The adsorption and activation of formic acid on different anatase TiO2 surfaces

Formic acid photodegradation is one of the most important reactions in organic pollution control, and helps to improve the hydrogen generation efficiency in titanium dioxide catalyzed water photodecomposition. Based on density functional theory and Reax FF molecular dynamics, the adsorption, diffusion and activation of formic acid on the different anatase TiO（101）,（001）,（010） surfaces are investigated.The result shows that the adsorption of COOH on anatase TiOsurface shrinks the energy gap between the dehydrogenation intermediate COOH and HCOO. On the anatase TiO（101） surface, the formic acid breaks the O–H bond at the first step with activation energy 0.24 eV, and the consequent break of α-H become much easier with activation energy 0.77 eV. The dissociation of α-H is the determination step of the HCOOH decomposition.

Dependence of Nonlinear Optical Response of Anatase TiO2 on Shape and Excitation Intensity

Nonlinear optical （NLO） properties of anatase TiO2 with nanostructures of nanopaxticle （NP）, nanowire （NW） and annealed nanowire （NWA） are studied by open-aperture and closed-aperture Z-scan techniques with a fem- tosecond pulsed laser at wavelengths of 532 nm and 780 nm simultaneously. At 532 nm, when increasing excitation intensity, NLO absorption of TiO2 NPs transforms from saturable absorption to reverse-saturable absorption. However, NWs and NWAs exhibit the opposite change. At 780nm, all samples show reverse-saturable absorption, but have different sensitivities to excitation intensity. Due to the larger surface-to-volume ratio of NPs and less defects of NWAs by annealing, nonlinear optical absorption coet^icients follow the order NPs≥ NWs≥ NWAs. The results also show that these shape and annealing effects axe dominant at low excitation intensity, but do not exhibit at the high excitation intensity. The NLO refractive index of NPs shows a positive linear relationship with the excitation intensity, whereas NW and NWAs exhibit a negative linear relationship. The results could provide some foundational guidance to applications of anatase TiO2 in optoelectronic devices or other aspects.

Surface energy-driven solution epitaxial growth of anatase TiO2 homostructures for overall water splitting

Titanium dioxide(TiO2)has been extensively investigated as a photocatalyst for water splitting to produce H2.However,an overall water splitting by using anatase TiO2 is extremely difficult due to the short lifetime of holes.In this work,we propose that a surface energy decrease from{001}to{101}of anatase TiO2 is able to drive an epitaxial growth.A novel anatase TiO2 homostructure has been successfully synthesized via a facile hydrothermal route,where{101}semi-pyramid nanoparticles epitaxially grew on the both sides of the{001}nanosheets.The epitaxial relationship between the nanoparticles and the nanosheets has been characterized to be{001}//{001}of anatase TiO2.For the first time,it is interesting to find that the homostructure with 12 wt%of{101}semi-pyramid can significantly improve the H2 evolution rate by nearly 5 times compared to the pure nanosheets under the ultraviolet irradiation.More importantly,such homostructure enables 10.78μmol g-1h-1 of O2 production whereas the pure nanosheets cannot evolve detectable O2 gas.Meanwhile,the time-resolved photoluminescence analysis indicates that the mean lifetime of the holes is increased from 2.20 ns of the nanosheets to 3.59 ns of the homostructure,accounting for the observed overall water splitting.The findings suggest that constructing a homostructure by a surface energy strategy could be promising towards overall water splitting,which may be applicable to other photocatalytic materials.

Preparation and Photocatalytic Behaviors of Nanoporous Polyoxotungstate-Anatase TiO_2 Composites

Nanoporous anatase TiO2 crystalline particles coupled with Keggin or Wells-Dawson unit, H3PW12O40/TiO2 or H6P2W18O62/TiO2, were prepared at a low temperature （200℃ ） using sol-gel method combined with hydrothermal treatment at programmed temperature. The as-prepared composites have uniform anatase phase, and they exhibit both micrand mesoporosities with pore sizes of 0.6 and 4.0 nm, respectively, and their average size is lower than 10 nm. Photocatalytic tests show the composites exhibit relatively higher photocatalytic activities to decompose the organocholorine pesticide hexachlorobenzene（HCB） than anatase TiO2, the starting polyoxotungstates, and EuEOa/TiO2 prepared by using sol-gel method, and this was attributed to （ 1 ） the synergistic effect of photoactive anatase TiO2 with the polyoxotungstate, and （2） the fascinating physical and chemical properties of the porous materials.

Fe^(3+)-Doped Anatase TiO_2 Study Prepared by New Sol-Gel Precursors

FeTi_1-O_2（= 0.00,0.05,0.10） nanocomposites are synthesized using a sol-gel method involving an ethanol solvent in the presence of ethylene glycol as the stabilizer,and acetic acid as the chemical reagent.Their structural and optical analyses are studied to reveal their physicochemical properties.Using the x-ray diffractometer（XRD）analysis,the size of the nanoparticles（NPs） is found to be 18-32 nm,where the size of the NPs decreases down to 18 nm when Fe impurity of up to 10% is added,whereas their structure remains unchanged.The results also indicate that the structure of the NPs is tetragonal in the anatase phase.The Fourier transform infrared spectroscopy analysis suggests the presence of a vibration bond（Ti-O） in the sample.The photoluminescence analysis indicates that the diffusion of Fe^（3＋） ions into the TiO_2 matrix results in a decreasing electron-hole recombination,and increases the photocatalytic properties,where the best efficiency appears at an impurity of10%.The UV-diffuse reflection spectroscopy analysis indicates that with the elevation of iron impurity,the band gap value decreases from 3.47 eV for the pure sample to 2.95 eV for the 10 mol% Fe-doped TiO_2 NPs.

Adsorption Regularity and Characteristics of sp^3-Hybridized Gas Molecules on Anatase TiO_2(101) Surface

We report the anatase titanium dioxide （101） surface adsorption of sp3-hybridized gas molecules, including NH3, 1-12 0 and CH4, using first-principles plane-wave ultrasoft pseudopotential based on the density functional theory. The results show that it is much easier for a surface with oxygen vacancies to adsorb gas molecules than it is for a surface without oxygen vacancies. The main factor affecting adsorption stability and energy is the polarizability of molecules, and adsorption is induced by surface oxygen vacancies of the negatively charged center. The analyses of state densities and charge population show that charge transfer occurs at the molecule surface upon adsorption and that the number of transferred charge reduces in the order of N, 0 and C. Moreover, the adsorption method is chemical adsorption, and adsorption stability decreases in the order of NH3, tt2 0 and CH4. Analyses of absorption and reflectance spectra reveal that after absorbed CH4 and H2 O, compared with the surface with oxygen vacancy, the optical properties of materials surface, including its absorption coefficients and reflectivity index, have slight changes, however, absorption coefficient and reflectivity would greatly increase after NH3 adsorption. These findings illustrate that anatase titanium dioxide （101） surface is extremely sensitive to NH3.

First-principles study on anatase TiO_2 (101) surface adsorption of NO

In this paper, the stable structure and the electronic and optical properties of nitric oxide （NO） adsorption on the anatase TiO2 （101） surface are studied using the plane-wave ultrasoft pseudopotential method, which is based on the density functional theory. NO adsorption on the surface is weak when the outermost layer terminates on twofold coordinated oxygen atoms, but it is remarkably enhanced on the surface containing O vacancy defects. The higher the concentration of oxygen vacancy defects, the stronger the adsorption is. The adsorption energies are 3.4528 eV （N end adsorption）, 2.6770 eV （O end adsorption）, and 4.1437 eV （horizontal adsorption）. The adsorption process is exothermic, resulting in a more stable adsorption structure. Furthermore, O vacancy defects on the TiO2 （101） surface significantly contribute to the absorption of visible light in a relatively low-energy region. A new absorption peak in the low-energy region, corresponding to an energy of 0.9 eV, is observed. However, the TiO2 （101） surface structure exhibits weak absorption in the low-energy region of visible light after NO adsorption.

Synthesis and characterization of anatase TiO_2 nanosheet arrays on FTO substrate

We have exploited a green approach to prepare layered titanate Na2_xHxTi2Os-H20 nanosheet arrays on FFO substrate by hydrothermal hydrolysis of titanium（IV） isopropoxide （TRIP） with aids of Na2EDTA and TEOA as co-coordination agents, which were then treated by HNO3 to replace Na＋ by H＋, followed by a calcination at 450℃ to topotactically transform into anatase TiO2 nanosheet arrays. SEM, TEM, XRD, and Raman spectroscopy have been employed to characterize the nanosheet films. The TiO2 nanosheet arrays were further applied as electron transport materials of CH3NH3PbI3 perovskite solar cells, achieving power conversion efficiency of 6.99%.

A Density Functional Study of N-Doped TiO_2 Anatase Cluster

A systematic study on geometry, electronic structure and vibrational properties of N-doped TiO2 anatase cluster, within the framework of the density functional theory, has been performed in this work. The calculations confirmed that the most structures in substitutional model consist of a two-coordinate bridge structure and a three-coordinate hollow structure. The calculated results can well explain the red shift in N-doped TiO2 observed in experiments. The study provides an illustration for the N-doped anatase from the viewpoint of chemical bonding theory.

Preparation of (Ti, Sn)O_2 Nano-Composite Photocatalyst by Supercritical Fluid Dry Combination Technology

A series of TiO2-SnO2 nano-sized composite photo-catalysts containing Sn (9.3%-30.1%) were prepared from TiCI4 and SnCl4·5H2O by using sol-gel, supercritical fluid dry and solid-phase reaction (SCFD) combination technology. Characterizations with X-ray diffraction (XRD), transmission electron microscopy (TEM) and Fourier Transform Infrared Spectroscopy (FTIR) showed that, in addition to anatase type TiO2, a new active phase (Ti, Sn)O2 (with particle size of 2.0-4.3 nm) formed, and there were no SnO2 crystals observed in the range of the doping concentration studied. Photo-catalytic reaction of phenol was used as a model reaction to evaluate the catalytic activities of the obtained catalysts. Compared with pure TiO2 or Ti-Sn catalyst prepared with general sol-gel method, Ti-Sn nano-composite photo-catalyst thus obtained showed significant improvement in catalytic activity. The photo-catalytic degradation rate of phenol could reach as high as 93.5% after 7 h. The preparation conditions of the new phase (Ti, Sn)O2 were investigated and its catalytic mechanism was proposed. The photo-catalytic particles prepared using SCFD combination technology exhibited small particle size, large surface area and high activity.

Fluoride-assisted synthesis of anatase TiO_2 nanocrystals with tunable shape and band gap via a solvothermal approach

A simple solvothermal approach employing oleic acid has been developed to prepare anatase TiO2 nanocrystals with different shapes, which were tuned from nanorods to nano-ellipsoids by increasing the amount of NaF from 0 to 0.5 retool, and the optical band gap decreased from 3.47 eV to 3.29 eV accordingly. However, when the fluoride was changed to NH4F, the resultant TiO2 nanocrystals possessed an anatase phase but were made up of smaller-sized nanocrystals and nanorods, and the band gap was increased to 3.53 eV. The X-ray photoelectron spectroscopy （XPS） results illustrated an increase of fluorine content with an increasing amount of NaF could account for the variation of the shape and optical band gap of TiO2 nanocrystals. Moreover, the absence of fluorine content brought about less change of shape and increase of optical band gap of the product synthesized in the presence of NH4F. This result may offer another way to alter the shape and band gap of metal oxide nanocrystals with the assistance of fluoride.

First principle study of the electronic structure of hafnium-doped anatase TiO_2

Crystal structures and electronic structures of hafnium doping anatase TiO2 were calculated by first principles with the plane-wave ultrasoft pseudopotential method based on the density functional theory within the generalized gradient approximation. The calculated results show that the lattice parameters a and c of Hf-doped anatase TiO2 are larger than those of intrinsic TiO2 under the same calculated condition. The calculated band structure and density of states show that the conduction band width of Hf-doped TiO2 is broadened which results in the band gap of Hf-doped being smaller than the band gap of TiO2.

Unique adsorption behaviors of NO and O_2 at hydrogenated anatase TiO_2(101)

Titanium dioxide（TiO2） is one of the most widely studied transition metal oxides, especially for its unique performances in heterogeneous photocatalysis. Different phases of TiO2 have been found to exhibit different photo-activities, though the origins are still not fully understood. In this work, we use the density functional theory（DFT） calculations, corrected by on-site Coulomb and long-range dispersion interactions, to study the adsorptions of nitric oxide（NO） and oxygen（O2） molecules on the clean and hydrogenated anatase TiO2（101） surfaces. We also compare the detailed calculated results regarding their structural, energetic and electronic properties with those obtained at rutile TiO2（110）. It has been found that the behaviors of the surface localized electrons being transferred from adsorbed H, as well as the adsorption behaviors of NO and O2 are quite different at the two surfaces, which can be attributed to their characteristic local bonding structures around the surface hydroxyl. These results may also help explain the different photocatalytic activities of these two main facets of anatase and rutile TiO2

LATTICE DEFORMATION AND PHASE TRANSFORMATION FROM NANO-SCALE ANATASE TO NANO-SCALE RUTILE TiO_2 PREPARED BY A SOL-GEL TECHNIQUE

Nano-scale rutile phase was transformed from nano-scale anatase upon heating, which was prepared by a sol-gel technique. The XRD data corresponding to the anatase and rutile phases were analyzed and the grain sizes of as-derived phases were calculated by Sherrer equation. The lattice parameters of the as-derived anatase and rutile unit cells were calculated and compared with those of standard lattice parameters on PDF cards. It was shown that the smaller the grain sizes, the larger the lattice deformation. The lattice parameter a has the negative deviation from the standard and the lattice parameter c has the positive deviation for both phases. The particles sizes had preferential in-fluence on the longer parameter between the lattice parameters of a and c. With increasing temperatures, the lattice parameters of a and c in both phases approached to the equilibrium state. The larger lattice deformation facilitated the nucleation process, which lowered the transformation temperature. During the transformation from nano-scale anatase to rutile, besides the mechanism involving retention of the {112} pseudo-close-packed planes of oxygen in anatase as the {100} pseudo-close-packed planes in rutile, the new phase occurred by relaxation of lattice deformation and adjustment of the atomic sites in parent phase. The orientation relationships were suggested to be anatase {101}//rutile {101} and anatase <201>//rutile<111>, and the habit plane was anatase (101).

Photodegradation of benzene by TiO_2 nanoparticles prepared by flame CVD process

Photodegradation of benzene at ppb levels by mixed-phase TiO2 nanoparticles, synthesized by the oxidation of TiCl4 in propane/air turbulent flame chemical vapor deposition （CVD） process, is investigated experimentally by using a tubular photoreactor with thin TiO2 films coated on the reactor wall by sedimentation. Effects of inlet benzene concentration from 10 to 300μg/m3, rutile mass fraction from about 20 to 50% and photoluminescence （PL） intensity of TiO2 nanoparticles on degradation degree are examined under the conditions of 70% relative humidity, 38 μg/cm2 catalyst loading, 24mW/cm2 UV irradiation of 254 nm and 5.7 s residence time in the reactor. Based on experimental results, separation of photoinduced electron （e-） and hole （h＋） pairs by rutile phase is discussed as photo-induced electron （e-） in anatase phase will migrate to rutile surface due to that the potential of conductive band of rutile is lower than that of anatase, leading to more holes ready on anatase surface for oxidation reactions.

Intracellular in situ labeling of Ti02 nanoparticles for fluorescence microscopy detection

Titanium dioxide （TiO2） nanoparticles are produced for many different purposes, including development of therapeutic and diagnostic nanoparticles for cancer detection and treatment, drug delivery, induction of DNA double-strand breaks, and imaging of specific cells and subcellular structures. Currently, the use of optical microscopy, an imaging technique most accessible to biology and medical patholog36 to detect TiO2 nanoparticles in cells and tissues ex vivo is limited with low detection limits, while more sensitive imaging methods （transmission electron microscopy, X-ray fluorescence microscop~ etc.） have low throughput and technical and operational complications. Herein, we describe two in situ post- treatment labeling approaches to stain TiO2 nanoparticles taken up by the cells. The first approach utilizes fluorescent biotin and fluorescent streptavidin to label the nanoparticles before and after cellular uptake; the second approach is based on the copper-catalyzed azide-alkyne cycloaddition, the so-called Click chemistry, for labeling and detection of azide-conjugated TiO2 nanoparticles with alkyne- conjugated fluorescent dyes such as Alexa Fluor 488. To confirm that optical fluorescence signals of these nanoparticles match the distribution of the Ti element, we used synchrotron X-ray fluorescence microscopy （XFM） at the Advanced Photon Source at Argonne National Laboratory. Titanium-specific XFM showed excellent overlap with the location of optical fluorescence detected by confocal microscopy. Therefore, future experiments with TiO2 nanoparticles may safely rely on confocal microscopy after in situ nanoparticle labeling using approaches described here.