Three-dimensionally ordered macroporous (3-DOM) niobium oxide was fabricated by aqueous organic gel method through the interstitial spaces between polystyrene spheres assembled on glass substrates. Freshly precipitated hydrous niobium oxide (Nb2O5·nH2O), which was prepared starting from Nb2O5, was used in combination with citric acid in an aqueous solution and then was transferred as a niobium source to synthesize 3-DOM Nb2O5. The morphologies of porous Nb2O5 were characterized by scanning electron microscope (SEM). The thermal decomposition and phase composition of 3-DOM Nb2O5 were investigated by Fourier transform infrared spectroscopy (FT-IR), Thermogravimetric–differential thermal analysis (TG–DTA), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). 相似文献
X-ray photoelectron spectroscopy and diffraction (XPS and XPD) are applied to analyze oxygen-induced surface structures on
the Nb(110) face formed due to oxygen segregation from the crystal bulk on thermal annealing to 2000 K in vacuum and/or oxygen
adsorption in situ at temperatures above 1100 K. The Nb3d, O1s electronic states and valence band spectra of the NbOx/Nb(110) surface are studied by XPS, and the results are compared with data for NbO, NbO2, and Nb2O5 oxides. It is shown that niobium atoms entering the composition of surface oxide structures on Nb(110), from the standpoint
of the nearest environment and chemical bond, are similar to metal states in NbO. The NbOx layer thickness is estimated to be 0.5 nm. Two chemically inequivalent oxygen states are distinguished on Nb(110), which
are, presumably, atomic chemisorbed oxygen on the parts of the clean surface of the Nb monolayer with hexagonal packing and
oxygen in the composition of NbOx-like linear clusters on Nb(110). A model of the NbOx/Nb(110) surface takes into account a distortion of the structure of NbOx clusters: a periodic vertical shift of metal atoms in Nb-chains and changes in Nb-O bond angles.
Original Russian Text Copyright ? 2009 by M. V. Kuznetsov, A. S. Razinkin, and E. V. Shalaeva
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Translated from Zhurnal Strukturnoi Khimii, Vol. 50, No. 3, pp. 536–543, May–June, 2009. 相似文献
The reaction of [CpnMCl4?x] (M=V: n=2, x=2; M=Nb: n=1, x=0; Cp=η5‐C5H5) with LiBH4 ? THF followed by thermolysis in the presence of dichalcogenide ligands E2R2 (E=S, Te; R=2,6‐(tBu)2‐C6H2OH, Ph) and 2‐mercaptobenzothiazole (C7H5NS2) yielded dimetallaheteroboranes [{CpV(μ‐TePh)}2(μ3‐Te)BH ? thf] ( 1 ), [(CpV)2(BH3S)2] ( 2 ), [(CpNb)2B4H10S] ( 3 ), [(CpNb)2B4H11S(tBu)2C6H2OH] ( 4 ), and [(CpNb)2B4H11TePh] ( 5 ). In cluster 1 , the V2BTe atoms define a tetrahedral framework in which the boron atom is linked to a THF molecule. Compound 2 can be described as a dimetallathiaborane that is built from two edge‐fused V2BS tetrahedron clusters. Cluster 3 can be considered as an edge‐fused cluster in which a trigonal‐bipyramidal unit (Nb2B2S) has been fused with a tetrahedral core (Nb2B2) by means of a common Nb2 edge. In addition, thermolysis of an in‐situ‐generated intermediate that was produced from the reaction of [Cp2VCl2] and LiBH4 ? THF with excess BH3 ? THF yielded oxavanadaborane [(CpV)2B3H8(μ3‐OEt)] ( 6 ) and divanadaborane cluster [(CpV)2B5H11] ( 7 ). Cluster 7 exhibits a nido geometry with C2v symmetry and it is isostructural with [(Cp*M)2B5H9+n] (M=Cr, Mo, and W, n=0; M=Ta, n=2; Cp*=η5‐C5Me5). All of these new compounds have been characterized by 1H NMR, 11B NMR, and 13C NMR spectroscopy and elemental analysis and the structural types were established unequivocally by crystallographic analysis of compounds 1 – 4 , 6 , and 7 . 相似文献
Summary: Ammonium group containing cellulose derivatives are prepared from homogeneously synthesized cellulose p-toluenesulfonic acid esters (tosyl cellulose) by conversion with sodium azide and subsequent reduction of the azido moiety applying NaBH4/CoBr2/2,2′-bipyridine as reagent. Regarding the tosylation, cellulose samples of different degree of polymerization and hemicellulose content possess a different reactivity. The deoxyamino cellulose is water soluble in the protonated state. Elemental analysis, FTIR- and NMR spectroscopy were carried out to analyze the degree of substitution and functionalization pattern. It was also studied to synthesize deoxyazido celluloses without isolation of the tosyl cellulose. However, a predominant formation of deoxychloro moieties occurs. 相似文献
Self-assembled nanorod of vanadium oxide bundles were synthesized by treating bulk V2O5 with high intensity sonochemical technique. The synthesized materials were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM) and temperature-programmed reduction (TPR) in H2. Catalytic behaviour of the materials over anaerobic n-butane oxidation was studied through temperature-programmed reaction (TPRn). Catalytic evaluation of the sonochemical treated V2O5 products was also studied on microreactor. XRD patterns of all the vanadium samples were perfectly indexed to V2O5. The morphologies of the nanorod vanadium oxides as shown in SEM and TEM depended on the duration of the ultrasound irradiation. Prolonging the ultrasound irradiation duration resulted in materials with uniform, well defined shapes and surface structures and smaller size of nanorod vanadium oxide bundles. H2-TPR profiles showed that larger amount of oxygen species were removed from the nanorod V2O5 compared to the bulk. Furthermore, the nanorod vanadium oxide bundles, which were produced after 90, 120 and 180 min of sonochemical treatment, showed an additional reduction peak at lower temperature (850 K), suggesting the presence of some highly active oxygen species. TPRn in n-butane/He over these materials showed that the nanorod V2O5 with highly active oxygen species showed markedly higher activity than the bulk material, which was further proven by catalytic oxidation of n-butane. 相似文献
Regioselectively ethylated celluloses, 2‐O‐ ( 1 ), 3‐O‐ ( 2 ), and 6‐O‐ethyl‐ ( 3 ) celluloses were synthesized via ring‐opening polymerization of glucopyranose orthopivalate derivatives. The number‐average degrees of polymerization (DPns) of compounds 1 and 2 were calculated to be 10.6 and 49.4, respectively. Three kinds of compound 3 with different DPns were prepared: DPns = 12.9 ( 3‐1 ), 60.3 ( 3‐2 ), and 36.1 ( 3‐3 ). The 2‐O‐, 3‐O‐, and 6‐O‐ethylcelluloses were soluble in water, confirmed by NMR analysis. Furthermore, the 3‐O‐ ( 2 ), and 6‐O‐ethyl‐ ( 3‐2 ) celluloses showed thermo‐responsive aggregation behavior and had a lower critical solution temperature (LCST) at about 40 °C and 70 °C, respectively, based on the results from turbidity tests and DSC measurements. The 6‐O‐ethyl‐cellulose ( 3‐3 ) with DPn = 36.1 and DPw = 54.6 showed gelation behavior over approx 70 °C, whereas the 6‐O‐ethyl‐celluloses 3‐1 and 3‐2 with lower and higher molecular weight, such as DPns 12.9 and 60.3, did not show gelation behavior at this temperature. It was revealed that the position of ethyl group affected the phase transition temperature. According to our experiments, the 3‐O‐ethyl and 6‐O‐ethyl groups along the cellulose chains caused the thermo‐responsive property of their aqueous solutions. The appropriate DP of the regioselective 6‐O‐ethyl‐cellulose existed for gelation of the aqueous solution.
Urease was entrap-immobilized on composite gel fibre of cellulose acetate and TiO2. The immobilization can be easily performed under mild conditions. The gel fibre is stable in high ionic solutions and in phosphate solutions with a range of pH 6–8.The pH and thermal stabilities of immobilized urease were higher than those of the native one. 相似文献
The evolution of spectral and luminescent properties of Ag-containing composite coatings prepared by liquid technique has been studied. Double stabilization allows forming thin oxide films containing luminescent small Agn (n?<?5) molecular clusters using the liquid technique. These clusters are non-stable intermediate products during the formation of Ag nanoparticles from the ions and neutral atoms. It was found that small luminescent Agn molecular clusters (n?<?5) formed in the solutions at the presence of polyvinylpyrrolidone (PVP) remain in PVP/metal nitrates composite coatings and in the calcined metal oxide coatings. Spatial separation of small Ag molecular clusters in the coatings by the oxide nanoparticles of ZnO and MgO prohibits silver clusters growth and non-luminescent silver nanoparticles formation and allows saving coatings’ luminescence properties during thermal treatment.
The influence of manganese precursors on the deposition rate of hydrous manganese oxide in the amorphous form (denoted as a-MnOx·nH2O) and the effect of oxide thickness on the electrochemical properties of a-MnOx·nH2O, for application as electrochemical supercapacitors, were systematically investigated in this work. The results showed that Mn(CH3COO)2·4H2O is a more promising precursor because of its high deposition rate at much lower potentials in comparison with MnSO4·5H2O, MnCl2·4H2O, and Mn(NO3)2·4H2O. The capacitive characteristics of a-MnOx·nH2O were found to be independent of precursors, probably due to the fact that the mean oxidation state of Mn is not significantly affected by changing the anions of manganese precursors (from the XPS results). The capacity of oxide deposits was found to be proportional to the charge density of deposition (i.e., loading) of a-MnOx·nH2O when it was equal to or less than a critical value (ca. 3.5 C cm–2), while poorer capacitive behavior with a lower capacity was clearly found beyond this critical value. The a-MnOx·nH2O deposit with 3.5 C cm–2, exhibiting an acceptable capacitive performance, showed the highest capacity of energy storage for supercapacitors. 相似文献
In this study we show that nanoparticles of various ferric oxides (hematite, maghemite, amorphous Fe2O3, β‐Fe2O3 and ferrihydrite) incorporated into carbon paste exhibit electro‐catalytic properties towards hydrogen peroxide reduction. The modified paste electrode performances were evaluated and compared with those obtained with Prussian Blue‐modified carbon paste electrode, which represents an excellent chemical mediator towards the H2O2 redox reaction (as widely described in literature). The best catalytic activity was found for carbon paste modified by amorphous ferric oxide with 2–4 nm particle size, which was further tested for possible application as hydrogen peroxide sensor. At pH 7, the limit of detection was 2×10?5 M H2O2 (S/N=3), the calibration curves were linear upto 8.5 mM H2O2 (R2=0.998), the measurement reproducibility (RSD=97%, n=4), the interelectrode reproducibility (RSD=16%, nelectrodes=5) and <3 s response time. 相似文献
Summary: Cellulose nanocrystals (CNC) were extracted from Kraft pulp of Eucalyptus urograndis. The CNC were isolated by acid hydrolysis with H2SO4 64% (w/w) solution, for 20 minutes at 45 °C. The morphology and crystallinity of the CNC were investigated by atomic force microscopy (AFM) and X-ray diffraction (XRD), respectively. The AFM image supports the evidence for the development of crystals of cellulose in nanometric scale. These nanoparticles were used as reinforcement material in carboxymethyl cellulose (CMC) matrix. Nanocomposites films were prepared by casting. The nanocomposites were characterized by thermal (TGA) and mechanical (DMA) analyses. A large reinforcing effect of the filler was observed. The tensile strength of nanocomposites was significantly improved by 107%, the elongation at break decreased by 48% and the thermal resistance increased slightly. The improvements in thermo-mechanical properties suggest a close association between filler and matrix. 相似文献
A Nb-containing siliceous porous clay heterostructure (PCH) with Nb contents from 0 to 30 wt %) was prepared from a bentonite and used as support in the preparation of supported NiO catalysts with NiO loading from 15 to 80 wt %. Supports and NiO-containing catalysts were characterised by several physicochemical techniques and tested in the oxidative dehydrogenation (ODH) of ethane. The characterisation studies on Nb-containing supports showed the presence of well-anchored Nb5+ species without the formation of Nb2O5 crystals. High dispersion of nickel oxide with low crystallinity was observed for the Nb-containing PCH supports. In addition, when NiO is supported on these Nb-containing porous clays, it is more effective in the ODH of ethane (ethylene selectivity of ca. 90 %) than NiO supported on the corresponding Nb-free siliceous PCH or on Nb2O5 (ethylene selectivities of ca. 30 and 60 %, respectively). Factors such as the NiO–Nb5+ interaction, the NiO particle size and the properties of surface Nin+ species were shown to determine the catalytic performance. 相似文献
Reaction of [CpnMCl4?x] (M=V: n=x=2; M=Nb: n=1, x=0) or [Cp*TaCl4] (Cp=η5‐C5H5, Cp*=η5‐C5Me5), with [LiBH4?thf] at ?70 °C followed by thermolysis at 85 °C in the presence of [BH3?thf] yielded the hydrogen‐rich metallaboranes [(CpM)2(B2H6)2] ( 1 : M=V; 2 : M = Nb) and [(Cp*Ta)2(B2H6)2] ( 3 ) in modest to high yields. Complexes 1 and 3 are the first structurally characterized compounds with a metal–metal bond bridged by two hexahydroborate (B2H6) groups forming a symmetrical complex. Addition of [BH3?thf] to 3 results in formation of a metallaborane [(Cp*Ta)2B4H8(μ‐BH4)] ( 4 ) containing a tetrahydroborate ligand, [BH4]?, bound exo to the bicapped tetrahedral cage [(Cp*Ta)2B4H8] by two Ta‐H‐B bridge bonds. The interesting structural feature of 4 is the coordination of the bridging tetrahydroborate group, which has two B? H bonds coordinated to the tantalum atoms. All these new metallaboranes have been characterized by mass, 1H, 11B, and 13C NMR spectroscopy and elemental analysis and the structural types were established unequivocally by crystallographic analysis of 1 – 4 . 相似文献
A method is described which allows the determination of the hydroxyl group(s) in glucose units of cellulose which react with formaldehyde at low degrees of substitution (0.2 to 1.5% CH2O on cellulose). It consists of permethylation of the cellulose by a sequence of two methylations with dimethylsulfate and NaOH (without solvent) followed by 2 exchange methylations with methyl iodide and sodium n-butoxide and further steps described earlier [2]. The results demonstrate that the use of the new permethylation method leads to a loss of material of less than 5%. 相似文献
A mechanistic study on the synthesis of propylene carbonate (PC) from CO2 and propylene oxide (PO) catalyzed by NbCl5 and organic nucleophiles such as 4‐dimethylaminopyridine (DMAP) or tetra‐n‐butylammonium bromide (NBu4Br) is reported. A combination of in situ spectroscopic techniques and kinetic studies has been used to provide detailed insight into the reaction mechanism, the formation of intermediates, and interactions between the reaction partners. The results of DFT calculations support the experimental observations and allow us to propose a mechanism for this reaction. 相似文献
Traditionally‐suggested combustion time of 1 h at 550°C) with the sealed‐tube combustion method for determining the 13C/ 12C ratio of cellulose nitrate or other nitrogen‐containing components could produce large negative deviation up to 1°. Three types of cellulose are used to ascertain possible causes. The presence of nitrous oxide (N2O) formed during combustion is most likely responsible for this deviation. Prolongation of the combustion time (at least 5 h at 550°C) and intimate contact between copper oxide and organic matter can greatly improve the analysis precision and effectively reduce this deviation to an acceptable level. Regardless of scattered carbon isotope data, hydrogen isotope data are all reproducible within 2° when this method is coupled with the high temperature uranium reduction method. Thus, care should be taken for determining carbon and nitrogen isotope compositions of nitrogen‐containing substances using the low temperature sealed‐tube combustion method. 相似文献