Preparation and characterization of vanadium(IV) oxide supported on SBA-15 and its catalytic performance in benzene hydroxylation to phenol using molecular oxygen

Preparation of dispersed transition metal oxides catalyst with low oxidation state still remains a challenging task in heterogeneous catalysis.In this study,vanadium oxides supported on zeolite SBA-15 have been prepared under hydrothermal condition using V 2 O 5 and oxalic acid as sources of vanadium and reductant,respectively.The structures of samples,especially the oxidation state of vanadium,and the surface distribution of vanadium oxide species,have been thoroughly characterized using various techniques,including N 2-physisorption,X-ray diffraction(XRD),transmission electron microscopy(TEM),X-ray photoelectron spectroscopy(XPS),UV-visible spectra(UV-Vis) and UV-visible-near infrared spectra(UV-Vis-NIR).It is found that the majority of supported vanadium was in the form of vanadium(IV) oxide species with the low valence of vanadium.By adjusting hydrothermal treatment time,the surface distribution of vanadium(IV) oxide species can be tuned from vanadium(IV) oxide cluster to crystallites.These materials have been tested in the hydroxylation of benzene to phenol in liquid-phase with molecular oxygen in the absence of reductant.The catalyst exhibits high selectivity for phenol(61%) at benzene conversion of 4.6%,which is a relatively good result in comparison with other studies employing molecular oxygen as the oxidant.     

Salt effect on molecular orientation at air/liquid methanol interface

The salt effects on molecular orientation at air/liquid methanol interface were investigated by the polarization-dependent sum frequency generation vibrational spectroscopy(SFG-VS). We clarified that the average tilting angle of the methyl group to be u = 308 58 at the air/pure methanol surface assuming a d-function orientational distribution. Upon the addition of 3 mol/L Na I, the methyl group tilts further away from the surface normal with a new u = 418 38. This orientational change does not explain the enhancement of the SFG-VS intensities when adding Na I, implying the number density of the methanol molecules with a net polar ordering in the surface region also changed with the Na I concentrations. These spectroscopic findings shed new light on the salt effects on the surfaces structures of the polar organic solutions. It was also shown that the accurate determination of the bulk refractive indices and Raman depolarization ratios for different salt concentrations is crucial to quantitatively interpret the SFG-VS data.     

Phase-field modeling of void evolution and swelling in materials under irradiation

Void swelling is an important phenomenon observed in both nuclear fuels and cladding materials in operating nuclear reactors. In this work we develop a phase-field model to simulate void evolution and void volume change in irradiated materials. Important material processes, including the generation of defects such as vacancies and self-interstitials, their diffusion and annihilation, and void nucleation and evolution, have been taken into account in this model. The thermodynamic and kinetic properties, such...     

Differential equation dynamical system based assessment model in GNSS interoperability

With the development of Global Navigation Satellite System (GNSS),the idea of GNSS interoperability is born and has become the focus of study in the field of satellite navigation.The popularity for GNSS to augment the interoperability with the existing ones necessitates the study of the assessment algorithm of this idea.In this paper,an assessment algorithm for interoperability comprehensive benefits based on the differential equation dynamical system is discussed.There are two important aspects in GNSS tha...     

A Direct Assembly Approach to the Synthesis of N,N′-Bridged Calix[4]pyrroles: The Synthesis of a 1,5-Diazacyclononatriene Locked in a Saddle Conformation

Ring closure of 1,2-bis(1-pyrrolylmethyl)benzene in the acid-catalysed condensation with acetone yields the 1,5-diazacyclononatriene [ O -C₆H₄(CH₂NC₄H₃-2)₂C(CH₃)₂] as the sole identifiable product. The twisted or saddle conformation of the 1,5-diazacyclononatriene, which was confirmed by X-ray crystal structure determination, is conformationally rigid in solution. The conformation of the 1,5-diazacyclononatriene prevents the formation of the target N,N′-bridged calix[4]pyrrole by further acid-catalysed condensation with acetone, the reaction affording unidentified oligomers/polymers instead. The acid-catalysed condensation of 1,3- and 1,4-bis(1-pyrrolylmethyl)benzene with acetone also yields unidentified oligomers/polymers.     

Room Temperature Phosphorescence of 1-Bromo-4-(bromoacetyl)naphthalene Induced by Sodium Deoxycholate

Sodium deoxycholate (NaDOC) can induce 1-bromo-4-(bromoacetyl)naphthalene (BBAN) to undergo strong room temperature phosphorescence (RTP) without the removal of dissolved oxygen from the solution. RTP spectra, phosphorescence polarization and ¹³C NMR results, along with the molecular modeling calculations, supported the conclusion that BBAN molecule was combined in a sandwich with two NaDOC molecules by a “back-to-back” hydrophobic interaction arising from the apolar faces of the NaDOC molecules, which provided BBAN with a rigid enough microenvironment to produce RTP.     

Study on the Supramolecular System of TAPP and Cyclodextrins by Spectroscopy

The ability of β-cyclodextrin (β-CD), γ-CD, hydroxypropyl-β-CD (HP-β-CD), trimethyl-β-CD (TM-β-CD), sulfurbutylether-β-CD (SBE-β-CD) and carboxymethyl-β-cyclodextrin (CM-β-CD) to break the aggregate of the meso-tetrakis(4-N-trimethylaminobenzyl)porphyrin (TAPP) and to form 2:1 inclusion complexes has been studied by absorption and fluorescence spectroscopy. The formation constants are calculated, respectively, by fluorimetry, from which the inclusion capacity of different CDs is compared and the inclusion mechanism of charged-β-CD (SBE-β-CD and CM-β-CD) is quite different from that of the parent β-CD. At lower pH, the complexation between TM-β-CD and H²TAPP²⁺ (the form of the diprotonated TAPP) hampers the continuous protonation of the pyrrole nitrogen of TAPP and the hydrophobic cavity may prefer to bind an apolar neutral porphyrin molecule. ¹HNMR data support the inclusion conformation of the porphyrin–cyclodextrin supramolecular system, indicating the interaction of the meso-phenyl groups of TAPP with the cavity of CDs. For this host–guest inclusion model, cyclodextrin being regarded as the protein component, which acts as a carrier enveloping the active site of heme prosthetic group within its hydrophobic environment, provides a protective sheath for the porphyrin, creating artificial analogues of heme-containing proteins. However, for TAPP, encapsulated within this saccharide-coated barrier, its photophysical and photochemical properties changed strongly.     

Fluorophore-labeled Polyamidoamine (PAMAM) Dendritic Architectures: Synthesis and Fluorescence Sensing Properties

Novel polyamidoamine (PAMAM) dendrimers (G=0.5–2.5) with a naphthalene core unit have been prepared. They were found to display acid as well as metal ion sensitive fluorescence signal amplification, making them of potential use as chemosensing materials. PAMAM dendritic wedges as well as naphthalene-centered PAMAM dendrimers were characterized by FT-IR, ¹H and ¹³C NMR spectroscopic methods and elemental analysis.     

Insights into support effects on Ce-Zr-O mixed oxide-supported gold catalysts in CO oxidation

Au/Ce1xZrxO2 catalysts (x=0-0.8) were prepared by a deposition-precipitation method using Ce1xZrxO2 nanoparticles as supports with variable Ce and Zr contents. Their structures were characterized by complimentary means such as X-ray diffraction, Raman, scanning transmission electron microscopy and X-ray photoelectron spectroscopy (XPS). These Au catalysts possessed similar sizes and crystalline phases of Ce1xZrxO2 supports as well as similar sizes and oxidation states of Au nanoparticles. The oxidation state of Au nanoparticles was dominated by Au 0 especially in CO oxidation. Their activities were examined in CO oxidation at different temperatures in the range of 303 333 K. The CO oxidation rates normalized per Au atoms increased with the increasing Ce contents, and reached the maximum value over Au/CeO2. Such change was in parallel with the change in the oxygen storage capacity values, i.e. the amounts of active oxygen species on Au/Ce1xZrxO2 catalysts. The excellent correlation between the two properties of the catalysts suggests that the intrinsic support effects on the CO oxidation rates is related to the effects on the adsorption and activation of O2 on Au/Ce1xZrxO2 catalysts. Such understanding on the support effects may be useful for designing more active Au catalysts, for example, by tuning the redox properties of oxide supports.