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1.
High-resolution scanning tunneling microscopy (STM) and temperature-programmed desorption (TPD) were used to study the interaction of O2 with reduced TiO2(110)–(1 × 1) crystals. STM is the technique of choice to unravel the relation between vacancy and non-vacancy assisted O2 dissociation channels as a function of temperature. It is revealed that the vacancy-assisted, first O2 dissociation channel is preferred at low temperature (~ 120 K), whereas the non-vacancy assisted, second O2 dissociation channel operates at temperatures higher than 150 K–180 K. Based on the STM results on the two dissociative O2 interaction channels and the TPD data, a new comprehensive model of the O2 chemisorption on reduced TiO2(110) is proposed. The model explains the relations between the two dissociative and the molecular O2 interaction channels. The experimental data are interpreted by considering the available charge in the near-surface region of reduced TiO2(110) crystals, the kinetics of the two O2 dissociation channels as well as the kinetics of the diffusion and reaction of Ti interstitials.  相似文献   

2.
Jens B?k Simonsen 《Surface science》2010,604(15-16):1300-1309
The interaction between 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) and the rutile TiO2(110)–(1 × 1) surface under ultrahigh vacuum (UHV) conditions was investigated using X-ray photoemission spectroscopy (XPS), ultraviolet photoemission spectroscopy (UPS), near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, and density functional theory (DFT) calculations. The NEXAFS results showed that HHTP molecules formed a submonolayer and a monolayer that aligned along the [001]-direction with, respectively, a more or less flat downward orientation and a more upright orientation to the TiO2 surface. The HHTP molecules that aligned along the [001]-direction were most likely grafted onto the TiO2(110) surface by a bidentate bridge between each of the oxygen atoms of one of the catechol units within the HHTP molecule and two adjacent Ti(5f)4+ ions on the TiO2(110) surface. The coordination is non-dissociative in the case of the submonolayer, but dissociative in the monolayer, according to the analysis of the C1s XPS, UPS, C1s NEXAFS data and complementary DFT calculations.  相似文献   

3.
The chemistry and photochemistry of methylene bromide (CD2Br2) on the rutile TiO2(110) surface was probed using temperature programmed desorption (TPD). CD2Br2 desorbed in three desorption states at 145, 160 and 250 K tentatively assigned to desorption from the multilayer, from an η1-CD2Br2 species and a bridging η2-CD2Br2 species, respectively. The latter two TPD states presumably involve binding of CD2Br2 molecules to the surface through Br coordination at five-coordinate Ti4+ surface sites. The 160 and 250 K TPD states saturated at coverages of 1.0 and 0.33 ML, respectively, where 1 ML is equivalent to the surface Ti4+ site density (5.2 × 1014 cm? 2). No thermal decomposition of CD2Br2 was observed on either the clean surface or with preadsorbed O2. UV irradiation of CD2Br2 on TiO2(110) resulted in predominately photodesorption, with trace amounts of photodecomposition evidenced in TPD. The rate of CD2Br2 photodesorption from TiO2(110) occurred with a low cross section (~ 2 × 10? 21 cm2) similar to that expected from direct optical excitation of CD2Br2. This observation suggests that charge carriers generated in TiO2(110) were no more effective in activating adsorbed CD2Br2 molecules than would be expected through direct molecular excitation. These findings suggest that photocatalytic destruction of halocarbons such as CD2Br2 on TiO2 may preferentially occur though indirect processes (such as OH radical attack) as opposed to direct electron transfer processes involving charge carriers generated in TiO2 by bandgap excitation.  相似文献   

4.
Brooke A. Timp  X.-Y. Zhu 《Surface science》2010,604(17-18):1335-1341
A number of solar energy conversion strategies depend on exciton dissociation across interfaces between semiconductor quantum dots (QDs) and other electron or hole conducting materials. A critical factor governing exciton dissociation and charge transfer in these systems is the alignment of electronic energy levels across the interface. We probe interfacial electronic energy alignment in a model system, sub-monolayer films of PbSe QDs adsorbed on single crystal ZnO(101?0) surfaces using ultraviolet photoemission spectroscopy. We establish electronic energy alignment as a function of quantum dot size and surface chemistry. We find that replacing insulating oleic-acid capping molecules on the QDs by the short hydrazine or ethanedithiol molecules results in pinning of the valence band maximum (VBM) of QDs to ZnO substrate states, independent of QD size. This is in contrast to similar measurements on TiO2(110) where the alignment of the PbSe QD VBM to that of the TiO2 substrate depends on QD size. We interpret these findings as indicative of strong electronic coupling of QDs with the ZnO surface but less with the TiO2 surface. Based on the measured energy alignment, we predict that electron injection from the 1se level in photo-excited PbSe QDs to ZnO can occur with small QDs (diameter ? = 3.4 nm), but energetically unfavorably for larger dots (? = 6.7 nm). In the latter, hot electrons above the 1se level are necessary for interfacial electron injection.  相似文献   

5.
The formation of a native oxide layer on the Ti(0001) surface is studied by means of FPMD simulations. In agreement with experimental findings, at low temperature we observe quick saturation of the surface reactivity, whereas incorporation of further O2 molecules in the oxide network takes place after thermal annealing at ~ 800 K. At an O coverage of 2 ML the oxide layer presents an amorphous structure, an approximate TiO stoichiometry, and a broad distribution of Ti oxidation states from + 1 to + 4. We find consistency between the computed Bader atomic charges on Ti atoms and the correspondent charges computed classically by simple electrostatic minimization methods. On this basis we develop an analytic potential to simulate Ti/TiOx interfaces, including only Coulomb interaction and short-range atomic repulsion terms. Two different parameter sets are proposed and their transferability among TiO2 allomorphs and thin-layer oxide structures is tested both in static relaxations and in room-temperature MD simulations. These show only negligible changes in the topology of the oxide network after annealing and relaxation of the reference quantum model at the classical level. Moreover, we show that superficial oxide layers can be successfully generated purely classically by truncation of a large-scale Ti/amorphous–TiO2 system. This may enable large-scale applications of our potential to tribology and biomolecular adsorption phenomena.  相似文献   

6.
One of the technologically most important requirements for the application of oxide-supported metal nanoparticles (NPs) in the fields of molecular electronics, plasmonics, and catalysis is the achievement of thermally stable systems. For this purpose, a thorough understanding of the different pathways underlying thermally-driven coarsening phenomena, and the effect of the nanoparticle synthesis method, support morphology, and degree of support reduction on NP sintering is needed. In this study, the sintering of supported metal NPs has been monitored via scanning tunneling microscopy combined with simulations following the Ostwald ripening and diffusion-coalescence models. Modifications were introduced to the diffusion-coalescence model to incorporate the correct temperature dependence and energetics. Such methods were applied to describe coarsening phenomena of physical-vapor deposited (PVD) and micellar Pt NPs supported on TiO2(110). The TiO2(110) substrates were exposed to different pre-treatments, leading to reduced, oxidized and polymer-modified TiO2 surfaces. Such pre-treatments were found to affect the coarsening behavior of the NPs.No coarsening was observed for the micellar Pt NPs, maintaining their as-prepared size of ~ 3 nm after annealing in UHV at 1060 °C. Regardless of the initial substrate pre-treatment, the average size of the PVD-grown NPs was found to increase after identical thermal cycles, namely, from 0.5 ± 0.2 nm to 1.0 ± 0.3 nm for pristine TiO2, and from 0.8 ± 0.3 nm to 1.3 ± 0.6 nm for polymer-coated TiO2 after identical thermal treatments. Although no direct real-time in situ microscopic evidence is available to determine the dominant coarsening mechanism of the PVD NPs unequivocally, our simulations following the diffusion-coalescence coarsening route were in significantly better agreement with the experimental data as compared to those based on the Ostwald-ripening model. The enhanced thermal stability of the micellar NPs as compared to the PVD clusters might be related to their initial larger NP size, narrower size distribution, and larger interparticle distances.  相似文献   

7.
The interaction of xenon atoms with the TiO2(1 1 0) surface of rutile has been studied by density functional theory methods. Five different possible adsorption sites on the relaxed and clean TiO2(1 1 0) surface and on two different type of oxygen vacancies possible on this oxide substrate have been considered. In the case of the defect-free substrate, and when compared with a previous study concerning the adsorption of Ar atoms also on TiO2(1 1 0), the xenon atom, as a larger and easier polarizable species, is shown to have a deeper physisorption well, as expected. Likewise, Xe atoms prefer to be bounded to positions nearby the outermost titanium atoms as found previously for Ar. This is in agreement with most studies concerning rare gases adsorbed on transition metal surfaces. In the case of the reduced surfaces, it is found that the interaction is more favourable in the protruding rows. The interaction is dominated by dispersion forces and DFT + dispersion energies are 3.5–5 times larger than the non-corrected DFT values and Xe-surface distances are smaller. Finally, an interesting correlation is obtained for the calculated interaction energies and the Xe–Ti distance.  相似文献   

8.
V.M. Bermudez 《Surface science》2010,604(7-8):706-712
The adsorption of dimethyl methylphosphonate (DMMP) on the (0 1 0) surface of anatase TiO2, which is isostructural with the (1 0 0), has been studied using density functional theory and two-dimensionally-periodic slab models. The experimentally-observed faceting of this surface has, for the first time, been included in the modeling. The relaxations of bare surfaces both with and without faceting are similar, leading to an atomic-scale roughening due to inward (outward) displacement of fivefold-coordinated Ti5c (sixfold-coordinated T6c) atoms together with outward displacement of threefold-coordinated O3c atoms. Molecular adsorption occurs by formation of a Ti5c?OP dative bond with one or more CH?O2c bonds between CH3 groups and unsaturated, twofold-coordinated (O2c) sites. The energies for molecular adsorption, obtained using the B3LYP functional, are virtually identical (about ?21.0 kcal/mol) for the two surfaces and are also close to those found elsewhere for the rutile (1 1 0) and anatase (1 0 1) surfaces. A possible first step in the dissociative adsorption of DMMP has also been modeled and is found to be thermodynamically favored over molecular adsorption to a degree which depends on faceting.  相似文献   

9.
Dye sensitized solar cells (DSSCs) were fabricated based on coumarin NKX-2700 dye sensitized bi-layer photoanode and quasi-solid state electrolyte sandwiched together with cobalt sulfide coated counter electrode. A novel bi-layer photoanode has been prepared using composite mixtures of 90 wt.% TiO2 nanoparticles + 10 wt.% TiO2 nanowires (TNPWs) as active layer and Nb2O5 is coated on the active layer, which acts as scattering layer. Hafnium oxide (HfO2) was applied over the TNPWs/Nb2O5 photoanode film, as a blocking layer. TiO2 nanoparticles (TNPs), TiO2 nanowires (TNWs) and TNPWs/Nb2O5 were characterized by X-ray diffractometer (XRD), scanning electron microscope (SEM) and transmission electron microscope (TEM). The sensitizing organic dye coumarin NKX-2700 displayed maximum absorption wavelength (λmax) at 525 nm, which could be observed from the UV–vis spectrum. DSSC-1 fabricated with composite bi-layer photoanode revealed enhanced photo-current efficiency (PCE) as compared to other DSSCs and illustrated photovoltaic parameters; short-circuit current JSC = 18 mA/cm2, open circuit voltage (VOC) = 700 mV, fill factor (FF) = 64% and PCE (η) = 8.06%. The electron transport and charge recombination behaviors of DSSCs were investigated by electrochemical impedance spectra (EIS) and the results illustrated that the DSSC-1 showed the lowest charge transport resistance (Rtr) and the longest electron lifetime (τeff). Therefore, in the present investigation, it could be concluded that the novel bi-layer photoanode with blocking layer increased the short circuit current, electron transport and suppressed the recombination of charge carriers at the photoanode/dye/electrolyte interface in DSSC-1.  相似文献   

10.
The interaction between Au nano-particles and oxide supports is recently discussed in terms of the catalytic activities. This paper reports the electronic charge transfer between Au nano-particles and TiO2-terminated SrTiO3(0 0 1) substrate, which is compared with that for stoichiometric(S)-, pseudo-stoichiometric(S1)- and reduced(R)-TiO2(1 1 0) supports. We observed the photoelectron spectra of Au 4f, O 2s, Ti 3p, and Sr 4p lines and also measured the work functions for Au/oxides supports using synchrotron-radiation light. As the results, all the O 2s, Ti 3p, and Sr 4p lines for Au/SrTiO3(0 0 1) show lower binding energy shifts in a quite same manner and abrupt increase in the work function is seen in an initial stage. This clearly evidences an electronic charge transfer from the substrate to Au probably due to a much larger work function of Au than SrTiO3(0 0 1), which leads to an upward band bending (0.3 eV) just like a Schottky contact. Electronic charge transfers also take place at Au/S- and Au/S1-TiO2(1 1 0) and Au/R-TiO2(1 1 0) interfaces, where electrons are transferred from Au to S- and S1-TiO2 and from R-TiO2 to Au, as predicted by ab initio calculations.  相似文献   

11.
The effects of temperature and solvation on uranyl ion adsorption at the water/rutile TiO2(110) interface are investigated by Density Functional Theory (DFT) in both static and Born–Oppenheimer molecular dynamics approaches. According to experimental observations, uranyl ion can form two surface complexes in a pH range from 1.5 to 4.5. Based on these observations, the structures of the complexes at 293 K are first calculated in agreement with vacuum static calculations. Then, an increase in temperature (293 to 425 K) induces the reinforcement of uranyl ion adsorption due to the release of water molecules from the solvation shell of uranyl ion. Finally, temperature can modify the nature of the surface species.  相似文献   

12.
Ferroelectric thin film with the perovskite ABO3 structure have been widely used in technology applications, e.g., actuators in MEMS/NEMS and nonvolatile random access memories (FeRAM). In order to clarify the effect of the shear strain on the ferroelectricity, the PbTiO3 thin film as a typical one is chosen. The focus of this study is to put on the PbO-terminated (1? × ?1) and c(2? × ?2) surfaces and the TiO2-terminated (1? × ?1) surface. Based on ab initio density functional theory calculations with the local density approximation, we have found out that in both the PbO and TiO2-terminated (1? × ?1) models, the ferroelectricity in the PbO layers was enhanced under the positive shear strain while it was suppressed under the negative one. For the TiO2 layers, the ferroelectricity was slightly enhanced and sharply suppressed under the positive and negative shear strains, respectively. In the PbO-terminated (2? × ?2) model, the AFE phase was suppressed by the FE phase under the positive shear strain while the opposite trend was found under the negative shear strain. For the PbO layers, the ferroelectricity was enhanced under the positive and negative shear strains. For the TiO2 layers, the influence of the negative shear strain on the ferroelectricity was larger than that of the positive one. In addition, the ideal strength of the PbTiO3 thin film with the different terminations was investigated as well.  相似文献   

13.
The morphology of TiO2(110)-(1 × 1) supported Cu particles has been investigated by Fourier Transform Reflection Absorption Infrared Spectroscopy (FT-RAIRS), employing adsorbed CO as a probe molecule sensitive to local surface structure. For Cu coverage (deposited at 300 K) less than 2.85 MLE nucleated Cu particles in the range 2 nm–4 nm are formed, as indicated by a final state shift in the core level Cu(2p3/2) binding energy and by the existence of only transmission bands in the FT-RAIRS spectra for adsorbed CO. νS(CO) indicates that these small particles expose sites similar to those of the stepped Cu surfaces Cu(211), Cu(311), and Cu(755). At Cu coverages in the range of 6 MLE and above, corresponding to particle sizes above 4.6 nm, νS(CO) indicates the predominance of (110), (100) and (111) adsorption sites. Annealing the Cu layers to 650 K results in the slight growth of the particle sizes, and transformation of the CO adsorption sites corresponding to the close packed facets. The transformation of the local dielectric from that of titania to that dominated by the Cu particle is shown to take place between 3.7 and 4.2 nm, and this change is also to a smaller extent sensitive to the dispersion of the particles.  相似文献   

14.
John T. Yates 《Surface science》2009,603(10-12):1605-1612
Photochemistry from TiO2 surfaces is described for two cases: The UV-induced photodesorption of O2 from TiO2(1 1 0) – 1 × 1; and the hydrophilic effect caused by UV irradiation on TiO2. In both cases fundamental information about how these processes occur has been found. In the case of the O2 photodesorption kinetics, it has been found that the rate of the process is proportional to the square root of the UV flux, showing that second-order electron–hole pair recombination is dominant in governing the photodesorption rate. In addition these measurements provide an estimate of the concentration of hole traps in the TiO2 crystal. In other measurements of the UV-induced hydrophilicity, starting with the atomically-clean TiO2 surface, it has been shown that the effect occurs suddenly at a critical point during irradiation as a result of photooxidation of a monolayer of hydrocarbon (n-hexane) at equilibrium with ppm concentration of n-hexane in O2 at 1 atmosphere pressure.  相似文献   

15.
Periodic density functional theory has been utilized to investigate the structure and stability of monomeric HVOx species on anatase support. The three most stable surfaces of anatase were investigated, namely the (001), (100) and (101) surfaces. Unlike previous theoretical studies it was found that on the (001) surface vanadia species with five-coordinated vanadium atom are more stable than those with tetrahedrally coordinated vanadium atom. On the other hand, on the (100) and (101) surfaces, the vanadium atom in the vanadia species is still tetrahedrally coordinated. The stability of different VOx/TiO2 structures which are not fully dehydrated has been systematically studied and the results show that the vanadia species on the three surfaces follow an order of TiO2 (001) > TiO2 (100) > TiO2 (101). This can be understood from the acidity and basicity of the three anatase surfaces. The results suggest that monomeric VOx species may be better stabilized if the support exposes more (001) surfaces. Our analyses on electronic structure of the most stable VOx/TiO2 structure (D001) suggest that its bridging V–O–Ti oxygen atoms may have higher reactivity than the terminal vanadyl oxygen atoms.  相似文献   

16.
Sonodynamic therapy (SDT) is a new treatment modality using ultrasound to activate certain chemical sensitizers for cancer therapy. In this study, effects of high intensity focused ultrasound (HIFU) combined with photocatalytic titanium dioxide (TiO2) nanoparticles on human oral squamous cell line HSC-2 were investigated. Viability of HSC-2 cells after 0, 0.1, 1, or 3 s of HIFU irradiation with 20, 32, 55 and 73 W cm−2 intensities in the presence or absence of TiO2 was measured immediately after the exposures in vitro. Immediate effects of HIFU (3 s, 73 W cm−2) combined with TiO2 on solid tumors were also examined by histological study. Cytotoxic effect of HIFU + TiO2 in vitro was significantly higher than that of TiO2 or HIFU alone with the tendency to increase for higher HIFU intensity, duration, and TiO2 concentration in the suspension. In vivo results showed significant necrosis and tissue damage in HIFU and HIFU + TiO2 treated samples. However, penetration of TiO2 nanoparticles into the cell cytoplasm was only observed in HIFU + TiO2 treated tissues. In this study, our findings provide a rational basis for the development of an effective HIFU based sonodynamic activation method. This approach offers an attractive non-invasive therapy technique for oral cancer in future.  相似文献   

17.
The interaction between the metal organic precursor molecule titanium(IV) isopropoxide (TTIP) and three different surfaces has been studied: Si(111)-(7 × 7), SiOx/Si(111) and TiO2. These surfaces represent the different surface compositions encountered during TTIP mediated TiO2 chemical vapor deposition on Si(111). The surface chemistry of the titanium(IV) isopropoxide precursor and the film growth have been explored by core level photoelectron spectroscopy and x-ray absorption spectroscopy using synchrotron radiation. The resulting film morphology has been imaged with scanning tunneling microscopy. The growth rate depends on both surface temperature and surface composition. The behavior can be rationalized in terms of the surface stability of isopropoxy and isopropyl groups, confirming that growth at 573 K is a reaction limited process.  相似文献   

18.
In order to reduce the density mismatch between TiO2 and the low dielectric medium and improve the dispersion stability of the electrophoretic particles in the low dielectric medium for electrophoretic display application, polystyrene/titanium dioxide (PS/TiO2) core–shell particles were prepared via in-situ sol–gel method by depositing TiO2 on the PS particle which was positively charged with 2-(methacryloyloxy)ehyl trimethylammonium chloride (DMC). The morphology and average particle size of PS/TiO2 core–shell particles were observed by transmission electron microscopy (TEM), scanning electron microscope (SEM) and particle size analyzer. It was found that density of PS/TiO2 core–shell particles were reduced obviously and the particles can suspend in the low dielectric medium of low density. The PS/TiO2 core–shell particles can endure ultrasonic treatment because of the interaction between TiO2 and PS. Zeta potential and electrophoretic mobility of the fabricated core–shell particles in a low dielectric medium with charge control agent was measured to be −44.3 mV and −6.07 × 10−6 cm2/Vs, respectively, which presents potential in electronic paper application.  相似文献   

19.
The composition and thermodynamic stability of the (110) surface of Sn1 - xTixO2 rutile solid solutions was investigated as a function of Ti-distribution and content up to the formation of a full TiO2 surface monolayer. The bulk and (110) surface properties of Sn1 - xTixO2 were compared to that of the pure SnO2 and TiO2 crystal. A large supercell of 720 atoms and a localized basis set based on the Gaussian and plane wave scheme allowed the investigation of very low Ti-content and symmetry. For the bulk, optimization of the crystal structure confirmed that up to a Ti-content of 3.3 at.%, the lattice parameters (a, c) of SnO2 do not change. Increasing further the Ti-content decreased both lattice parameters down to those of TiO2. The surface energy of these solid solutions did not change for Ti-substitution in the bulk of up to 20 at.%. In contrast, substitution in the surface layer rapidly decreased the surface energy from 0.99 to 0.74 J/m2 with increasing Ti-content from 0 to 20 at.%. As a result, systems with Ti atoms distributed in the surface (surface enrichment) had always lower energies and thus were thermodynamically more favorable than those with Ti homogeneously distributed in the bulk. This was attributed to the lower energy necessary to break the TiO bonds than SnO bonds in the surface layer. In fact, distributing the Ti atoms homogeneously or segregated in the (110) surface led to the same surface energy indicating that restructuring of the surface bond lengths has minimal impact on thermodynamic stability of these rutile systems. As a result, a first theoretical prediction of the composition of Sn1 - xTixO2 solid solutions is proposed.  相似文献   

20.
Hydrogen atoms on solid surfaces were measured directly by elastic recoil detection analysis (ERDA) using medium energy (100–150 keV) Ne+ ions with an excellent sensitivity of (~ 1 × 1012 H/cm2) without any absorber foils and time-of-flight techniques. An electrostatic toroidal analyzer acquired H+ ions with energy around 11 keV recoiled from Si(111)-1 × 1-H surfaces. The H+ fraction strongly depends upon emerging angle and takes a value more than 50% at the angle below 70° and a saturated value of 17% at the angle above 80° with respect to surface normal. We detected H atoms on the reduced TiO2(110) exposed to water molecules at room temperature (2 L) and estimated the absolute amount of H to be ~ 2.0 × 1014 H/cm2 corresponding to ~ 38% (~ 0.38 ML) of the bridging oxygen atoms.  相似文献   

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