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.     

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．     

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.     

Growth and structure of MBE grown TiO2 anatase films with rutile nano-crystallites

We have explored the systematics of TiO₂ polymorph nucleation during film growth by molecular beam epitaxy on perovskite substrates. The accidental lattice match between anatase (0 0 1) and LaAlO₃(0 0 1) or SrTiO₃(0 0 1) typically results in anatase nucleation at the interface. However, the growth conditions dictate whether or not rutile also nucleates, and the associated morphological and structural properties of the composite film. Four symmetry equivalent epitaxial orientations of rutile on anatase are observed when rutile nucleates as discrete particles on LaAlO₃(0 0 1). Such films constitute model systems for studying the anatase/rutile interface, which is of considerable current interest in photochemistry.     

Effect of thermal annealing on the structure and microstructure of TiO2 thin films

Nanostructured TiO₂ thin films have been prepared through chemical route using sol-gel and spin coating techniques. The deposited films were annealed in the temperature range 400–1000°C for 1 h. The structure and microstructure of the annealed films were characterized by GAXRD, micro-Raman spectroscopy and AFM. The as-deposited TiO₂ thin films are found to be amorphous. Micro-Raman and GAXRD results confirm the presence of the anatase phase and absence of the rutile phase for films annealed up to 700°C. The diffraction pattern of the film annealed at 800 to 1000°C contains peaks of both anatase and rutile reflections. The intensity of all peaks in micro-Raman and GAXRD patterns increased and their width (FWHM) decreased with increasing annealing temperature, demonstrating the improvement in the crystallinity of the annealed films. Phase transformation at higher annealing temperature involves a competition among three events such as: grain growth of anatase phase, conversion of anatase to rutile and grain growth of rutile phase. AFM image of the asdeposited films and annealed films indicated exponential grain growth at higher temperature.      

Photocatalytic reduction of potassium chromate by Zn-doped TiO2/Ti film catalyst

The aim of this work was to investigate the photocatalytic (PC) reduction of potassium chromate by Zn-doped TiO₂/Ti film catalysts. The film catalyst was prepared by plasma electrolytic oxidation method in H₂SO₄ solution with different dosages of ZnSO₄. The composition and structure of the film catalysts was studied by XRD, SEM and EPMA. The removal rate of potassium chromate was investigated under the conditions of the different dosages of ZnSO₄ and the initial concentration of chromate potassium, and the reductive product during the PC reduction process was analyzed. The results showed that the film catalyst was composed of anatase TiO₂ and rutile TiO₂ with the porous structure. When the dosage of ZnSO₄ was 0.2 g/L, the film catalyst presented the highest catalytic activity, which related to the amount and the crystal grain size of anatase TiO₂ in the film. The PC reduction of potassium chromate by the film catalyst obeyed the pseudo-first-order kinetic equation. The UV-vis spectrum and XPS analyses proved that chromate Cr(VI) was reduced to Cr(III), which existed in the form of insoluble Cr(OH)₃.     

Phase transition and thermodynamic properties of TiO2 from first-principles calculations

The pressure induced phase transitions of TiO2 from anatase to columbite structure and from rutile to columbite structure and the temperature induced phase transition from anatase to rutile structure and from columbite to rutile structure are investigated by ab initio plane-wave pseudopotential density functional theory method(DFT),together with quasi-harmonic Debye model.It is found that the zero-temperature transition pressures from anatase to columbite and from rutile to columbite are 4.55 GPa and 19.92 GPa,respectively.The zero-pressure transition temperatures from anatase to rutile and from columbite to rutile are 950 K and 1500 K,respectively.Our results are consistent with the available experimental data and other theoretical results.Moreover,the dependence of the normalized primitive cell volume V/V0 on pressure and the dependences of thermal expansion coefficient α on temperature and pressure are also obtained successfully.     

热处理对爆轰合成的纳米TiO_2混晶的结构相变的影响

采用爆轰法制备了纳米TiO2混晶体,初步研究了不同煅烧温度(600℃和720℃)和不同煅烧时间(1 h,2 h,3.5 h和5 h)对其微结构和结构相变行为的影响,并应用热动力学理论讨论了从锐钛矿相到金红石相的结构相变过程和相变机理.研究表明:随着煅烧温度的升高和煅烧时间的增加,纳米TiO2的粒径逐渐增大,混晶中金红石相的含量逐渐提高.与常规方法制备的纳米TiO2不同的是,在相同煅烧温度和煅烧时间下金红石相的平均生长速率明显低于锐钛矿相.锐钛矿相完全相变为金红石的温度也明显低于常规方法报道的相变温度.该研究会对控制纳米TiO2晶体尺寸和批量合成提供一定的理论和实验指导.     

Annealing effects on microstructural and optical properties of Nanostructured-TiO2 thin films prepared by sol-gel technique

In this paper we report on the effect of annealing on the microsctructural and optoelectronic properties of titanium dioxide (TiO₂) thin films prepared using sol-gel method onto silicon (Si) (100) and quartz substrates. The annealing temperatures range from 200 to 1000 °C. The Microstructural properties of annealed thin films were investigated by Thermal gravimetric analyses (TGA), X-ray diffraction (XRD) and Raman Spectroscopy. The surface morphology of the film was examined using Atomic Force Microscopy (AFM) method. The optical properties of TiO₂ thin films were characterized using UV-VIS and Spectroscopic ellipsometry. The results have shown that the TiO₂ thin films persist in the anatase phase even after annealing at 800 °C. The phase transformation from anatase to rutile occurred only when the films were annealed at 1000 °C. AFM studies revealed nanocrystalline structure where their shape and density depend strongly on the annealing temperatures. The elaborated nanostructured-TiO₂ thin films present a high transparency in the visible range. Spectroscopic ellipsometry (SE) study was used to determine the effect of annealing temperature on the thickness and on the optical constant of TiO₂ thin films. Spectroscopic ellipsometry and UV-VIS shows that the band gap of TiO₂ thin films was found to decrease when the annealing temperature increases. The Anatase phase was find to show higher photocatalytic activity than the rutile one.     

Photosensitization of nanocrystalline TiO2 film electrode with cadmium sulphoselenide

Nanocrystalline titanium dioxide (TiO₂) thin films composed of densely packed nanometer-sized grains have been successfully deposited onto an indium-doped-tin oxide (ITO) substrate. Then cadmium sulphoselenide (CdSSe) thin film was deposited onto pre-deposited TiO₂ to form a TiO₂/CdSSe film, at low temperature using a simple and inexpensive chemical method. The X-ray diffraction, selected area electron diffraction, scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and water contact angle techniques were used for film characterization. Purely rutile phase of TiO₂ with super-hydrophilic and densely packed nanometer-sized spherical grains of approximate diameter 30-40 (±2) nm was observed. The increase in optical absorption was observed after CdSSe film deposition. Nest like surface morphology of CdSSe on TiO₂ surface results in air trapping in the crevices which prevents water from adhering to the film with increase in water contact angle. Photosensitization of TiO₂ with CdSSe was confirmed with light illumination intensity of 80 mW/cm².     

Stabilization of the anatase phase in TiO2(Fe, PEG) nanostructured coatings

Multilayered TiO₂(Fe³⁺, PEG) films were deposited on glass and SiO₂/glass substrates by sol-gel dipping method. The influence of Fe³⁺ and PEG(polyethylene glycol) concentrations, the number of layers, the thermal treatment time and the temperature on the optical and microstructural properties of the TiO₂ films were studied.As-deposited TiO₂(Fe³⁺, PEG) films were very porous, but after the thermal treatment at 500 °C, the PEG decomposed and burned out to porosity decreasing. Homogeneous nanostructured films were obtained, where the amorphous and the anatase phases coexist. XRD analysis showed that no rutile phase is observed in the films deposited on SiO₂/glass as compared with those deposited directly on glass and that the presence of the anatase phase in the films without PEG is more evident in the three-layers film. The XRD intensity of the main peak of anatase from 25° decreases with the increase of PEG concentration.The optical gap of the TiO₂(Fe³⁺, PEG) films is found in 2.52-2.56 eV range and does not essentially depend on the PEG content.     

锐钛矿相和金红石相TiO2:Nb的光电性能研究

采用基于密度泛函理论的第一性原理计算了锐钛矿相和金红石相TiO₂:Nb的晶体结构、电子结构和光学性质. 结果表明, 在相等的摩尔掺杂浓度下(6.25%), 锐钛矿相TiO₂:Nb的导带底电子有效质量小于金红石相TiO₂:Nb, 且前者室温载流子浓度是后者的两倍左右, 即具有更大的施主杂质电离率, 从而解释了锐钛矿相TiO₂:Nb比金红石相TiO₂:Nb具有更优异电学性能的实验现象. 光学计算也表明锐钛矿相在可见光区有更大的透过率, 从而在理论上解释了锐钛矿相TiO₂:Nb比金红石相TiO₂:Nb更适于做透明导电材料的原因. 计算结果与实验数据能较好符合. 关键词： 2:Nb')" href="#">TiO₂:Nb 第一性原理 电子结构 光学性能     

Preparation and photoelectrochemical performance of Ag/graphene/TiO2 composite film

By dipping-lifting in sol-gel solution and reducing process, the graphene/TiO₂ composite film on the glass plate was first prepared. Then, the Ag/graphene/TiO₂ composite film was fabricated by interface reaction with AgNO₃ and N₂H₄·H₂O on the surface of graphene/TiO₂ composite film. The characterization results show that the uniform porous TiO₂ film is made up of the anatase crystal, and the Ag/graphene/TiO₂ composite film is constructed by doping or depositing graphene sheets and Ag nanoparticles on the surface of TiO₂ film. The photoelectrochemical measurement results indicate that the Ag/graphene/TiO₂ composite film has an excellent photoelectrochemical conversion property.     

Fabrication of nitrogen-doped TiO2 layer on titanium substrate

In this paper, macropores TiO₂ layer was fabricated on titanium substrates based on plasma based ion implantation (PBII). In order to increase the photodegradation efficiency of fabricated TiO₂ layer, two approaches are used: (1) preparation of macropores on TiO₂ layer to increase the total photodegradation area and (2) nitrogen doping (N-doping) to increase light absorption efficiency. The fabrication process of the N-doped macropores TiO₂ layer comprises four steps: firstly, helium plasma based ion implantation (He-PBII) is employed to generate He bubbles in substrate; secondly, oxygen plasma based ion implantation (O-PBII) and a followed annealing in air are executed to obtain rutile and anatase mixture TiO₂ phases; thirdly, He bubbles are exposed to the surface via an Ar ion sputter process; lastly, the samples are doped by nitrogen PBII (N-PBII). The photodegradation of Rhodamine B solution under Xe lamp indicates that the TiO₂ layer with surface macropores and N-doping has higher light photocatalysis efficiency.     

反应溅射法制备TiO2薄膜

报道了用反应溅射法制备TiO₂薄膜的实验研究.详细研究了氧分压、基底温度和退火温度对成膜结构的影响.制备出了具有金红石和锐钛矿晶体结构的TiO₂薄膜.分析了金红石和锐钛矿晶体的形成条件,并对薄膜的表面形貌进行了测量. 关键词： 反应溅射 2薄膜')" href="#">TiO₂薄膜     

Different effects of cerium ions doping on properties of anatase and rutile TiO2

Pure and Ce⁴⁺ doped anatase and rutile TiO₂ were prepared by hydrothermal methods and characterized by XRD, TEM, UV-vis diffusion spectroscopy, and XPS measurements. The photocatalytic reactivity of the catalysts was evaluated by the photodegradation of Rhodamine B (RB) under ultraviolet irradiation. The photocatalytic efficiency of the rutile sample doped with an appropriate amount of Ce⁴⁺ was enhanced while all Ce⁴⁺ doped anatase samples showed a much lower activity than pure anatase. The reasons were discussed     

Effect of crystalline structure of TiO2 substrates on initial growth of atomic layer deposited Ru thin films

Ru thin films were grown on polymorphic TiO₂ thin film substrates at 230 and 250 °C by atomic layer deposition using 2,4-(dimethylpentadienyl)(ethylcyclopentadienyl)Ru and an O₂ gas. While the Ru films grown on amorphous and rutile TiO₂ substrates showed a relatively long incubation cycle number of approximately 350 and 100 at 230 and 250 °C, respectively, the Ru films grown on anatase TiO₂ substrates exhibited a significantly shorter incubation delay which was attributed to the catalytic activity of anatase TiO₂. This difference in the incubation cycle affected the surface morphology of the Ru films on different TiO₂ substrates.     

Spectroscopic studies of interfacial structures of CeO2-TiO2 mixed oxides

We have investigated the geometric and electronic structures of the cerium oxide (CeO₂)-titanium dioxide (TiO₂) mixed oxides with various Ce/TiO₂ weight ratios prepared by the sol-gel method in detail by means of X-ray diffraction (XRD), high-resolution X-ray photoelectron spectroscopy (XPS), Raman spectroscopy excited by 325 and 514.5 nm lasers, and scanning electron microscope (SEM). Existence of cerium effectively inhibits the phase transition of TiO₂ from the anatase phase to the rutile phase. XRD peaks of TiO₂ anatase attenuate continuously with the increasing amount of CeO₂ in the mixed oxide, but the XRD peaks of cubic CeO₂ appear only after the weight ratio of Ce/TiO₂ reaches 0.50. The average crystalline sizes of TiO₂ anatase and cubic CeO₂ in CeO₂-TiO₂ mixed oxides are smaller than those in the corresponding individual TiO₂ anatase and cubic CeO₂. Raman spectroscopy excited by the 514.5 nm laser detects CeO₂ after the weight ratio of Ce/TiO₂ reaches 0.70 whereas Raman spectroscopy excited by the 325 nm laser detects CeO₂ after the weight ratio of Ce/TiO₂ reaches 0.90. XPS results demonstrate that Ti exists in the form of Ti⁴⁺ in the CeO₂-TiO₂ mixed oxide. Ce is completely in the form of Ce³⁺ in the mixed oxides with a 0.05 weight ratio of Ce/TiO₂. With the increasing weight ratio of Ce/TiO₂, Ce⁴⁺ dominates. On basis of these results, we proposed that CeO₂ initially nucleates at the defects (oxygen vacancies) within TiO₂ anatase, forming an interface bridged with oxygen between CeO₂ and TiO₂ anatase. At the interface, Ce species cannot substitute Ti⁴⁺ in the lattice of TiO₂ anatase whereas Ti⁴⁺ can substitute Ce⁴⁺ in the lattice of cubic CeO₂. The decreasing concentration of oxygen vacancies, the Ti-O-Ce interface, and the decreasing average crystalline size of TiO₂ anatase act to inhibit the phase transformation of TiO₂ anatase. With the increasing amounts of CeO₂, the CeO₂ clusters continuously grow and form cubic CeO₂ nanocrystals. Spectroscopic results strongly demonstrate that the surface region of CeO₂-TiO₂ mixed oxide is enriched with TiO₂.     

Effect of phase structures on the formation rate of hydroxyl radicals on the surface of TiO2

To study the relationship between the phase structures of TiO₂ and the photoinduced hydroxyl radicals (OH), TiO₂ nanocrystallines were synthesized by a hydrolysis-precipitate method using tetrabutylorthotitanate (TBOT) as precursor, and then calcined at 450, 600, 700, 800 and 900 °C for 2 h, respectively. The calcined samples were characterized by X-ray diffraction and N₂ sorption. The formation rate of OH on the surface of UV-illuminated TiO₂ was detected by the photoluminescence (PL) technique using terephthalic acid as a probe molecule. The results show that with increasing calcined temperatures, the amorphous (Am) TiO₂ precursor begins to turn into anatase (A) at 450 °C and rutile (R) phase appears at 600 °C, which is completely turned into the rutile phase at 900 °C. The BET specific surface areas of the catalyst decrease as the calcined temperatures increase. TiO₂ sample calcined at 600 °C, with a mixed phase of anatase and rutile, shows the highestOH formation rate, and the order of the OH formation rate is as follows: A+R>A>R>Am. Phase structures of TiO₂ play a more important role than specific surface areas in the OH formation rate. Two phase structure of anatase and rutile with a proper ratio is beneficial to the OH formation due to decrease of the combination rate of photo-generated electrons and holes. Our experimental result implies that the mixed phase of anatase and rutile can markedly enhance the photocatalytic activity of TiO₂.     

Photocatalytic activity of dc magnetron sputter deposited amorphous TiO2 thin films

For photocatalytic thin film applications TiO₂ is one of the most important materials. The most studied TiO₂ crystal phase is anatase, though also rutile and brookite show good photoactivity. Usually anatase or a mixture of rutile and anatase is applied for powder or thin film catalysts. It has been claimed that amorphous films do not exhibit any or only a very low photocatalytic activity.We have deposited amorphous thin films by dc magnetron sputtering from sub-stoichiometric TiO_2−x targets. The coatings are transparent and show a photocatalytic activity half of that of a thin layer of spin-coated reference photocatalyst powder. Annealing the thin films to yield anatase crystallization more than doubles their photocatalytic activity. At the same film thickness these thin films show the same activity as a commercially available photocatalytic coating.The dependence of the photocatalytic activity on deposition parameters like gas pressure and sputter power is discussed. A decrease in film density, as deduced from the refractive index and the microstructure, resulted in an increase in photocatalytic activity. Film thickness has a marked influence on the photocatalytic activity, showing a strong increase up to 300-400 nm, followed by a much shallower slope.