形态结构和光电特性对纳米TiO2光催化性能的影响

采用sol-gel法制备了系列纳米TiO2光催化剂,运用X射线衍射、BET比表面测定、紫外漫反射吸收光谱和表面光电压谱等手段对催化剂进行表征,并以乙烯作为光催化反应的指标反应分子,研究了TiO2纳米晶的性质对于光催化活性的影响.随着焙烧温度的升高,TiO2的晶粒逐渐增大,比表面积下降,晶相由锐钛矿向金红石转变,其吸收带边与光伏响应阈值向长波方向移动,氧化－还原能力降低,降解乙烯的转化率迅速下降.     

Photochromism-based detection of volatile organic compounds by W-doped TiO2 nanofibers

W-doped TiO(2) nanofibers with various compositions (W/Ti: 2-8%) were fabricated by the electrospinning method from respective precursor solutions containing tungsten(V) pentaethoxide, titanium tetraisopropoxide (TTIP), and polyvinylpyrrolidone (PVP), followed with calcination at 550 °C. Morphological and structural characteristics of these nanofibers were studied with SEM, XRD and XPS. W-doping inhibited the crystal growth and anatase-to-rutile transformation of TiO(2) nanofibers. W-doped TiO(2) nanofiber mats showed good photocatalytic oxidation abilities for acetone. Obvious color change from white to blue of mats during the photocatalysis process can be detected by naked eyes, which provides a good way in detection of pollutants in indoor air, especially for the volatile organic compounds (VOCs).     

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.     

C–Cl共掺杂TiO2/凹凸棒复合催化剂的制备及其可见光催化性能

TiO2光催化剂具有无毒、物理化学性质稳定及光催化活性较高等优点,因而在能源及环境净化等领域备受关注.但是,TiO2纳米颗粒作为催化剂仍存在以下不足:(1)TiO2带隙较宽,只能吸收利用太阳光能的紫外光部分,而照射到地球表面的太阳光大部分为可见光;(2)光生载流子(电子/空穴)的复合使得光催化活性不高;(3)纳米催化剂的回收利用困难;(4)单独使用TiO2,成本较高;(5)针对低浓度有机污染,常见TiO2催化剂比表面积较小,吸附富集能力较差,导致光催化降解效率较低.TiO2自身这些缺陷大大限制了其进一步的实际应用.针对上述这些问题,我们在本研究中设计了一种简便易行的溶胶凝胶法,在较低的温度(70℃)下合成了非金属C–Cl共掺杂的TiO2/凹凸棒(TiO2/ATT)复合催化剂.XRD及HRTEM分析证明,通过调节反应溶液的pH可以分别合成含锐钛矿/金红石、锐钛矿/金红石/板钛矿的两相和三相的混合相TiO2,且锐钛矿/金红石比例可以通过改变pH而进行调节.XPS分析证明,C和Cl同时成功掺进TiO2/ATT复合催化剂.UV-Vis漫反射结果显示,非金属C和Cl的掺杂使得所合成复合催化剂的光吸收性能明显拓展到可见光区,因而可以充分利用可见光能进行有机污染物催化降解,而ATT作为TiO2的载体,减少了TiO2使用量,改善了TiO2的表面特性和孔结构,且有利于光催化剂的回收利用.以酸性红G为目标有机污染物,在可见光照射下对复合催化剂的可见光催化活性进行了测试.结果表明,当合成反应体系的pH值为3.0时,所获得的锐钛矿/金红石/板钛矿三相TiO2/ATT复合催化剂具有良好的可见光吸收特性,其可见光催化活性远远高于市售P25型TiO2,对难降解的酸性红溶液G具有优异的脱色效果和良好的TOC去除性能.循环光催化实验和FTIR表征结果表明,在5次循环利用后,TiO2/ATT复合催化剂仍表现出很高的催化活性,表明其稳定性优异.荧光分析和自由基捕获实验表明,光催化降解反应中的主要活性物种是羟基自由基、空穴和超氧自由基.TiO2/ATT复合催化剂高效稳定的可见光催化性能主要归因于:(1)非金属C和Cl的共掺杂改善了其可见光吸收性能;(2)催化剂中的TiO2由金红石、锐钛矿和板钛矿混合相组成,有利于抑制光生载流子的复合;(3)多孔结构的ATT作为载体提高了TiO2的比表面积,增加了反应活性位,同时改善了孔结构,从而有利于模拟有机污染物(酸性红G)分子的吸附和降解,有利于反应产物扩散,从而提高了催化剂的可见光催化效率.     

高纯纳米氧化钛的制备及催化活性

以工业级硫酸钛为原料,在酸性环境下以EDTA作为络合剂,采用控制沉淀法制备高纯度纳米TiO2。考察了pH值、反应温度、煅烧温度等工艺条件对TiO2颗粒晶型、大小和分布影响。利用TEM、XRD、ICP等手段对产物进行表征,TiO2纯度超过99.9%,粒径为10-20nm,分布均匀。经过对其光催化降解苯酚反应活性实验,结果表明样品具有较好的光催化活性。     

Comparative examination of titania nanocrystals synthesized by peroxo titanic acid approach from different precursors

Titanium dioxide nanocrystalline particles were synthesized by peroxo titanium acid (PTA) approach from titanium alkoxide and inorganic salt precursors, and their structural and surface properties, porosities, and photocatalytic activities were comparatively examined by XRD, TG/DTA, DRIFT, UV-vis, low temperature N(2) adsorption, and methyl orange (MO) degradation. It was found that nanoparticles with single anatase phase can be obtained from alkoxide precursor even near room temperature if synthesis conditions are appropriately controlled. PTA-derived anatase nanoparticles from titanium alkoxide precursor have smaller crystalline sizes and better porosities, and contain less amount of peroxo group and no organic impurities as compared to those from TiCl(4) precursor. The advantages in structural property, porosity, and surface properties (few deficiencies) lead to a much better photocatalytic activity for TiO(2) nanoparticles from titanium alkoxide precursor in comparison with those from TiCl(4) precursor.     

Fabrication of hydroxyl group modified monodispersed hybrid silica particles and the h-SiO(2)/TiO(2) core/shell microspheres as high performance photocatalyst for dye degradation

The monodisperse hybrid silica particles (h-SiO(2)) were firstly prepared by a modified sol-gel process and the surface was modified in situ with double bonds, then abundant carboxyl moieties were introduced onto the surface of the silica core via thiol-ene click reaction. Afterward, the h-SiO(2)/TiO(2) core/shell microspheres were prepared by hydrolysis of titanium tetrabutoxide (TBOT) via sol-gel process in mixed ethanol/acetonitrile solvent, in which the activity of TBOT could be easily controlled. The carboxyl groups on the surface of silica particles promote the formation of a dense and smooth titania layer under well control, and the layer thickness of titania could be tuned from 12 to 100nm. The well-defined h-SiO(2)/TiO(2) core/shell structures have been confirmed by electron microscopy and X-ray photoelectron spectroscopy studies. After calcination at 500°C for 2h, the amorphous TiO(2) layer turned into anatase titania. These anatase titania-coated silica particles showed good photocatalytic performance in degradation of methyl orange aqueous solution under UV light.     

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.     

A new route towards nanoporous TiO2 as powders or thin films from the thermal treatment of titanium-based hybrid materials

Calcination of cyclopentadienyltitanium-based organic-inorganic hybrid materials at 450-500 °C led to the formation of anatase titanium dioxide as white powders consisting of a porous network of aggregated nanoparticles, the nanoporosity detected being related to the inter-particle space. Depending on the calcination temperatures, the surface area of the titanium dioxide particles varied from 65 to 158 m(2) g(-1).     

Effect of calcination temperature on the photocatalytic activity of carbon‐doped titanium dioxide revealed by photoluminescence study

Carbon‐doped titania (C‐TiO₂) nanoparticles were synthesized by the sol–gel method at different calcination temperatures (300–600°C) employing titanium tetraisopropoxide (TTIP) as the titanium source and polyoxyethylene sorbitan monooleate (Tween 80) as the carbon source. The physical properties of C‐TiO₂ samples were characterized by X‐ray diffraction (XRD) and scanning electron microscopy (SEM). The photocatalytic activities were checked through the photodegradation of phenolphthalein (PHP) under ultraviolet irradiation. The UV spectrum showed that the carbon doping extends the absorption range of TiO₂ to the visible region. However, the photocatalytic activity is affected by the electron–hole recombination phenomenon, as revealed by the photoluminescence (PL) study. According to the PL spectra, carbon doping reduces the edge‐to‐edge electron–hole recombination. Nevertheless, the number of defect sites is greatly influenced by the calcination temperature of C‐TiO₂. C‐TiO₂ that was calcined at 400°C showed the highest photodegradation percentage of PHP, which was mainly attributed to the synergic effect of the low direct edge‐to‐edge electron–hole recombination, high content of defect sites, and retention of active electrons on the surface hydroxyl group.     

Carbonated ferric green rust as a new material for efficient phosphate removal

Novel TiO(2)/carbon nanocomposites were prepared through the pyrolysis of TiO(2)/poly(furfuryl alcohol) hybrid materials, which were obtained by the sol-gel method, starting from titanium tetraisopropoxide (TTIP) and furfuryl alcohol (FA) precursors. Six different TiO(2)/C samples were prepared based on different TiO(2) nanoparticle sizes and TiO(2)/FA ratios. All of the samples were characterized using X-ray diffraction, infrared, and Raman spectroscopy. The results indicated effective FA polymerization onto the TiO(2) (anatase) nanoparticles, polymer conversion to disordered carbon following the pyrolysis, and a simultaneous TiO(2) anatase-rutile phase transition. The resulting TiO(2)/carbon composites were used as photocatalysts in the advanced oxidative process (AOP) for the degradation of reactive organic dyes in aqueous solution. The results indicate excellent photocatalytic performance (degradation of 99% of the dye after 60 min) with several advantages over traditional TiO(2)-based photocatalysts.     

Synthesis of titanium dioxide nano-powder via sol–gel method at ambient temperature

Titanium dioxide is a semiconductor with excellent photo catalytic properties and an important material with high regarded in nanotechnology. In this study, titanium dioxide nanoparticles was successfully synthesized via sol–gel method using tetra-n-butyl orthotitanate, hydrochloric acid and ammonia. Tetra-n-butyl orthotitanate was used as precursor. The ingredients were mixed at ambient temperature for 9 h on a magnetic stirring, sol was formed and converted to gel by adding ammonia. X-ray diffraction analysis clearly showed anatase and rutile phases so that, with increasing calcination temperature anatase converts to the rutile. Scanning electron microscopy was used for agglomerate observations. Energy-dispersive detector analysis was carried out and confirmed the formation of titanium dioxide. The influences of calcination temperature and pH value on particles size were studied. The results indicate that synthesis at room temperature reduced the particle size to 15 nm.     

TiO2-yNx纳米光催化剂的制备及其可见光响应机理

利用溶胶-凝胶技术,以尿素为氮源,采用原位掺杂方式制备了TiO2-yNx纳米粉体;以亚甲基蓝(MB)溶液在可见光下的光催化降解评价其可见光催化活性;考察了体系初始pH值、N的掺杂量和焙烧温度对样品可见光催化活性的影响。 结合XRD、XPS、ESR和DRS测试技术,研究了N掺杂纳米TiO2的可见光响应机理。 研究结果表明,TiO2-yNx纳米粉体的优化制备工艺条件为：体系初始pH=0.52,掺杂比n(N)∶n(Ti)=1∶6,焙烧温度为440 ℃。 此条件下制备的样品N含量为0.77%,为单一的锐钛矿相,平均粒径为19.0 nm,具有良好的可见光催化活性。 N掺杂导致TiO2纳米粉体的表面羟基含量增加,形成了大量束缚单电子的氧空位;N取代晶格O形成了N-Ti-O和O-N-Ti键合结构。 N掺杂导致TiO2纳米粒子的吸收带边红移,对可见光的吸收能力明显增强,这表明N掺杂改变TiO2电子结构,使带隙窄化,降低光响应阈值。 N掺杂TiO2纳米粒子的可见光响应归因于N取代掺杂形成的掺杂能级与氧空位形成的缺陷能级共同作用所致。     

Nanostructured Ti(1-x)S(x)O(2-y)N(y) heterojunctions for efficient visible-light-induced photocatalysis

Highly visible-light-active S,N-codoped anatase-rutile heterojunctions are reported for the first time. The formation of heterojunctions at a relatively low temperature and visible-light activity are achieved through thiourea modification of the peroxo-titania complex. FT-IR spectroscopic studies indicated the formation of a Ti(4+)-thiourea complex upon reaction between peroxo-titania complex and thiourea. Decomposition of the Ti(4+)-thiourea complex and formation of visible-light-active S,N-codoped TiO(2) heterojunctions are confirmed using X-ray diffraction, Raman spectroscopy, transmission electron microscopy, and UV/vis spectroscopic studies. Existence of sulfur as sulfate ions (S(6+)) and nitrogen as lattice (N-Ti-N) and interstitial (Ti-N-O) species in heterojunctions are identified using X-ray photoelectron spectroscopy (XPS) and FT-IR spectroscopic techniques. UV-vis and valence band XPS studies of these S,N-codoped heterojunctions proved the fact that the formation of isolated S 3p, N 2p, and Π* N-O states between the valence and conduction bands are responsible for the visible-light absorption. Titanium dioxide obtained from the peroxo-titania complex exists as pure anatase up to a calcination temperature as high as 900 °C. Whereas, thiourea-modified samples are converted to S,N-codoped anatase-rutile heterojunctions at a temperature as low as 500 °C. The most active S,N-codoped heterojunction 0.2 TU-TiO(2) calcined at 600 °C exhibits a 2-fold and 8-fold increase in visible-light photocatalytic activities in contrast to the control sample and the commercial photocatalyst Degussa P-25, respectively. It is proposed that the efficient electron-hole separation due to anatase to rutile electron transfer is responsible for the superior visible-light-induced photocatalytic activities of S,N-codoped heterojunctions.     

Absorption and action spectra analysis of ammonium fluoride-doped titania photocatalysts

The photocatalytic behaviour of a series of ammonium fluoride (NH(4)F)-doped titania (TiO(2)) photocatalysts was investigated in the decomposition of acetic acid in aqueous suspensions and in the gas phase mineralization of acetaldehyde. Very similar photocatalytic activity trends, usually increasing with increasing the calcination temperature for a given nominal dopant amount, were obtained for the two test reactions. Moderately doped TiO(2) calcined at 700 °C, consisting of pure anatase, was the best performing photocatalyst in both reactions. The photocatalytic oxidation of acetic acid was investigated systematically as a function of irradiation wavelength, by collecting so-called action spectra. By comparing the shapes of the action spectra with those of the absorption spectra of the investigated photocatalysts a model is proposed, based on spectral features deconvolution, which allows a clear distinction between inactive light absorption and effective photoactivity in acetic acid decomposition.     

二氧化钛纳米微粒的制备与光催化活性

本文采用溶液－凝胶法制备了粒径为１０－２０ｎｍ左右的二氧化钛纳米微粒。用ＸＲＤ研究了二氧化钛溶胶的热处理过程,研究表明温度在４７３Ｋ－６７３Ｋ左右ＴｉＯ２向量 粒呈不规整锐钛矿结构,粒径约为１０－２０ｎｍ。在８７３Ｋ左右ＴｉＯ２微粒出现锐钛矿与金红石型混晶结构。     

单斜与锐钛矿双晶相TiO2/MWNTs复合材料的制备及其可见光光催化活性

以超强耐酸碱的表面活性剂-丁基封端脂肪醇聚氧乙烯醚作为晶型调节剂,利用钛酸丁酯和氢氧化钠的水热反应制备了单斜相与锐钛矿相双晶相TiO2/多壁碳纳米管(简称MWNTs)复合材料,并考察了复合材料的可见光光催化活性。结果显示:MWNTs的加入可调控TiO2的晶相组成,增强TiO2的光催化活性,其中含5%MWNTs的样品具有较高的催化降解效率;随煅烧温度的升高,样品的光催化活性大幅提升。其机理归因于(1)促进单斜相和锐钛矿相双晶相结构的形成;(2)碳纳米管优良的导电作用及碳纳米管/TiO2间的异质结效应;(3)高温下碳纳米管分解产生的碳元素掺杂作用。     

Morphology phase diagram of ultrathin anatase TiO2 films templated by a single PS-b-PEO block copolymer

Ultrathin TiO2 films showing rich morphologies are prepared on Si(100) substrates using sol-gel chemistry coupled with an amphilic polystyrene-block-poly(ethylene oxide) (PS-b-PEO) diblock copolymer as a structure-directing agent. The block copolymer undergoes a good-poor solvent pair induced phase separation in a mixed solution of 1,4-dioxane, concentrated hydrochloric acid (HCl), and titanium tetraisopropoxide (TTIP). By adjusting the weight fractions of 1,4-dioxane, HCl, and TTIP, inorganic block copolymer composite films containing a variety of different morphologies are obtained. On the basis of the results a ternary phase diagram of the morphologies is mapped. By calcination, anatase TiO2 films are achieved. The morphologies and crystallographic phase of the films are studied with AFM, SEM, and XRD, respectively, and the formation mechanisms of the different morphologies are discussed.     

TiO2 synthesis inspired by biomineralization: control of morphology, crystal phase, and light-use efficiency in a single process

Hydroxyapatite is mineralized along the long axis of collagen fiber during osteogenesis. Mimicking such biomineralization has great potential to control inorganic structures and is fast becoming an important next-generation inorganic synthesis method. Inorganic matter synthesized by biomineralization can have beautiful and functional structures that cannot be created artificially. In this study, we applied biomineralization to the synthesis of the only photocatalyst in practical use today, titanium dioxide (TiO(2)). The photocatalytic activity of TiO(2) mainly relates to three properties: morphology, crystal phase, and light-use efficiency. To optimize TiO(2) morphology, we used a simple sequential peptide as an organic template. TiO(2) mineralized by a β-sheet peptide nanofiber template forms fiber-like shapes that are not observed for mineralization by peptides in the shape of random coils. To optimize TiO(2) crystal phase, we mineralized TiO(2) with the template at 400 °C to transform it into the rutile phase and at 700 °C to transform it into a mixed phase of anatase and rutile. To optimize light-use efficiency, we introduced nitrogen atoms of the peptide into the TiO(2) structure as doped elemental material during sintering. Thus, this biomineralization method enables control of inorganic morphology, crystal phase, and light-use efficiency in a single process.     

单斜与锐钛矿双晶相TiO2/MWNTs复合材料的制备及其可见光光催化活性

以超强耐酸碱的表面活性剂-丁基封端脂肪醇聚氧乙烯醚作为晶型调节剂,利用钛酸丁酯和氢氧化钠的水热反应制备了单斜相与锐钛矿相双晶相TiO₂/多壁碳纳米管(简称MWNTs)复合材料,并考察了复合材料的可见光光催化活性。结果显示:MWNTs的加入可调控TiO₂的晶相组成,增强TiO₂的光催化活性,其中含5%MWNTs的样品具有较高的催化降解效率;随煅烧温度的升高,样品的光催化活性大幅提升。其机理归因于(1)促进单斜相和锐钛矿相双晶相结构的形成;(2)碳纳米管优良的导电作用及碳纳米管/TiO₂间的异质结效应;(3)高温下碳纳米管分解产生的碳元素掺杂作用。