乙醇辅助低温水热法生长TiO2纳米棒阵列

本文采用乙醇作为添加剂，通过低温水热法在透明导电玻璃衬底上制备晶化良好的金红石相TiO₂纳米棒阵列。对样品进行了X射线衍射(XRD)、扫描电子显微镜(SEM)等结构形貌表征和光电化学性能测试。实验发现乙醇加入有利于前驱物水解缩聚反应，同时提高水热反应压力，促进TiO₂晶粒低温成核和生长，从而实现70℃直接在基底表面生长出TiO₂纳米棒阵列。通过调控水热反应温度、时间以及乙醇添加量等参数可有效调控TiO₂纳米棒阵列的形貌，改善其光电化学性能。同时低温水热制备工艺也降低了对衬底材料的限制，拓展了TiO₂纳米棒阵列的应用领域，表现出良好的应用前景。     

色氨酸辅助合成光催化活性增强的球形纳米TiO2

以L-色氨酸（L-Trp）为生物模板,采用简单水解及煅烧后制备了球形结构TiO₂纳米光催化剂。通过X射线衍射、扫描电子显微镜、红外光谱、紫外-可见漫反射光谱、光致发光光谱和N₂吸附-解吸等方法对制得的TiO₂纳米材料进行表征。在催化剂合成过程中,L-Trp作为生物模板发挥至关重要的作用,能够指导球形结构纳米TiO₂的形成。考察了不同煅烧温度下制备的TiO₂样品光催化活性,结果表明550℃时制备的TiO₂样品具有优异的光催化活性,紫外光照射30min对甲基橙溶液的降解率达到95%左右,主要是由于较大比表面积和球形结构的协同效应。光催化剂稳定性实验表明,所制备的TiO₂纳米材料可作为一种实用有效的光催化剂用于紫外光照射下降解有机染料。同时,对L-Trp辅助下球形结构TiO₂纳米颗粒的可能生长机理进行讨论。     

纳/微复合结构TiO2负载催化剂的加氢脱硫性能

以传统固相烧结法制备的不稳定的层状K₂Ti₂O₅为前驱体, 直接将钛酸钾晶须进行离子交换得到具有纳微复合结构的TiO₂载体, 等体积浸渍法制备出MoO₃/TiO₂催化剂, 运用SEM、XRD、BET、TEM等技术手段对载体和催化剂进行表征, 并考察了该TiO₂复合结构负载催化剂的加氢脱硫催化活性。SEM和XRD分析显示:该纳微米复合结构是由纳米颗粒与微米晶须构成的特殊结构, 拥有不同形貌和尺寸的TiO₂却具有相同的锐钛矿相。与单独TiO₂纳米粒子和TiO₂晶须相比, TiO₂复合结构负载催化剂表现出更佳的脱硫催化能力, 在温度310℃、压力2.1 MPa、体积空速6 h^-1、氢/油体积比600条件下, 催化剂表现出优异的DBT脱硫性能。     

纳米TiO2的溶胶凝胶合成及其光催化降解水面石油废料

通过在溶胶凝胶法中添加尿素作为燃料，成功调控合成锐钛矿/金红石相TiO₂和纯金红石相TiO₂。相结构表征和官能团信息表征确认了锐钛矿/金红石相TiO₂和纯金红石相TiO₂中不含其它杂质。经谢乐公式计算，锐钛矿/金红石相TiO₂和纯金红石相TiO₂的平均晶粒尺寸分别为30.28 nm和35.86 nm。扫描电镜发现，细的球形颗粒为锐钛矿相TiO₂,细长的纳米棒为金红石相TiO₂,颗粒尺寸与谢乐公式计算的结果类似。光学性质表征发现，与纯金红石相TiO₂相比，锐钛矿/金红石相TiO₂具有可见光吸收能力，表明其有可见光光催化活性。以水面原油废料为目标降解产物，将P25 TiO₂、锐钛矿/金红石相TiO₂和纯金红石相TiO₂负载在漂珠上，在模拟太阳光和可见光辐照下进行光催化降解实验。结果表明，由于空穴、羟基自由基和...     

TiO2协同增强ZIF-8光催化降解特性研究

工业有机废水污染危害人类健康,阻碍经济的发展,是当前急需解决的问题。金属有机骨架(MOFs)材料因其独特的孔道结构、较大的比表面积、优异的吸附性能,有望成为工业有机废水处理的潜在新材料。ZIF-8(沸石咪唑酯骨架-8)具有复杂的SOD拓扑结构和高稳定性,其工业废水吸附应用价值逐渐受到关注。本文首先通过溶胶-凝胶法和温度调控制备最佳相比例的锐钛矿/金红石混合相TiO₂纳米颗粒,采用溶剂法在TiO₂颗粒表面原位生长制备了包覆型ZIF-8复合材料。结果表明,引入10%(质量分数)TiO₂与ZIF-8构筑的复合材料对亚甲基蓝(MB)污染物的降解率和反应速率遵循一级动力学模型,分别是纯ZIF-8的1.27和2.3倍。可控制备且均匀分布在ZIF-8有机框架材料孔道中的Zn/ZnO_x纳米异质结作为活化位点,增加与MB分子的接触面积,提升对载流子的俘获数量,同时TiO₂与裸露的高活性异质结界面形成协同增强效应,构成立体催化降解复合体系,提高催化降解能力。     

PFSA-PES-纳米颗粒复合纳米纤维的制备及催化性能

利用静电纺丝法制备了全氟磺酸(PFSA)-聚醚砜(PES)-纳米颗粒(SiO₂、TiO₂和Al₂O₃)复合纳米纤维,比较了SiO₂、TiO₂和Al₂O₃等不同纳米颗粒对磺酸基团在纤维表面分布的影响,并利用乙酸乙酯合成反应考察了纤维结构对表面磺酸基团活性的关系。结果表明:静电纺复合纳米纤维的比表面积可达85.6 m²·g^-1,纳米颗粒均匀分布在纤维表面,表面酸性中心占PFSA酸性基团总量最高达71.2%。酯化反应实验表明,复合纳米纤维具有很好的催化性能,纳米颗粒的存在可以提高酸中心的活性;同时,所得复合纳米纤维膜表现出很好的回收与可再生性能,有望作为一种对环境友好的固体酸催化剂。     

WC/TiO2纳米复合材料晶相形成机理及电催化性能

以金红石相纳米TiO₂为载体,偏钨酸铵为钨源,采用表面修饰技术制备了纳米复合材料的前体,将前体在甲烷/氢气气氛下还原碳化并采用XRD对其进行表征,研究了还原碳化温度、时间对纳米复合材料晶相组成的影响,并探讨了WC/TiO₂纳米复合材料的形成机理。通过扫描电子显微镜、热重-差热分析等手段对WC/TiO₂纳米复合材料的形态结构和热稳定性进行了表征。采用循环伏安法研究了纳米复合材料物相组成与电催化性能之间的关系,结果表明由WC和TiO₂两相组成的WC/TiO₂纳米复合材料对对硝基苯酚电还原反应的电催化性能最佳。     

基于阳极氧化法的TiO2纳米管制备及生成过程分析

运用阳极氧化法制备TiO₂纳米管,探讨了TiO₂纳米管紫外光催化净化头孢噻肟钠抗生素废水的效果,采用扫描电镜（SEM）和X射线衍射仪（XRD）对TiO₂纳米管进行了表征分析。SEM结果显示,制备的TiO₂材料表面呈阵列排布的多孔状,内径大小均匀,管径分布在30~45nm之间,管阵列呈蜂窝状,与钛板表面垂直,对比煅烧前后的TiO₂纳米管XRD图,发现煅烧后样品的XRD图出现了TiO₂锐钛矿型特征衍射峰和金红石型特征衍射峰。讨论了TiO₂纳米管的生成机理,认为纳米管的形成过程主要有最初氧化层的形成、孔核的形成、由孔核演变成微孔、微孔生长并出现空隙、形成纳米阵列管过程。     

火焰法制备CNTs基复合材料及其应用研究进展

火焰法制备CNTs及其复合材料具有可连续操作、成本低廉等优势，是一种极具应用潜力的制备技术。然而，火焰环境的复杂性造成产品结构和组成难以精确控制，在实际应用时不利于产品性能的调控和提升。本文首先介绍了火焰法的基本构型(扩散火焰和预混合火焰)，并结合燃料、催化剂和制备CNTs的结构说明了不同火焰法工艺的特点。随后简要说明了火焰环境中CNTs生长的一般过程，即吸附-扩散-沉积过程，结合这一基本过程介绍了顶部/底部生长机理、颗粒接触生长机理和异形(螺旋状、竹节状、空心/实心结构、分支结构等) CNTs的生长机理。在全面总结火焰法制备CNTs基复合材料在储能、催化、光热转化等领域应用的基础上，指出现有火焰法制备工艺存在可控性差、产品组成复杂等问题，在实际应用时不利于相关性能的调控。在未来研究中，持续改进和优化火焰法工艺，如采用混合式制备工艺或构建分段式燃烧器构型，对于提高工艺过程可控性并实现产品组成和结构的调控具有积极作用。     

Ce-TiO2粉体的制备及其光催化性能研究

以钛酸丁酯为前驱体,采用溶胶-凝胶法制备Ce掺杂纳米TiO₂。结合XRD、TEM、UV-Vis等现代检测手段对所制备样品的结构和性能进行表征。以直接桃红12B为目标降解产物,考察了所制备样品的光催化活性。研究结果表明:样品在550℃煅烧后,TiO₂为锐钛矿型,Ce掺杂纳米TiO₂后晶粒尺寸由23.9 nm降低到19.8 nm。Ce掺杂引起TiO₂的光学吸收边红移,提高可见光的吸收,拓展了TiO₂光谱响应范围。催化剂投加量为0.5 g/L,直接桃红12B溶液的初始浓度为20 mg/L,p H值为5。在紫外光下2 h条件下,Ce掺杂TiO₂后去除率由83.6%提高到93.8%。低浓度下的光催化降解过程可用Langmuir-Hinshelwood一级动力学方程拟合,初始浓度20 mg/L时,吸附速率可达到0.063 04 min^-1。     

On the modification of photocatalysts for improving visible light and UV degradation of gas-phase toluene over TiO2

The photocatalytic behavior of different TiO₂-based photocatalysts was reported for gas-phase toluene removal under both UV and visible light illumination, and compared to that of commercial P25 (Degussa) TiO₂. Promotion by sulfates and the use of nanosized anatase TiO₂ were reported to strongly increase the toluene removal efficiency under UV illumination. Nanosized-anatase was prepared by a protecting group sol–gel synthesis using hexamethyldisilazane as crystallite growth inhibitor. Sulfates played a double positive role, with photogenerated electrons transfer effects limiting charge recombination and as repulsive species for strongly adsorbed aromatic intermediates that act as poisons. The decrease in particle size obtained on nanosized anatase TiO₂ (5 nm) yielded a considerable enhancement in the toluene removal efficiency. Pure high surface area rutile has been synthesized at low temperature by a polyethylenglycol-containing sol–gel method for visible light activation purposes. A two-way semiconductor coupling phenomenon, consisting of a reciprocal electron/hole transfer between two visible light-activated oxides, rutile TiO₂ and WO₃, was proposed to explain the large gain in efficiency when adding low amounts of WO₃ to rutile TiO₂.     

Ni-P-PTFE复合镀层对颗粒污垢沉积特性影响研究

为探究Ni-P-PTFE复合镀层对颗粒污垢沉积特性的影响,利用化学镀工艺在碳钢表面制备Ni-P-PTFE复合镀层,以TiO₂纳米颗粒为研究对象,通过实验和理论分析的方式研究了不同表面能（PTFE浓度）下Ni-P-PTFE复合镀层在TiO₂悬浮液中的颗粒污垢沉积特性。结果表明：相比于碳钢试样,Ni-P-PTFE复合镀层对于TiO₂颗粒沉积具有较好的抑制效果。随着PTFE浓度的增加,复合镀层的表面能降低,污垢沉积量呈下降趋势,在表面能为26.8 mJ/m²（PTFE=12 ml/L）时,TiO₂颗粒污垢在Ni-P-PTFE复合镀层的沉积量最小。实验结果与应用扩展的DLVO理论计算出的最佳表面能结果相一致,也为针对不同类型颗粒在换热表面的沉积的抑垢提供了指导施镀的依据。     

Ni-P-PTFE复合镀层对颗粒污垢沉积特性影响研究

为探究Ni-P-PTFE复合镀层对颗粒污垢沉积特性的影响,利用化学镀工艺在碳钢表面制备Ni-P-PTFE复合镀层,以TiO₂纳米颗粒为研究对象,通过实验和理论分析的方式研究了不同表面能（PTFE浓度）下Ni-P-PTFE复合镀层在TiO₂悬浮液中的颗粒污垢沉积特性。结果表明：相比于碳钢试样,Ni-P-PTFE复合镀层对于TiO₂颗粒沉积具有较好的抑制效果。随着PTFE浓度的增加,复合镀层的表面能降低,污垢沉积量呈下降趋势,在表面能为26.8 mJ/m²（PTFE=12 ml/L）时,TiO₂颗粒污垢在Ni-P-PTFE复合镀层的沉积量最小。实验结果与应用扩展的DLVO理论计算出的最佳表面能结果相一致,也为针对不同类型颗粒在换热表面的沉积的抑垢提供了指导施镀的依据。     

二维共轭碳材料/TiO2复合光催化剂制备及表征

选用两种二维共轭碳材料石墨烯(GR)和石墨炔(GD),通过水热合成的方法原位生长制备TiO_2-GR和尿素分散的TiO_2-GR以及TiO_2-GD复合材料光催化剂,对3种复合材料催化剂的表面形貌和物相结构进行表征,并测试3种催化剂光催化剂性能。结果表明,石墨烯和石墨炔的加入,对TiO_2起到明显的分散作用,TiO_2颗粒与石墨烯和石墨炔紧密结合;尿素的加入使TiO_2-GR颗粒尺寸进一步减小,TiO_2分散度进一步提高。在模拟太阳光辐射下,一定时间内光催化剂光降解有机染料亚甲基蓝和甲基橙,结果表明,二维共轭碳材料石墨烯和石墨炔的加入使复合材料光催化剂TiO_2-GR和TiO_2-GD的光催化性能为纯TiO_2光催化剂的1. 67倍和1. 68倍,复合材料光催化剂表现出更优秀的催化性能。     

异丙醇钛控制水解的小角X射线散射研究

由金属醇盐水解制备溶胶的方法已广泛应用于溶胶-凝胶法制备纳米孔无机膜,但对金属醇盐水解机理的认识十分有限。通过控制异丙醇钛[Ti（i-OC₃H₇）₄]在异丙醇（i-C₃H₇OH）中水解制备TiO₂溶胶,利用小角X射线散射（SAXS）方法研究了由不同H₂O/Ti（i-OC₃H₇）₄的反应混合物[Ti（i-OC₃H₇）₄：H₂O：i-C₃H₇OH=1：m：30（摩尔比）]形成TiO₂溶胶的过程,探讨了控制Ti（i-OC₃H₇）₄水解的过程中胶粒形成与长大的规律。研究结果表明,所合成的TiO₂溶胶的胶粒粒径小于10 nm,胶粒的形成和长大与H₂O/Ti（i-OC₃H₇）₄摩尔比密切相关。H₂O/Ti（i-OC₃H₇）₄（摩尔比） ≥ 2.0时,随着H₂O/Ti（i-OC₃H₇）₄增加,溶胶的稳定性下降。     

Au–TiO2 catalysts on carbon nanofibres prepared by deposition-precipitation and from colloid solutions

Au catalysts have been prepared (i) on TiO₂, (ii) on carbon nanofibres (CNF) and (iii) on TiO₂ deposited onto CNF. Catalysts prepared from deposition-precipitation (DP) and from colloid solutions have been characterised using XRD, TEM, TGA and XAS and tested in the water–gas shift (WGS) reaction. DP yields large Au particles (>50 nm) on CNF-containing supports. High Au dispersion on carbon nanofibres requires preparation via other methods such as colloid formation. Au particle growth is more pronounced during the synthesis steps than during thermal treatments. This increase is not observed for the Au particles on TiO₂ but only when CNF is present, indicating that the surface properties of TiO₂ are altered by the CNF. TiO₂ XANES analyses show that distortions in the lattice symmetry of TiO₂ are introduced when the oxide is deposited on CNF. The distortion of the TiO₂ structure by the CNF may also introduce changes that promote the turnover frequencies. The WGS activity significantly improves when titania is present. This shows that coexistence of Au and TiO₂ is needed to obtain high catalytic activity in the WGS reaction, indicating that the active sites are either on the Au–TiO₂ interface or that the reaction follows a bifunctional mechanism.     

Interface interaction and structural transformation in particles of ceramic and cermet composite powders in flame spraying

The behavior of particles of Al₂O₃, TiO₂, Al₂O₃ - TiO₂, Al₂O₃ - Ni, ZrO₂ - Ni, Al₂O₃ - Ni- Ti powders in flame spraying has been studied. The interaction between the surface tension forces and the wetting forces has been found to produce either a melt shell around the particles core or drops of the second component on the surface of the core. Subsequently a total or partial capture of drops of the second component melt by the core melt or their separation during the movement within the plasma jet volume are possible. At high particle heating and cooling rates, polymorphous transformations, higher - to - lower oxide transformations and metastable phase fixations in the coating take place. These effects influence the conditions of ceramic powder plasma coating formation and also the properties of the coatings.     

Preparation and characterization of TiO2–SiO2 nano-composite thin films

TiO₂ nanocrystalline particles dispersed in SiO₂ have been prepared by the sol-gel method using titanium- and silicon-alkoxides as precursors. Nano-composite thin films were formed on the glass substrates by dip-coating technique and heat treated at temperatures up to 500 °C for 1 h. The size of the TiO₂ nanocrystalline particles in the TiO₂–SiO₂ solution ranged from 5 to 8 nm. The crystalline structure of TiO₂ powders was identified as the anatase phase. As the content of SiO₂ increased, the anatase phase tended to be stabilized to higher temperature. TEM results revealed the presence of spherical TiO₂ particles dispersed in a disk-shaped glassy matrix. Photocatalytic activity of the TiO₂–SiO₂ (1:1) thin films showed decomposition of 95% of methylene blue solution in 2 h and a contact angle of 10°. The photocatalytic decomposition of methylene blue increased and the contact angle decreased with the content of TiO₂ phase. TiO₂–SiO₂ with the molar ratio of 1:1 showed a reasonable combination of adhesion, film strength, and the photocatalytic activity.     

超细颗粒聚团流化的临界流化速度

在内径50 mm的流化床实验台上,测量SiO₂、Al₂O₃和TiO₂ 3种超细颗粒原生粒径从30 nm增加到5 μm的临界流化速度（U_mf）,并以Geldart A类颗粒（粒径45 μm）为参照。结果表明：3种超细颗粒的U_mf随粒径的变化规律一致,随原生粒径从30 nm增加到5 μm,U_mf逐渐增大;当颗粒粒径增加到45 μm,U_mf大幅度减小,其与原生粒径为30和200 nm时接近。对于不同材料,U_mf由大至小的顺序依次为TiO₂、Al₂O₃、SiO₂。粉体安息角测量表明：对于同种材料颗粒,原生粒径对超细颗粒的U_mf和安息角的影响规律一致,即5 μm超细颗粒的安息角最大。聚团尺寸模型计算表明：稳定流化时,聚团尺寸随原生粒径的变化趋势以及随不同材料的变化趋势均与U_mf的变化趋势一致。研究结果为超细颗粒流化临界速度预测研究奠定了基础。     

Particle Size Effect on the Crystal Structure of Y2O3 Particles Formed in a Flame Aerosol Process

Y₂O₃ is a material with wide applications. Its cubic and monoclinic polymorphs have significantly different mechanical and optical properties. The flame aerosol technique offers unique advantages in the synthesis of Y₂O₃ particles, but it also faces the challenge of phase control for Y₂O₃. One possible strategy for Y₂O₃ phase control is to utilize the particle size effect that causes the formation of the monoclinic phase at atmospheric pressure. In this study, the particle size effect on crystal structure was experimentally investigated for Y₂O₃ particles synthesized in a high-temperature flame aerosol process. A critical particle diameter of approximately 1.5 μm was found by single-particle electron diffraction. At the critical diameter, the probability is 50% for a particle to be either cubic or monoclinic. Particles significantly smaller than the critical diameter were all monoclinic, while those significantly larger were all cubic. The critical diameter was interpreted using an analysis that involves the free energy of a particle, which includes the bulk Gibbs free energy and the surface energy.