Quantum molecular dynamics study of water on TiO2(110) surface

The adsorption of water on perfect TiO(2)(110) surface is studied by quantum molecular dynamics simulation adopting a periodic model formed by five water molecules on a (5 x 1) surface unit cell of a five layer slab of TiO(2). The total simulation time is 3.2 ps. At about 1.3 ps, one water molecule dissociates with the help of other adsorbed waters and surface bridging oxygens. During the remaining 1.9 ps, the waters and OH groups vibrate, but no more dissociation or recombination is observed. By comparing recent experimental O1s photoemission (x-ray photoelectron spectroscopy) spectra of H(2)O/TiO(2)(110) to the computed spectrum of the adsorbate in the configurations supplied by the molecular dynamics simulation, the observed peaks can be attributed to different oxygen species. The proposed assignment of the main spectral features supports the occurrence of partial water dissociation (approximately 20%) also on a perfect TiO(2) surface.     

Reactions of ammonia on stoichiometric and reduced TiO(2)(001) single crystal surfaces

The reaction of NH(3) on the surface of the 011-faceted structure of the TiO(2)(001) single crystal is studied and compared to that on the O-defected surface. Temperature-programmed desorption (TPD) conducted after NH(3) adsorption at 300 K shows only molecular desorption at 340 K. Modeling of TPD signals as a function of surface coverage indicated that the activation energy, E(d), and pre-exponential factor, v(eff), decrease with increasing coverage. Near zero surface coverage, E(d) was found to be equal to 92 kJ/mol and v(eff) to be close to 10(13) /s. Both parameters decreased to approximately 52 kJ/mol and approximately 10(7) /s at saturation coverage. The decrease is due to a repulsive interaction of adsorbed NH(3) molecules on the surface. Computing of the TPD results show that saturation is obtained at 1/2 monolayer coverage (referred to Ti atoms). Both the amount and shape of NH(3) peak change on the reduced (Ar(+)-sputtered) surfaces. The desorption peak at 340 K is considerably attenuated on mildly reduced surfaces (TiO( approximately )(1.9)) and has totally disappeared on the heavily reduced surfaces (TiO(1.6)(-)(1.7)), where the main desorption peak is found at 440 K. This 440-K desorption is most likely due to NH(x) + H recombination resulting from ammonia dissociation upon adsorption on Ti atoms in low oxidation states.     

Adsorption of organic molecules on the TiO2(011) surface: STM study

High resolution scanning tunneling microscopy has been applied to investigate adsorption and self-assembly of large organic molecules on the TiO(2)(011) surface. The (011) face of the rutile titania has been rarely examined in this context. With respect to possible industrial applications of rutile, quite often in a powder form, knowledge on behavior of organic molecules on that face is required. In the presented study we fill in the gap and report on experiments focused on the self-assembly of organic nanostructures on the TiO(2)(011) surface. We use three different kinds of organic molecules of potential interest in various applications, namely, PTCDA and CuPc representing flat, planar stacking species, and Violet Landers specially designed for new applications in molecular electronics. In order to reach a complete picture of molecular behavior, extended studies with different surface coverage ranging from single molecule up to 2 monolayer (ML) thick films are performed. Our results show that the adsorption behavior is significantly different from previously observed for widely used metallic templates. Creation of highly ordered molecular lines, quasi-ordered wetting layers, controlled geometrical reorientation upon thermal treatment, existence of specific adsorption geometries, and prospects for tip-induced molecule ordering and manipulation provide better understanding and add new phenomena to the knowledge on the (011) face of rutile titania.     

Density functional theory study of formic acid adsorption on anatase TiO2(001): geometries, energetics, and effects of coverage, hydration, and reconstruction

We present density functional theory calculations and first-principles molecular dynamics simulations of formic acid adsorption on anatase TiO(2)(001), the minority surface exposed by anatase TiO(2) nanoparticles. A wide range of factors that may affect formic acid adsorption, such as coverage, surface hydration, and reconstruction, are considered. It is found that (i) formic acid dissociates spontaneously on unreconstructed clean TiO(2)(001)-1 x 1, as well as on the highly reactive ridge of the reconstructed TiO(2)(001)-1 x 4 surface; (ii) on both the 1 x 1 and 1 x 4 surfaces, various configurations of dissociated formic acid exist with adsorption energies of about 1.5 eV, which very weakly depend on the coverage; (iii) bidentate adsorption configurations, in which the formate moiety binds to the surface through two Ti-O bonds, are energetically more favored than monodentate ones; (iv) partial hydration of TiO(2)(001)-1 x 1 tends to favor the bidentate chelating configuration with respect to the bridging one but has otherwise little effect on the adsorption energetics; and (v) physical adsorption of formic acid on fully hydrated TiO(2)(001)-1 x 1 is also fairly strong. Comparison of the present results for formic acid adsorption with those for water and methanol under similar conditions provides valuable insights to the understanding of recent experimental results concerning the coadsorption of these molecules.     

Adsorption-site-dependent electronic structure of catechol on the anatase TiO2(101) surface

The adsorption of catechol (1,2-benzendiol) on the anatase TiO(2)(101) surface was studied with synchrotron-based ultraviolet photoemission spectroscopy (UPS), X-ray photoemission spectroscopy (XPS), and scanning tunneling microscopy (STM). Catechol adsorbs with a unity sticking coefficient and the phenyl ring intact. STM reveals preferred nucleation at step edges and subsurface point defects, followed by 1D growth and the formation of a 2 × 1 superstructure at full coverage. A gap state of ～1 eV above the valence band maximum is observed for dosages in excess of ～0.4 Langmuir, but such a state is absent for lower coverages. The formation of the band gap states thus correlates with the adsorption at regular lattice sites and the onset of self-assembled superstructures.     

Ab initio study of surface acid-base reactions. The case of molecular and dissociative adsorption of ammonia on the (011) surface of rutile TiO2

The interaction of ammonia molecules with Lewis acid centers (Ti4+ metal ions) of the (011) surface of rutile TiO2 is investigated by density functional theory in order to understand, from first principle, the nature of acid-base reactions on solid surfaces. Unlike the rutile (110) surface that contains alternating rows of 5-fold and 6-fold Ti atoms, all Ti atoms of the (011) surface are 5-fold coordinated. This surface has shown considerable activity for numerous chemical reactions and is thus an ideal prototype. At 1/2 monolayer coverage, with respect to surface Ti atoms, the adsorption energy is found to be equal to 100 kJ mol-1, and drops to 58 kJ mol-1 at one monolayer coverage. Analysis of the electronic density of states (DOS) revealed information regarding the mode of adsorption. In particular, the nitrogen 3a1 and 2a1 orbitals appear to undergo significant changes upon adsorption, in agreement with photoelectron spectroscopy studies. Dissociative adsorption was also investigated on the same surface. Both NH2(Tis) + H(Os) and NH(Tis) + 2H(Os) modes of dissociative adsorption, where s stands for surface, are found to be less stable than the molecular (non dissociated) adsorption.     

Theoretical study of adsorption of O((3)P) and H(2)O on the rutile TiO(2)(110) surface

The adsorption of oxygen atoms O(3P) on both ideal and hydrated rutile TiO(2)(110) surfaces is investigated by periodic density functional theory (DFT) calculations within the revised Perdew-Burke-Ernzerhof (RPBE) generalized gradient approximation and a four Ti-layer slab, with (2 x 1) and (3 x 1) surface unit cells. It is shown that upon adsorption on the TiO(2) surface the spin of the O atom is completely lost, leading to stable surface peroxide species on both in-plane and bridging oxygen sites with O-binding energies of about 1.0-1.5 eV, rather than to the kinetically unstable terminal Ti-O and terminal O-O species with smaller binding energies of 0.1-0.7 eV. Changes in O-atom coverage ratios between 1/3 and 1 molecular layer (ML) and coadsorption of H(2)O have only minor effects on the O-binding energies of the stable peroxide configurations. High O-atom diffusion barriers of about 1 eV are found, suggesting a slow recombination rate of adsorbed O atoms on TiO(2)(110). Our results suggest that the TiOOTi peroxide intermediate experimentally observed in photoelectrolysis of water should be interpreted as a single spinless O adatom on TiO(2) surface rather than as two Ti-O* radicals coupled together.     

Reactivity of anatase TiO(2) nanoparticles: the role of the minority (001) surface

Methanol adsorption on clean and hydrated anatase TiO(2)(001)-1 x 1 is studied using density functional theory calculations and first principles molecular dynamics simulations. It is found that (i) dissociative adsorption is favored on clean TiO(2)(001) at both low and high methanol coverages; (ii) on the partially hydrated surface, methanol dissociation is not affected by the coadsorbed water and can still occur very easily; (iii) the dissociative adsorption energy of methanol is always larger than that of water under similar conditions. This implies that water replacement by methanol is energetically favored, in agreement with recent experimental observations on colloidal anatase nanoparticles.     

Molecular oxygen adsorption behaviors on the rutile TiO2(110)-1×1 surface: an in situ study with low-temperature scanning tunneling microscopy

A knowledge of adsorption behaviors of oxygen on the model system of the reduced rutile TiO(2)(110)-1×1 surface is of great importance for an atomistic understanding of many chemical processes. We present a scanning tunneling microcopy (STM) study on the adsorption of molecular oxygen either at the bridge-bonded oxygen vacancies (BBO(V)) or at the hydroxyls (OH) on the TiO(2)(110)-1×1 surface. Using an in situ O(2) dosing method, we are able to directly verify the exact adsorption sites and the dynamic behaviors of molecular O(2). Our experiments provide direct evidence that an O(2) molecule can intrinsically adsorb at both the BBO(V) and the OH sites. It has been identified that, at a low coverage of O(2), the singly adsorbed molecular O(2) at BBO(V) can be dissociated through an intermediate state as driven by the STM tip. However, singly adsorbed molecular O(2) at OH can survive from such a tip-induced effect, which implies that the singly adsorbed O(2) at OH is more stable than that at BBO(V). It is interesting to observe that when the BBO(V)s are fully filled with excess O(2) dosing, the adsorbed O(2) molecules at BBO(V) tend to be nondissociative even under a higher bias voltage of 2.2 V. Such a nondissociative behavior is most likely attributed to the presence of two or more O(2) molecules simultaneously adsorbed at a BBO(V) with a more stable configuration than singly adsorbed molecular O(2) at a BBO(V).     

O2 interaction and reactivity on a model hydroxylated rutile(110) surface

Recently several theoretical studies have examined oxygen adsorption on the clean, reduced TiO2(110) surface. However the photocatalytic behavior of TiO2 and the scavenging ability of oxygen are known to be influenced by the presence of surface hydroxyls. In this paper the chemistry of O2 on the hydroxylated TiO2 surface is investigated by means of first-principles total energy calculations and molecular dynamics (MD) simulations. The MD trajectories show a direct, spontaneous reaction between O2 and the surface hydroxyls, thus supporting the experimental hypothesis that the reaction does not necessarily pass through a chemisorbed O2 state. Following this reaction, the most stable chemisorbed intermediates are found to be peroxide species HO2 and H2O2. Although these intermediates are very stable on the short time scale of MD simulations, the energetics suggests that their further transformation is connected to a new 300 K feature observed in the experimental water temperature programmed desorption (TPD) spectrum. The participation of two less stable intermediate states, involving terminal hydroxyls and/or chemisorbed water plus oxygen adatoms, to the desorption process, is not supported by the total energy calculations. Analysis of the projected density of states, however, suggests the possibility that these intermediates have a role in completing the surface oxidation immediately before desorption.     

STM study of glycine on TiO2(110) single crystal surfaces

The adsorption of glycine (NH2CH2COOH) was examined by scanning tunneling microscopy (STM) on TiO2(110) surfaces at room temperature. A (2x1) ordered overlayer was observed on the TiO2(110)-(1x1) surface. The adsorption of acetic acid and propanoic acid was also investigated on this surface and their STM images were quite similar to that of glycine. Since acetate and propanoate are formed by dissociative adsorption of these acids on TiO2(110), it is proposed that glycine adsorbs in the same way to form a glycinate. The amino group in the glycinate adlayer structurally analogous to those formed from aliphatic carboxylic acids would be extended away from the surface and potentially free to participate in additional reactions. The underlying structure of the TiO2 surface is important in determining the structure of the glycinate adlayer; no ordering of these adsorbates was observed on the TiO2(110)-(1x2) surface.     

O2 and vacancy diffusion on rutile(110): pathways and electronic properties.

The binding structures and diffusion pathways of molecular oxygen on a defective TiO2(110) surface are studied by means of a recently developed first-principles string molecular dynamics approach. A variety of molecular and dissociated O2 adsorption states are identified and the kinetics of their interconversion is analyzed. These results, as well as calculations of the electronic properties and of scanning tunneling microscopy (STM) images, are used to discuss recent experimental observations of the interactions between surface oxygen vacancies and the adsorbed oxygen molecule.     

Ultrathin TiO(x) films on Pt(111): a LEED, XPS, and STM investigation

Ultrathin ordered titanium oxide films on Pt(111) surface are prepared by reactive evaporation of Ti in oxygen. By varying the Ti dose and the annealing conditions (i.e., temperature and oxygen pressure), six different long-range ordered phases are obtained. They are characterized by means of low-energy electron diffraction (LEED), X-ray photoemission spectroscopy (XPS), and scanning tunneling microscopy (STM). By careful optimization of the preparative parameters, we find conditions where predominantly single phases of TiO(x), revealing distinct LEED pattern and STM images, are produced. XPS binding energy and photoelectron diffraction (XPD) data indicate that all the phases, except one (the stoichiometric rect-TiO2), are one monolayer thick and composed of a Ti-O bilayer with interfacial Ti. Atomically resolved STM images confirm that these TiO(x) phases wet the Pt surface, in contrast to rect-TiO2. This indicates their interface stabilization. At a low Ti dose (0.4 monolayer equivalents, MLE), an incommensurate kagomé-like low-density phase (k-TiO(x) phase) is observed where hexagons are sharing their vertexes. At a higher Ti dose (0.8 MLE), two denser phases are found, both characterized by a zigzag motif (z- and z'-TiO(x) phases), but with distinct rectangular unit cells. Among them, z'-TiO(x), which is obtained by annealing in ultrahigh vacuum (UHV), shows a larger unit cell. When the postannealing of the 0.8 MLE deposit is carried out at high temperatures and high oxygen partial pressures, the incommensurate nonwetting, fully oxidized rect-TiO2 is found The symmetry and lattice dimensions are almost identical with rect-VO2, observed in the system VO(x)/Pd(111). At a higher coverage (1.2 MLE), two commensurate hexagonal phases are formed, namely the w- [(square root(43) x square root(43)) R 7.6 degrees] and w'-TiO(x) phase [(7 x 7) R 21.8 degrees]. They show wagon-wheel-like structures and have slightly different lattice dimensions. Larger Ti deposits produce TiO2 nanoclusters on top of the different monolayer films, as supported both by XPS and STM data. Besides the formation of TiO(x) surfaces phases, wormlike features are found on the bare parts of the substrate by STM. We suggest that these structures, probably multilayer disordered TiO2, represent growth precursors of the ordered phases. Our results on the different nanostructures are compared with literature data on similar systems, e.g., VO(x)/Pd(111), VO(x)/Rh(111), TiO(x)/Pd(111), TiO(x)/Pt(111), and TiO(x)/Ru(0001). Similar and distinct features are observed in the TiO(x)/Pt(111) case, which may be related to the different chemical natures of the overlayer and of the substrate.     

Reactivity of V2O3(0001) surfaces: molecular vs dissociative adsorption of water

The adsorption of water on V2O3(0001) surfaces has been investigated by thermal desorption spectroscopy, high-resolution electron energy loss spectroscopy, and X-ray photoelectron spectroscopy with use of synchrotron radiation. The V2O3(0001) surfaces have been generated in epitaxial thin film form on a Rh(111) substrate with three different surface terminations according to the particular preparation conditions. The stable surface in thermodynamic equilibrium with the bulk is formed by a vanadyl (VO) (1x1) surface layer, but an oxygen-rich (radical3xradical3)R30 degrees reconstruction can be prepared under a higher chemical potential of oxygen (microO), whereas a V-terminated surface consisting of a vanadium surface layer requires a low microO, which can be achieved experimentally by the deposition of V atoms onto the (1x1) VO surface. The latter two surfaces have been used to model, in a controlled way, oxygen and vanadium containing defect centres on V2O3. On the (1x1) V=O and (radical3xradical3)R30 degrees surfaces, which expose only oxygen surface sites, the experimental results indicate consistently that the molecular adsorption of water provides the predominant adsorption channel. In contrast, on the V-terminated (1/radical3x1/radical3)R30 degrees surface the dissociation of water and the formation of surface hydroxyl species at 100 K is readily observed. Besides the dissociative adsorption a molecular adsorption channel exists also on the V-terminated V2O3(0001) surface, so that the water monolayer consists of both OH and molecular H2O species. The V surface layer on V2O3 is very reactive and is reoxidised by adsorbed water at 250 K, yielding surface vanadyl species. The results of this study indicate that V surface centres are necessary for the dissociation of water on V2O3 surfaces.     

Charge transfer dynamics of model charge transfer centers of a multicenter water splitting dye complex on rutile TiO2(110)

Charge transfer dynamics between an adsorbed molecule and a rutile TiO(2)(110) surface have been investigated in three organometallic dyes related to multicenter water splitting dye complexes: Ru 535 (cis-bis(isothiocyanato)bis(2,2'-bipyridyl-4,4'-dicarboxylato)-ruthenium(II)), Ru 455 (cis-bis(2,2'-bipyridyl)-(2,2'-bipyridyl-4,4'-dicarboxylic acid)-ruthenium(II)), and Ru 470 (tris(2,2'-bipyridyl-4,4'-dicarboxylic acid)-ruthenium(II)). The adsorption of the dye molecules on the rutile TiO(2)(110) surface has been studied using core-level and valence photoemission. Dye molecules were deposited in situ using ultrahigh vacuum electrospray deposition. Core-level photoemission spectra reveal that each complex bonds to the surface via deprotonation of two carboxylic groups. All three dye complexes show evidence of ultrafast charge transfer to the TiO(2) substrate using the core-hole clock implementation of resonant photoemission spectroscopy.     

Scanning tunneling microscope imaging of (CH3S)2 on Cu(111)

Scanning tunneling microscope (STM) images of isolated molecules of dimethyl disulfide, (CH(3)S)(2), adsorbed on the Cu(111) surface were successfully obtained at a sample temperature of 4.7 K. A (CH(3)S)(2) molecule appears as an elliptic protrusion in the STM images. From density functional theory calculation, it was suggested that the bright part in the protrusion corresponds to the molecular orbital which is widely spread around H atoms in each CH(3) group in the (CH(3)S)(2) molecule. The STM images revealed that the molecules have a total of six equivalent adsorption orientations on Cu(111), which are given by the combination of three equivalent adsorption sites and two conformational isomers for each adsorption site.     

A new type of strong metal-support interaction and the production of H2 through the transformation of water on Pt/CeO2(111) and Pt/CeO(x)/TiO2(110) catalysts

The electronic properties of Pt nanoparticles deposited on CeO(2)(111) and CeO(x)/TiO(2)(110) model catalysts have been examined using valence photoemission experiments and density functional theory (DFT) calculations. The valence photoemission and DFT results point to a new type of "strong metal-support interaction" that produces large electronic perturbations for small Pt particles in contact with ceria and significantly enhances the ability of the admetal to dissociate the O-H bonds in water. When going from Pt(111) to Pt(8)/CeO(2)(111), the dissociation of water becomes a very exothermic process. The ceria-supported Pt(8) appears as a fluxional system that can change geometry and charge distribution to accommodate adsorbates better. In comparison with other water-gas shift (WGS) catalysts [Cu(111), Pt(111), Cu/CeO(2)(111), and Au/CeO(2)(111)], the Pt/CeO(2)(111) surface has the unique property that the admetal is able to dissociate water in an efficient way. Furthermore, for the codeposition of Pt and CeO(x) nanoparticles on TiO(2)(110), we have found a transfer of O from the ceria to Pt that opens new paths for the WGS process and makes the mixed-metal oxide an extremely active catalyst for the production of hydrogen.     

Surface structures of rutile TiO2 (011)

Surface structures of rutile TiO(2) (011) are determined by a combination of noncontact atomic force microscopy (NC-AFM), scanning tunneling microscopy (STM), and density functional calculations. The surface exhibits rowlike (n x 1) structures running along the [01] direction. Microfaceting missing-row structural models can explain the experimental results very well. Calculated images for NC-AFM and STM are in good agreement with the experimental results. A decrease of the density of dangling bonds stabilizes the surface energy, which results in the microfaceting missing-row reconstructions.     

Multilayer adsorption of water at a rutile TiO2)(110) surface: towards a realistic modeling by molecular dynamics

We present a model combining ab initio concepts and molecular dynamics simulations for a more realistic treatment of complex adsorption processes. The energy, distance, and orientation of water molecules adsorbed on stoichiometric and reduced rutile TiO(2)(110) surfaces at 140 K are studied via constant temperature molecular dynamics simulations. From ab initio calculations relaxed atomic geometries for the surface and the most probable adsorption sites were derived. The study comprises (i) large two-dimensional surface supercells, providing a realistically low concentration of surface oxygen defects, and (ii) a water coverage sufficiently large to model the onset of the growth of a bulk phase of water on the surface. By our combined approach the influence of both, the metal oxide surface, below, and the bulk water phase, above, on the water molecules forming the interface between the TiO(2) surface and the water bulk layer is taken into account. The good agreement of calculated adsorption energies with experimental temperature programmed desorption spectra demonstrates the validity of our model.     

STM observation of a ruthenium dye adsorbed on a TiO2(110) surface

Individual Ru(4,4'-dicarboxy-2,2'-bipyridine)2(NCS)2 molecules, commonly known as N3, adsorbed on a TiO2 surface were visualized with a scanning tunneling microscope (STM) operated in ultrahigh vacuum. A TiO2(110)-(1 x 1) crystal was taken out from the vacuum vessel and immersed into an acetonitrile solution of N3. A monolayer of pivalate ((CH3)3CCOO-) ions was used to protect the (1 x 1) surface from contamination during the wetting process of the N3 adsorption. The N3 molecules adsorbed on the flat terraces protruded by 0.65 nm from the pivalate monolayer. The image height difference of the admolecules could be understood with the assumption that the N3 molecules anchor to the TiO2 surface via two carboxyl groups. The number density of the N3 molecules on the steps was higher than that on the terraces. The poorly coordinated Ti atoms exposed at the step edges form preferential sites where the carboxyl groups can approach, due to a lower steric obstacle or because the structure of the adsorbed N3 molecules suffers less distortion.