超声辅助溶胶-凝胶法制备中空纤维TiO2超滤膜

TiO₂膜具有亲水性强和热化学稳定性好等优点而用于超滤分离, 但是TiO₂膜以管式膜为主, 渗透通量低且制备周期长。为了提高TiO₂膜的渗透通量, 并缩短膜的制备周期, 本工作以钛酸四丁酯为前驱体, 采用超声辅助溶胶-凝胶法制备高通量的中空纤维负载型TiO₂超滤膜。系统考察了硝酸与钛酸四丁酯的摩尔比(酸钛比)、超声时间和煅烧温度对TiO₂溶胶粒径及膜截留性能的影响。结果表明：当酸钛比为0.25时, 溶胶的平均粒径为3252 nm, 采用超声处理30 s后, 平均粒径减小至1817 nm。采用超声后的溶胶循环涂膜并在350 ℃煅烧两次后可得到完整无缺陷的中空纤维TiO₂超滤膜, 膜层平均厚度为1 μm, 膜的纯水渗透通量为145 L·m^-2·h^-1·bar^-1(1 bar=0.1 MPa), 葡聚糖截留分子量为2586 Da, 对应的平均孔径为2.5 nm。     

锐钛矿型TiO2纳米棒薄膜的溶胶-凝胶法制备研究

以钛酸丁酯Ti（OC₄H₉）₄、冰醋酸、去离子水和聚乙二醇（PEG）1000为原料,采用溶胶-凝胶法和旋转涂膜工艺,在玻璃衬底上制备出锐钛矿型TiO₂纳米棒。利用X射线衍射仪（XRD）、SEM和紫外可见光谱（UV/Vis）对TiO₂纳米棒薄膜进行了表征。结果表明,实验制备的TiO₂纳米棒为锐钛矿晶型,在TiO₂反应体系中,胶体粒子在加热过程中偶联在一起,1h后形成了TiO₂纳米棒,其直径为30～50nm,长度为100～200nm。同时,在42mL钛的胶体溶液中添加0.30g PEG（1000）后,纳米TiO₂薄膜的可见光透射峰值降低,TiO₂薄膜表面孔径为20～50nm。     

Er3+掺杂量对TiO2:Er粉体上转换发光性能的影响

通过溶胶-凝胶法制备了Er³⁺离子掺杂的TiO₂纳米粉体。通过X射线衍射、荧光检测对制备的纳米晶微结构、发光性能进行了表征。结果表明：纳米晶微结构及粒径随掺杂量呈规律性变化，掺杂稀土离子可抑制其相变。在980nm红外激光泵浦下，其发射峰分别位于527nm、548nm、660nm处，通过改变Er³⁺掺杂量，获得绿红强度比最高为29.3,最低为0.7,实现了单一掺杂改变发光颜色的调控。借助交叉弛豫与浓度猝灭理论，解释了其发光性能的规律性变化，并分析了其上转换机制。     

B掺杂TiO2光催化剂的制备和光催化性能

采用溶胶-凝胶法合成了B掺杂的TiO₂光催化剂,并用XRD、SEM、XPS、FT-IR、BET等手段进行了表征。结果表明,掺杂B可抑制TiO₂晶体的长大,对TiO₂表面形貌没有显著的影响,B-TiO₂催化剂的比表面积随着B离子掺杂量的提高而增大;B离子主要进入晶格间隙并与TiO₂晶体形成固溶体,以B-O-Ti结构存在。B掺杂量（质量分数）为3%时,制备出的TiO₂光催化剂对甲基橙的降解效果最好。N₂吸附-脱附结果表明,3%B-TiO₂的BET比面积为127.84 m²/g、平均孔径为10.53 nm。     

铕掺杂的TiO2空心微球的制备及光催化性能

通过溶胶-凝胶法制备未掺杂和铕掺杂的TiO₂空心微球, 采用XRD、SEM、TEM、HRTEM、BET和XPS等技术对样品进行表征, 以亚甲基蓝的光催化降解为目标反应, 评价其光催化活性。结果表明, 钛酸四丁酯(TBOT)的加入量对微球的形貌影响较大, 当滴加1.5 mL的TBOT时, 可得结构清晰、分散性良好的TiO₂空心微球。XRD分析表明, 400℃煅烧的纳米TiO₂空心微球为锐钛矿, 掺铕可抑制TiO₂的晶相转变。光催化实验表明, 铕掺杂能显著提高TiO₂空心微球的活性。当铕掺量为0.7%时, 所得样品粒径和孔径最小, 比表面积最大, 光催化活性最高。     

Mg掺杂TiO2纳米晶光氧化还原染料的可逆颜色转变研究

由于非直接接触、远程控制、高效及快捷的优点, 光可逆颜色转换材料在信息存储、显示器件、传感器等领域有着重要应用。复合无机材料和有机材料, 实现协同增效, 是新型光驱动可逆颜色转换材料的研究热点之一。本研究采用一步液相合成法制备粒径约为5 nm的锐钛矿型Mg²⁺掺杂TiO₂纳米晶, 通过X射线衍射、透射电子显微镜、X射线光电子能谱、红外光谱和拉曼光谱等表征手段确认材料的组成结构, 并对比研究了Mg²⁺掺杂TiO₂对亚甲基蓝(MB)光可逆颜色转换性能的增强效应。结果表明, 掺杂Mg²⁺在TiO₂晶格中能产生杂质能级, 有效抑制了光生载流子的复合, 提高了TiO₂光氧化还原MB的活性; 另一方面, 掺杂Mg²⁺降低了TiO₂纳米晶的吸收波长, 在可见光照射下能够有效地抑制MB向还原态LMB的转变, 提高系统着色速率。这种基于碱金属掺杂TiO₂纳米晶的光可逆颜色转换材料在许多光电子器件领域具有潜在的应用价值。     

Al2O3、TiO2溶胶涂覆粉煤灰/黄土支撑体制备陶瓷膜的研究

用溶胶-凝胶法制备了Al₂O₃、TiO₂两种溶胶,分别涂覆在粉煤灰/黄土支撑体表面制备陶瓷膜,并利用热重分析仪、X-射线衍射仪对膜材料的热稳定性、晶相组成进行分析,并对陶瓷膜的微观形貌、孔隙率、膜通量、膜通量恢复率进行测试与表征。结果表明,烧结温度及干燥条件能有效控制陶瓷膜晶相变化及膜层完整性,Al₂O₃、TiO₂膜材料分别在50,25℃时干燥,600℃时烧结,制得的Al₂O₃膜材料为γ-Al₂O₃,TiO₂膜材料为金红石相TiO₂;Al₂O₃、TiO₂陶瓷膜的孔隙率分别为28.56%、34.12%,膜通量分别为1 092.67和2 983.33 L/(m²·h),膜通量恢复率分别为97%、89%。与未覆膜的支撑体相比,Al₂     

离子液体中Co掺杂介孔TiO2可见光催化剂的制备及性能研究

以离子液体([C₄MIM]BF₄)为模板剂, 采用溶胶-凝胶法制备了介孔TiO₂和Co掺杂的介孔TiO₂光催化剂。研究了Co掺杂对样品的比表面积、晶相、元素价态、吸光特性及可见光活性的影响。结果表明: 所制备的Co/TiO₂光催化剂为介孔结构的具有较大比表面积的锐钛矿相纳米颗粒; XPS分析表明: Co以Co²⁺取代Ti⁴⁺进入TiO₂晶格形成杂质能级, 降低了TiO₂带隙能, 有效拓展了TiO₂的光响应范围。以亚甲基蓝水溶液为降解对象, 在可见光 (λ>420 nm)下考察制备样品的光催化活性, 结果表明: Co掺杂的TiO₂具有可见光活性, 且0.3%Co/TiO₂的活性最高。     

Al2O3微滤膜的超疏水改性研究

采用多层自组装技术在Al₂O₃微滤膜表面制备TiO₂纳米涂层, 并利用1H,1H,2H,2H-全氟辛基乙基三乙氧基硅烷(PFDS)对其表面进行氟化处理, 获得超疏水改性膜。通过X射线衍射仪, 傅立叶变换红外光谱仪, 原子力显微镜, 水接触角测试仪和扫描电子显微镜对改性膜进行表征。分析了TiO₂纳米涂层的晶型结构, 探讨了TiO₂沉积时间与改性膜表面粗糙度和疏水性之间的关系, 研究了PFDS改性次数对膜表面形貌和疏水性能的影响规律。结果表明: 在600℃退火1 h后, 获得锐钛矿结构的TiO₂纳米涂层。随TiO₂沉积时间的延长, 膜表面粗糙度增大, 水滴在膜表面的接触由Wenzel状态转变为Cassie状态; 当TiO₂沉积时间为50?min, PFDS改性3次时, 获得理想的微纳米二级超疏水表面形貌, 水接触角达到174.5°。     

介孔电气石/TiO2复合材料的制备及其模拟太阳光光催化性能

采用一步溶胶-凝胶共缩合结合溶剂热合成技术制备出一系列介孔电气石/TiO₂复合材料,表征了复合材料的相结构、形貌、孔隙率、光吸收性质以及组成结构.结果表明:制备的电气石/TiO₂复合材料具有纯锐钛矿晶相、均匀的介孔结构、较大的比表面积(205~242 m²·g^-1)、均匀的孔径分布(3.4~3.8 nm)以及较低的带隙能(3.0 eV).在模拟太阳光照射下,电气石/TiO₂复合材料可以被成功地应用于水中有机污染物罗丹明B和诺氟沙星的降解.降解动力学研究表明:电气石的掺杂提高了TiO₂的光催化量子效率,降低了TiO₂的带隙能.对罗丹明B的降解,电气石掺杂量为1wt%~5wt%的电气石/TiO₂复合材料表现出比纯TiO₂更高的降解速率,对诺氟沙星的降解,电气石/TiO₂复合材料的降解速率高于纯TiO₂的.     

Transmission electron microscopy studies of nanophase TiO2

The chemical and microstructural properties of nanosized TiO₂, obtained by sol—gel procedure, were investigated. The samples were characterized by analytical electron microscopy combining electron diffraction, high resolution electron microscopy and atomic force microscopy. These methods were supported by X-ray diffraction and thermal analysis. The chemical and structural properties, as well as the size of grains, depended on the temperature of TiO₂ preparation. In the temperature range between 293 and 820 K the TiO₂ grains consisted of anatase, as the dominant phase, and brookite. High resolution electron microscopy showed that the sample heated at 573 K had grain sizes from 2 to 10 nm, the average being (5 ± 1) nm, and the pore sizes from 4.5 to 12 nm. The sample heated at820 K revealed larger grain sizes, from 7 to 12 nm, the average being (9 ± 1) nm, and the pore sizes from 6 to 10 nm. These values were confirmed by X-ray diffraction broadening.     

CNTs/TiO2复合物制备及光催化性能研究

在不使用表面活性剂的情况下, 采用溶胶-凝胶法成功制备CNTs/TiO₂复合物, 利用XRD、TEM、HRTEM和SAED对样品的结构和形貌进行了表征。选取亚甲基蓝溶液为目标降解物, 利用紫外-可见(UV-Vis)分光光度计考察了CNTs/TiO₂复合物的光催化活性, 系统研究了CNTs掺杂量对催化降解效率的影响。实验结果表明: 经450℃煅烧, 锐钛矿相TiO₂通过C-O-Ti键均匀地涂覆在CNTs表面, TiO₂颗粒尺寸约16 nm。CNTs/TiO₂复合物光催化活性明显高于纯TiO₂, 当CNTs掺杂量为1wt%时, CNTs/TiO₂复合物对亚甲基蓝的催化降解效率最高, 比纯TiO₂提高11.7%。     

pH对离子液体辅助水热制备介孔二氧化钛结构的影响

以钛酸四丁酯为钛源, 离子液体1-丁基-3-甲基咪唑四氟化硼([C₄MIM]BF₄)为辅助剂, 采用水热法制备了锐钛矿相的介孔二氧化钛。用盐酸和氨水调节反应前驱体的pH, 考察了pH在1~11变化范围内对离子液体-水制备二氧化钛体系的影响。采用X射线衍射和N2吸附?脱附对样品的晶相和孔结构进行表征。结果表明: 离子液体抑制了板钛矿二氧化钛的形成, 随着pH的增大样品的晶化程度增强。pH在1~9较大范围变化时, 其孔径分布较窄, 平均孔径随pH增大由6.6 nm减小到5.0 nm, 此时离子液体能较好的将样品粒径控制在9 nm左右。这与透射电镜分析结果相一致。     

Synthesis and microstructure of boron-doped alumina membranes prepared by the sol–gel method

Pure and boron-doped γ-Al₂O₃ membranes have been synthesized by the sol–gel method. The thermal stability of the unsupported alumina membrane was studied by determining the pore structure (including average pore size, pore volume and BET surface area). The average pore size of the pure alumina membrane increased sharply after sintering at temperatures higher than 1000°C. Addition of 16% boron can considerably stabilize the pore structure of the unsupported alumina membrane. The pore diameter for the B-doped membrane was stabilized within 13 nm after sintering at 1200°C for 5 h. The substantial increase in the pore size for the pure alumina membrane at the sintering temperature of 1000–1200°C was accompanied by the phase transformation from γ-Al₂O₃ to -Al₂O₃. The addition of boron can raise the temperature of this phase transformation significantly and, thus, improves the thermal stability of the membranes.     

TiO2微波碳热合成纳米TiC及其转化过程研

以TiO₂和纳米炭黑为原料, 机械干法混合后, 在Ar气氛下微波碳热合成纳米TiC。合成产物通过XRD和SEM进行表征, 研究了TiO₂粒径、反应温度、保温时间对微波碳热合成纳米TiC物相、显微形貌和TiO₂自身转化率的影响。实验结果表明, 微波碳热还原合成纳米TiC经1300℃保温40 min和1400℃保温30 min可使TiO₂充分反应, 且粒径为40 nm的TiO₂的转化率可达到98.2%, 合成的TiC粒度分布均匀, 平均粒径约小于100 nm。此外, 根据固相扩散机制对不同反应温度下两种粒径TiO₂转化率随时间的变化进行了Avrami方程拟合, 并绘制了两种粒径TiO₂的转化曲线, 为TiO₂与纳米炭黑微波合成纳米TiC提供理论参考。     

Synthesis of nanocrystalline photocatalytic TiO2 thin films and particles using sol–gel method modified with nonionic surfactants

A simple sol–gel route has been developed for the preparation of nanocrystalline photocatalytic TiO₂ thin films and particles at 500 °C. The synthesis involved a novel chemistry method employing nonionic surfactant molecules as a pore directing agent along with acetic acid-based sol–gel route without direct addition of water molecules. This study investigated the effect of surfactant type and concentration on the homogeneity, morphology, light absorption, dye adsorption and degradation, and hydrophilicity of TiO₂ films as well as on the structural properties of the corresponding TiO₂ particles. The method resulted in the synthesis of mesoporous TiO₂ material with enhanced structural and catalytic properties including high surface area, large pore volume, pore size controllability, small crystallite size, enhanced crystallinity, and active anatase crystal phase. The prepared TiO₂ thin films were super-hydrophilic and possessed thermally stable spherical bicontinuous mesopore structure with highly interconnected network. Highly porous TiO₂ films prepared with polyethylene glycol sorbitan monooleate surfactant exhibited four times higher photocatalytic activity for the decoloration of methylene blue dye than the nonporous control TiO₂ films prepared without the surfactant. This sol–gel method modified with surfactant templates is useful in the preparation of nanostructured anatase TiO₂ thin films with high photocatalytic activity and desired pore structure.     

Preparation and visible-light-driven photoelectrocatalytic properties of boron-doped TiO2 nanotubes

In the present study, chemical vapour deposition (CVD) was applied to dope boron into TiO₂ nanotubes anodized Ti in C₂H₂O₄·2H₂O + NH₄F electrolyte with the goal of improving the photocatalytic (PC) activity under visible light. The undoped TiO₂ nanotubes had a highly self-organized structure. However, after doping through CVD, TiO₂ nanotubes suffered from an observable disintegration of morphological integrity. X-ray diffraction (XRD) results confirmed that annealing temperature had an influence on the phase structure and boron impurities could retard anatase–rutile phase transition. Diffuse reflectance absorption spectra (DRS) analysis indicated that B-doped samples displayed stronger absorption in both UV and visible range. B-doped TiO₂ nanotubes electrode annealed at 700 °C through CVD showed higher photoelectrocatalytic (PEC) efficiency in methyl orange (MO) degradation than that annealed at 400 °C and 550 °C. MO degradation was substantially enhanced with the increasing applied bias potential. Moreover, there was a synergetic effect between the electrochemical and photocatalytic processes, and the synergetic factor R reached 1.45. B-doped TiO₂ nanotubes electrode showed good stability after 10 times by repeating photoelectrocatalysis of MO.