High surface area crystalline titanium dioxide: potential and limits in electrochemical energy storage and catalysis

Titanium dioxide is one of the most intensely studied oxides due to its interesting electrochemical and photocatalytic properties and it is widely applied, for example in photocatalysis, electrochemical energy storage, in white pigments, as support in catalysis, etc. Common synthesis methods of titanium dioxide typically require a high temperature step to crystallize the amorphous material into one of the polymorphs of titania, e.g. anatase, brookite and rutile, thus resulting in larger particles and mostly non-porous materials. Only recently, low temperature solution-based protocols gave access to crystalline titania with higher degree of control over the formed polymorph and its intra- or interparticle porosity. The present work critically reviews the formation of crystalline nanoscale titania particles via solution-based approaches without thermal treatment, with special focus on the resulting polymorphs, crystal morphology, surface area, and particle dimensions. Special emphasis is given to sol-gel processes via glycolated precursor molecules as well as the miniemulsion technique. The functional properties of these materials and the differences to chemically identical, non-porous materials are illustrated using heterogeneous catalysis and electrochemical energy storage (battery materials) as example.     

Photocatalytic titania based surfaces: Environmental benefits

The use of photocatalytic titania nanoparticles in the development of self-cleaning and de-polluting paints and microbiological surfaces is demonstrated. In the former case surface erosion and sensitised photooxidation is shown to be controlled by the use of catalytic grades of anatase nanoparticles. For environmental applications in the development of coatings and cementitious materials for destroying atmospheric pollutants such as nitrogen oxides (NOX) stable substrates are also illustrated with photocatalytic nanoparticles. Here porosity of the coatings through calcium carbonate doping is shown to be crucial in the control of the effective destruction of atmospheric NOX gases. Good environmental stability of the coatings is also crucial for long-term durability and this aspect is examined for a variety of material substrates. For the development of microbiological substrates for the destruction of harmful bacteria/fungi effective nanoparticle anatase titania is shown to be important with hydrated high surface area particles giving the greatest activity. Data from commercial pilot studies is used to signify the important practicalities of this type of new technology.     

Characterization of titanium dioxide nanoparticles using molecular dynamics simulations

Molecular dynamics simulations of titanium dioxide nanoparticles in the three commonly occurring phases (anatase, brookite, and rutile) are reported. The structural properties inferred by simulated X-ray diffraction patterns of the nanoparticles were investigated. The titanium-oxygen bond length as a function of size, phase, and temperature was determined and was found to be dependent on the coordination environment of the titanium and independent of phase and size. The equilibrium Ti-O bond length is 1.86 A for a four-coordinated titanium ion, 1.92 A for a five-coordinated titanium ion, and 1.94 A for an octahedral titanium ion. Smaller nanoparticles are characterized by a higher fraction of titanium ions that are four and five coordinated, due to the larger surface area-to-volume ratios. The surface energies for anatase, rutile, and brookite particles were reported. The surface energy of the nanoparticle increases and approaches a constant value as the particle gets bigger. The surface energies of small rutile particles are higher than that for anatase particles of a similar size, consistent with anatase being the more stable phase of nanocrystalline titanium dioxide.     

Hydrated alumina surface treatment on a titanium dioxide pigment: changes at acidic and basic pH

Amphoteric, inorganic particles used as pigments and extenders in dried coatings are not completely inert, particularly when exposed to acidity similar to atmospheric pollution, or when in a water-borne paint suspension at alkaline pH. Changes to these materials may harm the integrity of the dried coating and thus its performance during weathering or affect the colloidal stability during storage within liquid paint. The effect on aqueous titanium dioxide pigment suspensions was examined under various pH conditions. A substantial amount of aluminum was dissolved, but little silicon or titanium. Dissolution occurred at both acid and alkali pH leaving a different balance of hydrated alumina phases and overall surface composition. Changes in particle surface were apparent in topography, colloidal properties and by thermogravimetry. Such changes show that other, more complicated, changes may be possible, particularly in an aqueous paint medium where there are many other ingredients in solution or suspension.     

Effects of Ti Addition on Alumina/Titania Composite Aerogels Synthesized by Sol–Gel Process and Supercritical Ethanol Drying

Alumina/titania composite aerogels with different titania contents were synthesized by the sol–gel process and supercritical ethanol drying. The structures and morphologies of synthesized aerogels were analyzed by X‐ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetry, and N₂ adsorption–desorption tests. Supercritical ethanol drying induced the crystallization of titania, which prompted the transformation of the structure from pseudoboehmite to γ‐Al₂O₃ . Reversely, alumina retarded the anatase‐to‐rutile transformation of titania. The content of titania significantly affected the structure and morphology of alumina/titania composite aerogels. A high content of titania (≥40%) resulted in the phase separation of titania particles, which grew to form the anatase phase octahedral particles with well‐developed facets. When the titania content was low, titania particles could be homogeneously dispersed in alumina particles to form spherical clusters with the poor crystallinity. Titania particles were in the anatase phase, and no rutile phase was formed until the temperature rose to 1000°C. In addition, titania addition resulted in a decrease in the specific surface area (SSA) of alumina aerogels because the SSA of titania was lower than that of alumina aerogels.     

Synthesis of Titanium Dioxide Nanoparticles for Photocatalytic Degradation of Cyanide in Wastewater

Cyanide is highly toxic, and although various approaches have been employed for its remediation, these methods do not have the required performance. This report describes the synthesis of titanium dioxide nanoparticles with maximum photocatalytic properties and their application for the treatment of cyanide in wastewater. Three types of crystalline titanium nanoparticles were synthesized: anatase, rutile, and a biphasic mix of rutile and anatase. The phase and microscopic properties were characterized by X-ray diffraction and scanning electron microscopy. The specific surfaces of the particles were determined, and their photocatalytic activity was studied under the ultraviolet irradiation for cyanide degradation. The results indicate that an increase in sulfate ion leads to changes in the phase ratios of rutile to anatase. The diameter of the nanoparticles was between 18 and 22 nm, and they displayed high photocatalytic properties. The biphasic form of the titanium dioxide nanoparticles demonstrated the highest removal of cyanide. Complete degradation of cyanide was observed in a pilot scale experiment.     

Large-scale preparation of ordered titania nanorods with enhanced photocatalytic activity

A titania layer with ordered nanostructures is expected to be of high photocatalytic activity due mainly to its high specific surface area. In the present work, large-area films with ordered titania nanorods were deposited on titanium substrates through a solution approach. The nanorods, with the phase composition of a mixture of anatase and rutile, grew on top of a condensed anatase interlayer along mainly the rutile [001]-axis. The photocatalytic activity was evaluated by decomposing rhodamine B in water and compared with the general sol-gel derived titania films and a commercial DP-25 titania coating. It is found that the as-deposited titania nanorods exhibited extremely high initial photocatalytic activity but declined to a poor value after the consumption of beneficial oxidative peroxo complexes coordinated to Ti(IV). A subsequent thermal treatment eliminated such complexes but at the same time improved the crystallinity of the titania nanorods. The photocatalytic activity of the thermally treated titania nanorods was stable and significantly higher than that of the sol-gel derived film and commercial DP-25 coating.     

Titania nanotubes (TNTs) prepared through the complex compound of gallic acid with titanium; examining photocatalytic degradation of the obtained TNTs

It was for the first time that the complex compound of gallic acid with titanium (IV) salt was used as a precursor to synthesize titania nanotubes. The study was separated into four main sections; (I) synthesizing the complex of titanium with gallic acid, (II) synthesizing anatase and rutile phases through thermal decomposing of the complex, (III) investigating the possibility to synthesize titania nanotubes from the rutile and anatase phases, and (IV) photocatalytic ability of all the nanoparticles.Different methods were applied to analysis, including X-ray diffraction, 1H NMR, FT-IR spectroscopy, elemental analysis, quantum-chemical modeling, Raman spectroscopy, thermal analysis, photoluminescence, BET analysis (to investigate the specific surface activity, total pore volume), EDX, electron microscopy (SEM), acceleration voltages, electrical conductivity, BJH method (to determine average pore diameter), and UV-Vis spectroscopy.We illustrated the possibility of the synthesis of the titania nanotubes from the anatase phase, while rutile phase was not turned to a tube shape.The photocatalytic ability of the obtained nanoparticles was tested by degrading bromophenol blue, as an organic pollutant, under weak light. TiO₂ in the form of nanotubes could reduce the concentration of bromophenol blue to 82%, as well as the rutile phase - to 70%, and finally anatase as nan-spheres to 36%.     

Thermal behaviour of titanium dioxide nanoparticles prepared by precipitation from aqueous solutions

Thermogravimetry-differential thermal analysis, emanation thermal analysis, mass spectrometry detection, Fourier transform infrared and XRD were used to characterize thermal behaviour of titanium dioxide photocatalyst precursors prepared by precipitation at various conditions from peroxotitanic acid sols. The transmission electron microscopy HRTEM technique was used to characterize the surface microstructure. The sols contained TiO₂ anatase particles of approximately 10 nm in diameter. During heating of the air dried samples, their chemical degradation took place giving rise to anatase. On further heating, the crystallization of anatase and formation of rutile phase was observed. To test the photocatalytic activity of the samples, the decomposition of 4-chlorophenol (4-CP) under ultraviolet and visible irradiation was monitored. It was shown that photocatalytic activities of the samples are comparable to the Degussa P25 photocatalyst reference material.     

Aerosol-assisted fabrication of mesoporous titania spheres with crystallized anatase structures and investigation of their photocatalitic properties

We demonstrate practical aerosol-assisted approach to synthesize spherical mesoporous titania particles with high surface areas. Scanning electron microscopy observation of the spray-dried products clearly shows spherical morphology. To remove surfactants and enhance crystallinity, the spray-dried products are calcined under various temperatures. The crystalline structures inside the particles are carefully detected by wide-angle XRD measurements. With increase of the calcination temperatures, anatase crystal growth proceeds and transformation from anatase to rutile is occurred. The effect of various calcination temperatures on the mesostructures is also studied by using N₂ adsorption desorption isotherms. The mesoporous titania particles calcined at 350, 400, and 500 °C exhibit type IV isotherms with a capillary condensation step and shows a hysteresis loop, which is a characteristic of mesoporous materials. The reduction in the surface areas and the pore volumes is confirmed by increasing the calcination temperatures, while the average pore diameters are increased gradually. This is attributed to the distortion of the mesostructures due to the grain growth of the anatase phase and the transformation to the rutile phase during the calcination process. As a preliminary experimental photocatalytic activity, oxidative decomposition of acetaldehyde under UV irradiation is examined. The mesoporous titania calcined at 400 °C shows the highest photocatalytic activity, due to both high surface area and well-developed anatase crystalline phase.     

Eu3＋、Si4＋共掺杂TiO2光催化剂的协同效应

采用溶胶-凝胶-浸渍法制备了Eu/Ti/Si纳米光催化剂, 并通过XRD、FT-IR、EPR等进行了表征.结果表明,掺入Eu3＋和Si4＋, 阻止了TiO2从锐钛矿晶型向金红石晶型的转变, 使TiO2的粒径减小, 且Eu3＋能够促进Si4＋进入TiO2的晶格中.以甲基橙为光催化反应模型化合物, 考察了光催化剂的活性.测定了甲基橙在不同光催化剂上的吸附常数,探讨了催化剂对甲基橙的吸附机理. Eu3＋和Si4＋的最佳掺入量分别为wEu=0.03％、wSiO2=39.06％,且Eu3＋和Si4＋同时掺入TiO2光催化剂产生协同效应.讨论了光催化活性与催化剂性质的关系.     

Hydrothermal synthesis, characterization, and photocatalytic performance of silica-modified titanium dioxide nanoparticles

Silica-modified titanium dioxides were prepared by a hydrothermal method and then characterized by XRD, FT-IR, XPS, TEM, and UV-visible spectroscopy. The silica-modified titanium dioxides were in anatase phase and had large surface areas. There was strong interaction between SiO2 and TiO2, and TiOSi bonds formed during the hydrothermal process. The addition of silica in TiO2 particles could effectively suppress the formation of the rutile phase and the growth of titanium dioxide crystals. DRS spectra proved an increase in the band-gap transition with the increase of silica. The silica-modified TiO2 nanoparticles exhibited better photocatalytic activity, which increased with the silica amount, in comparison with pure TiO2 nanoparticles. Due to better thermal stability, the photocatalytic activity of the silica-modified TiO2 sample held good photocatalytic activity even after calcined at 1273 K.     

Eu~(3 )、Si~(4 )共掺杂TiO_2光催化剂的协同效应

采用溶胶-凝胶-浸渍法制备了Eu/Ti/Si纳米光催化剂,并通过XRD、FT-IR、EPR等进行了表征.结果表明,掺入Eu3 和Si4 ,阻止了TiO2从锐钛矿晶型向金红石晶型的转变,使TiO2的粒径减小,且Eu3 能够促进Si4 进入TiO2的晶格中.以甲基橙为光催化反应模型化合物,考察了光催化剂的活性.测定了甲基橙在不同光催化剂上的吸附常数,探讨了催化剂对甲基橙的吸附机理.Eu3 和Si4 的最佳掺入量分别为wEu=0.03%、wSiO2=39.06%,且Eu3 和Si4 同时掺入TiO2光催化剂产生协同效应.讨论了光催化活性与催化剂性质的关系.     

Visible light photocatalyst: iodine-doped mesoporous titania with a bicrystalline framework

Iodine-doped (I-doped) mesoporous titania with a bicrystalline (anatase and rutile) framework was synthesized by a two-step template hydrothermal synthesis route. I-doped titania with anatase structure was also synthesized without the use of a block copolymer as a template. The resultant titania samples were characterized by X-ray diffraction, Raman spectroscopy, Fourier transform infrared, nitrogen adsorption, transmission electron microscopy, X-ray photoelectron spectroscopy, and UV-visible absorption spectroscopy. Both I-doped titania samples, with and without template, show much better photocatalytic activity than commercial P25 titania in the photodegradation of methylene blue under the irradiation of visible light (>420 nm) and UV-visible light. Furthermore, I-doped mesoporous titania with a bicrystalline framework exhibits better activity than I-doped titania with anatase structure. The effect of rutile phase in titania on the adsorptive capacity of water and surface hydroxyl, and photocatalytic activity was investigated in detail. The excellent performance of I-doped mesoporous titania under both visible light and UV-visible light can be attributed to the combined effects of bicrystalline framework, high crystallinity, large surface area, mesoporous structure, and high visible light absorption induced by I-doping.     

Effect of polycrystalline structure of TiO2 particles on the light scattering efficiency

The opacifying power of synthesized polycrystalline TiO2 particles in a cellulose matrix was found experimentally and theoretically to be superior to that of a commercial rutile pigment, depending on crystal structure of the synthesized particles. The crystal structure of the particles was varied by calcination of amorphous titania nanoparticles at different temperatures and was characterized using SEM, TEM, and XRD. Polycrystalline anatase pigments had less opacifying power than commercial rutile, while polycrystalline pigments containing a one-to-one mixture of anatase and rutile had similar opacifying power as the commercial pigment if they have a similar overall particle size. The polycrystalline rutile pigments composed of a linear linkage of several individual rutile crystals gave 6% more opacity than the commercial rutile pigment. Theoretical light scattering calculations using the T-matrix method showed the light scattering efficiency of linearly arranged polycrystalline rutile particles to depend on number and size of crystals composing the particle. It is suggested that the efficiency of rutile pigments can be increased dramatically by controlling both the primary crystal size and the overall particle size. It is believed that the greater than expected light scattering efficiency of the biphasic pigment results from reflection and refraction of light at the grain boundaries between crystals of different phase, which have different refractive indices.     

Electrophotographic and microwave photodielectric studies on titanium dioxide pigments in the solid state

In this paper, we report some novel preliminary findings on the photoactivity of titanium dioxide pigments using photoconductive and microwave dielectric techniques. A variety of pigment types were investigated by both methods, including the two crystalline forms of titanium dioxide, anatase and rutile, and a variety of coated pigments. Analysis of the data obtained indicates that there are possible relationships between the photoconductive and photodielectric results, and that these may be used to characterize the pigment types rapidly. Photoconductive measurements were carried out on pigmented films of poly(N-vinylcarbazole) (PVK). Uncoated pigments were found to be more photoconductive than coated pigments with the anatase modification being the more active. It is believed that the pigments act as “trapping” sites to the holes produced by PVK, and that the more photoactive the pigment, the easier it is to regenerate the holes. Various factors influence the band gap of the pigment and these have a significant effect on the photoactivity and photoconductivity of the pigment samples. These include the presence of traps and recombination centres (present as coatings on the surface of the pigment particle) and impurities which can act as acceptors or donors.

Microwave dielectric measurements were carried out on the different anatase and rutile pigments, each exhibiting a different microwave resonant frequency loss depending on the nature of the crystalline modification and the coating. However, on illumination on the pigments with polychromatic light in the microwave cavity, the resonant frequency losses exhibit shifts, the nature of which depend on the pigment type and the coating. Thus the anatase pigments exhibit greater responses than the rutile pigments, particularly with regard to the shift in the resonant frequency values and the change in the Q factor of the resonant peak. The resonant frequency values of the anatase samples are also higher than those obtained for the rutile samples. Furthermore, the frequency shifts are in opposite directions, with the anatase modification exhibiting a more rapid shift to lower frequencies and rutile a slower shift to higher frequencies. It appears that, when the anatase samples are irradiated, their dielectric properties change from those characteristic of a conductor-like material to those of an insulator-like material. However, these changes are reversible once the illumination is terminated. With the rutile samples, irradiation increases the resonant frequency values and hence their dielectric constants. Thus the pigments appear to become more like conductors.     

微乳法合成纳米SiO2/TiO2及其光催化性能

采用聚乙二醇辛基苯基醚(Triton X-100)/正己醇/环己烷/氨水微乳体系合成了纳米TiO2和SiO2/TiO2复合物,用X射线衍射、红外光谱和透射电镜对其结构进行了表征,并以甲基橙降解评价了其光催化性能,讨论了SiO2/TiO2摩尔比、晶相组成及粒径与光催化活性的关系.结果表明,SiO2/TiO2催化剂中形成了新的Ti-O-Si键和无定形SiO2;在纳米TiO2中复合SiO2能有效抑制锐钛矿向金红石的转变,增加锐钛矿的稳定性,并阻止TiO2晶粒的聚集生长.催化剂的光催化活性随金红石含量的增加而降低,加入适量SiO2能明显提高TiO2的光催化活性,其中摩尔比为1/7的SiO2/TiO2光催化活性最高.     

Synthesis and characterization of nano titania powder with high photoactivity for gas-phase photo-oxidation of benzene from TiOCl(2) aqueous solution at low temperatures

Nano rutile, anatase, and bicrystalline (anatase + brookite) titania powders with an average crystal size of below 10 nm are prepared from aqueous TiOCl(2) solution at low temperatures by adjusting pH values of the starting solution and adding different additives. Adding a small amount of octyl phenol poly(ethylene oxide) into aqueous TiOCl(2) solution leads to the change of particle morphologies of obtained nano titania from needlelike to nano spherical rutile crystals. Amorphous-anatase transformation of titania could proceed in liquid-solid reaction at low temperatures, even at room temperature. A formation mechanism of rutile, anatase, and brookite titania was proposed. It is found that H(+) or H(3)O(+) plays a catalytic role in the phase transformation from amorphous to anatase titania and that the presence of a small amount of SO(4)(2)(-) ion is unfavorable to the formation of both rutile and brookite. By carefully adjusting preparation conditions, nano pure anatase with higher surface area, good crystallinity, and a lower recombination rate of photoexcited electrons and holes was obtained. This nano pure anatase showed a very good photocatalytic activity for gas-phase photo-oxidation of benzene.     

Synthesis of TiO<Subscript>2</Subscript> nano powder by the sol-gel method and its use as a photocatalyst

In this work the titanium dioxide powder was prepared by the optimized and simple Sol-Gel method and then characterized. The gelling pH was set to values of 3 (TiO₂-A), 7 (TiO₂-N) and 9 (TiO₂-B) to observe the effect on the properties of the material. In these three cases nanoparticulated materials were obtained with particle sizes between 10nm and 20nm. The larger surface areas were obtained at pH 3, which is several times larger than the others. Furthermore, with the gelling condition pH 3, it was possible to synthesize pure anatase phase titania. Some preliminary results on the test of the photocatalytic activity of the synthesized materials in the reduction of nitric oxide are presented. Based on these results the nanoparticle TiO2, which was prepared in acidic pH 3 with the pure anatase phase and the lowest particle size has the highest reactivity for the photocatalytic reduction of nitric oxide.     

Low Temperature Sol-Gel Processed Photocatalytic Titania Coating

Transparent thin film coatings of sol-gel derived titanium dioxide were produced on cotton fabrics at a low temperature of 150°C. The photocatalytic activity of the formed layers was studied by means of their antibacterial property. SEM images show the formation of continuous layers of titanium dioxide with grains of about 20 nm in diameter. The UV-blocking effect of titania coatings was also studied. XRD patterns revealed the existence of anatase phase in a small scale within the titania layers.