聚合物分散剂对纳米TiO_2水悬浮液分散稳定性的影响

纳米TiO2复合乳胶漆的制备一般要求预先分散纳米TiO2并制成水悬浮液。为了制备稳定分散的纳米TiO2水悬浮液,研究了乳胶漆中常用的分散剂SN5040和PEG对纳米TiO2在水溶液中分散稳定性的影响,并分析了分散剂的作用机理。实验结果表明:SN5040能有效分散纳米TiO2,按照先SN5040后PEG的方式添加一定比例的混合分散剂,PEG能在SN5040吸附层上嵌入式吸附,显著提高了纳米TiO2的Zeta电位值,更有利于纳米TiO2水悬浮液的分散稳定性。红外光谱分析(FT-IR)表明:SN5040主要是通过与表面裸露的Ti4+形成配位键而吸附到纳米TiO2粒子表面上的。     

纳米TiO_2-Ni基镀层的电刷镀沉积行为研究

为了使纳米颗粒均匀地悬浮在镀液中从而获得纳米颗粒均匀分布的复合镀层,研究了不同表面活性剂对纳米TiO2在镀液中的分散行为的影响,采用电刷镀方法制备纳米TiO2-Ni基复合镀层,并运用SEM、EDS和XRD研究了纳米TiO2-Ni基镀层的表面形貌和成分特点。结果表明,阳离子型表面活性剂十六烷基三甲基氯化铵(CTAB)对纳米TiO2颗粒的分散效果最好,沉降时间超过40min;CTAB分散的纳米TiO2-Ni基镀层显微硬度比不加表面活性剂的提高50%左右,镀层结合性较好,孔隙率显著降低;CTAB分散的纳米TiO2-Ni基镀层均匀细致、晶粒细小,纳米TiO2被生长着的镍晶粒夹持嵌埋,分布于镍基间隙中,镀层由纳米TiO2颗粒和镍基组成。纳米粉末与镍共沉积符合迁移、吸附、嵌埋的过程。     

环氧树脂／纳米TiO2复合材料的制备与性能研究

以纳米TiO2和聚苯胺包覆纳米TiO2后的颗粒作为增强组分，通过溶液共混法制备环氧树脂基纳米复合材料。IR结果表明，纳米TiO2颗粒表面舜口聚苯胺之间存在强烈的相互作用：这种包覆后的纳米粒子作为填料，能提高其与基体环氧树脂的界面相容性，使其能均匀地分散在环氧树脂基体中，在添加量为3％（质量分数，下同）时，拉伸强度比纯的环氧树脂提高了39．3％。     

表面活性剂对磁流体稳定性及外层包覆结构的影响

采用化学共沉淀法制备粒径分布均匀的纳米Fe3O4颗粒,用油酸钠和聚乙二醇4000(PEG4000)对纳米Fe3O4颗粒进行表面修饰,制得分散稳定的纳米Fe3O4磁流体,通过电动电位(Zeta电位)、粒径测试、离心沉淀、红外光谱分析(FT-IR)和热分析(TG)对修饰后的纳米Fe3O4颗粒进行了稳定性能评价与结构表征。结果表明,油酸钠与纳米Fe3O4颗粒存在两种不同类型的化学键作用;增大油酸钠加入量不会改变Fe3O4颗粒表面包覆结构,但是,其在纳米Fe3O4颗粒表面的吸附量呈先增加后降低的趋势;PEG4000物理吸附于油酸钠包覆的纳米Fe3O4颗粒表面,PEG4000的加入会进一步提高磁流体的稳定性。     

超分散剂对纳米TiO2的表面改性研究

采用超分散剂对纳米TiO2粉体进行表面改性,可将超分散剂分子成功地包覆于TiO2表面,对TiO2表面进行非极性修饰,使其表面由极性亲水性变为非极性亲油性。由沉降性实验观测到超分散剂改性后的纳米TiO2粒子可在非极性溶液中稳定悬浮960h以上;透射电镜(TEM)观测到改性后的TiO2粒子在非极性溶剂中呈纳米级分散状态,团聚体的粒径基本控制在100nm以内;通过润湿性测试及红外分析观察到,颗粒表面由亲水性变为疏水性,纳米TiO2颗粒表面增加了-CH2-和C=O-O基团键的振动峰,因而可以判断纳米TiO2表面状态发生了改变,使TiO2与非极性材料具有较好亲和相容性。本实验也证明了TiO2表面亲油改性的可行性。     

金红石型TiO2纳米棒的制备及其在染料敏化太阳电池中的应用

采用十二烷基苯磺酸钠表面活性剂(DBS)辅助水热法合成TiO2纳米材料,XRD和TEM测试表明,不含DBS的TiO2溶胶水热处理后得到10~20nm锐钛矿型TiO2纳米颗粒;添加DBS后,生成了金红石型TiO2纳米棒.虽然金红石型TiO2纳米棒光电极的染料吸附性能和光电性能均不如锐钛矿型TiO2纳米颗粒光电极,但金红石型TiO2纳米棒漫反射性能较高.可用其制备具有光电转换性能的反射层,这种新型反射层使染料敏化太阳能电池光电转换效率提高了26.14%,而含Ti-nanoxide 300大颗粒TiO2构成的反射层仅能使电池光电转换效率提高11.04%.这种差异的根源在于金红石型TiO2纳米棒不仅具有散射光能力,其本身还可吸附染料进行光电转换.随着反射层厚度的增加,电池短路电流逐步提高.而不吸附染料且无光电转换能力的Ti-nanoxide 300传统反射层则没有这种功能.     

氢氧焰燃烧合成核壳结构纳米 TiO2/SiO2复合颗粒及机理分析

利用多重射流氢氧焰燃烧反应器，通过控制进料方式，以TiCl4和SiCl4为原料合成了具有典型核壳结构的纳米TiO2／SiO2复合颗粒，并分析了氢氧焰燃烧合成过程中核壳结构的形成机理．在纳米TiO2／SiO2复合颗粒中，无定形的SiO2均匀地包覆在晶态TiO2颗粒表面形成核壳结构，引入SiO2不但有效抑制TiO2晶粒的生长，而且抑制了锐钛相向金红石相的转变．在TiCl4和SiCl4次序进料时，TiCl4优先反应并通过成核生长生成TiO2纳米颗粒，SiCl4反应生成的SiO2通过在TiO2颗粒表面非均相成核生长，形成核壳结构的纳米复合颗粒．     

MWNTs-TiO2和AC-TiO2复合材料制备及其在染料吸附降解中的应用

采用溶胶-凝胶法,以钛酸四丁酯为原料,分别以多壁碳纳米管和活性炭为载体,并分别在载体表面上负载纳米TiO2颗粒,制备出碳纳米管-TiO2(MWNTs-TiO2)和活性炭-TiO2(AC-TiO2)两种复合材料。采用X射线粉末衍射(XRD)和透射电子显微镜(TEM)对样品进行表征,结果显示,经500℃热处理后,TiO2主要以锐钛矿形式存在,纳米TiO2颗粒均匀的负载于载体的表面。吸附降解的实验结果表明,MWNTs-TiO2和AC-TiO2两种复合材料对活性染料甲基橙吸附降解效果均好于纯纳米TiO2颗粒,而MWNTs-TiO2复合材料的吸附降解效果更好,更适合作为纳米TiO2光催化载体。     

表面活性剂Span80和促进剂对TiO2/硅油电流变液性能的影响

用液相包覆法研究了非离子表面活性剂Span80在锐钛矿型微米和纳米TiO2颗粒上的包覆工艺,并在研制的电流变仪上测定了不同电流变液配方TiO2/硅油电流变体的静态剪切应力τ与外加直流电场强度E的关系.结果表明:颗粒完全被Span80包覆,表面活性剂提高TiO2分散性和悬浮性;在直流电场作用下,表面活性剂Span80在颗粒表面形成的胶层促进电流变体的极化;加入适量促进剂提高了电流变性;在微米TiO2/硅油体系中混入少量纳米TiO2可提高电流变体的抗剪应力.     

TiO_2纳米颗粒/纳米棒阵列复合薄膜的制备及其光电催化性能

以金属钛箔为钛源,采用双氧水和盐酸体系,通过水热法制备合成TiO2纳米棒阵列薄膜,并通过调节双氧水和盐酸的用量,调控TiO2纳米棒阵列薄膜的微观形貌和物相构成。结合溶剂挥发自组装法将TiO2纳米颗粒引入纳米棒阵列中,得到复合型TiO2光催化剂。以亚甲基蓝为模拟污染物,考察TiO2复合薄膜的光催化活性。通过扫描电镜(SEM)和X射线衍射(XRD)测试对TiO2复合薄膜的物相和表面形貌等进行了表征,并采用电化学交流阻抗法(EIS)分析其表面电荷转移特性。TiO2纳米颗粒/纳米棒阵列复合薄膜在光电协同条件下,展示出高的光电催化活性。     

炭包覆TiO2复合物对低浓度苯的光催化降解

通过将TiO2粉末和聚乙二醇混合,随后在氮气气氛下热处理合成了炭包覆TiO2.利用粉末X射线衍射、紫外-可见漫反射光谱、透射电子显微镜和氮吸附对炭包覆TiO2复合物样品进行了表征,并研究了其对浓度为～1.2×10-5苯的光催化活性.结果表明:炭包覆量受热处理温度和聚乙二醇用量的影响,随着温度的升高和聚乙二醇量的减少而减少;TiO2的结晶度随着温度的升高而提高,但是炭包覆对TiO2晶体的生长有抑制作用.炭包覆锐钛矿样品比纯TiO2表现出对苯更高的光催化活性,这是由于炭吸附作用导致锐钛矿颗粒周围的苯浓度增加以及包覆炭可导致电荷的有效分离;另一个原因是锐钛矿相结晶度的提高.因此,要获得对苯具有高光催化活性的炭包覆TiO2需要综合考虑碳含量和锐钛矿晶体结构.

Abstract：

Carbon-coated TiO2 was synthesized by mixing TiO2 powders and polyethylene glycol,followed by heat treatment in nitrogen atmosphere. All samples were characterized by powder X-ray diffraction,UV diffuse reflectance spectroscopy,high-resolution transmission electron microscopy,and nitrogen adsorption. The photocatalytic activity of carbon-coated TiO2 for benzene degradation was investigated with a benzene concentration of ～ 1.2 × 10-5. Results showed that the residual carbon content was influenced greatly by heat treatment temperature (HTT)and the amount of PEG,which decreased and increased with increasing the temperature and the amount of PEG,respectively. The crystallinity of TiO2 was improved when the HTT increased. However,the carbon residue had an inhibition effect on the crystal growth of TiO2. The carbon-coated anatase samples were shown to exhibit higher photocatalytic activities than the pristine TiO2 because of the adsorption enrichment of benzene by carbon around the anatase particles and of the effective charge separation due to the electronic conduction of carbon. Another important factor affecting photocatalytic activity was the crystallinity of the anatase phase. High photocatalytic activity for benzene requires a balance between the carbon content and the anatase crystalline structure.     

Dispersion stability of nano-Sb2O3 particles modified with polyethylene glycol

The surface of nano-Sb₂O₃ particles was modified with polyethylene glycol (PEG) using the mechanochemical method, and the dispersion mechanism of modified nano-Sb₂O₃ particles was also discussed. The modified nano-Sb₂O₃ particles were characterized by transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), thermal analysis (TGA) and UV absorbance. The results showed that the surface of nano-Sb₂O₃ particles was successfully coated by PEG molecules through the effect of hydrogen bonding, and the dispersion of nano-Sb₂O₃ particles in ethyl alcohol (C₂H₅OH) was significantly improved. Due to the different adsorption conformations of PEG molecules, the dispersion stability of nano-Sb₂O₃ particles was gradually improved with the increase of PEG average molecular weight and concentration. However, the superfluous PEG molecules would weaken the dispersion stability of nano-Sb₂O₃ particles.     

Synthesis of nano titania particles embedded in mesoporous SBA-15: characterization and photocatalytic activity

Supported nanocrystalline titanium dioxide (TiO2) has been prepared by a post-synthesis step via Ti-alkoxide hydrolysis through the use of mesoporous SBA-15 silica. TiO2/SBA-15 composites with various TiO2 loading have been prepared and characterized by X-ray diffraction, nitrogen adsorption, Fourier transform infrared spectroscopy and diffusive reflective UV-vis spectroscopy. The addition of mesoporous SBA-15 prevents the anatase to rutile phase transformation and the growth of crystal grain. TiO2 did not block the SBA-15 pores, and their surface was fully accessible for nitrogen adsorption. Calcination in air of the composites up to 800 degrees C did not change the nanocrystal phase and slightly increased the domain size from 5.0 to 7.5 nm, indicating that the anatase TiO2 grains in the mesostructures have a relatively high thermal stability and proper pore diameter allows controlling the size of obtained titania particles. The TiO2/SBA-15 composites prepared by this study showed much higher photodegradation ability for methylene blue (MB) than commercial pure TiO2 nanoparticles P-25. Experimental results indicate that the photocatalytic activity of titania/silica mixed materials depends on the adsorption ability of composite and the photocatalytic activity of the titania, and there is an optimal ratio of Ti:Si, too high or low Ti:Si ratio will lower the photodegradation ability of the composites.     

表面TiO2包膜对制备CaCO3／TiO2复合材料颜料性能的影响

采用机械力化学方法，通过对碳酸钙进行表面TiO2包膜制备了CaCO3／TiO2复合材料，对CaCO3／TiO2复合材料的颜料性能、CaCO3和TiO2的结合形态与反应机理进行了研究。结果表明：CaCO3／TiO2复合材料形成了具有类似钛白粉的颜料性质，遮盖力为钛白粉的90％，吸油量和紫外线吸收功能与钛白粉相同；CaCO3／TiO2复合材料中TiO2在CaCO3颗粒表面形成均匀包覆和二者通过各自表面羟基形成化学结合是导致其呈现钛白粉颜料性质的内在机制。     

Formation of Janus TiO2 nanoparticles by a pickering emulsion approach applying phosphonate coupling agents

Anisotropic surface modification of TiO2 nanoparticles was achieved applying a Pickering emulsion approach. TiO2 nanoparticles were prepared by sol-gel routes which allowed an excellent control over their size and morphology. The obtained colloids were further used as stabilizers in the formation of oil-in-water Pickering emulsion. For reasons of comparison, also commercially available titanium dioxide nanoparticles (Evonik AEROXIDE TiO2 P25) were used in the functionalization experiments. An organophosphorus coupling agent present in the oil phase coordinated to the surface of the anatase nanoparticles. In such a way an anisotropic surface modification of the particles was achieved which increased the stability of the Pickering emulsion. Spectroscopic studies revealed the presence of organophosphorus coupling agents which exhibited a covalent bonding to the surface of the particles. Thermogravimetric analyses confirmed a lower surface coverage of the particles modified in emulsion compared to those modified in suspension. Reactions of organophosphorus coupling agents containing an additional methacrylate group applying an organic monomer (methyl methacrylate) as the oil phase of the Pickering emulsion resulted in hybrid TiO2@polymer spheres. Spectroscopic characterization of the resulting particles revealed that the phosphonates were coordinated to the TiO2 surface and at the same time copolymerized with the MMA within the oil droplet. Morphological investigations of the isolated final product showed that the material was composed of polymer spheres with the stabilizing TiO2 nanoparticles on their surface.     

溶胶／凝胶法制备纳米TiO2／Al2O3

采用溶胶-凝胶法制备纳米TiO2／Al2O3，考察了陈化温度及络舍比对TiO2／Al2O3比表面积及孔结构参数的影响。结果表明，TiO2／Al2O3平均粒径〈70nm，比表面积超过210m^2／g，平均孔径0．8-1．4nm。适当降低陈化温度及加络合剂有利于TiO2／Al2O3粒子的分散。Al2O3的存在提高了TiO2／Al2O3的热稳定性。     

Synergy between surface adsorption and photocatalysis during degradation of humic acid on TiO2/activated carbon composites

A photocatalyst comprising nano-sized TiO(2) particles on granular activated carbon (GAC) was prepared by a sol-dipping-gel process. The TiO(2)/GAC composite was characterized by scanning electron microscopy (SEM), X-ray diffractiometry (XRD) and nitrogen sorptometry, and its photocatalytic activity was studied through the degradation of humic acid (HA) in a quartz glass reactor. The factors influencing photocatalysis were investigated and the GAC was found to be an ideal substrate for nano-sized TiO(2) immobilization. A 99.5% removal efficiency for HA from solution was achieved at an initial concentration of 15 mg/L in a period of 3h. It was found that degradation of HA on the TiO(2)/GAC composite was facilitated by the synergistic relationship between surface adsorption characteristics and photocatalytic potential. The fitting of experimental results with the Langmuir-Hinshelwood (L-H) model showed that the reaction rate constant and the adsorption constant values were 0.1124 mg/(L min) and 0.3402 L/mg. The latter is 1.7 times of the calculated value by fitting the adsorption equilibrium data into the Langmuir equation.     

Ag掺杂APS改性的TiO2颗粒的制备及其光催化降解作用

为提高Ag/TiO2纳米颗粒的光催化降解作用,采用聚合凝胶工艺路线,以钛酸四丁酯为前驱体,硝酸银为银源,通过向反应体系引入鳌合剂醋酸、表面改性剂γ-氨丙基三乙氧基硅烷(APS)以及还原剂甲醛等添加剂,制备出TiO2粉体及Ag/TiO2纳米复合粉体。利用FT-IR、XRD、TG-DTA、TEM和UV-Vis-NIR等手段对样品进行表征。结果表明,经γ-氨丙基三乙氧基硅烷改性的TiO2颗粒掺Ag后分散性得到改善,粒径约1 nm的Ag颗粒较均匀地分布在10～15 nm TiO2颗粒上;可见光的利用和锐钛矿热稳定性都得到提高;Ag/TiO2纳米颗粒在光照下对甲基橙具有良好的光催化降解效果。     

Adsorption and degradation of model volatile organic compounds by a combined titania-montmorillonite-silica photocatalyst

A series of adsorptive photocatalysts, combined titania-montmorillonite-silica were synthesized. The resultant photocatalysts consisted of more and more spherically agglomerated TiO(2) particles with increasing of TiO(2) content, and anatase was the only crystalline phase with nano-scale TiO(2) particles. With increasing of the cation exchange capacity to TiO(2) molar ratio, specific surface area and pore volume increased very slightly. In a fluidized bed photocatalytic reactor by choosing toluene, ethyl acetate and ethanethiol as model pollutants, all catalysts had relatively high adsorption capacities and preferred to adsorb higher polarity pollutants. Langmuir isotherm model better described equilibrium data compared to Freundlich model. Competitive adsorptions were observed for the mixed pollutants on the catalysts, leading to decrease adsorption capacity for each pollutant. The combined titania-montmorillonite-silica photocatalyst exhibited excellent photocatalytic removal ability to model pollutants of various components. Almost 100% of degradation efficiency was achieved within 120 min for each pollutant with about 500 ppb initial concentration, though the efficiencies of multi-component compounds slightly decreased. All photocatalytic reactions followed the Langmuir-Hinshelwood model. Degradation rate constants of multi-component systems were lower than those for single systems, following the order of toluene相似文献