167 research outputs found
Electronic states and magnetic structure at the Co3O4 (110) surface: a first principles study
Tricobalt tetraoxide (Co3O4) is an important catalyst and Co3O4(110) is a
frequently exposed surface in Co3O4 nanomaterials. We employed
Density-functional theory with on-site Coulomb repulsion U term to study the
atomic structures, energetics, magnetic and electronic properties of the two
possible terminations, A and B, of this surface. These calculations predict A
as the stable termination in a wide range of oxygen chemical potentials,
consistent with recent experimental observations. The Co3+ ions do not have a
magnetic moment in the bulk, but become magnetic at the surface, which leads to
surface magnetic orderings different from the one in the bulk. Surface
electronic states are present in the lower half of the bulk band gap and cause
partial metallization of both surface terminations. These states are
responsible for the charge compensation mechanism stabilizing both polar
terminations. The computed critical thickness for polarity compensation is 4
layers
Solvent Effects on the Adsorption Geometry and Electronic Structure of Dye-Sensitized TiO2: A First-Principles Investigation
The performance of dye-sensitized solar cells (DSSCs)
depends significantly on the adsorption geometry of the dye on the
semiconductor surface. In turn, the stability and geometry of the adsorbed
molecules is influenced by the chemical environment at the electrolyte/
dye/TiO2 interface. To gain insight into the effect of the solvent on the
adsorption geometries and electronic properties of dye-sensitized TiO2
interfaces, we carried out first-principles calculations on organic dyes and
solvent (water or acetonitrile) molecules coadsorbed on the (101) surface
of anatase TiO2. Solvent molecules introduce important modifications on
the dye adsorption geometry with respect to the geometry calculated in
vacuo. In particular, the bonding distance of the dye from the Ti anchoring
atoms increases, the adsorption energy decreases, and the two C−O bonds
in the carboxylic moieties become more symmetric than in vacuo. Moreover, the adsorbed solvent induces the deprotonation of
the dye due to the changing the acid/base properties of the system. Analysis of the electronic structure for the dye-sensitized
TiO2 structures in the presence of coadsorbed solvent molecules shows an upward shift in the TiO2 conduction band of 0.2 to
0.5 eV (0.5 to 0.8 eV) in water (acetonitrile). A similar shift is calculated for a solvent monolayer on unsensitized TiO2. The
overall picture extracted from our calculations is consistent with an upshift of the conduction band in acetonitrile (2.04 eV vs
SCE) relative to water (0.82 eV vs SCE, pH 7), as reported in previous studies on TiO2 flatband potential (Redmond, G.;
Fitzmaurice, D. J. Phys. Chem. 1993, 97, 1426−1430) and suggests a relevant role of the solvent in determining the dye−
semiconductor interaction and electronic coupling
Formation and stability of reduced TiO_x layers on anatase TiO_2(101): identification of a novel Ti_2O_3 phase
We use density functional theory (DFT) calculations to investigate structural
models consisting of anatase TiO2(101) slabs covered by reduced overlayers
formed by (101) crystallographic shear planes (CSPs). Ab initio thermodynamics
supports the stability of these structures under a wide range of experimental
conditions. The overlayers are found to have Ti2O3 stoichiometry with a crystal
structure different from the known corundum-like Ti2O3 (here denoted
{\alpha}-Ti2O3) phase. DFT calculations predict this new "csp-Ti2O3" phase to
be energetically close to {\alpha}-Ti2O3 and to have also a similar band gap.
These results suggest a possible role of the csp-Ti2O3 phase in the properties
of black TiO2, a promising photocatalytic material made of nanoparticles with a
crystalline TiO2 core and a highly reduced TiOx shell that is capable of
absorbing the whole spectrum of visible light
Band Alignment in Molecular Devices: Influence of Anchoring Group and Metal Work Function
We present periodic Density Functional Theory calculations of the electronic
properties of molecular junctions formed by amine-, and thiol-terminated alkane
chains attached to two metal (Au, Ag) electrodes. Based on extensive analysis
that includes molecular monolayers of varying densities, we establish a
relationship between the alignment of the molecular energy levels and the
interface dipoles, which shows that the band alignment (BA) in the limit of
long, isolated chains is independent of the link group and can be computed from
a reference system of non interacting molecule + metal electrodes. The main
difference between the amine and thiol linkers is the effective dipole moment
at the contact. This is very large, about 4.5 D, for amine linkers, leading to
a strong dependence of the BA on the monolayer density and a slow convergence
to the isolated molecule limit. Instead, this convergence is fast for S anchors
due to the very small, ~ 0.2 D, effective dipoles at the contacts
Electronic structure and bonding properties of cobalt oxide in the spinel structure
The spinel cobalt oxide Co3O4 is a magnetic semiconductor containing cobalt
ions in Co2+ and Co3+ oxidation states. We have studied the electronic,
magnetic and bonding properties of Co3O4 using density functional theory (DFT)
at the Generalized Gradient Approximation (GGA), GGA+U, and PBE0 hybrid
functional levels. The GGA correctly predicts Co3O4 to be a semiconductor, but
severely underestimates the band gap. The GGA+U band gap (1.96 eV) agrees well
with the available experimental value (~ 1.6 eV), whereas the band gap obtained
using the PBE0 hybrid functional (3.42 eV) is strongly overestimated. All the
employed exchange-correlation functionals predict 3 unpaired d electrons on the
Co2+ ions, in agreement with crystal field theory, but the values of the
magnetic moments given by GGA+U and PBE0 are in closer agreement with the
experiment than the GGA value, indicating a better description of the cobalt
localized d states. Bonding properties are studied by means of Maximally
Localized Wannier Functions (MLWFs). We find d-type MLWFs on the cobalt ions,
as well as Wannier functions with the character of sp3d bonds between cobalt
and oxygen ions. Such hybridized bonding states indicate the presence of a
small covalent component in the primarily ionic bonding mechanism of this
compound.Comment: 24 pages, 8 figure
Inherent electronic trap states in TiO2 nanocrystals: effect of saturation and sintering
We report a quantum mechanical investigation on the nature of electronic trap states in realistic models of
individual and sintered anatase TiO2
nanocrystals (NCs) of ca. 3 nm diameter. We find unoccupied
electronic states of lowest energy to be localized within the central part of the NCs, and to originate
from under-coordinated surface Ti atoms lying mainly at the edges between the (100) and (101) facets.
These localized states are found at about 0.3–0.4 eV below the fully delocalized conduction band states,
in good agreement with both electrochemical and spectro-electrochemical results. The overall DensityOf-States (DOS) below the conduction band (CB) can be accurately fitted to an exponential distribution
of states, in agreement with capacitance data. Water molecules adsorbed on the NC surface raise the
energy and reduce the number of localized states, thus modifying the DOS. As a possible origin of
additional trap states, we further investigated the oriented attachment of two TiO2
NCs at various
possible interfaces. For the considered models, we found only minor differences between the DOS of
two interacting NCs and those of the individual constituent NCs. Our results point at the presence of
inherent trap states even in perfectly stoichiometric and crystalline TiO2
NCs due to the unavoidable
presence of under-coordinated surface Ti(IV) ions at the (100) facets
The Reactivity of Anatase TiO2 (211) Surface and the Bond- Charge Counting Model
In this chapter, we intend to present a generic understanding of surface reactivity and water dissociation on TiO2 surfaces through a study of anatase TiO2 (211) surface—an idea model surface containing both four-coordinated Ti atom (Ti4) and five-coordinated Ti atom (Ti5). Our first-principles calculations show that the (211) surface is a high reactivity surface and reveal that water molecule can be easily dissociated on a Ti4 site while it hardly dissociates on Ti5 site. Furthermore, we introduce bond-charge counting model to clarify the mechanism. More generally, after an intensive investigation of literature, we found that the bond-charge counting model is applicable to all anatase and rutile TiO2 surfaces including step edges and vacancies where the reactivity of surfaces enable to dissociate water attribute to the existence of Ti4 atom or equivalent Ti4 atom
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TiO2/Ferroelectric Heterostructures as Dynamic Polarization-Promoted Catalysts for Photochemical and Electrochemical Oxidation of Water
Using first-principles density functional theory calculations, we explore the chemical activity of epitaxial heterostructures of TiO2 anatase on strained polar SrTiO3 films focusing on the oxygen evolution reaction (OER), the bottleneck of water splitting. Our results show that the reactivity of the TiO2 surface is tuned by electric dipoles dynamically induced by the adsorbed species during the intermediate steps of the reaction while the initial and final steps remain unaffected. Compared to the OER on unsupported TiO2, the combined effects of the dynamically induced dipoles and epitaxial strain strongly reduce rate-limiting thermodynamic barriers and significantly improve the efficiency of the reaction.open5
Incorporation of Non-metal Impurities at the Anatase TiO(001)-(14) Surface
We use first-principles calculations to investigate the adsorption and
incorporation of non-metal impurities (N, C) at the anatase
TiO(001)-(14) reconstructed surface. We analyze in detail the
influence of the surface structure and local strain on the impurity binding
sites and incorporation pathways and identify important intermediates which
facilitate impurity incorporation. We find various subsurface interstitial
binding sites and corresponding surface subsurface penetration
pathways on the reconstructed surface. This surface also favors the presence of
subsurface oxygen-vacancies, to which adsorbed species can migrate to form
substitutional impurities. Most notably, we show that the non-exposed oxygen
sites just below the surface have a key role in the incorporation of nitrogen
and carbon in TiO(001).Comment: 5 figure
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