Roles of γ-Fe2O3 in fly ash for mercury removal: Results of density functional theory study

First-principle calculations based on density function theory (DFT) are used to clarify the roles of γ-Fe₂O₃ in fly ash for removing mercury from coal-fired flue gases. In this study, the structure of key surface of γ-Fe₂O₃ is modeled and spin-polarized periodic boundary conditions with the partial relaxation of atom positions are employed. Binding energies of Hg on γ-Fe₂O₃ (0 0 1) perfect and defective surfaces are calculated for different adsorption sites and the potential adsorption sites are predicted. Additionally, electronic structure is examined to better understand the binding mechanism. It is found that mercury is preferably adsorbed on the bridge site of γ-Fe₂O₃ (0 0 1) perfect surface, with binding energy of −54.3 kJ/mol. The much stronger binding occurs at oxygen vacancy surface with binding energy of −134.6 kJ/mol. The calculations also show that the formation of hybridized orbital between Hg and Fe atom of γ-Fe₂O₃ (0 0 1) is responsible for the relatively strong interaction of mercury with the solid surface, which suggests that the presently described processes are all noncatalytic in nature. However, this is a reflection more of mercury's amalgamation ability.     

Theoretical study of CO adsorption on the illuminated TiO2 (0 0 1) surface

A quantum modeling of the CO adsorption on illuminated anatase TiO₂ (0 0 1) is presented. The calculated adsorption energy and geometries of illuminated case are compared with the ground state case. The calculations were achieved by using DFT formalism and the BH and HLYP. Upon photoexcitation, an electron-hole pair is generated. Comparing of natural population in the ground state and the exited state, shows that an electron is trapped in a Ti⁴⁺ ion and a hole is localized in an oxygen ion. The photoelectron helps generation of a CO₂ molecule on the TiO₂ surface. As shown by optimization of these systems, the CO molecule adsorbed vertically on the TiO₂ (0 0 1) surface in the ground state case while the CO molecule made an angle of 134.3° to this surface at the excited state case. Based on the here used model the obtained adsorption energy was 0.36 eV which is in excellent agreement with the reported experimental value. In the present work the C-O stretch IR frequencies are calculated which are 1366.53 and 1423.16 cm⁻¹. These results are in good agreement with the earlier reported works for the surface carbonaceous compounds, and oxygenated carbon species.     

TiO2 activation using acid-treated vermiculite as a support: Characteristics and photoreactivity

Vermiculite was treated by sulfuric or nitric acid aqueous solutions with different concentration. These modified materials as the promising supports, were used to immobilize TiO₂. TiO₂ was prepared by the precursor, which was obtained by substituting partly isopropyl alcohol with Cl⁻ in titanium chloride {[Ti(IV)(OR)_nCl_m] (n = 2-3, m = 4 − n)}. The TiO₂/vermiculite composites were characterized by X-ray diffraction, scanning electron microscopy, and the nitrogen absorption. Their photocatalytic activity was evaluated by removal of methylene blue (MB). The pure anatase type crystalline phase was well deposited on the supports. The concentrations of acid for treatment had a significant influence on pore sizes and surface area of vermiculite. The treatment process changed microstructure of vermiculite, modified its characteristics, and farther improved the catalytic activity and absorption capacity of TiO₂/vermiculite composites. The treatment effect of nitric acid was superior to that of sulfuric acid.     

Preparation and characterization of iodine-doped mesoporous TiO2 by hydrothermal method

Iodine-doped mesoporous TiO₂ (I/TiO₂) was prepared by hydrothermal method, using tetrabutyl titanate as precursor, potassium iodate as iodine sources. The as-prepared I/TiO₂ catalysts were characterized by UV-vis, XRD, TEM, BET, TG/DTA, XPS and photoluminescence (PL) spectroscopy. Production of OH radicals on the I/TiO₂ surface was detected by the PL technique using terephthalic acid as a probe molecule. The effects of hydrothermal reaction temperature, calcination temperature and iodine doping content on the structure and properties of the catalysts were investigated. The results showed that iodine-doped TiO₂ calcinated at 300 °C have good anatase crystal. The optimal hydrothermal conditions have been determined to be that reaction temperature 120 °C, calcinated temperature 300 °C and added 1.16 mmol iodine dopants. The average particle size of I/TiO₂ synthesized under optimal condition (I-3 sample) is about 3.9 nm. The I-3 photocatalyst contains 100% anatase crystalline phase of TiO₂. BET specific surface area of I-3 sample is184.8 m² g⁻¹ and is 3.67 times that of pure TiO₂ (50.37 m² g⁻¹). Iodine in I/TiO₂ catalyst mainly exists in the form of I₂, and photoactivity of I/TiO₂ catalyst in visible light comes from photosensitize of I₂. I/TiO₂ catalysis shows very high efficiency for the degradation of phenol under visible light.     

Investigation of chemical decomposition of CCl4 on TiO2 near room temperature

Dissociative adsorption of CCl₄ on TiO₂ at 35 °C has been studied by Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, and electron spin resonance. CCl₄ decompose to form CO, CO₂, and CO₃ on the surface, at such a low temperature, in which CO₂ formation is not from CO oxidation on TiO₂, but CO₃ can be produced by CO and CO₂ adsorption. The Cl generated from CCl₄ decomposition is left on the surface and bonded to titanium ions. Mineralization of CCl₄ on TiO₂ involves the lattice oxygens. Thermodynamical driving force and possible reaction routes for CO and CO₂ formation in the CCl₄ decomposition on TiO₂ are discussed.     

Adsorption of CO, CO2 and NO molecules on a BaTiO3 (0 0 1) surface

Since the development of Scanning Tunnelling Microscopy (STM) technique, considerable attention has been devoted to various molecules adsorbed on various surfaces. Also, a new concept emerged with molecules on surfaces considered as nano machines by themselves. In this context, a thorough knowledge of surfaces and adsorbed molecules at an atomic scale are thus particularly invaluable. The present work describes the first Density Functional Theory (DFT) study of adsorption of CO, CO₂ and NO molecules on a BaTiO₃ surface following a first preliminary calculation of O and O₂ adsorption on the same surface. In the previously considered work, we found that a (0 0 1) surface with BaO termination is more stable than the one with TiO₂-termination. Consequently, we extended our study to CO, CO₂ and NO molecules adsorbed on a (0 0 1) surface with BaO termination. The present calculation was performed on a (1 × 1) cell with one monolayer of adsorbed molecules. Especially, a series of cases implying CO molecules adsorbed in various geometrical configurations has been examined. The corresponding adsorption energy varies in the range of −0.17 to −0.10 eV. The adsorption energy of a CO₂ molecule directly located above an O surface atom (called O_s) is of the order of −0.18 eV. The O-C distance length is then 1.24 Å and the O-C-O and O-C-O_s angles are 134.0° and 113.0°, respectively. For NO adsorption, the most important induced structural changes are the followings: (i) the N-O bond is broken when a NO molecule is absorbed on a Ba-O_s bridge site. In that case, N and O atoms are located above an O and a Ba surface atom, respectively, whereas the O-Ba-O_s and N-O_s-Ba angles are 106.5° and 63.0°, respectively. The N-O distance is as large as 2.58 Å and the adsorption energy is as much as −2.28 eV. (ii) In the second stable position, the NO molecule has its N atom adsorbed above an O_s atom, the N-O axis being tilted toward the Ba atom. The N-O_s-Ba angle is then 41.1° while the adsorption energy is only −0.10 eV. At last, the local densities of states around C, O as well as N atoms of the considered adsorbed molecules have also been discussed.     

A periodic model for the V2O5-TiO2 (anatase) catalyst. Stability of dimeric species

We present periodic DFT calculations to study the structure of the V₂O₅-TiO₂ (anatase) catalyst. Linear and cyclic dimeric V₂O₅ species represent the active phase. The support TiO₂ (anatase) is represented for the perfect (1 0 0) and (0 0 1) surfaces. The maximum interaction between the active phase and the support is favored, and low coverage is assumed. The most stable models allow the compensation of the surface dangling bonds, and can be understood as a continuation of the bulk anatase structure. The more suitable models for studying reactivity possess uncoordinated atoms available for reactivity, such as terminal oxygen atoms in V₂O₅. Relaxation plays an important role in the adsorption systems, and cannot be discarded when modeling the V₂O₅-anatase catalyst.     

Adsorption of CO2 on PbO at ambient temperature

The adsorption of CO₂ on metal oxides at ambient temperature received less study largely due to the small adsorption amount. However, the adsorption is of interest in refreshing the atmosphere of isolated spaces. It was shown in the present work that P_bO was sensitive to low concentration CO₂ in the presence of water. An XPS examination indicated that P_bO changed to P_bCO₃ after the adsorption of CO₂; therefore, the adsorption is chemical in nature. In order to enlarge the CO₂ capacity, P_bO was dispersed on the surface of a silica gel with large surface area (710 m²/g). Both CO₂ capacity and adsorption rate indicated that the optimal dispersion manner of P_bO is the mono-molecular layer surface coverage. Breakthrough experiments showed that the prepared adsorbent could effectively capture low-concentration CO₂ at ambient temperature and pressure yielding a CO₂ capacity of 59.1 mg g⁻¹. The saturated adsorbent was regenerated on heating at 380 °C and the CO₂ capability was recovered.     

A density functional theory study of ethylene adsorption on Ni10(1 1 1), Ni13(1 0 0) and Ni10(1 1 0) surface cluster models and Ni13 nanocluster

Ethylene adsorption was studied by use of DFT/B3LYP with basis set 6-31G(d,p) in Gaussian’03 software. It was found that ethylene has adsorbed molecularly on all clusters with π adsorption mode. Relative energy values were calculated to be −50.86 kcal/mol, −20.48 kcal/mol, −32.44 kcal/mol and −39.27 kcal/mol for Ni₁₃ nanocluster, Ni₁₀(1 1 1), Ni₁₃(1 0 0) and Ni₁₀(1 1 0) surface cluster models, respectively. Ethylene adsorption energy is inversely proportional to Ni coordination number when Ni₁₀(1 1 1), Ni₁₃(1 0 0) and Ni₁₀(1 1 0) cluster models and Ni₁₃ nanocluster are compared with each other.     

甲醇分子在金红石TiO2(110)和锐钛矿TiO2(001)表面吸附和反应的活性位点

通过高分辨的扫描隧道显微术研究并比较了金红石型TiO₂(110)-(1×1)和锐钛矿型TiO₂(001)-(1×4)两种表面的活性位点． 在金红石型TiO₂(110)-(1×1)表面, 观察到氧空位缺陷是O₂和CO₂分子的活性吸附位点,而五配位的Ti原子是水分子和甲醇分子的光催化反应活性位点．在锐钛矿型TiO₂(001)-(1×4)表面,观察到完全氧化的表面,Ti原子更可能是六配位的,H₂O和O₂分子均不易在这些Ti原子上吸附．经还原后表面出现富Ti的缺陷位点, 这些缺陷位点对H₂O和O₂分子表现出明显的活性． 锐钛矿型TiO₂(001)-(1×4)表面的吸附和反应活性并不具有很高的活性,某种程度上其表现出的活性似乎低于金红石型TiO₂(110)-(1×1)表面．     

Visible-light-activated Ce-Si co-doped TiO2 photocatalyst

To enhance the visible photocatalytic activity and thermal stability of TiO₂, Ce-Si co-doped TiO₂ materials were synthesized through a nonaqueous method of which the purpose was to reduce the aggregation between TiO₂ particles. The obtained materials maintained anatase phase and large surface area of 103.3 m² g⁻¹ even after calcined at 800 °C. The XPS results also indicated that Si was weaved into the lattice of TiO₂, and Ce mainly existed as oxides on the surface of TiO₂ particles. The doped Si might enhance surface area and suppress transformation from anatase to rutile, while the doped Ce might cause visible absorption and inhibit crystallite growth during heat treatment. Evaluated by decomposing dye Rhodamine B, visible photocatalytic activity of Ce-Si co-doped TiO₂ was obviously higher than that of pure TiO₂ and reached the maximum at Ce and Si contents of 0.5 mol% and 10 mol%.     

Role of Cl ions in photooxidation of propylene on TiO2 surface

The effect of Cl⁻ ions on photooxidation of propylene on TiO₂ semiconductor was investigated. Cl⁻/TiO₂ catalysts were prepared by annealing Degussa P25 TiO₂ in the gas flow of N₂ and Cl₂ under 100-400 °C. The photocatalytic oxidation of propylene was carried out in a continuous flow system, with the chromatograph to analyze the products on line. The experimental results showed that the activity of Cl⁻/TiO₂ catalysts increased as heat-treated temperature decreased. The activity of the sample heat-treated at 100 °C was about two times higher than that of pure TiO₂. Moreover, as to TiO₂, the main product of the propylene photocatalytic oxidation was CO₂, but with Cl⁻/TiO₂ catalysts, not only CO₂ but also trace CO was determined. The adsorbed species on TiO₂ surface before and after reaction were analyzed by X-ray photoelectron spectroscopy (XPS) and thermogravimetric/differential thermal analyses (TG-DTA) coupled to a mass spectrometer (MS). XPS analysis showed that there was Cl⁻ absorbed on the Cl⁻/TiO₂ surface, and the absorption amount of Cl⁻ decreased after the photooxidation reaction of propylene. TG-DTA-MS analysis confirmed chlorine absorbed on the surface of TiO₂ in the form of Cl⁻ ion. These results illuminated that absorbed Cl⁻ on the surface of TiO₂ formed a weak physical absorption on TiO₂ at low temperature, and subsequently participated in the photooxidation of propylene, finally removed from TiO₂ surface.     

Adsorption kinetics of alkanes on TiO2 nanotubesarray - structure-activity relationship

Presented are thermal desorption spectroscopy (TDS) measurements of iso-/n-butane adsorption on a variety of TiO₂ nanotubes (TiNTs) samples which are characterized by different crystal structures. The results are compared with a prior study on anatase(0 0 1) thin films grown on SrTiO₃(0 0 1). A distinct kinetic structure-activity relationship was present, i.e., the binding energies of the alkanes depend on the polymorph (anatase vs. mixed anatase/rutile) of TiO₂. A direct-fitting procedure of the TDS data has been applied to extract the kinetics parameters. The binding energies in the limit of zero coverage decrease as anatase thin film > amorphous-TiNTs ∼ polycrystalline anatase TiNTs > polycrystalline mixed anatase/rutile TiNTs.     

Theoretical modeling of photocatalytic active species on illuminated TiO2

A theoretical study of the H₂O and O₂ adsorption on an illuminated TiO₂ anatase surface is presented. The electronic structure and the spin distribution were examined by employing the DFT formalism and the BHandHLYP functional. The adsorbates geometries were fully optimized, including the cluster relaxation. Our results show the dissociative adsorption of the H₂O molecule on the photoactivated TiO₂ (0 0 1) surface. This reaction produces one hydroxyl group with radical character (OH) and an unpaired electron localized in the 5c-Ti atom. In case of the O₂ molecule, the non-dissociative chemisorption was obtained. This molecule shows one unpaired electron and a negative charge. In these sense, the adsorbed O₂ acts as a superoxide species (O₂⁻).     

The synthesis and kinetic growth of anisotropic silver particles loaded on TiO2 surface by photoelectrochemical reduction method

Silver nanorods with average diameters of 120-230 nm and aspect ratio of 1.7-5.0 were deposited on the surface of TiO₂ films by photoelectrochemical reduction of Ag⁺ to Ag under UV light. The composite films prepared on soda-lime glass substrates were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The results show that the TiO₂ film after UV irradiation in AgNO₃ solution is composed of anatase phase TiO₂ and metallic silver with face centered cubic structure. Other compounds cannot be found in the final films. The maximum deposition content of silver particles on the surface of TiO₂ film was obtained with the AgNO₃ concentration of 0.1 M. The kinetic growth rates of silver particles can be controlled by photocatalytic activity of TiO₂ films. The studies suggest that the growth rates of silver particles increase with the enhancement of photocatalytic activity of TiO₂ films. The maximum growth rate of silver particles loaded on TiO₂ films can be up to 0.353 nm min⁻¹ among samples 1#, 2# and 3#, while the corresponding apparent rate constant of TiO₂ is 1.751 × 10⁻³ min⁻¹.     

First-principles calculations on electronic structures of Fe-vacancy-codoped TiO2 anatase (1 0 1) surface

The electronic structures of Fe-doped TiO₂ anatase (1 0 1) surfaces have been investigated by all spin-polarized density functional theory (DFT) plane-wave pseudopotential method. The general gradient approximation (GGA)+U (Hubbard coefficient) method has been adopted to describe the exchange-correlation effects. Through the density functional calculations for the formation energies of various configurations, the complex of a substitutional Fe plus an O vacancy was found to form easily in the most range of O chemical potential. The calculated density of the states of the system of Fe-doped surface with a surface oxygen vacancy shows a band gap narrowing from 2.8 to 1.9 eV comparing with the pure surface due to the synergistic effects of surface Fe impurities with O vacancies. The system processes high visible light sensitivity and photocatalytic ability by decreasing extrinsic absorption energy. By comparing the partial DOS of some O and Ti atoms lying in the outermost and bottom layers of Fe-doped surfaces, it was found that the influence of Fe impurities on the electronic structure of the system is localized.     

Synthesis and CO2 capture property of high aspect-ratio Li2ZrO3 nanotubes arrays

High aspect-ratio Li₂ZrO₃ nanotubes were prepared by hydrothermal method using ZrO₂ nanotubes layers as templates. Characterizations of SEM, XRD, TEM and CO₂ adsorption were performed. The results showed that tetragonal Li₂ZrO₃ nanotubes arrays containing a little monoclinic ZrO₂ can be obtained using this simple method. The mean diameter of the nanotubes is approximately 150 nm and the corresponding specific surface area is 57.9 m² g⁻¹. Moreover, the obtained Li₂ZrO₃ nanotubes were thermally analyzed under a CO₂ flow to evaluate their CO₂ capture property. It was found that the as-prepared Li₂ZrO₃ nanotubes arrays would be an effective acceptor for CO₂ at high temperature.     

Effect of annealing on TiO2 nanoparticles

TiO₂ nanoparticles have been prepared by simple chemical precipitation method and annealed at different temperatures. The as-prepared TiO₂ are amorphous, and they transform into anatase phase on annealing at 450 °C, and rutile phase on annealing at 900 °C. The X-ray diffraction results showed that TiO₂ nanoparticles with grain size in the range of 21–24 nm for anatase phase and 69–74 nm for rutile phase have been obtained. FESEM images show the formation of TiO₂ nanoparticles with small size in structure. The FTIR and Raman spectra exhibited peaks corresponding to the anatase and rutile structure phases of TiO₂. Optical absorption studies reveal that the absorption edge shifts towards longer wavelength (red shift) with increase of annealing temperature.     

Synthesis of anatase TiO2 nanowires by modifying TiO2 nanoparticles using the microwave heating method

Anatase TiO₂ nanowires with a diameter of 5-10 nm and length of 500 nm to 2 μm have been successfully synthesized by modifying TiO₂ nanoparticles (P25) using the microwave heating method. The microwave power, reaction pressure, and reaction time for the synthesis of TiO₂ nanowires were 500 W, 0.5-3.0 MPa (corresponding to a temperature range of 175-260), and 40-70 min, respectively. X-ray diffraction (XRD), field-emission scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and the BET techniques were used to investigate the phase structures, morphologies, and specific surface areas of the TiO₂ nanowires. The effects of reaction time, pressure, and different post-treatment processes on the microstructures of TiO₂ nanowires were discussed. It has been shown that the microwave heating method is efficient in transforming TiO₂ nanoparticles to anatase TiO₂ nanowires.     

Surface modification of nanocrystalline anatase with CTAB in the acidic condition and its effects on photocatalytic activity and preferential growth of TiO2

The nanocrystalline anatase TiO₂, which was synthesized by a sol-hydrothermal process in advance, has successfully modified with cetyltrimethylammonium bromide (CTAB) in the acidic condition as well as in the basic condition. On the basis of the measurements of infrared spectrum and X-ray photoelectron spectroscopy of the resulting TiO₂, together with the phase-transfer experiments, it is suggested that the modification mechanism in the acidic condition is closely related to Br⁻. Interestingly, compared with un-modified TiO₂, the modified TiO₂ exhibits high photocatalytic activity for degrading Rhodamine B (RhB) solution, especially for that modified in the acid. The enhanced photocatalytic activity of modified TiO₂ in the acid is attributed to the role that the Br⁻ can easily capture photo-induced holes and then form active Br, consequently effectively inducing photocatalytic oxidation reactions, based on the surface photovoltage responses of the resulting TiO₂. After that, a one-pot sol-hydrothermal route at the temperature as low as 80 °C is developed to directly synthesize CTAB-modified nanocrystalline TiO₂ with a little preferred growth along 〈0 0 1〉 direction, which can be easily dispersed in the organic system and possess good photocatalytic performance. This work provides a feasible strategy to further improve the photocatalytic performance of nanocrystalline anatase and to synthesize TiO₂ nanocrystals with preferential growth.