Quantitative measurement of the coverage on single crystal surfaces

Summary Two methods for the quantitative determination of the surface coverage of adsorbates on single crystal surfaces are discussed. In the first case a quartz crystal microbalance is used to calibrate an Auger spectrometer. The frequency change of the quartz and the Auger signal of the adsorbate are measured simultaneously during adsorption. With the calibrated Auger spectrometer the absolute coverage of oxygen on Ni (110) and Ni (111) is determined. The second method is used for adsorbates which can be thermally desorbed. The desorption spectra of the sample are compared with the calibration spectrum. This test spectrum can be obtained by introducing a well defined amount of gas into the vacuum chamber. The gas introduced produces a pressure increase comparable to a flash desorption spectrum. With this method the saturation coverages of H₂-Ni (111), H₂-Ni (100) and H₂-W (100) are determined.

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Absolutbestimmung adsorbierter Gasmengen an Einkristalloberflächen

Zusammenfassung Für die quantitative Bestimmung der Oberflächenbedeckung an Einkristallen werden zwei Methoden diskutiert. Im ersten Fall wird eine Schwingquarzmikrowaage zur Eichung des Augerspektrometers verwendet. Auf den Schwingquarz wird ein Adsorbens aufgedampft und anschließend das Augersignal des Adsorbats und die Frequenzänderung des Schwingquarzes während der Gasadsorption gleichzeitig gemessen. Mit diesem geeichten Augersignal werden absolute Bedeckungsbestimmungen an den Systemen O₂-Ni (110) und O₂-Ni (111) durchgeführt. Die zweite Methode eignet sich für thermisch desorbierbare Adsorbate. Die Desorptionsspektren der Probe werden mit einem Eichspektrum verglichen. Dieses erhält man, indem eine definierte Gasmenge in den Rezipienten eingelassen und damit ein Desorptionsspektrum erzeugt wird. Mit dieser Methode werden die Sättigungsbedeckungen der Adsorptionssysteme H₂-Ni (111), H₂-Ni (100) und H₂-W (100) bestimmt.

     

The fluorination of titanium dioxide surfaces

Summary Gaseous hydrogen fluoride gave a bulk attack on titanium dioxide but dilute aqueous hydrofluoric acid gave a partial surface fluorination. A specific fluoride for chloride exchange reaction occurs on chloride containing titanium dioxide surfaces. A weak and a strong form of fluoride adsorption may be distinguished, the former being removed by prolonged treatment with water, the latter requiring steam at 1020 K for its complete removal. Some infra-red, electrophoretic and acidity studies on various fluorinated surfaces are reported.

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Zusammenfassung Eine verdünnte wäßrige Fluorwasserstoffsäure fluoriert Titandioxid teilweise an der Oberfläche, während Fluorwasserstoffgas auch das Kristallinnere angreift. Eine spezifische Austauschreaktion Fluorid gegen Chlorid tritt an chloridhaltigen Titandioxidoberflächen auf. Man kann zwischen einer schwachen und einer starken Fluoridadsorption unterscheiden. Die schwächer adsorbierten Fluoridionen werden durch längere Behandlung mit Wasser verdrängt, die stärker adsorbierten dagegen nur durch Dampf bei 1020 K. In der Arbeit wird außerdem über IR-Studien sowie über elektrophoretische Messungen und Aziditätsuntersuchungen an verschiedenen fluorierten Oberflächen berichtet.

     

The influence of titanium dioxide phase composition on dyes photocatalysis

A comparative study of TiO₂ powders prepared by sol–gel methods is presented. Titanium tetraisopropoxide was used as the precursor for the sol–gel processes. The effects of the annealing treatment on phase, crystallite size, porosity and photodegradation of dyes (methyl orange and methylene blue) were studied. The phase structure, microstructure and surface properties of the films were characterized by using X-ray diffraction (XRD) and Atomic Force Microscopy (AFM). The X-ray diffraction was used for crystal phase identification, for the accurate estimation of the anatase–rutile ratio and for the crystallite size evaluation of each polymorph in the samples. It was found that the only TiO₂ anatase phase of the synthesized TiO₂ develops below 500 °C, between 600 and 800 °C the anatase coexist with rutile and above 800 °C only the rutile phase was found in the samples. Attention has been paid not only to crystal structures, but also to the porosity, the particle size and the photocatalytic properties. However, the annealing temperature was found to have significant influence on the photocatalytic properties. Different TiO₂ doctor blade thin films were obtained mixing the sol gel powder (100% anatase) and TiO₂ Aldrich with TiO₂ Degussa P25. The surfactant (Triton X100 or sodium dodecyl sulfate) affects the packing density of the particles during deposition and the photocatalytic degradation efficiency of the dyes. The photocatalytic degradation kinetics of methyl orange and methylene blue using TiO₂ thin film were investigated.     

Adsorption behavior of carboxymethyl starch on titanium dioxide surfaces

The adsorption of carboxymethyl starch (CMS) on titanium dioxide surface from aqueous solution of electrolyte was investigated by adsorption and electrokinetics mobility measurements. Zeta potential measurements showed that the addition of CMS resulted in a shift of isoelectric point to the more acidic region, indicating the adsorption of CMS from the aqueous solution onto titanium dioxide surface. The positively charged and hydrophilic surface sites of titanium dioxide favor the adsorption of CMS molecules. The adsorption capacity of CMS on titanium dioxide surface was found to be controlled by the number of functional group on CMS that promotes surface charge CMS adsorption in agreement with Langmuir isotherm. For the adsorption of CMS, the pseudo-second-order kinetics of chemical reaction provides the best correlation of the experimental data.     

XPS studies of amino acids adsorbed on titanium dioxide surfaces

Summary Adsorption of amino acids from aqueous solutions on TiO₂ surfaces as a function of pH is monitored quantitatively by X-ray photoelectron spectroscopy (XPS). Because of the amphoteric character of the TiO₂ and the zwitterionic behaviour of the amino acids the pH of adsorption indicates what chemical groups are involved in the adsorption reaction. The results confirm the ligand exchange model: in acidic milieu the carboxylic group replaces a basic surface hydroxyl group on a Ti site and binds to this Ti. For homocysteine the resulting position of the adsorbed molecule can also be concluded by comparing peak intensities.     

A selective etching phenomenon on {001} faceted anatase titanium dioxide single crystal surfaces by hydrofluoric acid

A selective etching phenomenon on {001} faceted anatase TiO(2) single crystal surfaces by HF and associated etching mechanism are reported. Density functional theory (DFT) calculations reveal that HF stabilizes the grown {001} facets at low concentrations, but selectively destroys the grown {001} facets at high concentrations.     

Use of titanium dioxide photocatalysis on the remediation of model textile wastewaters containing azo dyes

The photocatalytic degradation of two commercial textile azo dyes, namely C.I Reactive Black 5 and C.I Reactive Red 239, has been studied. TiO(2) P25 Degussa was used as catalyst and photodegradation was carried out in aqueous solution under artificial irradiation with a 125 W mercury vapor lamp. The effects of the amount of TiO(2) used, UV-light irradiation time, pH of the solution under treatment, initial concentration of the azo dye and addition of different concentrations of hydrogen peroxide were investigated. The effect of the simultaneous photodegradation of the two azo dyes was also investigated and we observed that the degradation rates achieved in mono and bi-component systems were identical. The repeatability of photocatalytic activity of the photocatalyst was also tested. After five cycles of TiO(2) reuse the rate of colour lost was still 77% of the initial rate. The degradation was followed monitoring the change of azo dye concentration by UV-Vis spectroscopy. Results show that the use of an efficient photocatalyst and the adequate selection of optimal operational parameters may easily lead to a complete decolorization of the aqueous solutions of both azo dyes.     

SECM characterization of immobilised enzymes by self-assembled monolayers on titanium dioxide surfaces

SECM in generator-collector mode was used to detect the presence of immobilised enzymes on titanium dioxide layers which were chemically or electrochemically generated with possible application as chemical sensors and biosensors. Glucose oxidase (GOx) and horseradish peroxidase (HRP) were immobilised by SAM generation using aminopropyltriethoxysilane (APTES) and ascorbic acid. The enzymes were successfully immobilised on two different TiO(2) surfaces. A simple test of durability of the system was made and a model of SAM organisation is presented.     

Molecular-dynamics simulation of nanoclusters of crystal modifications of titanium dioxide

The thermodynamic and structural properties of titanium dioxide nanoclusters belonging to the two most common crystal modifications, rutile and antase, were studied by molecular-dynamics simulation. The local densities of particles in the systems, two-particle distribution functions, and electric potential profiles were calculated. The influence of the size of nanoclusters on their properties and structure was examined.     

Photocatalytic activity enhancement in doped titanium dioxide by crystal defects

Visible light sensitive Fe(3+) and Ce(4+) co-doped nano TiO(2) photocatalyst has been prepared by a modified aqueous sol-gel method and the activity has been measured in terms of degradation of MB dye. Both dopants shifted the absorption profile of TiO(2) to the visible region and improved activity. Fe(3+) ions trapped the charge carriers due to the stable electronic configuration and improved their separation. Ce(4+) ions, which were mainly located at the grain boundaries, cause dislocations by bending the valence and conduction bands of TiO(2) and prevent the recombination of photoexcited electrons and holes. The co-doped TiO(2) compositions exhibited higher photocatalytic activity than that of pure titania and commercially available Degussa P25 under visible light by utilising the individual and synergistic contributions of Fe(3+) and Ce(4+) dopants, respectively.     

二氧化钛微晶结构和光催化性能关联性研究

研究了不同煅烧温度、煅烧时间的系列二氧化钛样品悬浮体系光催化降解X-3B活性艳红的催化活性。分析了晶粒尺寸、晶相、晶格畸变应力和光催化体系等诸多因素对二氧化钛光催化活性的影响。发现晶格畸变应力对空穴电子对复合速率的影响在诸因素中占主导地位,并在一定程度上决定了二氧化钛悬浮体系的光催化效能。     

Arrangement of acid sites on the surfaces of anatase titanium dioxide nanoparticles according to cluster models

Computer-implemented cluster models have been devised for ～2-nm anatase nanoparticles with exposed (001) and (100) faces. The Lewis acid sites occurring in these faces have been characterized by calculating the enthalpy of CO adsorption. In the Ti₁₁₄O₂₂₈ and Ti₁₈₇O₃₇₆H₄ clusters, the corner oxygen atoms compensating the electric charge are bound to titanium atoms by double bonds with a length of approximately 1.7 Å, which is in agreement with experimental data. The average enthalpy of CO adsorption on the (001) and (100) faces at a zero coverage is ?87.62 and ?135.31 kJ/mol, respectively. The deviation from the average value is 20.2 and 8.8%, respectively. The average enthalpy of CO adsorption for the Ti₁₁₄O₂₂₈ cluster is ?129.40 kJ/mol, and that for the Ti₁₈₇O₃₇₆H₄ cluster is ?119.79 kJ/mol.     

Investigating the properties of supported vesicular layers on titanium dioxide by quartz crystal microbalance with dissipation measurements

Adsorption of phospholipid vesicles on titanium dioxide was studied by a combination of quartz crystal microbalance with dissipation (QCM-D) and atomic force microscopy techniques. Vesicle size, concentration in solution, and bilayer composition were systematically varied. A strong dependence of the QCM-D response (magnitude of the frequency and dissipation factor shifts) on the vesicle concentration in solution was observed. QCM-D data were compared with a linear viscoelastic model based on the Voight element to determine layer thickness, density, elastic modulus, and viscosity. Based on the results of this comparison, it is proposed that (i) layer thickness and density, as sensed by QCM-D, saturate much earlier (in time) than the actual surface coverage of the vesicles (number of vesicles per unit area); (ii) changes in surface coverage that occur after the density and thickness, as sensed by QCM-D, have saturated, are interpreted by the model as changes in the layer's viscoelastic properties. This is caused by the replacement of the viscous media (water) between the vesicles by viscoelastic media of similar density (vesicles); (iii) viscoelastic properties of layers formed at different vesicle concentrations differ significantly, while the vesicle surface coverage in those layers does not. Based on the comparison between the atomic force microscopy images and QCM-D data acquired at various vesicle concentrations it is proposed that QCM-D response is not directly related to the surface coverage of the vesicles.     

Nitrogen oxide activation on the surfaces of titanium carbide and titanium nitride

The mechanism of NO activation on the surfaces of crystalline titanium monocarbide and titanium mononitride has been studied within the framework of semiempirical SCF LCAO NDDO method. The adsorption has been shown to be accompanied by electron density transfer from the crystal surface to the adsorbate molecule. Stronger activation of the NO molecule is observed on the TiC surface as compared with that on TiN surface.     

Nanodisperse photocatalysts based on titanium dioxide

A new method for synthesizing amorphous ultradisperse titanium oxide particles immobilized on the surface of SiO₂ aerogel was suggested. TiO₂/SiO₂ systems containing 3–15 wt % TiO₂ were prepared. The chemical composition, structure, and morphology of the surface of the synthesized catalysts were studied by transmission electron microscopy, X-ray diffraction, and IR spectroscopy. The Brunauer-Emmett-Teller method was used to estimate the specific surface area of the samples. The photocatalytic activity of the systems was studied in the model reaction of the decomposition of methylene blue dye. The systems synthesized were found to be more active than TiO₂ Degussa P25.     

Reactions of sulfur dioxide on calcium carbonate single crystal and particle surfaces at the adsorbed water carbonate interface

Sulfur dioxide reactions with calcium carbonate interfaces at 296 K in the presence and absence of adsorbed water result in the formation of adsorbed sulfite and sulfate. The extent of reaction is significantly enhanced, approximately five- to ten-fold for particulate and single crystal CaCO(3) (calcite), respectively, in the presence of adsorbed water between 30 and 85% RH. Atomic force microscopy following the reaction shows that adsorbed water facilitates surface reactivity by enhancing the mobility of surface ions, giving rise to the formation of nanometer sized product crystallites approximately 1 nm in height. Simultaneous with the formation of these crystallites is pitting and etching of the underlying substrate, which occurs preferentially in the vicinity of monoatomic surface steps. In the absence of water, there is little pitting and no evidence for the formation of crystallites. X-Ray photoelectron core and valence band spectra confirm the presence of two sulfur adsorbed species, SO and SO, with nearly equal amounts of SO and SO in the absence of adsorbed water and approximately five times more SO relative to SO in the presence of adsorbed water. From these data, it is proposed that the nanometer-sized crystallites are composed primarily of CaSO(3).     

Theoretical study of water coverage on MgO surfaces

Ab initio and semiempirical calculations have been performed on an (MgO)₁₆ cluster model in order to study the effects of water coverage on pure MgO (100) surfaces. The geometries of various adsorbed water molecules have been optimized and the binding energies, charge transfer, and preferential sites of interaction analyzed. We have used Mulliken and natural bond population analysis methods in order to analyze charge distributions and the direction of charge transfer processes. We have also investigated the effects of low and high coverage on energy gaps, density of states, self‐consistent field (SCF) orbital energies, and stretching frequencies. ©1999 John Wiley & Sons, Inc. Int J Quant Chem 71: 153–165, 1999     

Visible spectrum of titanium dioxide

The electronic spectrum in the region 17?500 cm(-1) to 18?850 cm(-1) of a cold molecular beam of TiO(2) has been investigated using laser induced fluorescence (LIF) and mass-resolved resonance enhanced multi-photoionization (REMPI) spectroscopy. Bands at 18?412 cm(-1), 18?470 cm(-1) and 18?655 cm(-1) were recorded at a resolution of 35 MHz, rotationally analyzed, and assigned as the ?(1)B(2) (0,1,2) ←X[combining tilde](1)A(1) (0,0,0), ?(1)B(2) (1,0,0) ←X[combining tilde](1)A(1) (0,0,0) and ?(1)B(2) (1,1,0) ←X[combining tilde](1)A(1) (0,0,0) transitions. The dispersed fluorescence from the ?(1)B(2) (0,1,2) and ?(1)B(2) (1,0,0) levels were combined with previous results to produce an improved set of vibrational parameters for the X[combining tilde](1)A(1) state. The optical Stark effect in the ?(1)B(2) (0,1,2) ←X[combining tilde](1)A(1) (0,0,0) and ?(1)B(2) (1,0,0) ←X[combining tilde](1)A(1) (0,0,0) bands were recorded and combined with earlier results for ?(1)B(2) (1,1,0) ←X[combining tilde](1)A(1) (0,0,0) to determine the permanent electric dipole moment for these states. The origin and harmonic vibrational constants for the ?(1)B(2) state are determined to be: T(000) = 17?593(5) cm(-1), ω(1) = 876(3) cm(-1), ω(2) = 184(1) cm(-1), and ω(3) = 316(2) cm(-1). A normal coordinate analysis was performed and Franck-Condon factors calculated.     

Decolorization and mineralization of textile dyes at solution bulk by heterogeneous nanophotocatalysis using immobilized nanoparticles of titanium dioxide

Nanophotocatalysis using nanostructured semiconductors constitute one of the emerging technologies for destructive oxidation of organics such as dyes. This paper deals with the decolorization and mineralization of reactive dyes by heterogeneous nanophotocatalysis using an immobilized TiO₂ nanoparticle photocatalytic reactor. A simple and effective method was used to immobilization of titanium dioxide nanoparticles. Reactive Orange 107 (RO 107, sulphatoethylsulphonyl reactive dye) and Reactive Red 152 (RR 152, monochlorotriazine reactive dye) were used as model compounds. UV–vis and ion chromatography (IC) analyses were employed to obtain the details of the photocatalytic degradation of the selected dyes. The effects of operational parameters such as H₂O₂, dye concentration, anions (NO₃⁻, Cl⁻, SO₄²⁻, HCO₃⁻ and CO₃²⁻) and pH were investigated. Formate, acetate and oxalate anions were detected as dominant aliphatic intermediates where, they were further oxidized slowly to CO₂. Nitrate, sulfate and chloride anions were detected as the photocatalytic mineralization of RO 107 and RR 152. Kinetics analysis indicates that the photocatalytic decolorization rates can usually be approximated zero-order model for RO 107 and first-order model for RR 152 dyes. Results show that the photocatalytic process occurred at solution bulk and the employment of optimal operational parameters may lead to complete decolorization and mineralization of dye solutions.