The location of excess electrons on H2O/TiO2(110) surface and its role in the surface reactions

Excess electrons play a key role in many of the properties of Titanium dioxide (TiO₂). Understanding their behaviour is important for improving the performance of TiO₂ in energy-related applications. Here, we describe a DFT + U study of the locations of the unpaired electron (UPE) on rutile TiO₂(110) (R-TiO₂(110)) surface and H₂O/R-TiO₂(110) surface. Our results show that the subsurface are preferred with R-TiO₂(110) surface. In contrast to previous studies, we find that the UPE tends to migrate to the surface H₂O-Ti_5c (the five-coordinated titanium (Ti_5c) at surface with H₂O adsorption) with the increasing of H₂O coverage and UPE concentration. In addition, we have shown that the UPE plays an important role in the O-H bond dissociation and other important elementary reactions in photo-catalytic H₂O dissociation on R-TiO₂(110) such as H, OH and H₂ desorption. Specifically, it enhances the O-H bond dissociation, as well as H and H₂ desorption from bridging hydroxyl and Ti_5c-OH (the Ti_5c with OH adsorption), but hinders the OH and H desorption from Ti_5c. We believe our results afford a further understanding of the adsorbent dependent UPE migration, and the role of UPE in the surface reactions.     

Effect of two-step functionalization of Ti by chemical processes on protein adsorption

Titanium and its alloys are widely used for orthopedic and dental implants because of their superior mechanical properties, low modulus, excellent corrosion resistance and good biocompatibility. However, it takes several months for titanium implants and bone tissue to reach integration. Hence, there is growing interest in shortening the process of osseointegration and thereby reducing surgical restrictions. Various surface modifications have been applied to form a bioactive titanium oxide layer on the metal surface, which is known to accelerate osseointegration.The present work shows that titanium dioxide (TiO₂) layers formed on titanium substrates by etching in a solution of sodium hydroxide (NaOH) or hydrogen peroxide/phosphoric acid (H₃PO₄/H₂O₂, with a volume ratio of 1:1) are highly suitable pre-treatments for apatite-like coating deposition. Using a two-step procedure (etching in an alkaline or acidic solution followed by soaking in Hanks’ medium), biomimetic calcium phosphate coatings were deposited on porous TiO₂ layers. The combined effects of surface topography and chemistry on the formation of the calcium phosphate layer are presented. The topography of the TiO₂ layers was characterized using HR-SEM and AFM techniques. The nucleation and growth of calcium phosphate (Ca-P) coatings deposited on TiO₂ porous layers from Hanks’ solution was investigated using HR-SEM microscopy. AES, XPS and FTIR surface analytical techniques were used to characterize the titanium dioxide layers before and after deposition of the calcium phosphate coatings, as well as after the process of protein adsorption. To evaluate the potential use of such materials for biomedical applications, the adsorption of serum albumin, the most abundant protein in the blood, was studied on such surfaces.     

表面缺陷对一氧化碳和甲基基团在金红石TiO2(110)表面吸附的影响

本文利用程序升温脱附技术研究了氧空位浓度对甲基基团和CO在R-TiO₂(110)表面吸附的影响. 结果表明,随着氧空位浓度的变化,吸附在桥氧位的甲基基团和吸附在五配位Ti⁴⁺位点上的CO分子的脱附温度呈现了不同的趋势,揭示了表面缺陷可能对R-TiO₂(110)不同位点上的物质吸附具有重要影响.     

CO2 laser assisted removal of UO2 and ThO2 particulates from metal surface

Pulsed laser assisted removal of uranium dioxide and thorium dioxide particulates from stainless steel surface have been studied using a TEA CO₂ laser. Decontamination efficiency is measured as a function of laser fluence and number of pulses. Threshold fluence for the removal of UO₂ particulates has been found to be lower than that required for the removal ThO₂ particulates. Usage of a ZnSe substrate, that is transparent to the laser wavelength used here, enabled us to decouple the cleaning effect arising out of absorption in the particulates from that in the substrate and has contributed towards understanding the mechanism responsible for cleaning. The experimental observations are also corroborated by simple theoretical calculations.     

The decomposition of ammonia on the flat (111) and stepped (557) platinum crystal surfaces

Ammonia adsorption, desorption and decomposition to H₂ and N₂ has been studied on the flat (111) and stepped (557) single crystal faces of platinum using molecular beam surface scattering techniques. Both surfaces show significant adsorption with sticking coefficients on the order of unity. The stepped (557) surface is 16 times more reactive for decomposition of ammonia to N₂ and H₂ than the flat (111) surface. Kinetic parameters have been determined for the ammonia desorption process from the Pt(111) surface. The mechanism of ammonia decomposition on the (557) face of platinum has been investigated.     

Visible-light photocatalytic activity of nitrogen-doped TiO2 thin film prepared by pulsed laser deposition

Nitrogen-doped titanium dioxide (TiO_2−xN_x) thin films have been prepared by pulse laser deposition on quartz glass substrates by ablated titanium dioxide (rutile) target in nitrogen atmosphere. The x value (nitrogen concentration) is 0.567 as determined by X-ray photoelectron spectroscopy measurements. UV-vis spectroscopy measurements revealed two characteristic deep levels located at 1.0 and 2.5 eV below the conduction band. The 1.0 eV level is attributable to the O vacancy state and the 2.5 eV level is introduced by N doping, which contributes to narrowing the band-gap by mixing with the O2p valence band. The enhanced degradation efficiency in a broad visible-light range was observed from the degradation of methylene blue and methylene orange by the TiO_2−xN_x film.     

Desorption of carbon dioxide from small potassium niobate particles induced by the particles’ ferroelectric transition

The aim of this work is to understand surface properties of ferroelectric crystals related to gas adsorption. Various ferroelectric crystals involved in these studies readily adsorb carbon dioxide, thus our studies were centered on adsorption studies of this molecule. It has been claimed that a dipole moment is induced on carbon dioxide molecules that are near an oxide surface. Our experiments explored the possibility of a dipole-dipole interaction between the gas molecule and the ferroelectric oxide surface in order to explain its adsorption. We characterized the samples with scanning electron microscopy, X-ray diffraction and Raman spectroscopy. We determined the ferroelectric nature of the particles and studied the temperature-dependent phase transitions in small particles of KNbO₃ using Raman spectroscopy. We were able to correlate desorption of CO₂ from one surface state of KNbO₃ with the occurrence of the orthorhombic to tetragonal transition in KNbO₃ in particles of 1 μm size. This CO₂ surface site was not observed in KTaO₃, which does not show ferroelectricity at room temperature.     

Thermodynamics and kinetics of Xe monolayer adsorption on Cu(100) by LEED and AES

The thermodynamical properties of the adsorption of the first layer of Xe on a Cu(100) surface have been studied by LEED and AES. We show, from the adsorption isotherms, that the adsorbed xenon undergoes a first order 2D gas ? 2D solid phase transition. The presence of impurities and heterogeneities on the surface alters the form of the isotherm in the prestep region, but does not change the phase transition pressure. The value of the latent heat of transformation is 6.2 kcal/mole. The kinetics of adsorption and desorption have been studied using AES. We determined that both the adsorption and desorption are zero order processes. The sticking coefficient has been found to be practically equal to the unity and the value of the activation energy for the desorption is about 6 kcal/mole.     

Comparison of theoretical and experimental 3He desorption behaviour of titanium tritide films

Helium-3 formed by tritium radioactive decay from tritide layer desorbs at room temperature slowly in a first step, more strongly afterwards. A helium-3 desorption model has been established, based on the positions of He-3 atom and trapping sites in the γ tritide lattice, CaF₂ type, supposed in a perfect state. Theoretical desorption curves as a function of time or helium concentration in the layer has been computed, for metal tritide or deutero-tritide layers. Experimental curves, for a wide tritium concentration range, are given here in the case of titanium layers. They show good agreement with theoretical curves for appropriate parameter values, up to a helium/titanium atomic ratio of 0.25 to 0.30. For higher helium concentrations, rapid helium desorption can be explained by gas bubble growth and percolation, and mechanical degradation of the layer: at this stage, the theoretical model does not apply.     

Annealing temperature effect on the properties of mercury-doped TiO2 films prepared by sol-gel dip-coating technique

This work presents the annealing temperature effect on the properties of mercury (Hg)-doped titanium dioxide (TiO₂). Thin films and polycrystalline powders have been prepared by sol-gel process. The structure, surface morphology and optical properties, as a function of the annealing temperature, have been studied by atomic force microscopy (AFM), Raman, reflectance and ellipsometric spectroscopies. In order to determine the transformation points, we have analyzed the xerogel-obtained powder by differential scanning calorimetry (DSC). Raman spectroscopy shows the crystalline anatase and rutile phases for the films annealed at 400 °C and 1000 °C respectively. The AFM surface morphology results indicate that the particle size increases from 14 to 57 nm by increasing the annealing temperature. The complex index and the optical band gap (E_g) of the films were determined by the spectroscopic ellipsometry analysis. We have found that the optical band gap decreases by increasing the annealing temperature.     

H2 and CO chemisorption on polycrystalline titanium studied by flash desorption mass spectrometry

We have used flash desorption mass spectroscopy to study the adsorption and desorption of H₂ and CO from clean titanium at room temperature. CO flash desorption occurs predominantly from a low temperature state whose binding energy is 20.3 kcal/mole. H₂ flash desorption is complex. Only one peak is observed; it is broader than flash desorption spectra normally corresponding to first or second order kinetics. The shift in the peak temperature to lower values with increasing coverage has been analysed using the isothermal desorption rate technique. The apparent order of H₂ desorption is 1.5 and is independent of temperature from 888 to 1077 K. The activation energy is 21 kcal/mole. These results will be discussed in terms of absorption of H₂ into titanium and thermal decomposition of a titanium hydride compound.     

The role of poly(methacrylic acid) conformation on dispersion behavior of nano TiO2 powder

To exploit the advantages of nanoparticles for various applications, controlling the dispersion and agglomeration is of paramount importance. Agglomeration and dispersion behavior of titanium dioxide (TiO₂) nanoparticles was investigated using electrokinetic and surface chemical properties. Nanoparticles are generally stabilized by the adsorption of a dispersant (polyelectrolyte) layer around the particle surface and in this connection ammonium salt of polymethacrylic acid (Darvan C) was used as dispersant to stabilize the suspension. The dosages of polyelectrolyte were optimized to get best dispersion stability by techniques namely particle charge detector (13.75 mg/g) and adsorption (14.57 mg/g). The surface charge of TiO₂ particles changed significantly in presence of dispersant Darvan C and isoelectric point (iep) shifted significantly towards lower pH from 5.99 to 3.37. The shift in iep has been quantified in terms of free energy of interaction between the surface sites of TiO₂ and the adsorbing dispersant Darvan C. Free energies of adsorption were calculated by electrokinetic data (−9.8 RT unit) and adsorption isotherms (−10.56 RT unit), which corroborated well. The adsorption isotherms are of typical Langmuir type and employed for calculation of free energy. The results indicated that adsorption occurs mainly through electrostatic interactions between the dispersant molecule and the TiO₂ surface apart from hydrophobic interactions.     

Surface state of TiO2 treated with low ion energy plasma

The effect of low pressure radio frequency (rf) plasma treatment on TiO₂ surface states has been studied using X-ray photoelectron spectroscopy. Three different oxidation states of oxygen in untreated TiO₂ powder were observed, which suggests the existence of adsorbed water and carbon on the surface. The ratio of oxygen to titanium (O/Ti) was decreased for the low ion dose plasma treated samples due to desorption of water from the surface. In the case of Ti 2p about 20% of surface states were converted to Ti³⁺ 2p_3/2 state after plasma treatment with a very good stability, whereas untreated TiO₂ remained mostly as Ti⁴⁺ state. A rapid decrease in the ratio of carbon to titanium (C/Ti) at TiO₂ surface was also observed after plasma treatment and more than 90% of carbon atoms were removed from the surface. Therefore, the plasma treatment of TiO₂ has advantages to surface carbon cleaning, increasing O⁻ and Ti³⁺ surface states, hence improving the activity of TiO₂ for different environmental, energy and biological applications.     

Studies of catalytic process of complete oxidation of methane by SSITKA method

This paper presents the results obtained by means of the steady state isotopic transient kinetic analysis for complete methane oxidation over the Pd(PdO)Al₂O₃ catalyst. The average surface life-time and surface concentration of methane and carbon dioxide were determined. It was found out that on the palladium catalyst there are adsorbed small amounts of methane (which does not take part in the process of oxidation) only at the temperature corresponding to the starting point of methane oxidation. Additionally, in the steady state of methane oxidation on the palladium catalyst there are present two different kinds of carbon dioxide: short- and long-resided on the catalyst surface. The average surface life-time of both kinds of carbon dioxide decreases with temperature. The surface concentration of long-resided carbon dioxide increases with temperature whereas the small maximum at about 380 °C is noticed for the surface concentration of short-resided carbon dioxide.     

Studies of Atmospherically Relevant Reactions Using Differentially Pumped Mass Spectrometer and Fourier Transform Infrared Spectroscopy

This article describes recent studies of atmospherically relevant reactions using spectroscopic techniques by our group at the Wadsworth Center. Heterogeneous reactions of SO₂ with either HOBr or HOCl on ice have been studied using a coated-wall flow reactor coupled with differentially pumped quadrupole mass spectrometer, and the reaction of NO₂+HI has been investigated using Fourier transform infrared spectroscopy (FTIR). Reaction probabilities or rate constants have been determined at relevant atmospheric temperatures. Specular reflection-absorption infrared spectroscopy and the temperature programmed desorption technique were employed to study the adsorption of oxalic acid on a Cu surface at 175 K. Reflection-absorption infrared spectroscopy showed that oxalic acid is molecularly adsorbed on the Cu surface. The results obtained from these studies provide a better understanding of atmospheric reactions at a molecular level and enable an assessment of the relative importance of the reactions in the atmosphere.     

Surface reaction characteristics at low temperature synthesis BaTiO3 particles by barium hydroxide aqueous solution and titanium tetraisopropoxide

Well-crystallized cubic phase BaTiO₃ particles were prepared by heating the mixture of barium hydroxide aqueous solution and titania derived from the hydrolysis of titanium isopropoxide (TTIP) at 328 K, 348 K or 368 K for 24 h. The morphology and size of obtained particles depended on the reaction temperature and the Ba(OH)₂/TTIP molar ratio. By the direct hydrolytic reaction of titanium tetraisopropoxide, the high surface area titania (TiO₂) was obtained. The surface adsorption characteristics of the titania particles had been studied with different electric charges OH⁻ ions or H⁺ ions. The formation mechanism and kinetics of BaTiO₃ were examined by measuring the concentration of [Ba²⁺] ions in the solution during the heating process. The experimental results showed that the heterogeneous nucleation of BaTiO₃ occurred on the titania surface, according to the Avrami's equation.     

Enhanced photocatalytic degradation of Safranin-O by heterogeneous nanoparticles for environmental applications

Nanostructure titanium dioxide (TiO₂) has been synthesized by hydrolysis of titanium tetrachloride in aqueous solution and Ag-TiO₂ nanoparticles were synthesized by photoreduction method. The resulting materials were characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), Fourier-transform infrared (FT-IR) and UV-vis absorption spectroscopy. The experimental results showed that the sizes of the synthesized TiO₂ and Ag-TiO₂ particles are in the range of 1.9-3.2 nm and 2-10 nm, respectively. Moreover, Ag-TiO₂ nanoparticles exhibit enhanced photocatalytic activity on photodegradation of Safranin-O (SO) dye as compared to pure TiO₂. The positive effect of silver on the photocatalytic activity of TiO₂ may be explained by its ability to trap electrons. This process reduces the recombination of light generated electron-hole pairs at TiO₂ surface and therefore enhances the photocatalytic activity of the synthesized TiO₂ nanoparticles. The effects of initial dye and nanoparticle concentrations on the photocatalytic activity have been studied and the results demonstrate that the dye photodegradation follows pseudo-first-order kinetics. The observed maximum degradation efficiency of SO is about 60% for TiO₂ and 96% for Ag-TiO₂.     

The adsorption of hydrogen and the reaction of hydrogen with oxygen on Pt (100)

The adsorption of hydrogen on Pt (100) was investigated by utilizing LEED, Auger electron spectroscopy and flash desorption mass spectrometry. No new LEED structures were found during the adsorption of hydrogen. One desorption peak was detected by flash desorption with a desorption maximum at 160 °C. Quantitative evaluation of the flash desorption spectra yields a saturation coverage of 4.6 × 10¹⁴ atoms/cm² at room temperature with an initial sticking probability of 0.17. Second order desorption kinetics was observed and a desorption energy of 15–16 kcal/mole has been deduced. The shapes of the flash desorption spectra are discussed in terms of lateral interactions in the adsorbate and of the existence of two substates at the surface. The reaction between hydrogen and oxygen on Pt (100) has been investigated by monitoring the reaction product H₂O in a mass spectrometer. The temperature dependence of the reaction proved to be complex and different reaction mechanisms might be dominant at different temperatures. Oxygen excess in the gas phase inhibits the reaction by blocking reactive surface sites. At least two adsorption states of H₂O have to be considered on Pt (100). Desorption from the prevailing low energy state occurs below room temperature. Flash desorption spectra of strongly bound H₂O coadsorbed with hydrogen and oxygen have been obtained with desorption maxima at 190 °C and 340 °C.     

AES and LEED studies of xenon adsorption on (100)NaCl

The thermal and electro impact behaviour of NO adsorbed on Pt(111) and Pt(110) have been studied by LEED, Auger spectroscopy, and thermal desorption. NO was found to adsorb non-dissociatively and with very similar low coverage adsorption enthalpies on the two surfaces at 300 K. In both cases, heating the adlayer resulted in partial dissociation and led to the appearance of N₂ and O₂ in the desorption spectra. The (111) surface was found to be significantly more active in inducing the thermal dissociation of NO, and on this surface the molecule was also rapidly desorbed and dissociated under electron impact. Cross sections for these processes were obtained, together with the desorption cross section for atomically bound N formed by dissociation of adsorbed NO. Electron impact effects were found to be much less important on the (110) surface. The results are considered in relation to those already obtained by Ertl et al. for NO adsorption on Ni(111) and Pd(111), and in particular, the unusual desorption kinetics of N₂ production are considered explicitly. Where appropriate, comparisons are made with the behaviour of CO on Pt(111) and Pt(110), and the adsorption kinetics of NO on the (110) surface have been examined.     

蓝色氧化钨吸附丙烯和氧的热脱附谱

在超高真空条件下,用对样品进行闪烁加热的方法测定了蓝色氧化钨WO_2.90吸附丙烯和氧的热脱附谱。发现在室温下,丙烯在蓝色氧化钨表面只有一个吸附态,对应于热脱附谱中在100℃附近出现一个脱附峰。实验测定的热脱附参数为n=1(一级脱附),脱附活化能E_D=10.1kcal/mol。温度升高,丙烯在蓝色氧化钨表面形成稳定吸附态的几率减小。在125℃以上,不能形成稳定的吸附态,蓝色氧化钨在室温下对氧的吸附并不明显,温度升高到300℃以上,WO_2.90 关键词：