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The preparation of vanadium-phosphate catalysts by Atomic Layer Deposition (ALD) was studied for application to selective oxidation of n-butane to maleic anhydride (MA). Modification of bulk V2O5 by ALD with trimethylphosphate significantly increased the selectivity to MA but the catalyst performance was still much worse than that observed for bulk vanadium phosphate (VPO). Silica-supported VPO was then prepared by ALD of P and V and compared to a VPO/SiO2 catalyst prepared by impregnation. Raman spectra showed that the ALD-prepared materials were more homogeneous, and temperature-programmed desorption of 2-propanol demonstrated that the VPO phase covered the silica more uniformly when deposited by ALD. However, the bulk VPO catalyst remained the most selective for MA. Possible reasons for why the supported catalysts showed lower performance are discussed and suggestions made for improving these catalysts. [ABSTRACT FROM AUTHOR]

Vanadium phosphorus oxide (VPO) was immobilized on SBA-15 via a facile impregnation process. The structure and VPO species on SBA-15 were characterized by XRD, TEM, BET, FTIR and XPS techniques. It was found the VPO/SBA-15 catalysts maintained the two-dimensional hexagonal structure of SBA-15, and the supported VPO species existed in a highly dispersed amorphous state. VPO/SBA-15 catalyst was tested for the ammoxidation of dichlorotoluenes (DCTs) to corresponding dichlorobenzonitriles (DCNs) in a lab-scale tube reactor. Compared with VPO/SiO2 (large-pore silica-supported VPO), VPO/SBA-15 exhibited appreciable enhancement in the catalytic performance due to the unique channel structure of SBA-15. The yield and selectivity toward 2,4-DCN increased by 7% and 6%, while toward the sterically hindered 2,6-DCN increased by 7% and 13%, respectively. [ABSTRACT FROM AUTHOR]

The vanadium phosphorous oxide (VPO) catalysts, supported on Santa Barbara amorphous molecular sieve (SBA-15) with different vanadium loadings, were prepared by the precipitation method in an organic phase. Techniques such as X-ray diffraction, Bruner–Emmett–Teller method, scanning electron micrograph (SEM), and transmission electron micrograph (TEM) were used for characterization of the catalysts. The high surface area, large pore volume, and pore size of SBA-15 provide an excellent dispersion of (VO)2P2O7species on the support surface. Oxidation of various alcohols was studied in the liquid phase over the VPO/SBA-15 catalyst, usingtert-butylhydroperoxide as an oxidant. The activities of VPO/SBA-15 samples were considerably higher than that of the bulk VPO catalyst. At 90°C, the obtained activities were 0.567 andover the bulk VPO and 15 wt.% VPO/SBA-15 catalysts, respectively. The effects of substrates, oxidants, reaction time, oxidant/alcohol molar ratio, solvents, amount of catalyst, catalyst recycling, and leaching of VPO in the liquid phase were also investigated. [ABSTRACT FROM PUBLISHER]

We report here the results of density functional theory quantum mechanical (QM) studies of the detailed chemical mechanism underlying the n-butane selective oxidation to form maleic anhydride (MA) on vanadyl pyrophosphate [(VO)PO] and vanadyl phosphate [VOPO] surfaces. This QM-derived mechanism differs substantially from previous suggestions but is in excellent agreement with key experimental observations. We find that the O(1)=P bond of the oxidized X1 phase of the VOPO surface is the active site for initiating the VPO chemistry, by extracting the H from the n-butane C-H bond. This contrasts sharply with previous suggestions, all of which involved the V=O bonds. The ability of O(1)=P to cleave alkane C-H bonds arises from a new unique mechanism that decouples the proton transfer and electron transfer components of this H atom transfer reaction. We find that the juxtaposition of a highly reducible V next to the P=O bond but coupled via a bridging oxygen dramatically enhances the activity of the P=O bond to extract the proton from an alkane, while simultaneously transferring the electron to the V to form V. This Reduction-Coupled Oxo Activation (ROA) mechanism had not been known prior to these QM studies, but we believe that it may lead to a new strategy in designing selective catalysts for alkane activation and functionalization, and indeed it may be responsible for the selective oxidation by a number of known mixed metal oxide catalysts. To demonstrate the viability of this new ROA mechanism, we examine step by step the full sequence of reactions from n-butane to MA via two independent pathways. We that find that every step is plausible, with a highest reaction barrier of 21.7 kcal/mol. [ABSTRACT FROM AUTHOR]

Vanadium phosphorus oxide (VPO) catalysts synthesized via hydrothermal method were introduced with some different dopants, Cr, Ni, Fe, and Mn during the preparation of the precursors, VOHPO4 · 0.5H2O. All modified precursors were subsequently transformed under reaction conditions to give the active phase, (VO)2P2O7. Several techniques were used to characterize the physicochemical properties of the catalysts, such as X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), H2-temperature programmed reduction (TPR), laser Raman spectroscopy (LRS), and chemical analysis. The catalytic performance of the catalysts for selective oxidation of n-butane to maleic anhydride has been carried out by using a fixed bed microreactor (673 K, gas hourly space velocity [GHSV] = 2,400 hr-1). The results show that the addition of dopants into the VPO catalysts increased the surface area of the catalysts and induced the formation of V5+ phases as shown in XRD and LRS spectra that promoted the catalytic performance. A further water reflux treatment to all the precursors gave catalysts with only (VO)2P2O7 phase. However, the activity and selectivity of these catalysts were reduced markedly. [ABSTRACT FROM AUTHOR]

The molecular organization of N,N'-dimethyl-N,N'-dioctylhexylethoxymalonamide (DMDOHEMA), the current reference extractant for the DIAMEX (DIAMide EXtraction) process, is correlated with its water extraction properties from neutral media. The aggregation of DMDOHEMA in n-heptane was investigated by vapor pressure osmometry (VPO) and the aggregate speciation characterized by combined small-angle neutron and X-ray scattering (SANS and SAXS, respectively). Two approaches were taken to model the aggregation of the diamide and the water extraction as a function of the diamide concentration by taking into account a single aggregation equilibrium with an average aggregation number N equal to 4.28 ± 0.05; and a competition between two types of aggregates in the organic phase, namely, aggregates of the reverse micelle type with 4 diamides per aggregate, and an oligomeric structure composed of about 10 diamide molecules which appears at high extractant concentration (>1 mol/L). In both cases, the supramolecular speciation representing the monomers/aggregates distribution was determined, and for each supramolecular organization, a solubilization parameter was calculated using the Sergievskii-Dannus relationship. Thus, the correlation between the two types of micellization of the diamide and the extraction of water into the organic phase was demonstrated. The larger aggregates can extract about five times more water than monomers. [ABSTRACT FROM AUTHOR]

The present article describes the synthesis, spectral, coordination and thermal aspects of N,N′-polymethylene bis(1-phenyl-3-methyl-4-trifluoroacetylimino-2-pyrazoline-5-ol)oxovanadium(IV) or copper(II) Schiff base complexes with alkyl backbones ranging from two to four carbons have been characterized on the basis of elemental analysis, magnetic moments, molar conductivity measurements, spectra (FTIR, ESR, UV-Visible, MS), VPO and thermal studies. The vapour pressure osmometry (VPO) and mass spectral studies indicate that the complexes are monomeric. An ESR study of all these complexes of VO(IV) and Cu(II) are consistent with the square pyramidal and square planar geometries of these metal ions, respectively. In addition, the kinetics and thermodynamic parameters for the different thermal decomposition steps of the complexes have been studied employing Horowitz-Metzger and Freemen-Carroll methods. [ABSTRACT FROM AUTHOR]

This paper describes the development of a new technique, atomic beam deposition (ABD), for the fabrication of catalysts with different active sites capable of catalyzing different chemical reactions. Using ABD, submonolayer amounts of Te and Cu atoms were deposited on vanadyl pyrophosphate (VPO) catalyst particles, and precise non-steady-state kinetic characterization was performed using the temporal analysis of products (TAP) reactor immediately following deposition. Results from TAP Knudsen pulse response experiments determine if small changes in the metal surface composition would produce detectable changes in catalytic properties. Partial oxidation of 1-butene to furan was used as the test reaction. Furthermore, this paper also demonstrates the sensitivity of the TAP reactor by measuring oxygen uptake on a single 350 μm diameter polycrystalline Pt particle packed in a bed with 100,000 inert quartz particles of similar dimensions. The Pt experiments demonstrate the precise manipulation of surface oxygen content. [ABSTRACT FROM AUTHOR]

In unsupported V-containing catalysts, V4+ sites are frequently present in amorphous oxidic clusters and/or crystalline paramagnetic bulk phases in which they are coupled by effective spin–spin exchange interactions. This work presents two EPR procedures for evaluating these interactions and relating their strength to the degree of disorder and catalytic performance, namely (1) evaluating permanent structural disorder by calculating exchange energies and integrals and (2) monitoring transient electronic disorder caused by catalyst–reactant interaction in working catalysts using the ratio of the fourth and the square of the second moment of the EPR signal. Selected application examples comprise VPO catalysts such as (i) (VO)2P2O7, in which a certain degree of structural disorder revealed to be essential for high catalytic performance in the selective oxidation of n-butane to maleic anhydride, (ii) (NH4)2(VO)3(P2O7)2 in which transient perturbation of spin–spin exchange sensitively reflects the strength of reactant adsorption during ammoxidation of toluene and (iii) (NH4)2VOP2O7 in which an amorphous VO2+-containing phase could be identified as active component besides inactive crystalline phases. Based on operando-EPR measurements, reasons for activity differences in MoVTeNb oxide catalysts could be suggested. [ABSTRACT FROM AUTHOR]

Semirubins are analogs for one-half of the bilirubin structure and capable of intramolecular hydrogen bonding. Semirubin amides of ammonia and primary amines are also capable of intramolecular hydrogen bonding. From a combination of spectroscopic methods (1H NMR, N OE, and VPO), the primary amide is found to engage very effectively in intramolecular hydrogen bonding. The secondary and tertiary amides engage in both intramolecular ( i) and intermolecular ( ii) hydrogen bonding: N-methyl ( i, monomer + ii, dimer), N- tert-butyl ( ii, dimer), N, N-diethyl ( i, monomer + ii, dimer). With an oxo-group at C(10), all of the amides are monomeric and most engage in intramolecular hydrogen bonding. [ABSTRACT FROM AUTHOR]

By applying fumed SiO2 and the deposition–precipitation method based on organic medium, the composite VPO/fumed SiO2 catalysts were first prepared and tried for partial oxidation of n-butane to maleic anhydride. In the temperature range of 653–693 K the fumed SiO2-based catalysts not only showed good activity but also maintained sufficiently high MA selectivity in comparison to some conventional supported VPO catalysts. As an example, the catalyst with 30% VPO content showed butane conversion of 60% and MA selectivity of 58 mol% at 673 K. The turnover rates of low loading samples are found to be higher than that of high loading sample as well as unsupported catalyst. Besides the unique interaction which may exist between VPO component and the fumed SiO2 material, co-existence of dominant (VO)2P2O7 and minor VOPO4 in these non-equilibrated catalysts may be favorable for MA formation. Moreover, introducing the additive of polyethylene glycol (PEG) in the preparation medium can obviously enhance the dispersion of VPO component and hence lead to a more selective catalyst. [ABSTRACT FROM AUTHOR]

In situ analysis of the surface of a working selective oxidation catalyst is an essential yet rarely conducted experiment in attempts to derive structure–function relationships. The case study of n-butane oxidation over vanadyl pyrophosphate (VPP) is used to develop a general working hypothesis and to illustrate that the molecular properties of the substrate sets boundary conditions on the surface chemical properties of the catalyst. Experiments using in situ X-ray photoelectron spectroscopy (XPS) and in situ low-energy X-ray absorption spectroscopy are used to derive compositional, electronic, and geometric structural information of the surface of the working VPP. These data allow the conclusion that a surface phase different from VPP must be present covering at least part of the active material. The recent data together with literature observations are used to derive a scenario explaining the function of VPP as a unique catalytic system. [ABSTRACT FROM AUTHOR]

This study presents information about crystal imperfections in the main phase of industrial vanadium phosphorous oxide catalysts that are used to catalyze the oxidation of n-butane to maleic anhydride, being an important intermediate in the chemical industry. The mechanism of this reaction is still debated, and the catalytically active and selective surface centers have not yet been identified. The results presented are based on X-ray diffraction data obtained by both laboratory-scale and synchrotron powder diffraction experiments, as well as laboratory-scale single-crystal diffraction experiments. It has been proven that pronounced Bragg reflection broadening effects found in laboratory-scale powder diffraction patterns of industrial VPO catalysts are real and not due to an insufficient 2-θ resolution of the apparatus. In the framework of this work, a powder diffraction full profile fitting strategy was developed using the TOPAS software, which was applied to analyze the X-ray diffraction data of four differently activated industrial catalyst samples, originating from one batch after they had been catalytically tested. It was found that the reflection broadening is mainly caused by an anisotropic crystal size, which results in platelet-shaped crystallites of vanadyl pyrophosphate. A further contribution to the reflex broadening, especially for (111), was found to be a result of stacking faults perpendicular to the a direction in the crystal structure of vanadyl pyrophosphate. These results were used to elaborate on possible correlations between structural proxies and catalytic performance. A direct correlation between the extension of coherently scattering domains in the z direction and the catalyst's selectivity could be proven, whereas the activity turned out to be dependent on the crystallite shape. Regarding the phase contents, it could be shown that sample catalysts containing a higher amount of β-VO(PO3)2 showed increased catalytic activity. [ABSTRACT FROM AUTHOR]