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1.
J Phys Condens Matter ; 32(39): 395001, 2020 May 22.
Artigo em Inglês | MEDLINE | ID: mdl-32442988

RESUMO

Monolayer WSe2 has aroused strong interest as a semiconducting 2D material. The tuning of its electronic properties is important for expanding the range of applications. In this work, by hybrid density functional theory calculations, we investigate the effect of Na adsorption on the electronic and magnetic properties of stoichiometric and defective WSe2 monolayers and their WSe2xS2(1-x) alloys. Our results suggest that Na adsorption on defective WSe2xS2(1-x) monolayers would split and partially fill the empty defect states in the gap region inducing a local magnetic moment of 1 µ B per alkaline atom. The efficient tuning of the electronic and magnetic properties of WSe2 monolayer by Na adsorption combined with the Se vacancy and S alloying would benefit its wide applications.

2.
Phys Rev Lett ; 123(18): 186101, 2019 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-31763909

RESUMO

Iron oxide magnetic nanoparticles (NPs) are stimuli-responsive materials at the forefront of nanomedicine. Their realistic finite temperature simulations are a formidable challenge for first-principles methods. Here, we use density functional tight binding to open up the required time and length scales and obtain global minimum structures of Fe_{3}O_{4} NPs of realistic size (1400 atoms, 2.5 nm) and of different shapes, which we then refine with hybrid density functional theory methods to accomplish proper electronic and magnetic properties, which have never been accurately described in simulations. On this basis, we develop a general empirical formula and prove its predictive power for the evaluation of the total magnetic moment of Fe_{3}O_{4} NPs. By converting the total magnetic moment into the macroscopic saturation magnetization, we rationalize the experimentally observed dependence with shape. We also reveal interesting reconstruction mechanisms and unexpected patterns of charge ordering.

3.
Nanoscale ; 11(33): 15576-15588, 2019 Sep 07.
Artigo em Inglês | MEDLINE | ID: mdl-31403155

RESUMO

Drug delivery systems are based on reversible interactions between carriers and drugs. Spacers are often introduced to tailor the type of interaction and to keep drugs intact. Here, we model a drug delivery system based on a functionalized curved TiO2 nanoparticle of realistic size (700 atoms - 2.2 nm) by the neurotransmitter dopamine to carry the anticancer chemotherapeutic agent doxorubicin (DOX). The multiscale quantum chemical study aims at unraveling the nature and mechanism of the interactions between the components and the electronic properties of the composite system. We simulate the temperature effect through molecular dynamics runs of thermal annealing. Dopamine binds preferentially to low coordinated Ti sites on the nanoparticle through dissociated bidentate and chelate modes involving the diol groups. DOX is tethered by H-bonds, π-π stacking, dipole-dipole interactions and dispersion forces. Comparing different coverage densities of the spacer on the nanoparticle surface, we assess the best conditions for an effective drug transport and release: only at full coverage, DOX does not slip among the dopamine molecules to reach the nanoparticle surface, which is crucial to avoid the formation of stable coordinative bonds with under-coordinated Ti atoms. Finally, given the strong absorption properties and fluorescence of DOX and of the TiO2 photocatalyst, we model the effect of light irradiation through excited state calculations to localize excitons and to follow the charge carrier's life path. This fundamental study on the nature and mechanism of drug/carrier interaction provides a solid ground for the rational design of new experimental protocols for a more efficient drug transport and release and its combination with photodynamic therapy.


Assuntos
Portadores de Fármacos/química , Nanopartículas Metálicas/química , Teoria Quântica , Antineoplásicos/química , Antineoplásicos/metabolismo , Catálise , Dopamina/química , Dopamina/metabolismo , Doxorrubicina/química , Doxorrubicina/metabolismo , Humanos , Luz , Simulação de Dinâmica Molecular , Fotoquimioterapia , Temperatura , Titânio/química
4.
J Colloid Interface Sci ; 555: 519-531, 2019 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-31404836

RESUMO

TiO2 nanoparticles (NPs) are attracting materials for biomedical applications, provided that they are coated with polymers to improve solubility, dispersion and biocompatibility. Conformation, coverage density and solvent effects largely influence their functionality and stability. In this work, we use atomistic molecular dynamics simulations to study polyethylene glycol (PEG) grafting to highly curved TiO2 NPs (2-3 nm) in different solvents. We compare the coating polymer conformations on NPs with those on (1 0 1) flat surfaces. In water, the transition from mushroom to brush conformation starts only at high density (σ = 2.25 chains/nm2). In dichloromethane (DCM), at low-medium coverage (σ < 1.35 chains/nm2), several interactions between the PEG chains backbone and undercoordinated Ti atoms are established, whereas at σ = 2.25 chains/nm2 the conformation clearly becomes brush-like. Finally, we demonstrate that these spherical brushes, when immersed in water, but not in DCM, follow the Daoud-Cotton (DC) classical scaling model for the polymer volume fraction dependence with the distance from the center of star-shaped systems.

5.
J Phys Chem C Nanomater Interfaces ; 123(13): 7682-7695, 2019 Apr 04.
Artigo em Inglês | MEDLINE | ID: mdl-30976374

RESUMO

Despite the many successful syntheses and applications of dopamine-functionalized TiO2 nanohybrids, there has not yet been an atomistic understanding of the interaction of this 1,2-dihydroxybenzene derivative ligand with the titanium dioxide surfaces. In this work, on the basis of a wide set of dispersion-corrected hybrid density functional theory (DFT) calculations and density functional tight binding (DFTB) molecular dynamics simulations, we present a detailed study of the adsorption modes, patterns of growth, and configurations of dopamine on the anatase (101) TiO2 surface, with reference to the archetype of 1,2-dihydroxybenzene ligands, i.e., catechol. At low coverage, the isolated dopamine molecule prefers to bend toward the surface, coordinating the NH2 group to a Ti5c ion. At high coverage, the packed molecules succeed in bending toward the surface only in some monolayer configurations. When they do, we observe a proton transfer from the surface to the ethyl-amino group, forming terminal NH3 + species, which highly interact with the O atoms of a neighboring dopamine molecule. This strong Coulombic interaction largely stabilizes the self-assembled monolayer. On the basis of these results, we predict that improving the probability of dopamine molecules being free to bend toward the surface through thermodynamic versus kinetic growth conditions will lead to a monolayer of fully protonated dopamine molecules.

6.
J Chem Phys ; 150(9): 094703, 2019 Mar 07.
Artigo em Inglês | MEDLINE | ID: mdl-30849917

RESUMO

Magnetite has attracted increasing attention in recent years due to its promising and diverse applications in biomedicine. Theoretical modelling can play an important role in understanding magnetite-based nanomaterials at the atomic scale for a deeper insight into the experimental observations. However, calculations based on density functional theory (DFT) are too costly for realistically large models of magnetite nanoparticles. Classical force field methods are very fast but lack of precision and of the description of electronic effects. Therefore, a cheap and efficient quantum mechanical simulation method with comparable accuracy to DFT is highly desired. Here, a less computationally demanding DFT-based method, i.e., self-consistent charge density functional tight-binding (SCC-DFTB), is adopted to investigate magnetite bulk and low-index (001) surfaces with newly proposed parameters for Fe-O interactions. We report that SCC-DFTB with on-site Coulomb correction provides results in quantitatively comparable agreement with those obtained by DFT + U and hybrid functional methods. Therefore, SCC-DFTB is valued as an efficient and reliable method for the description magnetite. This assessment will promote SCC-DFTB computational studies on magnetite-based nanostructures that attract increasing attention for medical applications.

7.
ChemSusChem ; 12(9): 1995-2007, 2019 May 08.
Artigo em Inglês | MEDLINE | ID: mdl-30600934

RESUMO

Metal-doped and metal-supported two-dimensional materials are attracting a lot of interest as potentially active electrocatalysts for reduction and oxidation processes. Previously, when a non-regular 2 D h-BN layer was grown on a Cu(111) surface, metal adatoms were found to spontaneously emerge from the bulk to fill the atomic holes in the structure and become available for surface catalysis. Herein, computational electrochemistry is used to investigate and compare the performance of Cu-doped and Cu-supported pristine and defective h-BN systems for the electrocatalytic water oxidation reaction. For the various model systems, the intermediate species of this multistep oxidation process are identified and the free-energy variations for each step of reaction are computed, even for those steps that do not involve an electron or a proton transfer. Both associative and O2 direct evolution mechanisms are considered. On this thermodynamic basis, the potential-determining step, the thermodynamic-determining step, and consequently the theoretical overpotential are determined for comparison with experiments. Small Cu clusters (tetramers) trapped in the h-BN defective lattice on a Cu(111) support are found to be very active for the water oxidation reaction since such systems are characterized by a low overpotential and by a small energy cost for O2 release from the catalyst, which is often observed to be a major limit for other potential electrocatalysts.

8.
Molecules ; 23(11)2018 Nov 13.
Artigo em Inglês | MEDLINE | ID: mdl-30428551

RESUMO

Metal oxide nanoparticles (NPs) are regarded as good candidates for many technological applications, where their functional environment is often an aqueous solution. The correct description of metal oxide electronic structure is still a challenge for local and semilocal density functionals, whereas hybrid functional methods provide an improved description, and local atomic function-based codes such as CRYSTAL17 outperform plane wave codes when it comes to hybrid functional calculations. However, the computational cost of hybrids are still prohibitive for systems of real sizes, in a real environment. Therefore, we here present and critically assess the accuracy of our electrostatic embedding quantum mechanical/molecular mechanical (QM/MM) coupling between CRYSTAL17 and AMBER16, and demonstrate some of its capabilities via the case study of TiO2 NPs in water. First, we produced new Lennard⁻Jones (LJ) parameters that improve the accuracy of water⁻water interactions in the B3LYP/TIP3P coupling. We found that optimizing LJ parameters based on water tri- to deca-mer clusters provides a less overstructured QM/MM liquid water description than when fitting LJ parameters only based on the water dimer. Then, we applied our QM/MM coupling methodology to describe the interaction of a 1 nm wide multilayer of water surrounding a spherical TiO2 nanoparticle (NP). Optimizing the QM/MM water⁻water parameters was found to have little to no effect on the local NP properties, which provide insights into the range of influence that can be attributed to the LJ term in the QM/MM coupling. The effect of adding additional water in an MM fashion on the geometry optimized nanoparticle structure is small, but more evident effects are seen in its electronic properties. We also show that there is good transferability of existing QM/MM LJ parameters for organic molecules⁻water interactions to our QM/MM implementation, even though these parameters were obtained with a different QM code and QM/MM implementation, but with the same functional.


Assuntos
Nanopartículas Metálicas/química , Teoria Quântica , Titânio/química , Modelos Moleculares , Solventes/química , Água/química
9.
Phys Chem Chem Phys ; 20(41): 26161-26172, 2018 Nov 07.
Artigo em Inglês | MEDLINE | ID: mdl-30311617

RESUMO

The structure and electronic properties of carbon-based nanostructures obtained by metal surface assisted synthesis is highly dependent on the nature of the precursor molecule. Here, we report on a combined scanning tunneling microscopy, soft X-ray spectroscopy and density functional theory investigation on the surface assisted polymerization of Br-corannulene at Ag(110) and on the possibility of building a mesh of π-conjugated polymers starting from buckyball shaped molecules. Indeed, the corannulene units form one-molecule-wide ribbons in which the natural concavity of the precursor molecule is maintained. These C-based nanostructures are corrugated and merge into a covalent network on the surface.

10.
Nanomaterials (Basel) ; 8(7)2018 Jun 29.
Artigo em Inglês | MEDLINE | ID: mdl-29966319

RESUMO

2D tungsten diselenide (2D-WSe2) is one of the most successful bidimensional materials for optoelectronic and photonic applications, thanks to its strong photoluminescence properties and to a characteristic large exciton binding energy. Although these optical properties are widely recognized by the scientific community, there is no general understanding of the atomistic details of the excitonic species giving rise to them. In this work, we present a density functional theory investigation of excitons in 2D-WSe2, where we compare results obtained by standard generalized gradient approximation (GGA) methods (including spin-orbit coupling) with those by hybrid density functionals. Our study provides information on the size of the self-trapped exciton, the number and type of atoms involved, the structural reorganization, the self-trapping energy, and the photoluminescence energy, whose computed value is in good agreement with experimental measurements in the literature. Moreover, based on the comparative analysis of the self-trapping energy for the exciton with that for isolated charge carriers (unbound electrons and holes), we also suggest a simplified approach for the theoretical estimation of the excitonic binding energy, which can be compared with previous estimates from different approaches or from experimental data.

11.
Nanoscale ; 10(23): 11021-11027, 2018 Jun 14.
Artigo em Inglês | MEDLINE | ID: mdl-29868664

RESUMO

Surfaces and their interaction with water play an important role in most of materials' applications. Magnetite has attracted continued interest in the fields of catalysis, spintronic devices, magnetic resonance imaging (MRI) and drug delivery. In this work, water adsorption and its effect on the stability diagram and on the electronic structure of the Fe3O4(001) surface are investigated by hybrid density functional theory calculations combined with an ab initio atomistic thermodynamic approach. We span a wide range of gaseous O2 and vapor H2O partial pressures. At low water pressure, a reconstructed SCV surface model is confirmed to be the most stable model at common working O2 partial pressures. However, at high water coverage, an unexpected stability inversion is observed that makes the hydrated bulk-terminated DBT surface the most favored. These results open up new horizons in Fe3O4 surface chemistry when working in an aqueous environment and are of key importance to develop rational strategies to surface engineering for high performance Fe3O4 nanomaterials.

12.
ACS Appl Mater Interfaces ; 10(35): 29943-29953, 2018 Sep 05.
Artigo em Inglês | MEDLINE | ID: mdl-29950088

RESUMO

In most technological applications, nanoparticles are immersed in a liquid environment. Understanding nanoparticles/liquid interfacial effects is extremely relevant. This work provides a clear and detailed picture of the type of chemistry and physics taking place at the prototypical TiO2 nanoparticles/water interface, which is crucial in photocatalysis and photoelectrochemistry. We present a multistep and multiscale investigation based on hybrid density functional theory (DFT), density functional tight-binding, and quantum mechanics/molecular mechanics calculations. We consider increasing water partial pressure conditions from ultra-high vacuum up to the bulk water environment. We first investigate single water molecule adsorption modes on various types of undercoordinated sites present on a realistic curved nanoparticle (2-3 nm) and then, by decorating all the adsorption sites, we study a full water monolayer to identify the degree of water dissociation, the Brønsted-Lowry basicity/acidity of the nanoparticle in water, the interface effect on crystallinity, surface energy, and electronic properties, such as the band gap and work function. Furthermore, we increase the water coverage by adding water multilayers up to a thickness of 1 nm and perform molecular dynamics simulations, which evidence layer structuring and molecular orientation around the curved nanoparticle. Finally, we clarify whether these effects arise as a consequence of the tension at the water drop surface around the nanosphere by simulating a bulk water up to a distance of 3 nm from the oxide surface. We prove that the nanoparticle/water interfacial effects go rather long range since the dipole orientation of water molecules is observed up to a distance of 5 Å, whereas water structuring extends at least up to a distance of 8 Å from the surface.

13.
J Am Chem Soc ; 140(4): 1415-1422, 2018 01 31.
Artigo em Inglês | MEDLINE | ID: mdl-29325412

RESUMO

Heterogeneous photocatalysis is vital in solving energy and environmental issues that this society is confronted with. Although photocatalysts are often operated in the presence of water, it has not been yet clarified how the interaction with water itself affects charge dynamics in photocatalysts. Using water-coverage-controlled steady and transient infrared absorption spectroscopy and large-model (∼800 atoms) ab initio calculations, we clarify that water enhances hole trapping at the surface of TiO2 nanospheres but not of well-faceted nanoparticles. This water-assisted effect unique to the nanospheres originates from water adsorption as a ligand at a low-coordinated Ti-OH site or through robust hydrogen bonding directly to the terminal OH at the highly curved nanosphere surface. Thus, the interaction with water at the surface of nanospheres can promote photocatalytic reactions of both oxidation and reduction by elongating photogenerated carrier lifetimes. This morphology-dependent water-assisted effect provides a novel and rational basis for designing and engineering nanophotocatalyst morphology to improve photocatalytic performances.

14.
ACS Appl Mater Interfaces ; 10(6): 5793-5804, 2018 Feb 14.
Artigo em Inglês | MEDLINE | ID: mdl-29368503

RESUMO

Beyond two-dimensional (2D) materials, interfaces between 2D materials and underlying supports or 2D-coated metal or metal oxide nanoparticles exhibit excellent properties and promising applications. The hybrid interface between graphene and anatase TiO2 shows great importance in photocatalytic, catalytic, and nanomedical applications due to the excellent and complementary properties of the two materials. Water, as a ubiquitous and essential element in practical conditions and in the human body, plays a significant role in the applications of graphene/TiO2 composites for both electronic devices and nanomedicine. Carbon vacancies, as common defects in chemically prepared graphene, also need to be considered for the application of graphene-based materials. Therefore, the behavior of water on top and at the interface of defective graphene on anatase TiO2 surface was systematically investigated by dispersion-corrected hybrid density functional calculations. The presence of the substrate only slightly enhances the on-top adsorption and reduces the on-top dissociation of water on defective graphene. However, at the interface, dissociated water is largely preferred compared with undissociated water on bare TiO2 surface, showing a prominent cover effect. Reduced TiO2 may further induce oxygen diffusion into the bulk. Our results are helpful to understand how the presence of water in the surrounding environment affects structural and electronic properties of the graphene/TiO2 interface and thus its application in photocatalysis, electronic devices, and nanomedicine.

15.
J Phys Chem C Nanomater Interfaces ; 121(46): 25736-25742, 2017 Nov 22.
Artigo em Inglês | MEDLINE | ID: mdl-29201266

RESUMO

Magnetite exhibits a famous phase transition, called Verwey transition, at the critical temperature TV of about 120 K. Although numerous efforts have been devoted to the understanding of this interesting transition, up to now, it is still under debate whether a charge ordering and a band gap exist in magnetite above TV. Here, we systematically investigate the charge ordering and the electronic properties of magnetite in its cubic phase using different methods based on density functional theory: DFT+U and hybrid functionals. Our results show that, upon releasing the symmetry constraint on the density but not on the geometry, charge disproportionation (Fe2+/Fe3+) is observed, resulting in a band gap of around 0.2 eV at the Fermi level. This implies that the Verwey transition is probably a semiconductor-to-semiconductor transition and that the conductivity mechanism above TV is small polaron hopping.

16.
J Chem Phys ; 147(16): 164701, 2017 Oct 28.
Artigo em Inglês | MEDLINE | ID: mdl-29096504

RESUMO

TiO2 nanoparticles (NPs) are nowadays considered fundamental building blocks for many technological applications. Morphology is found to play a key role with spherical NPs presenting higher binding properties and chemical activity. From the experimental point of view, the characterization of these nano-objects is extremely complex, opening a large room for computational investigations. In this work, TiO2 spherical NPs of different sizes (from 300 to 4000 atoms) have been studied with a two-scale computational approach. Global optimization to obtain stable and equilibrated nanospheres was performed with a self-consistent charge density functional tight-binding (SCC-DFTB) simulated annealing process, causing a considerable atomic rearrangement within the nanospheres. Those SCC-DFTB relaxed structures have been then optimized at the DFT(B3LYP) level of theory. We present a systematic and comparative SCC-DFTB vs DFT(B3LYP) study of the structural properties, with particular emphasis on the surface-to-bulk sites ratio, coordination distribution of surface sites, and surface energy. From the electronic point of view, we compare HOMO-LUMO and Kohn-Sham gaps, total and projected density of states. Overall, the comparisons between DFTB and hybrid density functional theory show that DFTB provides a rather accurate geometrical and electronic description of these nanospheres of realistic size (up to a diameter of 4.4 nm) at an extremely reduced computational cost. This opens for new challenges in simulations of very large systems and more extended molecular dynamics.

17.
ACS Catal ; 7(10): 7081-7091, 2017 Oct 06.
Artigo em Inglês | MEDLINE | ID: mdl-29034122

RESUMO

The photoactivity of methanol adsorbed on the anatase TiO2 (101) surface was studied by a combination of scanning tunneling microscopy (STM), temperature-programmed desorption (TPD), X-ray photoemission spectroscopy (XPS), and density functional theory (DFT) calculations. Isolated methanol molecules adsorbed at the anatase (101) surface show a negligible photoactivity. Two ways of methanol activation were found. First, methoxy groups formed by reaction of methanol with coadsorbed O2 molecules or terminal OH groups are photoactive, and they turn into formaldehyde upon UV illumination. The methoxy species show an unusual C 1s core-level shift of 1.4 eV compared to methanol; their chemical assignment was verified by DFT calculations with inclusion of final-state effects. The second way of methanol activation opens at methanol coverages above 0.5 monolayer (ML), and methyl formate is produced in this reaction pathway. The adsorption of methanol in the coverage regime from 0 to 2 ML is described in detail; it is key for understanding the photocatalytic behavior at high coverages. There, a hydrogen-bonding network is established in the adsorbed methanol layer, and consequently, methanol dissociation becomes energetically more favorable. DFT calculations show that dissociation of the methanol molecule is always the key requirement for hole transfer from the substrate to the adsorbed methanol. We show that the hydrogen-bonding network established in the methanol layer dramatically changes the kinetics of proton transfer during the photoreaction.

18.
ACS Appl Mater Interfaces ; 9(35): 29932-29941, 2017 Sep 06.
Artigo em Inglês | MEDLINE | ID: mdl-28795791

RESUMO

The presence of defects in the graphenic layers deposited on metal surfaces modifies the nature of the interaction. Unsaturated carbon atoms, due to vacancies in the lattice, form strong organometallic bonds with surface metal atoms that highly enhance the binding energy between the two materials. We investigate by means of a wide set of dispersion-corrected density functional theory calculations how such strong chemical bonds affect both the electronic properties of these hybrid interfaces and the chemical reactivity with water, which is commonly present in the working conditions. We compare different metal substrates (Cu vs Pt) that present a different type of interaction with graphene and with defective graphene. This comparative analysis allows us to unravel the controlling factors of water reactivity, the role played by the carbon vacancies and by the confinement or "graphene cover effect". Water is capable of breaking the C-Cu bond by dissociating at the undercoordinated carbon atom of the vacancy, restoring the weak van der Waals type of interaction between the two materials that allows for an easy detachment of graphene from the metal, but the same is not true in the case of Pt, where C-Pt bonds are much stronger. These conclusions can be used to rationalize water reactivity at other defective graphene/metal interfaces.

19.
J Chem Theory Comput ; 13(8): 3862-3873, 2017 Aug 08.
Artigo em Inglês | MEDLINE | ID: mdl-28679048

RESUMO

A water/(101) anatase TiO2 interface has been investigated with the DFT-based self-consistent-charge density functional tight-binding theory (SCC-DFTB). By comparison of the computed structural, energetic, and dynamical properties with standard DFT-GGA and experimental data, we assess the accuracy of SCC-DFTB for this prototypical solid-liquid interface. We tested different available SCC-DFTB parameters for Ti-containing compounds and, accordingly, combined them to improve the reliability of the method. To better describe water energetics, we have also introduced a modified hydrogen-bond-damping function (HBD). With this correction, equilibrium structures and adsorption energies of water on (101) anatase both for low (0.25 ML) and full (1 ML) coverages are in excellent agreement with those obtained with a higher level of theory (DFT-GGA). Furthermore, Born-Oppenheimer molecular dynamics (MD) simulations for mono-, bi-, and trilayers of water on the surface, as computed with SCC-DFTB, evidence similar ordering and energetics as DFT-GGA Car-Parrinello MD results. Finally, we have evaluated the energy barrier for the dissociation of a water molecule on the anatase (101) surface. Overall, the combined set of parameters with the HBD correction (SCC-DFTB+HBD) is shown to provide a description of the water/water/titania interface, which is very close to that obtained by standard DFT-GGA, with a remarkably reduced computational cost. Hence, this study opens the way to the future investigations on much more extended and realistic TiO2/liquid water systems, which are extremely relevant for many modern technological applications.

20.
ACS Appl Mater Interfaces ; 9(27): 23212-23221, 2017 Jul 12.
Artigo em Inglês | MEDLINE | ID: mdl-28622467

RESUMO

The nature of the interaction of water with the WO3 surface is of crucial importance for the use of this semiconductor oxide in photocatalysis. In this work, we investigate water adsorption and dissociation on both clean and O-deficient (001) WO3 surfaces by means of an accurate DFT approach. The O vacancy formation energy (computed with respect to O2) has been evaluated for all possible surface configurations, and the removal of the terminal O atom along the c axis is found to be preferred, costing about half the corresponding energy in the bulk. The presence of oxygen vacancies leads to a semiconductor to metal transition, confirming the experimental evidence of n-type conductivity in defective WO3 films. H2O preferably adsorbs on WO3 in a molecular undissociated form, due to the presence of W ions at the surface that act as Lewis acid sites. This interaction, about -1 eV per H2O molecule, is not very strong. Contrary to what is usually expected, the presence of oxygen vacancies does not significantly affect H2O adsorption. Finally, we investigated the H2O desorption from a hydroxylated surface. This suggests that the exposure of WO3 to H2 directly results in a hydroxylated surface and the corresponding H2O desorption turns out to be a very efficient mechanism to generate a reduced oxide surface, with important consequences on the electronic structure of this oxide.

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