cores. The stars formed through these mechanisms could be the origin seeds of intermediate mass black holes found within dwarf galaxies today, or even create a secondary tier of less massive but still highly luminous quasars at a redshift z > 7. Some of these stars form in binaries and small clusters, raising the possibility of future detections of gravitational waves from BH mergers by LISA. This investigation considers the tidal disruption events (TDEs) of lower mass Pop III stars that form within the nuclear accretion disc of these DCBHs, the potential observation of these TDE afterglows in the radio, and thesubsequent identification of their host DCBHs. We find that the radio observation of the afterglow of 15 M⊙ and 40 M⊙ TDEs due to 104 M⊙ DCBHs would be visible up to z = 20 by SKA and ngVLA.

Cytomorphological characteristics of low-grade papillary urothelial carcinoma in voided urine samples: Distinction from benign and high-grade papillary urothelial carcinoma.

Given its frequent recurrence and the potential for high-grade transformation, accurate diagnosis of low-grade papillary urothelial carcinoma (LGPUC) in urine cytology is clinically important. We attempted to identify cytomorphologic features in urine samples, which could be helpful for the identification of LGPUC. We conducted a retrospective review of voided urine specimens collected from patients with histopathologic diagnoses of LGPUC. Their cytomorphological features were compared with those from patients with benign conditions and high-grade papillary urothelial carcinoma (HGPUC). A total of 115 voided urine specimens were evaluated, including 30 benign, 41 LGPUC, and 44 HGPUC cases. In LGPUC, 18 cases (44%) were diagnosed as atypical, a proportion significantly higher than that observed in benign cases (4 cases, 13%), while the remaining 23 cases (56%) were diagnosed as negative. LGPUC urine samples tended to have higher cellularity than benign cases, but the difference was not statistically significant. Three cytological features, namely nuclear enlargement, higher nuclear-to-cytoplasmic (N/C) ratio, and presence of small cell clusters, were statistically more prevalent in LGPUC compared to benign cases, although the changes were relatively subtle. In contrast, cytomorphological distinction between LGPUC and HGPUC was evident, as high cellularity, nuclear enlargement, hyperchromasia, high N/C ratio, irregular nuclear membrane, and apoptosis were significantly more prevalent in HGPUC cases. Several cytomorphologic features in voided urine samples were more prevalent in cases with LGPUC, albeit not observed in all instances. Since these alterations were relatively subtle, meticulous attention to these cytomorphologic details is crucial to suggest the possibility of LGPUC.

The Mechanism of Air Blocking in the Impeller of Multiphase Pump

The exploitation and transportation of deep-sea and remote oil and gas fields have risen to become important components of national energy strategies. The gas–liquid separation and gas blocking caused by the large density difference between the gas and liquid phases are the primary influencing factors for the safe and reliable operation of gas–liquid mixed transportation pump systems. This paper takes the independently designed single-stage helical axial-flow mixed transportation pump compression unit as the research object. Through numerical simulation, the internal flow of the mixed transportation pump is numerically calculated to study the aggregation and conglomeration of small gas clusters in the flow passage hub caused by gas–liquid phase separation, influenced by the shear flow of phase separation, forming axial vortices at the outlet where gas clusters gather in the flow passage. The work performed by the impeller on the gas clusters is insufficient to overcome the adverse pressure gradient formed at the outlet of the flow passage due to the gathering of the liquid phase in adjacent flow passages, resulting in the phenomenon of gas blocking, with vortex gas clusters lingering near the hub wall of the flow passage.

Landau free energy of small clusters beyond mean-field approach

Landau free energy of small clusters beyond mean-field approach

Triadic percolation induces dynamical topological patterns in higher-order networks

Abstract Triadic interactions are higher-order interactions which occur when a set of nodes affects the interaction between two other nodes. Examples of triadic interactions are present in the brain when glia modulate the synaptic signals among neuron pairs or when interneuron axo-axonic synapses enable presynaptic inhibition and facilitation, and in ecosystems when one or more species can affect the interaction among two other species. On random graphs, triadic percolation has been recently shown to turn percolation into a fully-fledged dynamical process in which the size of the giant component undergoes a route to chaos. However, in many real cases, triadic interactions are local and occur on spatially embedded networks. Here we show that triadic interactions in spatial networks induce a very complex spatio-temporal modulation of the giant component which gives rise to triadic percolation patterns with significantly different topology. We classify the observed patterns (stripes, octopus and small clusters) with topological data analysis and we assess their information content (entropy and complexity). Moreover we illustrate the multistability of the dynamics of the triadic percolation patterns and we provide a comprehensive phase diagram of the model. These results open new perspectives in percolation as they demonstrate that in presence of spatial triadic interactions, the giant component can acquire a time-varying topology. Hence, this work provides a theoretical framework that can be applied to model realistic scenarios in which the giant component is time-dependent as in neuroscience.

Chiral Solvent-Induced Homochiral Hierarchical Molecular Assemblies at the Liquid/Solid Interface.

We herein investigate the formation of homochiral hierarchical self-assembled molecular networks (SAMNs) via chirality induction by the coadsorption of a chiral solvent at the liquid/graphite interface by means of scanning tunneling microscopy (STM). In a mixture of achiral solvents, 1-hexanoic acid, and 1,2,4-trichlorobenzene, an achiral dehydrobenzo[12]annulene (DBA) derivative with three alkoxy and three hydroxy groups in an alternating manner forms chiral hierarchical triangular cluster structures through dynamic self-sorting. Enantiomorphous domains appear in equal probability. On the other hand, in chiral 2-methyl-1-hexanoic acid as a solvent, this molecule produces (i) homochiral small triangular clusters at a low solute concentration, (ii) a chirality-biased hierarchical structure consisting of triangular cluster structures with different cluster sizes at a medium concentration, and (iii) a dense structure with no chirality bias at a high concentration. We attribute the concentration-dependent degree of the chirality transmission to the number of coadsorbed solvent molecules in the SAMNs and to the difference in nucleus structure and size in the initial stage of the SAMN formation.

Analytical Solutions of Symmetric Isotropic Spin Clusters Using Spin and Point Group Projectors

Spin models like the Heisenberg Hamiltonian effectively describe the interactions of open-shell transition-metal ions on a lattice and can account for various properties of magnetic solids and molecules. Numerical methods are usually required to find exact or approximate eigenstates, but for small clusters with spatial symmetry, analytical solutions exist, and a few Heisenberg systems have been solved in closed form. This paper presents a simple, generally applicable approach to analytically solve isotropic spin clusters, based on adapting the basis to both total spin and point group symmetry to factor the Hamiltonian matrix into sufficiently small blocks. We demonstrate applications to small rings and polyhedra, some of which are straightforward to solve by successive spin-coupling for Heisenberg terms only; additional interactions, such as biquadratic exchange or multi-center terms necessitate symmetry adaptation.

INTERACTION OF COPPER CLUSTERS WITH DIOXIDINE

DFT-modelling with B3LYP5 parametrization was performed for small copper clusters (Cu2, Cu3, Cu13) and their complexes with antibacterial drug dioxidine (2,3-bis-(hydroxymethyl)quinoxaline 1,4-di-N-oxide, Dx). The tendencies of changing of geometry con gurations and interaction energies depending on metal cluster size are identi ed. Dissociation energy increases with the cluster size. The dissociation energy of the most stable “Cu3-Dx” complex is 55.1 kcal/mol. Metal atoms form coordination bonds with either one or two oxygen atoms of in all complexes.

Maximizing pollutant removal and greenhouse gas emission reduction in vertical flow constructed wetlands: an orthogonal experimental approach.

Owing to the impact of the effluent C/N from the secondary structures of urban domestic wastewater treatment plants, the denitrification efficiency in constructed wetlands (CWs) is not satisfactory, limiting their widespread application in the deep treatment of urban domestic wastewater. To address this issue, we constructed enhanced CWs and conducted orthogonal experiments to investigate the effects of different factors (C/N, fillers, and plants) on the removal of conventional pollutants and the reduction of greenhouse gas (GHG) emission. The experimental results indicated that a C/N of 8, manganese sand, and calamus achieved the best denitrification efficiencies with removal efficiencies of 85.7%, 95.9%, and 88.6% for TN, NH4+-N, and COD, respectively. In terms of GHG emission reduction, this combination resulted in the lowest global warming potential (176.8mg/m2·day), with N2O and CH4 emissions of 0.53 and 1.25mg/m2·day, respectively. Characterization of the fillers revealed the formation of small spherical clusters of phosphates on the surfaces of manganese sand and pyrite and iron oxide crystals on the surface of pyrite. Additionally, the surface Mn (II) content of the manganese sand increased by 8.8%, and the Fe (III)/Fe (II) and SO42-/S2- on pyrite increased by 2.05 and 0.26, respectively, compared to pre-experiment levels. High-throughput sequencing indicated the presence of abundant autotrophic denitrifying bacteria (Sulfuriferula, Sulfuritalea, and Thiobacillus) in the CWs, which explains denitrification performance of the enhanced CWs. This study aimed to explore the mechanism of efficient denitrification and GHG emission reduction in the enhanced CWs, providing theoretical guidance for the deep treatment of urban domestic wastewater.

Light-driven acetic acid coupling for the production of succinic acid

Treating and recycling high concentration acetic acid in the exhaust water has long posed a challenge in industry. These wastes containing acetic acid are typically processed via basic neutralization, characterized by high acidity and resistance to degradation, which can bring potential economic burden and environmental hazards. Here we report a new photocatalytic conversion route for addressing high concentrations of acetic acid. This process transforms acetic acid into valuable succinic acid through dehydrogenation coupling. Additionally, the photocatalytic conversion of acetic acid exhibits structural sensitivity when employing Pt cocatalysts of varying sizes. Through inhibiting the undesirable H termination of active free radicals over small Pt atoms and clusters, the rate of undesired decarboxylation reactions can be decreased by 75%. This effectively enhances the selectivity of the coupling product succinic acid by 2.1 times, achieving a succinic acid formation rate of 7.28mmol/(gcat•h). This work offers a theoretical guidance for searching reaction pathways, thereby establishing an innovative approach for treating high concentration exhaust acetic acid treatment and converting low value monocarboxylic molecules into valuable diacid polymerization monomers under a mild and green condition.

Graphene-supported MN4 single-atom catalysts for multifunctional electrocatalysis enabled by axial Fe tetramer coordination

Multifunctional electrocatalysts for oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER) are crucial for development of the key electrochemical energy storage and conversion devices, for which single-atom catalyst (SAC) has present great promises. Very recently, some experimental works showed that structurally well-defined ultra-small transition-metal clusters (such as Fe and Co tetramers, denoted as Fe4 and Co4, respectively), can efficiently modulate the catalytic behavior of SACs by axial coordination. Herein, taking the graphene-supported MN4 SACs as representatives, we theoretically explored the feasibility of realizing multifunctional SACs for ORR, OER and HER by this novel axial coordination engineering. Through extensive first-principles calculations, from 23 candidates, IrN4 decorated with Fe4 (IrN4/Fe4) is identified as the promising trifunctional catalyst with the theoretical overpotential of 0.43, 0.51 and 0.30 V for OER, ORR and HER, respectively. RhN4/Fe4 and CoN4/Fe4 are recognized as potential OER and ORR bifunctional catalysts. In addition, NiN4/Fe4 exhibits the best ORR activity with an overpotential of 0.30 V, far superior to the pristine NiN4 SAC (0.88 V). Electronic structure analyses reveal that the significantly enhanced ORR/OER activity can be ascribed to the orbital and charge redistribution of Ni/Ir active center, resulting from its electronic interaction with Fe4 cluster. This work could stimulate and guide the rational design of graphene-based multifunctional SACs realized by axial coordination of small TM clusters, and provide insights into the modulation mechanism.

Effects of side-chain lengths on the structure and properties of anhydrides modified starch micelles: Experimental and DPD simulation studies

Anhydride-modified starch micelles have great potential in the delivery of hydrophobic guest molecules. This study aimed to experimentally explore the effects of side-chain lengths on the structure and properties of anhydride-modified starch micelles, and to visualize the self-assembly and loading process of these micelles through Dissipative particle dynamics (DPD) simulations. Starch micelles could only form when the carbon chain length exceeded four. The highly hydrophobic C18 starch micelle exhibited the minimum particle size (65 nm) and maximum loading capability (59.10 μg/mg). For each addition carbon atom in the anhydride side chains, the critical micelle concentration (CMC) of starch micelles decreased average of 1.79 %. Thermodynamic results showed that the micellization was an entropy-dominated driven process, and longer carbon chains enhanced the stability of starch micelles. DPD results showed that the starch chains formed the small clusters then spherical aggregates and finally core-shell structure spherical micelle. Curcumin was loaded into micelles by adjoint aggregation-micellization-adsorption mechanism. Overall, this study provides microscopic insight into the micellization and drug-loading mechanisms for anhydrides modified starch micelles.

Synthesis and Characterization of Vanadium Nitride/Carbon Nanocomposites.

The present work focuses on the synthesis of a vanadium nitride (VN)/carbon nanocomposite material via the thermal decomposition of vanadyl phthalocyanine (VOPC). The morphology and chemical structure of the synthesized compounds were characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), Fourier transformed infrared spectroscopy (FTIR), X-ray diffraction (XRD), and X-ray photoemission spectroscopy (XPS). The successful syntheses of the VOPC and non-metalated phthalocyanine (H2PC) precursors were confirmed using FTIR and XRD. The VN particles present a needle-like morphology in the VN synthesized by the sol-gel method. The morphology of the VN/C composite material exhibited small clusters of VN particles. The XRD analysis of the thermally decomposed VOPC indicated a mixture of amorphous carbon and VN nanoparticles (VN(TD)) with a cubic structure in the space group FM-3M consistent with that of VN. The XPS results confirmed the presence of V(III)-N bonds in the resultant material, indicating the formation of a VN/C nanocomposite. The VN/C nanocomposite synthesized through thermal decomposition exhibited a high carbon content and a cluster-like distribution of VN particles. The VN/C nanocomposite was used as an anode material in LIBs, which delivered a specific capacity of 307 mAh g-1 after 100 cycles and an excellent Coulombic efficiency of 99.8 at the 100th cycle.

Tracking Prenucleation Molecular Clustering of Salicylamide in Organic Solvents.

Crystal nucleation shapes the structure and product size distribution of solid-state pharmaceuticals and is seeded by early-stage molecular self-assemblies formed in host solution. Here, molecular clustering of salicylamide in ethyl acetate, methanol, and acetonitrile was investigated using photon correlation spectroscopy. Cluster size steadily increased over 3 days and with concentration across the range from undersaturated to supersaturated solutions. Solute concentration normalized by solubility provided more sensitive characterization of molecular-level conditions than concentration alone. In saturated solution, cluster size is independent of solvent, while at equal supersaturation, solvent-dependent cluster size increases as methanol < acetonitrile < ethyl acetate, commensurate with increasing nucleation propensity. In ethyl acetate, with largest prenucleation clusters, the driving force required for nucleation is lowest, compared to methanol with smallest clusters and highest driving force. To understand solvent-solute effects, we performed IR spectroscopy supported by molecular simulations. We observe solute-solvent interaction weakening in the same order: methanol < acetonitrile < ethyl acetate, quantifying the weaker solvent-solute interactions that permit the formation of larger prenucleation clusters. Our results support the hypothesis that nucleation is easier in weaker solvents because weak solute-solvent interactions favor growth of large clusters, as opposed to relying solely on ease of desolvation.

Habitat requirements of deadwood‐dependent invertebrates that occupy tree hollows

ABSTRACTTree hollows support a specialised species‐rich fauna. We review the habitat requirements of saproxylic (= deadwood dependent) invertebrates which occupy tree hollows. We focus on studies quantifying relationships between species occurrence patterns and characteristics of tree hollows, hollow trees, and the surrounding landscape. We also explore the processes influencing species occurrence patterns by reviewing studies on the spatio‐temporal dynamics of populations, including their dispersal and genetic structure. Our literature search in the database Scopus identified 52 relevant publications, all of which were studies from Europe. The dominant taxonomic group studied was beetles. Invertebrates in hollow trees were often more likely to be recorded in trees with characteristics reflecting a large amount of resources or a stable and warm microclimate, such as a large diameter, large amounts of wood mould (= loose material accumulated in the hollows mainly consisting of decaying wood), a high level of sun exposure, and with entrance holes that are large and either at a low or high height, and in dry hollows, with entrances not directed upwards. A stable microclimate is probably a key factor why some species of saproxylic invertebrates are confined to tree hollows. Other factors that are different in comparison to downed dead wood is the fact that hollows at a given height from the ground provide shelter from ground‐living predators, that hollows persist for longer, and that the content of nutrients might be enhanced by the accumulation of dead leaves, insect frass, and remains from dead insects. Several studies have identified a positive relationship between species occupancy per tree and the amount of habitat in the surrounding landscape, with a variation in the spatial scale at which characteristics of the surrounding landscape had the strongest effect over spatial scales from 200 to 3000 m. We found empirical support for the extinction threshold hypothesis, which predicts that the frequency of species presence per tree is greater if a certain number of trees are aggregated into a few large clusters of hollow trees rather than distributed among many small clusters. Observed thresholds in species occurrence patterns can be explained by colonisation–extinction dynamics, with species occupancy per tree influenced by variation in rates of immigration. Consistent with this assumption, field studies suggest that dispersal rate and range can be low for invertebrates occupying tree hollows, although higher in a warmer climate. For one species in which population dynamics has been studied over 25 years (Osmoderma eremita), the observed population dynamics have characteristics of a “habitat‐tracking metapopulation”, as local extinctions from trees occur possibly because those trees become unsuitable as well as due to stochastic processes in small populations. The persistence of invertebrate fauna confined to tree hollows may be improved by prolonging the standing life of existing hollow trees. It is also important to recruit new generations of hollow trees, preferably close to existing larger groups of hollow trees. Thus, the spatio‐temporal dynamics of hollow trees is crucial for the invertebrate fauna that rely upon them.

Structure and reactivity of surface vanadia sites in bi-layered supported VOx/AlOx/SiO2 catalysts via solid-state NMR, first-principles calculations, and catalytic studies

By combining multinuclear 1H, 29Si, 27Al and 51V solid-state NMR experimental measurements with reactivity and selectivity data, as well as first-principles calculations, for ternary bi-layered supported VOx/Al2O3/SiO2 catalysts, the structure of the dehydrated surface vanadia species was determined for each combination of supported VOx and AlOx active components. The specific structure of the surface vanadia sites in the ternary bi-layered supported VOx/Al2O3/SiO2 catalyst system have been investigated for the first time.The following vanadia sites are proposed based on the current findings:At low vanadia content, surface VO(OH)(OSi)2 sites form on the alumina-free surface of the SiO2 support in the bi-layered supported VOx/Al2O3/SiO2 catalyst system. In addition, two types of VO(OSi)3 surface species are likely present in this system. On small alumina clusters, weakly bonded surface VO(OH)(OAl)2 sites also form, along with the sites containing mixed Si/Al pods VO(OH)(OAl)(OSi). As the size of alumina clusters increases, strongly bonded VO(OAl)3 centers form, alongside the surface sites containing mixed pods VO(OAl)2(OSi) and VO(OAl)(OSi)2. The content of these sites increases with the loading of vanadia. Comparing supported VOx/SiO2, VOx/Al2O3, and bi-layered VOx/Al2O3/SiO2 catalyst systems revealed differences in catalytic activity due to the presence of new sites with different pods, with OH groups as well as the influence of Al-O-Si bonds on the electronic structure of surface vanadia sites on the alumina clusters. During the formation of dimethyl ether (DME), the turnover frequency (TOFDME) of the catalysts decreases with increasing domain size of the alumina clusters on SiO2. Addition of surface VOx sites, however, slightly decreases the TOFDME with the higher vanadia content weakening the activity of the alumina clusters. When surface VOx exists predominantly as V/Al1 and V/Al2, TOFredox depend on the vanadia content with lower vanadia content resulting in higher the TOFredox values. The 51V NMR spectra show that this decrease in redox TOF value correlates with the appearance of vanadia sites associated with silica pods. The activity of the catalysts was tested in methanol conversion reactions.