TiO2/蒙脱石纳米复合材料结构组装过程与表征

将氧化钛前驱体钛酸丁酯引入到不同用量十六烷基三甲基溴化铵(CTAB)柱撑蒙脱石的层间域中,经原位水解、脱羟、成核结晶作用制备TiO2/蒙脱石纳米复合结构材料。采用X射线衍射(XRD)分析手段对比研究了CTA+/蒙脱石、(Ti(OH)4/CTA+)/蒙脱石和TiO2/蒙脱石复合结构,揭示了不同阶段样品层间物在蒙脱石层间域中的组装方式。在季铵盐用量不同情况下,CTA+/蒙脱石复合物和(Ti(OH)4/CTA+)/蒙脱石复合物中季铵盐阳离子的排布方式均出现单层平卧、单层倾斜和双层倾斜排布,但单层倾斜和双层倾斜排布的倾斜角度不同,在(Ti(OH)4/CTA+)/蒙脱石层间域中季铵盐阳离子仍起到骨架作用;TiO2/蒙脱石复合材料中锐钛矿相含量随季铵盐用量的增加而增大,但锐钛矿晶粒的尺寸逐渐减小,蒙脱石层间域对锐钛矿相晶粒的长大和转化为金红石相都具有显著的阻滞作用。     

热处理过程对纳米TiO2结构和性能的影响

以钛酸丁酯为钛源,采用溶胶-凝胶法制备纳米TiO2,结合TG-DTA,XRD,TEM等分析了不同热处理温度对纳米TiO2的晶型结构、晶粒粒径及微观形貌的影响.以甲基橙溶液为目标降解物,探讨了热处理温度对纳米TiO2光催化活性影响.利用Eastman的粒子生长理论对晶粒生长的动力学过程进行初步分析.研究表明:随着热处理温度升高,TiO2粒径逐渐从11.2 nm增大到78.6 nm;热处理温度为450～ 550℃时,纳米TiO2晶粒以锐钛矿为主,温度升至650℃时,出现了锐钛矿和金红石的混合相(质量比A∶R =9∶1),此时晶粒对甲基橙的降解率达到97.75;.而煅烧温度高于850℃后,TiO2几乎完全为金红石相,光催化活性显著下降.50;锐钛矿型TiO2转变金红石型TiO2的温度约为730℃,锐钛矿和金红石相晶粒表观活化能分别18.15 kJ/mol和42.56 kJ/mol;晶粒生长最快温度分别为546℃和1280℃.     

胶溶法制备具有自清洁与抗菌性能的TiO2薄膜

采用胶溶法合成了纳米晶锐钛矿溶胶,在玻璃基底上用提拉法制备出TiO2纳米薄膜。使用XRD、TEM、SEM和AFM和接触角等方法对TiO2溶胶和薄膜的结构进行了表征。结果表明,胶溶法合成的TiO2溶胶为锐钛矿型且结晶度较高,TiO2晶粒为针状,平均粒径约为8 nm;TiO2薄膜表面光滑,颗粒平均粒径约为86 nm。3层薄膜的厚度约为150 nm,涂膜层数对膜表面结构形貌影响有限。常温制备出的薄膜经紫外光照80 min,对亚甲基蓝的降解率达到93.6%,其活性随着热处理温度升高而提高。薄膜具备超亲水性,自清洁和抗菌性能。     

煅烧条件对纳米TiO2/膨胀珍珠岩复合材料性能的影响

以膨胀珍珠岩为载体,TiOSO4为钛源,采用均匀沉淀法制备了纳米TiO2/膨胀珍珠岩复合材料,通过XRD、SEM和FT-IR对复合材料的TiO2晶体结构、表面性质和形貌进行分析表征.研究了煅烧温度和煅烧时间对复合材料中TiO2结晶和光催化性能的影响.结果显示在550℃下煅烧2h时,复合材料的光催化性能最高,此时TiO2为锐钛矿,晶粒尺寸为11.93 nm,对罗丹明溶液的降解率达到95;以上.复合材料具有良好的再生重复使用性能,经5次回收再利用后仍表现较高的光催化性能.     

CuO/SnO2/TiO2复合光催化剂的制备及光催化性能

采用硬脂酸法制备了CuO/SnO2/TiO2复合光催化剂,采用XRD及TG-DTA分析对其物相和热稳定性进行了表征,并通过苯酚的光催化降解行为对所制备催化剂的活性进行了评价.结果表明,经500 ℃热处理的CuO/SnO2/TiO2复合光催化剂属于单一的锐钛矿相,且铜、锡氧化物的引入抑制了TiO2的结晶和晶粒的生长.当催化剂组成为Cu:Sn:Ti=0.25:5:100(物质的量比),焙烧温度为500 ℃,催化剂投加量为0.5 g·L-1,溶液pH为4.0时,经3 h光催化反应苯酚的降解率达97.1;.     

稀土Sm掺杂对纳米TiO2结构和可见光催化性能的影响

采用溶胶-凝胶法制备了纯TiO2和稀土Sm掺杂TiO2纳米粉体( Sm-TiO2),通过XRD、XPS、FT-IR、UV-Vis-DRS、PL和Nano-sizer纳米粒度仪等对样品进行表征,以亚甲基蓝( MB)的光催化降解为探针反应,探讨稀土Sm掺杂对纳米TiO2的结构和可见光催化性能的影响。结果表明,Sm掺入TiO2后在表面存在Sm3+和Sm2+两种价态, Sm掺杂抑制了TiO2从锐钛矿向金红石的相转变,阻碍纳米晶粒生长,增加了纳米粉体表面羟基含量;适量的Sm掺杂能使TiO2吸收光谱的阈值波长红移,有效降低光生e-/h+的复合率,提高TiO2光催化活性。热处理温度500℃时,掺杂1.0wt;Sm的纳米TiO2样品在普通日光灯下对MB在6 h内的光催化降解效率达97;,明显高于同等条件下Degussa公司产品P25的降解率56;。     

磁控溅射（TiO2-ZnO）/TiO2梯度复合薄膜的制备及光致亲水性研究

采用磁控溅射离子镀设备制备了(TiO2-ZnO)/TiO2梯度复合薄膜,通过TEM、AFM、Raman、XPS分析了复合薄膜的结构、形貌和表面羟基含量,以甲基橙作为有机降解物,研究了(TiO2-ZnO)/TiO2梯度复合薄膜与普通TiO2-ZnO复合薄膜和TiO2薄膜在光催化性能和光致亲水性能上的差异。结果表明:(TiO2-ZnO)/TiO2梯度复合薄膜具有以主体为TiO2-ZnO层、顶层为TiO2的梯度结构,且薄膜表面致密、粒径均匀(10～14 nm),光催化性和亲水性均优于普通TiO2-ZnO复合薄膜和TiO2薄膜,且其光波响应范围红移至450 nm、表面羟基含量高达12.53%,同时梯度复合薄膜的抗光腐蚀性能良好,4 h以后其润湿角仍保持不变。     

TiO2/SiO2纤维的表征及其光催化活性

本文采用溶胶-凝胶法及离心甩丝,以TiCl4为钛源、乙酰丙酮为螯合剂成功制备了TiO2/SiO2纤维,并采用XRD 、FE-SEM、FT-IR和DSC -TG等手段对样品结构和性能进行表征.结果表明掺入SiO2可以抑制TiO2晶粒长大和晶型转变,700℃热处理后,未掺SiO2和掺15wt; SiO2的样品晶粒大小分别为32.4 nm和7.6 nm.TiO2/SiO2纤维直径为10～20μm,且表面含有大量纳米气孔.以活性艳红X-3B溶液为降解对象,研究了掺杂量、热处理温度对纤维光催化活性的影响,表明最优的方案为掺15wt; SiO2、热处理制度为700℃/2 h.     

TiO2-ZnTiO3纳米复合薄膜的制备及光催化性能

将ZnO粉末加入TiO2溶胶中制备出TiO2/ZnTiO3复合薄膜.利用X射线衍射仪、扫描电子显微镜、X射线光电子能谱、紫外-可见吸收光谱对其形貌、晶体结构、化学组成和光谱响应特征进行了表征.以亚甲基蓝(MB)溶液的脱色降解为模型反应,考察了不同ZnO掺入比例对复合薄膜光催化性能的影响.结果表明,所得材料的光催化性能与复合结构中TiO2的结晶结构有关.Ti/Zn=6∶1时,所得复合薄膜由锐钛矿相TiO2与钙钛矿相ZnTiO3构成,薄膜中晶粒尺寸较小(约为30 nm)、结晶度较高、催化性能最好.在紫外光下5h可使亚甲基蓝(MB)溶液脱色降解率达到94;,明显高于纯TiO2薄膜(87;).     

纳米TiO2薄膜的制备与光催化性能研究

以四氯化钛为前驱体,采用水解沉淀法,在不同的水解温度下,在硅藻土基多孔陶瓷上负载纳米TiO2薄膜,结合XRD和TEM对负载的纳米TiO2粒径进行了表征。对比分析了测试方法及水解温度对纳米TiO2粒径的影响。以罗丹明B为目标降解物,考察了水解温度对光催化剂活性的影响。结果表明:样品经550℃煅烧后,TiO2薄膜为锐钛矿型;水解温度为50℃时TiO2粒径小于水解温度为75℃时所负载纳米TiO2粒径;两种方法所测TiO2粒径有一定差异:dXRD>dTEM;水解温度为50℃所负载纳米TiO2薄膜,紫外光照300 min,对罗丹明B的去除率为89.9%,而75℃时,样品在紫外光照330 min,对罗丹明B的去除率为78.6%。     

Phonons in TiO2---SiO2 glasses

We report the infrared and Raman studies of titanium doped vitreous silica glasses for a number of titanium concentrations. The vibrational modes associated with the randomly oriented chains of SiO₄ tetrahedra show broadenings and shifts. The LO-TO splitting of some Raman active modes decreases with increasing titanium concentration. This is attributed to the decrease in long-range coulomb fields associated with the chains of SiO₄ tetrahedra which are broken by the titanium atoms. The results are discussed in the context of random network models. An increase in the average intertetrahedral angle of the SiO₄ network is calculated from the data. This explains the anomalous decrease in the density of TiO₂---SiO₂ glasses with increasing titanium content. We identify two new modes associated with the distorted titanium tetrahedra. A polarized Raman mode at 1115 cm⁻¹ which is infrared inactive and an unpolarized Raman mode at 945 cm⁻¹ which is infrared active are observed.     

TiO2-SiO2 monolithic glass formation from sol-gel

This study demonstrates that hydrolysis should be carried out in a step manner in gel synthesis. The key to the increase in the amount of water added is the control of the hydrolysis rate of Ti(OC₄H₉)₄. The hydrolysis of Si(OC₂H₅)₄ can be carried out at about 75°C. The amount of added water (γ_WI), which varied with TiO₂ content (in mol%), was about 64–88% of the total amount of added water. The hydrolysis reaction should be performed at room temperature while Ti(OC₄H₉)₄ is added. The total amount of added water (γ_W) is related to the amount of solvent (R). For example, if TiO₂ is 40mol%, γ_W will vary from 3.2 to 8.0 when R varies from 0.8 to 2.0. The amount of added water was affected by the distribution of solvent in the metal alkoxides. The amount of added water can be increased when R_Si(OC2H5)4 = 1, R_Ti(OC4H9)4 > 1. The rate of rise in temperature of the thermolysis of the dried gel should be less than 10°C per hour, and the heat treatment temperatyre is related to the TiO₂ content (in mol%). Gel glasses without devitrification can only be obtained by thermolysis at 600°C from the gel with no less than 20 mol% TiO₂.     

Interaction between colloidal particles in SiO2 and TiO2 sols

The effect of the interaction between colloidal particles in SiO₂ and TiO₂ sols on the viscosity of the sols has been examined. It was found that the interaction was significantly influenced by the zeta potential of electrical double layers and terminal bonds associated with particle surfaces. Water/alkoxide mole ratio and pH affect the zeta potential and the terminal bonds and, consequently, change the interaction between the particles and the viscosity of the sols. In addition, the relationship of viscosity with the volume fraction of the colloidal particles in SiO₂ sol has been described by a Dougherty-Kreiger equation when the viscosity reached a stable value with time.     

Colloidal sol/gel processing of ultra-low expansion TiO2/SiO2 glasses

A series of titania-silica glasses with 0–9% TiO₂ were fabricated using a sol/gel process. The sol was prepared by dispersing colloidal silica fume in an aqueous solution of titania which was synthesized through the acid-catalyzed hydrolysis of titanium isopropoxide. The sols gelled in 2–4 days, and then were dried for 6–8 days. The dry gels were sintered at 1450–1500°C to produce clear, dense, microstructure-free glasses. The gels underwent a total shrinkage of 50% to yield glass rods about 50 mm long and 5 mm in diameter, or glass discs about 4 cm in diameter and 5 mm thick. The drying step was most critical in the production of crack-free specimens.

In the gel, the transmission electron microscope (TEM) revealed the presence of 1–5 nm rutile microcrystallites uniformly distributed within a network of colloidal silica particles. After sintering to 1450–1500°C, though, a dense, transparent, microstructure-free glass was created. Fourier transform infrared spectroscopy (FTIR) verified the formation of an amorphous solid-solution of titania and silica after sintering.

The thermal expansion of the glasses was measured using a differential dilatometer. The average linear coefficients of thermal expansion (CTE @ 25–675°C) varied between +5 × 10⁻⁷ and −0.2 × 10⁻⁷°C⁻¹ in the range 0 to 9% TiO₂. The glass with 7.2% TiO₂ exhibited a zero thermal expansion coefficient at 150–210°C. The hysteresis in CTE on heating and cooling was of the order of 0.01–0.02 ppm.     

Apatite formation on TiO2 anatase microspheres

Titanium dioxide (TiO₂) coatings have been long considered as biocompatible interfaces to promote the physico-chemical bonding between the bone tissues and implant material (e.g., titanium and stainless steel). Monodispersed TiO₂ (anatase, the low temperature polymorph of TiO₂) microspheres, produced in the form of colloidal precipitates, were deposited on different substrates and apatite formation was induced on the resulted surface by immersing the coated substrates in simulated body fluid solution. Analytical and microstructural investigations, conducted by X-ray diffraction, energy depressive X-ray spectroscopy and scanning electron microscopy techniques, showed considerable higher rates of apatite formation, in vitro, on the anatase microspheres compared to the sol-gel-derived thin films of the same oxide. We concluded that the particular surface morphology of the packed TiO₂ microspheres, promotes a faster apatite formation in vitro.     

Multilayer SiO2 and TiO2 coatings on glasses by the sol-gel process

Glass films of pure SiO₂ and TiO₂ have been prepared on sodalime silica flat slide glasses by the sol-gel process using the dip-coating technique from TEOS and Ti(OC₃H₇)₄ solutions. The various parameters such as chemicals concentrations, viscosity, type of catalyst, withdrawal speed and temperature of densification leading to the obtention of good and adherent coatings with definite film thicknesses are reported. The same technique has been used for the depositon of layers of colored films SiO₂---M_xO_y (M = Co, Mn, Nd and Cr). Brilliant yellow coatings have been obtained with TiO₂---CeO₂.     

Semiconducting TiO2SiO2 glasses (II): Optical properties

The refractive index, optical absorption coefficient α and the thermomodulated absorption dα/dT have been measured on 70% TiO₂?30% SiO₂ glasses with up to 8% Ti³⁺. The direct absorption data show intense ligand field absorption at photon energies hν = 1.9 and 3.0 eV, arising from Ti³⁺ in a distorted octahedral environment. In the bandgap region at 3.5 eV α obey αhν ～ (hν ? E_g)²; it is qualitatively different from the bandgap absorption in crystalline TiO₂. The da/dT spectra show peaks in the bandgap region and at 1.1 eV in the near IR. This last peak is attributed to absorption by small polarons, and its line shape is compared with theoretical predictions.     

Structural transformation of the TiO2---SiO2 system gel during heat-treatment

The gel formation of the (100-x)TiO₂·xSiO₂ (x = 0–10 mol%) system has been studied. The progressive elimination of residues was followed by DTA and TGA curves. DTA curves showed that the formation of anatase during heat treatment could be sensibly slowed down with the increase of SiO₂. The relationship between the gel composition and crystallization temperature of anatase has been systematically investigated. The X-ray diffraction spectra demonstrated that the crystallization temperature of anatase is 400°C for TiO₂ gel and 430°C for 90TiO₂ - 10SiO₂ gel. The infrared absorption spectra were used to follow the structural transformation of gels heat-treated at different temperatures. With the help of EPR it is evident that titanium ions exist only in tetravalence.     

Preparation and physical properties of amorphous V2O5 containing TiO2, Na2O or Li2O

V₂O₅ gels containing up to 18 mol% of TiO₂ were obtained through the simultaneous hydrolysis of alkoxides in ethanol solution. V₂O₅ gels containing Na₂O or Li₂O were obtained through the ion exchange method. The crystallization temperature, T_cr, of the gels increased and the H₂O content of the gels decreased by the addition of TiO₂ or Na₂O. These additives seem to stabilize the amorphous state of the gels. On the other hand, T_cr and the H₂O-content slightly varied with the addition of Li₂O. No ionic polarization was observed in coating films of the gels dried at temperatures below T_cr. The dc conductivity of the films was anisotropic, and increased with the addition of Li₂O or Na₂O. However, it decreased with increasing TiO₂ content. The fiber-like structure of gels was observed by TEM. The gels obtained from alkoxides were thin and short in comparison with the gels obtained through the ion exchange method.     

Synthesis of narrow size distribution sub-micron TiO2 spheres

Ultra-fine spheres of TiO₂ are synthesized through sol-gel colloidal processing. Compared to previous studies, the present work shows a considerable achievement in controlling the shape of the produced particles as well as a relatively narrow size distribution.