The study of optimal oxidation time and different temperatures for high quality VO2 thin film based on the sputtering oxidation coupling method

The high quality Vanadium dioxide (VO₂) thin films have been fabricated successfully on sapphire by a simple novel sputtering oxidation coupling (SOC) method. All VO₂ thin film samples exhibit a good metal-insulator transition (MIT) at about 340 K. The optimal oxidation time at different temperatures has been experimentally investigated. We report on the relationship between optimal oxidation time and different temperatures of metal vanadium thin film samples of 101 nm thickness by oxidation in air. It is found that the optimal oxidation time ln(t) as a function of temperature 1/T shows a significant linear relationship among 703 K-783 K, in good agreement with the Wagner's high-temperature oxidation model.     

Analysis of high-resolution infrared and CARS spectra of SO3

Three fundamental modes and several hot bands of ³⁴S¹⁸O₃ have been investigated using both infrared spectroscopy and coherent anti-Stokes Raman scattering spectroscopy (CARS). Coriolis coupling effects are particularly noticeable in ³⁴S¹⁸O₃ due to the close proximity of the ν₂ and ν₄ fundamental vibrations, whose wavenumber values are 477.50864(5) and 502.05565(4) cm⁻¹. The uncertainties in the last digits are shown in parentheses and are two standard deviations. Hot band transitions from ν₂, ν₄ levels give access to infrared inactive ν₂, ν₄ combination/overtone levels which interact strongly with levels of the Raman-active ν₁ symmetric stretching mode due to indirect Coriolis couplings, l-resonances, and Fermi resonances. The result is a complex ν₁ CARS Q-branch spectrum that is the most perturbed of the four SO₃ isotopomers we have studied. The relative importance of these interaction terms on the ν₁ CARS spectrum is examined in some detail and accurate rovibrational constants are determined for all of the mixed states, leading to deperturbed values of 1004.662(24), 0.0003503(9), and 0.0007066(12) cm⁻¹ for ν₁, α₁^B, and α₁^C, respectively. The B_e value is found to be 0.310875(12) cm⁻¹, which gives an equilibrium bond length r_e of 141.7339(3) pm, in excellent agreement with values of 141.7340(1) and 141.7347(7) pm reported earlier for ³²S¹⁶O₃ and ³⁴S¹⁶O₃.     

On the high resolution spectroscopy and intramolecular potential function of SO2

Two weak stretching bands, ν₁ + 3ν₃ and 3ν₁ + ν₃, of the sulfur dioxide molecule have been recorded at high resolution and analyzed for the first time with using a Fourier transform Bruker IFS-120 HR interferometer. About 1000 transitions with J^max. = 51, , and 900 transitions with J^max. = 53, have been assigned to the bands ν₁ + 3ν₃ and 3ν₁ + ν₃, respectively. Analysis of the recorded spectra was made using the model of isolated vibrational states. Parameters obtained from the fit reproduce the initial experimental ro-vibrational energies with the rms deviation of 0.0006 and 0.0012 cm⁻¹ for the bands, 3ν₁ + ν₃ and ν₁ + 3ν₃, respectively. The problem of determination of the intramolecular potential function of SO₂ is discussed.     

Selective CO oxidation in hydrogen-rich gas over CuO/CeO2 catalysts

A series of CuO/CeO₂ catalysts with different Cu-Ce compositions were synthesized by co-precipitation method and characterized by X-ray diffraction, H₂-TPR, CO-TPD, SEM and X-ray photoelectron spectroscopy (XPS) techniques. The effects of Cu-Ce composition and water vapor on the catalytic properties for the selective CO oxidation in the hydrogen-rich gas were investigated. The results indicated that CuO (10%)/CeO₂ catalyst remained the maximum CO conversion and selectivity at 140 and 160 °C, while the performance of CuO/CeO₂ catalysts deteriorated with the CuO molar ratio further increased. The interfacial CuO and CeO₂ interaction and synergistic effect enhanced the redox properties of CuO/CeO₂ catalyst and the highly dispersed copper species were proposed as the active sites for the selective CO oxidation. The blockage of catalytic active sites by absorbed water and the formation of CO-H₂O surface complexes reduced the activity of CuO (10%)/CeO₂ catalyst. The decreasing of surface lattice oxygen and absorbed oxygen species and the agglomeration of copper particles were the plausible interpretations for the deactivation of CuO (10%)/CeO₂ catalyst.     

Reactivity of monolayer V2O5 films on TiO2(1 1 0) produced via the oxidation of vapor-deposited vanadium

The growth, and reactivity of monolayer V₂O₅ films supported on TiO₂(1 1 0) produced via the oxidation of vapor-deposited vanadium were studied using X-ray photoelectron spectroscopy and temperature programmed desorption (TPD). Oxidation of vapor-deposited vanadium in 10⁻⁷ Torr of O₂ at 600 K produced vanadia films that contained primarily V³⁺, while oxidation in 10⁻³ Torr at 400 K produced films that contained primarily V⁵⁺. The reactivity of the supported vanadia layers for the oxidation of methanol to formaldehyde was studied using TPD. The activity for this reaction was found to be a function of the oxidation state of the vanadium cations in the film.     

Synthesis of narrow band gap (V2O5)x-(TiO2)1−x nano-structured layers via micro arc oxidation

V₂O₅-TiO₂ layers with a sheet-like morphology were synthesized by micro arc oxidation process for the first time. Surface morphology and topography of the layers were investigated by scanning electron microscope (SEM) and atomic force microscope (AFM). Phase structure and chemical composition of the layers were also studied by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) techniques. It was revealed that the composite layers had a sheet-like structure average thickness of which was about 100 nm depending on the applied voltage. The layers consisted of anatase, rutile, and vanadium pentoxide phases fractions of which varied with the applied voltage. The optical properties of the layers were also examined employing a UV-vis spectrophotometer. It was found that the absorption edge of the grown composite layers shifted toward the visible wavelengths when compared to MAO-synthesized pure titania layers. The band gap energy of the composite layers was calculated as 2.58 eV. Furthermore, photo-catalytic performance of the layers was examined by measuring the decomposition rate of methylene blue under ultraviolet and visible irradiations. The results demonstrated that about 90% and 68% of methylene blue solution was decomposed after 120 min ultraviolet and visible irradiations over the composite layers, respectively.     

Electric-pulse-induced local conducting area and joule heating effect in VO2/Al2O3 films

We investigated the effect of an electric-pulse on the insulator–metal phase transition of VO₂/Al₂O₃ films using synchrotron-based infrared microspectroscopy. By monitoring the time-resolved optical response, we could demonstrate that local conducting areas are formed under the influence of the electric-pulse, and the Joule heat generated from the local current flow drives a consecutive thermal phase transition in the adjacent sample area.     

Evaluation for the configurational and electronic state of SO3 adsorbed on Pt surface

We evaluate the adsorption of SO₃ molecule on the Pt (1 1 1) surface using the first-principles calculations by a slab model with a periodic boundary condition. We find that there are four stable adsorption configurations on the Pt surface, where SO₃ molecules are adsorbed above the three-fold fcc and hcp sites. In two of these configurations, S and two O atoms are bound to the Pt atoms, and in two other of them, all the three O atoms are bound to Pt surface atoms. Besides, it is found that molecular orbitals of SO₃ and those of Pt surface are hybridized in the active metal d-bands region, that the localized molecular orbitals in SO₃ are stabilized, and that the charge is transferred from Pt to S 3p by SO₃ adsorption on Pt surface though the other interaction of S and O (bound to Pt) component with Pt is little. In addition, the bond between S and O bound to Pt become weak by SO₃ adsorption on Pt surface because the charge polarization to O-Pt bond weakens the bond between S and O bound to Pt. This interaction is assumed to encourage the breakage of S-O bond.     

Nd- or Zr-modified CuO-CeO2/Al2O3/FeCrAl monolithic catalysts for preferential oxidation of carbon monoxide in hydrogen-rich gases

This work presents a study on the role of the additives over CuO-CeO₂/Al₂O₃/FeCrAl monolithic catalysts for the preferential oxidation of CO. The monolithic catalysts were prepared by in situ combustion method and characterized using SEM, XRD and TPR techniques. The results show that the addition of neodymium or zirconium in the CuO-CeO₂/Al₂O₃/FeCrAl catalysts influences the dispersion state of copper oxide and ceria, lowers the activity of hydrogen oxidation and broadens the temperature window for total CO-conversion.     

Preparation and characterization of novel Pd/SiO2 and Ca-Pd/SiO2 egg-shell catalysts with porous hollow silica

Novel egg-shell structured monometallic Pd/SiO₂ and bimetallic Ca-Pd/SiO₂ catalysts were prepared by an impregnation method using porous hollow silica (PHS) as the support and PdCl₂ and Ca(NO₃)₂·4H₂O as the precursors. It was found from transmission electron microscope (TEM), scanning electron microscope (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) that Pd was loaded on PHS with a particle size of 5-12 nm in Pd/SiO₂ samples and the Pd particle size in Ca-Pd/SiO₂ was smaller than that in Pd/SiO₂ since Ca could prevent Pd particles from aggregating. X-ray photoelectron spectroscopy (XPS) analyses exhibited that Pd 3d_5/2 binding energies of Pd/SiO₂ and Ca-Pd/SiO₂ were 0.2 and 0.9 eV lower than that of bulk Pd, respectively, as a result of the shift of the electron cloud from Pd to oxygen in Pd/SiO₂ and to both oxygen and Ca in Ca-Pd/SiO₂. The activity of Ca-Pd/SiO₂ egg-shell catalyst for CO hydrogenation and the selectivity to methanol, with a value of 36.50 mmol_CO mol⁻¹_Pd s⁻¹ and 100%, respectively, were much higher than those of the catalysts prepared with traditional silica gel as the support, owing to the porous core-shell structure of the PHS support.     

A microwave and ab initio investigation of N2-SO3, OC-SO3, and OC-SO3-Ar

Microwave spectra have been observed for N₂-SO₃, OC-SO₃, Ar-SO₃-CO, and several of their isotopic derivatives. All three complexes are symmetric tops with little or no out-of-plane distortion of the SO₃. In Ar-SO₃-CO, the Ar and CO lie on opposite sides of the sulfur, an arrangement which has not been previously observed for trimers involving SO₃. In N₂-SO₃ and OC-SO₃, the N-S and C-S bond lengths are 2.934(12) and 2.854(12), respectively. In Ar-SO₃-CO, the C-S distance is 2.849(4) Å, which is identical, within the estimated uncertainties, to that in OC-SO₃. The Ar-S distance, on the other hand, is 3.411(11) Å, which represents a small but distinct lengthening of 0.061(12) Å relative to that previously determined for Ar-SO₃. Stark effect measurements for OC-SO₃ and Ar-SO₃-CO give dipole moments of 0.8488(13) and 0.602(15) D, respectively. The latter is very nearly equal to the difference between the dipole moments of OC-SO₃ and Ar-SO₃, suggesting that the dipole moment of the trimer is simply the vector sum of the unperturbed dimer dipole moments. Counterpoise corrected optimized geometries and binding energies have been computed at the MP2/aug-cc-pVTZ level for Ar-SO₃ (1.08 kcal/mol), N₂-SO₃ (2.60 kcal/mol), OC-SO₃ (3.92 kcal/mol), and Ar-SO₃-CO (4.90 kcal/mol). The binding energy of Ar-SO₃-CO is nearly equal to the sum of the Ar-SO₃ and OC-SO₃ binding energies, indicating that the two-body interactions on opposite sides of the SO₃ plane are not strongly coupled. Taken together, the experimental and theoretical results indicate that Ar-SO₃-CO is best regarded as a composite of Ar-SO₃ and OC-SO₃ moieties.     

环式M(SO2)(M=Zn, Cd)分子及其阴离子的基质隔离红外光谱和密度泛函理论计算

激光溅射锌和镉原子与SO₂分子反应的低温基质隔离红外光谱实验表明,在氩和氖的惰性基质中,形成了环式M(SO₂)分子及其阴离子M(SO₂)^- (M=Zn, Cd)．相关同位素(³⁴SO₂和S¹⁸O₂)替代实验及密度泛函理论计算均证实了这一结果．此外,自然电荷布居分析表明电子从金属锌和镉的s轨道转移到了SO₂配体上形成了M⁺(SO₂)^-“离子对”复合物,且该分子中的Zn-O键以及Cd-O键均表现出强的极化共价性．而Hg原子在与SO₂反应中所表现出来的惰性可由其较强的相对论效应所致的6s价电子层收缩与高电离电位得以解     

VO2金属-绝缘体相变机理的研究进展

VO₂是一种热致相变金属氧化物. 在341 K附近, VO₂发生由低温绝缘体相到高温金属相的可逆转变, 同时伴随着光学、电学和磁学等性质的可逆突变, 这种独特的性质使得VO₂在光电开关材料、智能玻璃、存储介质材料等领域有着广阔的应用前景. 因此, VO₂金属-绝缘体可逆相变一直是人们的研究热点, 但其相变机理至今未有定论. 首先, 简要概述了VO₂相变时晶体结构和能带结构的变化情况: 从晶体结构来讲, 相变前后VO₂从低温时的单斜相VO₂(M)转变为高温稳定的金红石相VO₂(R), 在一定条件下此过程也可能伴随着亚稳态单斜相VO₂(B)与四方相VO₂(A)的产生; 从能带结构来看, VO₂处于低温单斜相时, 其d_//能带和π^*能带之间存在一个禁带, 带宽约为0.7 eV, 费米能级恰好落在禁带之间, 表现出绝缘性, 而在高温金红石相时, 其费米能级落在π^*能带与d_//能带之间的重叠部分, 因此表现出金属导电性. 其次, 着重总结了VO₂相变物理机理的研究现状. 主要包括: 电子关联驱动相变、结构驱动相变以及电子关联和结构共同驱动相变的3种理论体系以及支撑这些理论体系的实验结果. 文献报道争论的焦点在于, VO₂是否是Mott绝缘体以及结构相变与MIT相变是否精确同时发生. 最后, 展望了VO₂材料研究的发展方向.     

The synthesis and characterization of Ti/SnO2-Sb2O3/PbO2 electrodes: The influence of morphology caused by different electrochemical deposition time

For the electrochemical oxidative degradation of wastewater, it is crucial for electrodes to be highly catalytic active, stable in performance and inexpensive in price. This study focuses on the preparation of the Ti/SnO₂-Sb₂O₃/PbO₂ anodes by anodic deposition under galvanostatic conditions and their electrocatalytic activity affected by crystal structure and surface roughness under different electrochemical deposition time, with phenol taken as the model pollutant to evaluate the electrocatalytic activity. The electrode surface morphology is characterized by XRD and SEM-EDX. The treatment effect of phenol is reflected by electrochemical analysis like CV and LSV. An important conclusion from experiment is that electrochemical deposition time has a major impact on electrocatalytic activity with the optimal deposition time observed around 30 min. At both deposition time beyond this optimal time window, electrocatalytic activity of phenol is substantially lowered. Increasing in electrochemical deposition time leads to a more uniform and smooth electrode surface, which enjoys a more compact structure than the “cracked-mud” one but lower specific surface area and catalytic activity. On the contrary, the “cracked-mud” structure means potentially a unique porous structure, which makes morphology at 30 min a perfect one for high electrocatalytic activity.     

Al2O3 supported Ru catalysts prepared by thermolysis of Ru3(CO)12 for catalytic wet air oxidation

Low loading catalysts Ru/γ-Al₂O₃ and Ru-Ce/γ-Al₂O₃ were prepared by thermolysis of Ru₃(CO)₁₂ on γ-Al₂O_3. The catalysts were characterized by XPS, XRD and SEM. Two new Ru species (Ru_A and Ru_B) were detected during the Ru₃(CO)₁₂ decomposition process due to chemical interaction with the active OH groups on the surface of Al₂O₃ support, and the reduction of them can lead to more dispersed metallic phases. The sample was completely decomposed at 673 K in H₂, and RuO₂ was formed with minor amounts of Ru⁰. When the temperature was increased to 773 K to heat the sample, the ratio of Ru⁰ to RuO₂ increased. However, after the addition of CeO₂, only RuO₂ was detected on surface. The catalysts exhibited high activities in Catalytic Wet Air Oxidation (CWAO) of different organic compounds at high concentration such as isopropyl alcohol, phenol, acetic acids and N,N-dimethylformamide, which is attributed to the better dispersion of Ru particles and the addition of CeO₂ further enhanced number of effectively active sites on the cluster-derived catalyst surface.     

The surface properties and the activities in catalytic wet air oxidation over CeO2-TiO2 catalysts

No-noble metal CeO₂-TiO₂ catalysts prepared by sol-gel method were developed and examined for catalytic wet air oxidation (CWAO) of acetic acid. The structure of the catalysts was measured by BET, SEM, XRD, XPS and DTA-TG. We investigated the effect of the interactions of Ce and Ti on the structure of CeO₂-TiO₂ catalysts. The mechanisms of the relationships between the different content of Ti and the activity of CeO₂-TiO₂ catalysts were discussed. The results showed that the average crystal size of CeO₂ decreased and the surface areas increased; the low valence of Ce³⁺ increase, and the chemisorbed oxygen slightly decreased with the increase of Ti content on the surface of CeO₂-TiO₂ catalysts. The order of the activity in CWAO of acetic acid followed: Ce/Ti 1/1 > Ce/Ti 3/1 > Ce/Ti 1/3 > Ce/Ti 5/1 > CeO₂ > TiO₂ > no catalyst. In CWAO of acetic acid, the optimal atomic ratio of Ce and Ti was 1, and the highest COD removal was over 64% at 230 °C, 5 MPa and 180 min reaction time over Ce/Ti 1/1 catalyst. The excellent activity and stability of CeO₂-TiO₂ catalysts was observed in our study.     

Study of flowerlike CeO2 microspheres used as catalyst supports for CO oxidation reaction

Porous flowerlike CeO₂ microspheres were synthesized via a novel hydrothermal method and were used as supports for the oxidation of CO. After loaded with Au or CuO, it exhibited an excellent low-temperature catalytic activity toward CO oxidation reaction. Especially, for the Au-loaded flowerlike CeO₂ microsphere catalyst, CO gas started its conversion into CO₂ above 80% at room temperature. The possible reasons for the superior catalytic activity of flowerlike CeO₂ microsphere catalysts were discussed.     

Electrochemical oxidation of methanol on Pt nanoparticles composited MnO2 nanowire arrayed electrode

By use of the membrane-template synthesis route, MnO₂ nanowire arrayed electrodes are successfully synthesized by means of the anodic deposition technique. The Pt nanoparticles composited MnO₂ nanowire arrayed electrodes (PME) are obtained through depositing Pt on MnO₂ nanowire arrayed electrode by cathode deposition technique. For comparison of electrochemical performance, Pt nanowire arrayed electrodes which have the same amount of Pt with PME are also prepared. The electro-oxidation of methanol on PME and Pt nanowire arrayed electrodes is investigated at room temperature by cyclic voltammetry, which show that about 110 mV decreased overpotential and 2.1-fold enhanced votammetric current are achieved on PME. The chronoamperometry result demonstrates that the resistance to carbon monoxide for PME is improved.     

NO dissociation and N2 production in the presence of co-adsorbed SO2 and D2 on Pt(3 3 2)

NO dissociation and subsequent N₂ production in the presence of co-adsorbed S¹⁸O₂ and D₂ on the surface of stepped Pt(3 3 2) were studied using Fourier transform infra red reflection–absorption spectroscopy (FTIR-RAS) combined with thermal desorption spectroscopy (TDS). Reduction of NO by D (D₂ is adsorbed dissociatively on Pt surfaces) proceeds to a limited extent, because this reaction is rate-controlled by NO dissociation and the supply of D atoms at the higher surface temperatures at which NO dissociation becomes significant (350 K and higher). NO–D reaction is suppressed in the presence of S¹⁸O₂, depending significantly on the S¹⁸O₂ coverage and the competition between the reactions NO–D and S¹⁸O₂–D. When the supply of D₂ is limited, e.g., 0.1 L in this study, the presence of S¹⁸O₂ suppresses the NO–D reaction. With a sufficient supply of D₂, e.g., 0.4 L and higher, D-atom competing reactions do not play a role any more because the reactions of both NO and S¹⁸O₂ with D proceed only to a very limited extent. As such, generation of O atoms from S¹⁸O₂ dissociation is the main reaction that leads to the suppression in NO dissociation and consequently, N₂ production.It is also concluded that the presence of S¹⁸O₂ does not seriously poison the active sites on the Pt surface, providing that there is a sufficient D supply to remove O atoms from both NO dissociation and S¹⁸O₂ dissociation.     

Characterization of ZrO2-promoted Cu/ZnO/nano-Al2O3 methanol steam reforming catalysts

Three Cu/ZnO/ZrO₂/Al₂O₃ methanol reforming catalysts were investigated using X-ray photoelectron spectroscopy (XPS). The catalysts which contained ZrO₂ from a monoclinic nanoparticle ZrO₂ precursor exhibit both a higher activity toward the methanol steam reforming reaction and a lower CO production rate compared to catalysts composed of an XRD-amorphous ZrO₂ produced by impregnation using a Zr(NO₃)₂ precursor. The presence of a monoclinic phase appears to result in an increased charge transfer between the Zr and Cu species, as evidenced by a relatively electron-rich ZrO₂ phase and a partially oxidized Cu species on reduced catalysts. This electron deficient Cu species is more reactive toward the methanol reforming reaction and partially suppresses CO formation through the reverse water gas shift or methanol decomposition reactions.