Synthesis of nano-sized anatase TiO2 with reactive {001} facets using lamellar protonated titanate as precursor

Nano-sized anatase TiO(2) with exposed {001} facets was synthesized from lamellar protonated titanate precursor. Owing to small size (ca. 11 nm) and high surface area (155 m(2) g(-1)), the crystals with 26.1% {001} facets exhibited markedly superior photoactivity to reference ca. 76 nm anatase TiO(2) nanosheets with 88.4% {001} facets.     

Hierarchical TiO2 nanospheres with dominant {001} facets: facile synthesis, growth mechanism, and photocatalytic activity

Hierarchical TiO(2) nanospheres with controlled surface morphologies and dominant {001} facets were directly synthesized from Ti powder by a facile, one-pot, hydrothermal method. The obtained hierarchical TiO(2) nanospheres have a uniform size of 400-500?nm and remarkable 78?% fraction of {001} facets. The influence of the reaction temperature, amount of HF, and reaction time on the morphology and the exposed facets was systematically studied. A possible growth mechanism speculates that Ti powder first dissolves in HF solution, and then flowerlike TiO(2) nanostructures are formed by assembly of TiO(2) nanocrystals. Because of the high concentration of HF in the early stage, these TiO(2) nanostructures were etched, and hollow structures formed on the surface. After the F(-) ions were effectively absorbed on the crystal surfaces, {001} facets appear and grow steadily. At the same time, the {101} facets also grow and meet the {101} facets from adjacent truncated tetragonal pyramids, causing coalescence of these facets and formation of nanospheres with dominant {001} facets. With further extension of the reaction time, single-crystal {001} facets of hierarchical TiO(2) nanospheres are dissolved and TiO(2) nanospheres with dominant {101} facets are obtained. The photocatalytic activities of the hierarchical TiO(2) nanospheres were evaluated and found to be closely related to the exposed {001} facets. Owing to the special hierarchical architecture and high percentage of exposed {001} facets, the TiO(2) nanospheres exhibit much enhanced photocatalytic efficiency (almost fourfold) compared to P25 TiO(2) as a benchmark material. This study provides new insight into crystal-facet engineering of anatase TiO(2) nanostructures with high percentage of {001} facets as well as opportunities for controllable synthesis of 3D hierarchical nanostructures.     

Facile fabrication of anatase TiO2 microspheres on solid substrates and surface crystal facet transformation from {001} to {101}

Anatase TiO(2) microspheres with controlled surface morphologies and exposed crystal facets were directly synthesized on metal titanium foil substrates by means of a facile, one-pot hydrothermal method without use of any templating reagent. The obtained products were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelecron spectroscopy (XPS), and the focused ion beam (FIB) technique. The sizes of the resultant microspheres ranged from 1.1 to 2.1 μm. The transformation of anatase TiO(2) microspheres with exposed {001} facets surface to nanosheets surface with {101} facets was achieved by simply controlling the hydrothermal reaction time. The anatase TiO(2) microspheres with exposed square-shaped plane {001} facets were obtained by controlling the reaction time at 1 h. The prolonged reaction time transforms the anatase TiO(2) microspheres with exposed square-shaped plane {001} facets to eroded {001} facets then to a nanosheet surface with exposed {101} facets. With hydrothermal synthesis, the surface morphological structure and crystal facets formation are highly dependent on dissolution/deposition processes, which can be strongly influenced by attributes, such as pH of the reaction media, the total concentration of dissolved and suspended titanium species, and the concentration of fluoride in the reaction solution. The changes of these attributes during the hydrothermal process were therefore measured and used to illustrate the morphology and crystal-facet transformation processes of anatase TiO(2) microspheres. The surface morphologies and crystal-facet transformations during hydrothermal processes were found to be governed by the compositional changes of the reaction media, driven by dynamically shifted dissolution/deposition equilibria. The photocatalytic activities of the photoanodes made of anatase TiO(2) microspheres were evaluated. The experimental results demonstrated that the photocatalytic activity of anatase TiO(2) microspheres with exposed {001} facets was found to be 1.5 times higher than that of the anatase TiO(2) microspheres with exposed {101} facets.     

Tunable photocatalytic selectivity of TiO2 films consisted of flower-like microspheres with exposed {001} facets

TiO(2) films composed of flower-like TiO(2) microspheres with exposed {001} facets were synthesized by a simple one-pot hydrothermal method and exhibited tunable photocatalytic selectivity towards decomposition of azo dyes in water by modifying the surface of TiO(2) microspheres as well as by varying the degree of etching of {001} facets.     

Microwave-induced synthesis of porous single-crystal-like TiO2 with excellent lithium storage properties

Porous anatase TiO(2) single crystal architectures with large specific surface area and remarkable crystalline phase-stability were fabricated via a green microwave-assisted process. Ionic liquid was chosen as both an essential structure-directing agent for the formation of the {001} facets exposed TiO(2) and an etching agent source for selective erosion of the exposed {001} facets, leading to robust porous framework with exposed {101} facets. These porous anatase single crystals were thermally stable up to 800 °C, indicating excellent structure stability. The product showed stable cyclability at high current rate, better reversibility, and high Coulumbic efficiency of 100% for lithium storage.     

Anatase TiO(2) microspheres with exposed mirror-like plane {001} facets for high performance dye-sensitized solar cells (DSSCs)

Anatase TiO(2) microspheres with exposed mirror-like plane {001} facets were successfully synthesized via a facile hydrothermal process. The photoanode composed of TiO(2) microsphere top layer shows an improved DSSCs efficiency owing to the superior light scattering effect of microspheres and excellent light reflecting ability of the mirror-like plane {001} facets.     

Hierarchical TiO2 microspheres: synergetic effect of {001} and {101} facets for enhanced photocatalytic activity

Well-faceted nanocrystals of anatase TiO(2) with specific reactive facets have attracted extraordinary research interest due to their many intrinsic shape-dependent properties. In this work, hierarchical TiO(2) microspheres consisting of anatase nanosheets or decahedrons were synthesized by means of a facile hydrothermal technique; meanwhile, the percentage of {001} facets can be tuned from 82 to 45%. Importantly, by investigating the photo-oxidation reactions for ˙OH radical generation and photoreduction reactions for hydrogen evolution, the TiO(2) microspheres consisting of nano-decahedrons with 45% {001} facets show superior photoreactivity (more than 4.8-times) compared to the nanosheets with 82% {001} facets. By analyzing the results of scanning electron microscopy (SEM), photoluminescence (PL) and first-principles density functional theory (DFT) calculations, a model of charge separation between the well-formed {001} and {101} facets is proposed, and the enhanced photocatalytic efficiency is largely attributed to the efficient separation of photogenerated charges among the crystal facets co-exposed.     

{111}晶面暴露对介孔金红石TiO2单晶光催化产氢的促进作用

光催化反应发生在半导体材料的表面,材料表面的原子/电子结构直接影响光催化剂的活性或选择性。因此,发展具有特定晶面的半导体光催化剂受到各国学者的普遍关注,被认为是调控光催化材料性能的有效途径之一。自2008年yang等首次合成高表面能{001}晶面占优的锐钛矿TiO2单晶以来,控制合成暴露不同晶面TiO2晶体的研究得到了迅猛的发展,已发展了多种方法合成了具有不同晶面的TiO2晶体。研究表明,选择性地暴露特定的活性晶面能够显著地提高光催化剂的活性或者改变光催化反应的选择性。但是,含有完整晶面构型的TiO2单晶样品的颗粒尺寸一般都较大,通常为几微米,因而显著增加了光生载流子传输与分离的难度,并且导致材料较小的比表面积,限制了对光催化活性的进一步提高。能否在合成含特定晶面单晶的同时增加多孔结构成为有效解决这一问题的关键。最近, Crossland等采用晶种模板法成功合成了介孔的锐钛矿TiO2单晶,并且通过光电器件研究证实了采用该思路可进一步提高材料的光电性能。金红石TiO2在光催化全分解水方面具有独特的优势,然而关于多孔单晶金红石TiO2的研究相对较少,尤其是合成热力学不稳定的高表面能{111}晶面完全暴露的多孔金红石单晶面临较大的技术挑战因而一直未见文献报道。本文利用晶种模板法,以TiCl4溶液为含Ti前驱体、NaF为形貌控制剂、采用水热处理制备出不同比例{111}晶面的介孔金红石单晶。我们前期工作表明, NaF可作为形貌控制剂合成低表面能{110)晶面占优的介孔金红石单晶。本文发现,通过改变NaF的添加量,可有效调变{111}/{110}晶面比例,最终合成完全暴露{111}高表面能的介孔金红石TiO2单晶。扫描电镜结果显示,当添加20 mg NaF时,合成{110}占优的具有高长径比的介孔晶体;当NaF用量增加到40 mg时{110}晶面进一步缩短;至80 mg时则制备出{111})高能面完全暴露的金红石TiO2晶体。值得注意的是,对比研究表明,不采用模板合成了与多孔晶体完全相对应的不同{111}/(110}晶面比例的实心金红石晶体。透射电镜及选区电子衍射以及结合X射线衍射进一步证实,多孔的金红石TiO2晶体与实心金红石单晶均都为单晶结构,孔结构贯穿于样品内部且具有较高的晶面结晶性。氮气吸附实验发现,虽然三个不同晶面比例介孔金红石单晶样品间的形貌具有显著的差异,但比表面积非常相近(分别为24,25,28 m2/g),孔径也都为50 nm左右,该值与所用SiO2模板球的直径以及TEM观察结果相一致。光催化产氢性能结果表明,选择性的暴露活性晶面显著提高了光催化活性,仅含高能面{111}的介孔金红石单晶样品具有最高的产氢速率(约800μmol h–1 g–1),比常规{110}晶面占优的介孔单晶样品速率提高了约一倍。尤其比实心单晶样品的产氢速率提高了至少一个数量级,这应归结于介孔结构特性所导致的表面反应活性位增加、电子传输距离缩短以及光吸收增强协同作用的结果。     

铂修饰的{001}面暴露的二氧化钛纳米片阵列的制备和光催化性能

采用有机溶剂热法在FTO衬底上制备{001}面暴露的单晶锐钛矿相TiO2纳米片阵列,通过FESEM和XRD研究样品的形貌和晶体结构. 与水热法制备的纳米片阵列相比,有机溶剂热法制备的样品取向性更好. 采用光沉积方法在纳米片阵列上沉积Pt,所得到的Pt纳米颗粒粒径更为均匀,并且更容易沉积在{001}面上. 所负载的Pt 纳米颗粒增强了TiO2纳米片的光吸收性能,同时大大减弱了光致发光强度. 在光催化性能测试中,具有最优负载量的样品催化性能提高了一倍. 与传统的Pt负载相比,{001}面的最优负载量显得相当小,这可能源于高活性{001}面的原子结构.     

Nitrogen self-doped nanosized TiO2 sheets with exposed {001} facets for enhanced visible-light photocatalytic activity

Nitrogen self-doped TiO(2) nanosheets with exposed {001} facets (ca. 67%) were synthesized by solvothermal treatment of TiN in a HNO(3)-HF ethanol solution and exhibited much higher visible-light photocatalytic H(2)-production activity than nitrogen doped TiO(2) microcrystallites with exposed {001} facets (ca. 60%) by a factor of 4.1.     

Effect of defects in TiO2 nanoplates with exposed {001} facets on the gas sensing properties

The gas-sensing properties and mechanism of anatase TiO₂ with complete and defective {001} facets were explored and compared, which provides a more direct evidence for the high sensitivity of TiO₂ with the complete {001} crystal facets.     

Novel photocatalytic antibacterial activity of TiO2 microspheres exposing 100% reactive {111} facets

TiO(2) microspheres constructed by well-crystallized faceted nanorods with high aspect ratios expose 100% photocatalytic reactive {111} facets on the spherical surface. The microspheres demonstrated excellent photocatalytic antibacterial activity towards Staphylococcus aureus due to effective suppression of photoinduced electron-hole pair recombination and active TiO(2)@˙OH core-shell structure.     

Synthesis and facet-dependent photoreactivity of BiOCl single-crystalline nanosheets

BiOCl single-crystalline nanosheets with exposed {001} and {010} facets were selectively synthesized via a facile hydrothermal route. The resulting BiOCl single-crystalline nanosheets with exposed {001} facets exhibited higher activity for direct semiconductor photoexcitation pollutant degradation under UV light, but the counterpart with exposed {010} facets possessed superior activity for indirect dye photosensitization degradation under visible light.     

The formation of mesoporous TiO2 spheres via a facile chemical process

The mesoporous TiO(2) solid and hollow spheres have been synthesized via a controllable and simple chemical route. Structural characterization indicates that these TiO(2) mesoporous spheres after calcined at 500 degrees C have an obvious mesoporous structure with the diameters of 200-300 nm for solid spheres and 200-500 nm for hollow spheres. The average pore sizes and BET surface areas of the mesoporous TiO(2) solid and hollow spheres are 6.8, 7.0 nm and 162, 90 m(2)/g, respectively. Optical adsorption investigation shows that TiO(2) solid and hollow spheres possess a direct band gap structure with the optical band gap of 3.68 and 3.75 eV, respectively. A possible formation mechanism for TiO(2) solid and hollow spheres is discussed.     

A facile synthesis of anatase TiO2 nanosheets-based hierarchical spheres with over 90% {001} facets for dye-sensitized solar cells

Anatase TiO(2) nanosheets-based hierarchical spheres with over 90% {001} facets synthesized via a diethylene glycol-solvothermal route were used as photoanodes of dye-sensitized solar cells, which generated an energy conversion efficiency of 7.51%.     

A selective etching phenomenon on {001} faceted anatase titanium dioxide single crystal surfaces by hydrofluoric acid

A selective etching phenomenon on {001} faceted anatase TiO(2) single crystal surfaces by HF and associated etching mechanism are reported. Density functional theory (DFT) calculations reveal that HF stabilizes the grown {001} facets at low concentrations, but selectively destroys the grown {001} facets at high concentrations.     

Synthesis of titanium dioxide nanoparticles with mesoporous anatase wall and high photocatalytic activity

Mesoporous titanium dioxide nanosized powder with high specific surface area and anatase wall was synthesized via hydrothermal process by using cetyltrimethylammonium bromide (CTAB) as surfactant-directing agent and pore-forming agent. The resulting materials were characterized by XRD, nitrogen adsorption, FESEM, TEM, and FT-IR spectroscopy. The as-synthesized mesoporous TiO2 nanoparticles have mean diameter of 17.6 nm with mean pore size of 2.1 nm. The specific surface area of the as-synthesized mesoporous nanosized TiO2 exceeded 430 m2/g and that of the samples after calcination at 600 degrees C still have 221.9 m2/g. The mesoporous TiO2 nanoparticles show significant activities on the oxidation of Rhodamine B (RB). The large surface area, small crystalline size, and well-crystallized anatase mesostructure can explain the high photocatalytic activity of mesoporous TiO2 nanoparticles calcined at 400 degrees C.     

暴露{001}面TiO2纳米片分等级花状结构的制备及其光催化活性

以钛酸盐纳米管为前驱体,在HF-H2O-C2H5OH的混合溶液中,采用一种简单的醇热方法合成了具有87%暴露{001}面的TiO2纳米片自组装形成的分等级花状TiO2超结构.运用X射线衍射、扫描电镜、透射电镜和N2吸附-脱附等方法对样品进行了表征,并在紫外光照射下于空气和溶液中分别考察了其光催化降解丙酮和甲基橙反应活性...     

含 TiO2(B) 介孔氧化钛材料的制备、特性和应用

 综述了近年来本课题组依据材料化学工程研究思想, 对含 TiO2(B)(一种比金红石和锐钛矿相结构更松散的氧化钛晶型) 介孔氧化钛材料在制备、结构和性能方面所取得的研究进展. 该介孔材料由二钛酸钾经水合、离子交换和热处理得到, 具有良好原子尺度晶格匹配界面特征的锐钛矿和 TiO2(B) 核壳结构. 研究表明, 该介孔材料在兼备高比表面积、高晶化孔壁和高热稳定性的同时, 还表现出良好的纳米颗粒担载稳定性, 在光催化、油品加氢精制、药物载体、固体酸催化和电化学电容器等方面已凸显出良好的应用潜力和推广价值. 目前该新型含 TiO2(B) 介孔氧化钛材料已经实现低成本、规模化制备.     

Nitrogen-doped titanate-anatase core-shell nanobelts with exposed {101} anatase facets and enhanced visible light photocatalytic activity

Anatase TiO(2) with specifically exposed facets has been extensively studied for maximizing its photocatalytic activity. However, most previous preparation methods involve high-pressure processing and corrosive chemicals. Few works have been conducted on hierarchical composite nanostructures assembled from well-defined TiO(2) nanocrystals. Here, we report a facile method for the preparation of nitrogen-doped titanate-anatase core-shell nanobelts. Anatase nanorods with specifically exposed {101} facets were obtained from a simple evaporation-induced, self-assembly (EISA) process and coupled with another semiconductor photocatalyst. The composite material with improved visible-light-harvesting ability, high charge-hole mobility, and low electron-hole recombination exhibited high photocatalytic performance and stability. The results presented here will make significant contributions toward the development of delicate composite photocatalysts for photocatalytic water purification and solar energy utilization.