139 research outputs found
Using Density Functional Theory to Model Realistic TiO2 Nanoparticles, Their Photoactivation and Interaction with Water
Computational modeling of titanium dioxide nanoparticles of realistic size is
extremely relevant for the direct comparison with experiments but it is also a
rather demanding task. We have recently worked on a multistep/scale procedure
to obtain global optimized minimum structures for chemically stable spherical
titania nanoparticles of increasing size, with diameter from 1.5 nm (~300
atoms) to 4.4 nm (~4000 atoms). We use first self-consistent-charge density
functional tight-binding (SCC-DFTB) methodology to perform thermal annealing
simulations to obtain globally optimized structures and then hybrid density
functional theory (DFT) to refine them and to achieve high accuracy in the
description of structural and electronic properties. This allows also to assess
SCC-DFTB performance in comparison with DFT(B3LYP) results. As a further step,
we investigate photoexcitation and photoemission processes involving
electron/hole pair formation, separation, trapping and recombination in the
nanosphere of medium size by hybrid DFT. Finally, we show how a recently
defined new set of parameters for SCC-DFTB allows for a proper description of
titania/water multilayers interface, which paves the way for modeling large
realistic nanoparticles in aqueous environment
Reactive molecular dynamics simulations of hydration shells surrounding spherical TiO 2 nanoparticles: Implications for proton-transfer reactions
In many potential applications, nanoparticles are typically in an aqueous medium. This has strong influence on the stability, optical properties and reactivity, in particular for their functionalization. Therefore, the understanding of the chemistry at the interface between the solvent and the nanoparticle is of utmost importance. In this work, we present a comparative ReaxFF reactive molecular dynamics investigation on spherical TiO2 nanoparticles (NSs) of realistic size, with diameters from 2.2 to 4.4 nm, immersed in a large drop of bulk water. After force field validation for its use for a curved anatase TiO2 surface/water interface, we performed several simulations of the TiO2 nanoparticles of increasing size in a water drop. We found that water can be adsorbed jointly in a molecular and dissociative way on the surface. A Langmuir isotherm indicating an adsorption/desorption mechanism of water on the NS is observed. Regarding the dissociative adsorption, atomistic details reveal two different mechanisms, depending on the water concentration around the NS. At low coverage, the first mechanism involves direct dissociation of a single water molecule, whereas, at higher water coverage, the second mechanism is a proton transfer reaction involving two water molecules, also known as Grotthuss-like mechanism. Thermal annealing simulations show that several water molecules remain on the surface in agreement with the experimental reports. The capacity of adsorption is higher for the 2.2 and 3.0 nm NSs than for the 4.4 nm NS. Finally, a comparative investigation with flat surfaces indicates that NSs present a higher water adsorption capacity (undissociated and dissociated) than flat surfaces, which can be rationalized considering that NSs present many more low-coordinated Ti atoms available for water adsorption. This journal is.Fil: Soria, Federico Ariel. Universita Di Milano Bicocca; Italia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Di Valentin, Cristiana. Università Di Milano Bicocca; Itali
Anisotropic Effects of Oxygen Vacancies on Electrochromic Properties and Conductivity of -Monoclinic WO
Tungsten trioxide (WO) is a paradigmatic electrochromic material, whose
peculiar optical properties in the presence of oxygen vacancies or intercalated
alkali atoms have been observed and investigated for a long time. In this paper
we propose a rationalization of experiments based on first-principles
calculations of optical and electrical properties of oxygen deficient (reduced)
WO. Our approach is based on a parameter-free dielectric-dependent hybrid
density functional methodology, used in combination with the charge transition
levels formalism, for studying excitation mechanisms in the presence of
defects. Our results indicate that oxygen vacancies lead to a different physics
in -monoclinic WO, depending on the orientation of the W-O-W chain
where the vacancy is created, thus evidencing strong anisotropic effects rooted
in the peculiar structural properties of the original nondefective monoclinic
cell. Different types of oxygen vacancies can hence be classified on the basis
of the calculated ground state properties, electronic structure, and
excitation/emission energies, giving a satisfactory explanation to a range of
experimental observations made on oxygen deficient WO.Comment: Accepted for publication in J. Phys. Chem.
Can Single Metal Atoms Trapped in Defective h-BN/Cu (111) Improve Electrocatalysis of the H2 Evolution Reaction?
Metal-supported hexagonal boron nitride monolayers (h-BN/M) are emerging as new potential electrocatalysts for various energy-related oxidation or reduction process. So far, several preparation methods have been developed to introduce, in a controlled way, defects such as vacancies or substitutional heteroatoms. Herein, we investigate by dispersion-corrected density functional theory (DFT) calculations, defective and metal-doped h-BN/Cu(111) systems as electrocatalysts for the hydrogen evolution reaction (HER). By calculating the hydrogen binding energy (ΔG*H) at different coverage conditions, we observe how the interaction between the defective/metal-doped h-BN layer and the Cu(111) substrate plays a key role in tuning the reactivity, leading to a thermoneutral hydrogen adsorption step (i.e., ΔG*H ≈ 0). These results could be generalized to other h-BN/M interfaces and may help their rational design for an improved H2-evolving electrocatalysis
Electronic structure and phase stability of oxide semiconductors: Performance of dielectric-dependent hybrid functional DFT, benchmarked against band structure calculations and experiments
We investigate band gaps, equilibrium structures, and phase stabilities of
several bulk polymorphs of wide-gap oxide semiconductors ZnO, TiO2,ZrO2, and
WO3. We are particularly concerned with assessing the performance of hybrid
functionals built with the fraction of Hartree-Fock exact exchange obtained
from the computed electronic dielectric constant of the material. We provide
comparison with more standard density-functional theory and GW methods. We
finally analyze the chemical reduction of TiO2 into Ti2O3, involving a change
in oxide stoichiometry. We show that the dielectric-dependent hybrid functional
is generally good at reproducing both ground-state (lattice constants, phase
stability sequences, and reaction energies) and excited-state (photoemission
gaps) properties within a single, fully ab initio framework.Comment: Minor changes in the final published versio
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