高比表面TiO2光催化剂的制备及产氢性能研究

以钛酸四丁酯为前驱体，十六烷基三甲基溴化铵(CTAB)为模板剂合成了高比表面的TiO₂超细纳米粉体。采用XRD、TEM、BET分析方法对催化剂的物相、颗粒粒径及比表面积进行了表征，结果显示TiO₂的晶粒尺寸和比表面积与CTAB添加量和焙烧温度有关。重点考察了不同条件下制备的TiO₂系列光催化剂无氧条件下的光催化分解水产氢性能。实验结果表明，当CTAB与Ti的投料的物质的量之比为0.15，焙烧温度为450 ℃时，获得的晶粒尺寸为5.73 nm、比表面为150 m²·g^-1的TiO₂粉体具有最好的光催化产氢活性，测得的3 h内平均产氢速率为12.5 mL·h^-1。     

超声场中纳米TiO2表面包覆氧化硅的研究

在超声场中，通过硅酸钠水解生成的无定形氧化硅对金红石相纳米TiO₂进行表面包覆，利用红外光谱、X射线光电子能谱、X射线衍射和透射电镜对所得样品进行了表征，并对纳米TiO₂的光稳定性和分散性进行了评价。红外光谱和X射线光电子能谱表明，氧化硅以化学键合的方式沉积在纳米TiO₂的表面，在包覆层和纳米TiO₂颗粒之间的界面上形成了Ti-O-Si键。TEM照片、表面元素分析和光稳定性实验显示，氧化硅在纳米TiO₂表面形成了均匀的包覆层，超声场有助于提高包覆层的均匀性和致密性。氧化硅的表面包覆提高了纳米TiO₂在水中的分散性、紫外线屏蔽能力和可见光透过性。随着氧化硅含量的增加，纳米TiO₂的光稳定性逐渐提高，当m(SiO₂)∶m(TiO₂)>1∶5时，纳米TiO₂的光稳定性基本不变，而且在热处理过程中纳米TiO₂的晶粒生长得到有效抑制。     

纳米TiO2低温水解法的晶型控制合成及其表面织构的研究

分别以TiCl₄，Ti(NO₃)₄和Ti(SO₄)₂为前驱体，在低温和强酸性条件下，通过水解反应可控地合成了具有不同晶相组成，且比表面积较高的纳米TiO₂，并用XRD，TEM和N₂^-吸附脱附技术对其晶相、粒径大小、形貌及比表面积进行了表征。结果表明，钛离子在有Cl^-、NO₃^-存在的酸性溶液中水解，水解温度≤80 ℃，可以生成结晶良好的具有细小晶粒尺寸和较高比表面积的金红石型纳米TiO₂粉体，水解温度>80 ℃，反而有锐钛矿型TiO₂生成，而在有SO₄^2-存在的酸性溶液中，TiO₂样品的晶相组成不随水解温度的变化而改变，均为锐钛矿型，其比表面积可达300 m²·g^-1。     

双介孔结构的纳米TiO2/I2复合材料的制备及其可见光催化性能

以钛酸丁酯为前驱体, 碘溶胶为碘源, 在室温下采用水解沉淀法制备了单质碘和纳米TiO₂复合的双介孔结构光催化剂(M-I₂-TiO₂). 采用X射线衍射(XRD)、透射电子显微镜(TEM)、比表面分析(BET)、紫外-可见(UV-Vis)漫反射光谱和傅里叶变换-红外光谱(FT-IR)对M-I₂-TiO₂进行了表征. 以次甲基蓝(MB)溶液为模拟废水, 对M-I₂-TiO₂的光催化性能进行了评价, 研究了不同热处理温度对光催化活性的影响. 结果表明, M-I₂-TiO₂在可见光区有显著的吸收, 300 ℃热处理得到的样品比表面积高达227.6 m²/g, 600 ℃热处理所得样品的比表面积仍高达111.8 m²/g, 而400 ℃热处理所得样品具有最好的光催化降解性能. 双介孔结构纳米TiO₂/I₂复合材料的光催化降解性能显著高于相同方法制备的纯TiO₂和Degussa P-25商业产品. 催化剂经6次重复使用其光催化活性基本保持不变.     

焙烧温度对In2TiO5纳米带晶型结构及光催化性能的影响

以Ti(OC₄H₉)₄、In(NO₃)₃和聚乙烯吡咯烷酮(PVP-K30)为原料,采用静电纺丝技术制备了In₂TiO₅纳米带。利用X射线衍射(XRD)、扫描电子显微镜(SEM)、紫外-可见漫反射光谱(UV-Vis DRS)和N₂吸附-脱附等技术对不同焙烧温度处理得到的样品进行表征,详细研究了焙烧温度对In₂TiO₅纳米带晶粒尺寸、形貌、比表面积和孔径的影响。以20 mg·L^-1的氟喹诺酮类抗生素左氧氟沙星(LEV)为目标降解物,125 W高压汞灯为光源,评价了不同焙烧温度下In₂TiO₅纳米带的光催化活性。结果表明,焙烧温度对In₂TiO₅的形貌与光催化活性有明显影响。当焙烧温度为800℃时,制备的In₂TiO₅纳米带表面光滑,其宽度为(552±58) nm、厚度约为140 nm,光催化活性最强,光照60 min,LEV的降解率可以达到95%。     

焙烧温度对In2TiO5纳米带晶型结构及光催化性能的影响

以Ti(OC₄H₉)₄、In(NO₃)₃和聚乙烯吡咯烷酮(PVP-K30)为原料,采用静电纺丝技术制备了In₂TiO₅纳米带。利用X射线衍射(XRD)、扫描电子显微镜(SEM)、紫外-可见漫反射光谱(UV-Vis DRS)和N₂吸附-脱附等技术对不同焙烧温度处理得到的样品进行表征,详细研究了焙烧温度对In₂TiO₅纳米带晶粒尺寸、形貌、比表面积和孔径的影响。以20 mg·L^-1的氟喹诺酮类抗生素左氧氟沙星(LEV)为目标降解物,125 W高压汞灯为光源,评价了不同焙烧温度下In₂TiO₅纳米带的光催化活性。结果表明,焙烧温度对In₂TiO₅的形貌与光催化活性有明显影响。当焙烧温度为800℃时,制备的In₂TiO₅纳米带表面光滑,其宽度为(552±58) nm、厚度约为140 nm,光催化活性最强,光照60 min,LEV的降解率可以达到95%。     

一种纳米TiO2粉体防团聚的新方法

开发了一种新的低成本防团聚方法——泡沫悬浮法。对泡沫悬浮法和共沸蒸馏法的防团聚效果进行了系统比较。结果表明，泡沫悬浮法可以有效抑制煅烧过程中纳米TiO₂晶粒的粗化和一次粒径的长大。泡沫悬浮法所得纳米TiO₂的粉体还具有团聚粒径小、粒度分布窄以及比表面积大的优点。通过FTIR、TG、DTA和松装密度实验对泡沫悬浮法的防团聚机理进行了研究，提出了纳米TiO₂防团聚模型。     

CO2在纳米SiO2/TiO2悬浮体系中的光催化还原

用水热法合成了氧化硅改性的具有高比表面积、高催化活性的锐钛型二氧化钛, 并在其悬浮体系中将CO₂光催化还原合成甲醇. 采用XRD, TEM, 物理吸附, UV-Vis吸收光谱和FTIR等表征手段对催化剂结构特征进行了研究. 结果表明: 添加氧化硅后, 氧化硅和二氧化钛之间形成Si—O—Ti键, 抑制了TiO₂晶粒生长, 提高了锐钛型TiO₂的比表面积, 且随着含硅量的增加, SiO₂/TiO₂的UV吸收逐步蓝移, 禁带宽度增加. 还原反应结果表明: SiO₂/TiO₂具有光催化还原活性, 且随着含硅量的增加先增加后减小, 当SiO₂质量分数为3.5%时, SiO₂/TiO₂复合催化剂反应活性最强, 5 h内甲醇产量可达到21.0 mg/L, 并有少量甲醛生成.     

TiO2形态结构与光催化活性关系的研究

本文介绍了TiO₂多相光催化剂的作用机理及其结构特性对光催化活性的影响,并对TiO₂的晶相组成、晶粒尺寸、比表面积、表面形态与光催化活性的关系作了综述。     

水热条件对板钛矿相二氧化钛微结构的影响

以四氯化钛和氢氧化钠为原料制备TiO₂前驱体，通过水热法合成了不同形貌板钛矿相TiO₂，利用X射线衍射和透射电镜对所得样品进行了表征。研究了反应初始pH值、水热反应温度和水热反应时间对TiO₂形貌、物相和晶粒尺寸的影响。结果表明，pH_initial是决定TiO₂粉体物相、粒径和形貌的主要因素。随着水热反应温度的升高和水热反应时间的延长，板钛矿相TiO₂的晶粒逐渐长大。pH_initial的增大，导致无定形TiO₂转化成板钛矿相所需的水热温度升高，水热时间变长；同时，所形成板钛矿相TiO₂的晶粒尺寸和颗粒粒径也较大。XRD和TEM结果表明，板钛矿相TiO₂颗粒是由多个纳米微晶组成的聚集体。当pH_initial为9.00～12.00时，200 ℃下水热反应24 h合成了纯板钛矿相TiO₂。     

微乳法合成可控粒径纳米Pt/Al2O3电催化CO氧化的尺寸效应

采用微乳法室温下合成了粒径可控Pt/Al₂O₃催化剂(1～10 nm), 以CO电催化氧化为探针反应考察了Pt微粒尺寸与催化反应性能之间的关系. 利用透射电镜(TEM), 扫描电镜(SEM), 循环伏安法(CV)等手段对催化剂进行表征, 结果表明催化剂性能与Pt粒径之间存在明显的尺寸效应, 催化剂存在最佳活性尺寸.     

Optimization of silica support pore size for Pt catalysts in the complete oxidation of volatile organic compounds

Highest catalytic performance for complete oxidation of propylene and toluene was obtained by using a Pt catalyst on a mesoporous silica support with pore sizes from 20 to 50 nm and 10 to 40 nm, respectively.     

Dehydrogenation of cyclohexane over Pt/SiO2?AlPO4 catalysts, I. Influence of the catalyst particle size

The influence of Pt loading on the metal dispersity and catalytic activity of Pt catalysts on SiO₂−AlPO₄ in the dehydrogenation of cyclohexane to benzene has been analyzed. Kinetic parameters and apparent reaction rate constants were determined by the Bassett-Habgood equation. Thermodynamic parameters for the reaction were determined.     

Preparation and optical properties of Bi2S3 microcrystallite doped glass and thin film by the sol-gel process

The Bi₂S₃ microcrystallite doped thin films and glass lumps have been successfully prepared by the sol-gel process from the hydrolysis of a complex solution of Si(OC₂H₅)₄ Bi(NO₃)₃ · 5H₂O and SC(NH₂)₂, and the size of the microcrystallites in glass heated for different times at 400°C was decided by the method of HRTEM. The optical transmission valley shifted towards longer wavelengths with longer heat-treatment time at 500°C in the Bi₂S₃ doped thin films, showing the experimental evidence of quantum size effects. The red-shift of emission peaks in luminenscence spectrum excited with longer wavelength is attributed to the broad distribution of particle size in Bi₂S₃ doped glass.     

A study on the kinetics of thermal decomposition of CaCO3

By means of TG, the thermal decomposition of the powdered CaCO₃ was tested with its various dispersities, range of size, and the different content of CO₂ in flowing nitrogen. Formulae for calculating the rate and time of decomposition were obtained.     

Effect of TiO2 crystallite size on the dispersion of Co on nanocrystalline TiO2

Nanocrystalline TiO₂ powders with average crystallite sizes of 9–15 nm were synthesized by the solvothermal method and employed as supports for Co catalysts. The value of H₂ chemisorption/specific surface area of Co/TiO₂ increased significantly with increasing TiO₂ crystallite size. It was suggested that the higher amount of Ti³⁺ surface defects on the larger crystalline TiO₂ resulted in a stronger interaction between Co and TiO₂, hence, higher dispersion of Co was obtained.     

The Effect of SiO2 Addition on the Grain Size and Photocatalytic Activity of TiO2 Thin Films

The uniform transparent TiO₂/SiO₂ nanometer composite thin films were prepared via sol-gel method on the soda lime glass substrates, and were characterized by X-ray photoelectron spectroscopy (XPS), FTIR spectroscopy, UV-VIS spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD) and BET surface areas. It was found that the addition of SiO₂ to TiO₂ thin films could suppress the grain growth of TiO₂ crystal and increase the hydroxyl content of the surface of TiO₂ films. The photocatalytic activity of the as-prepared TiO₂/SiO₂ composite thin films increases for SiO₂ content of less than 5 mol%.     

可控粒径纳米Fe_3O_4的制备及其磁性研究

本文用空气氧化法,在可见光作用下,添加配合剂(EDTA、柠檬酸、酒石酸、谷氨酸)在室温进行了不同粒径纳米Fe3O4的制备及其磁性能研究。结果表明:在可见光作用下,随EDTA、柠檬酸、酒石酸、谷氨酸等配合剂的添加,得到纳米Fe3O4的粒径有所减小、分散性有所提高;配合剂及可见光共存时,体系反应速率得到提高,高的反应速率使纳米Fe3O4晶粒减小;控制适当的光照度和添加剂的量,室温可得到11.8~29.6nm的Fe3O4颗粒。不同粒径纳米Fe3O4分别呈现出超顺磁性、铁磁性特征。     

Annealing Temperature Dependence of the Size of C60 Clusters in C60-Doped Silicon Oxide Films

C₆₀-doped silicon oxide thin films were prepared by spin-coating a viscous solution formed upon soaking at 40°C an acidic toluene/ethanol solution of C₆₀, phenyltriethoxysilane, and tetraethoxysilane with a C₆₀–to–Si molar ratio of 2.5 × 10^–3. The films were submitted to annealing at 300–500°C in Ar to investigate variation in the size of C₆₀ clusters embedded in the films by photoluminescence spectroscopy. The film before annealing was found to contain the clusters consisting of ca. 60 C₆₀ molecules, suggesting that C₆₀ is present well-dispersed in the film. The molecules in the film aggregated to increase the size with increasing annealing temperature, indicating that the molecules diffuse easily in the film upon heating and therefore the size of the clusters is controllable with the annealing temperature.     

Size regulation and prediction of the SiO2 nanoparticles prepared via Stöber process

In this study, monodispersed SiO₂ nanoparticles with controllable size ranging from 20 to 100 nm have been successfully prepared by using a Stöber sol-gel process. The particle size, distribution, and morphology were examined by dynamic light scattering (DLS) and transmission electron microscopy (TEM). In order to accurately regulate the particle size, the effects of various reaction parameters on the particle size and morphology of SiO₂ nanoparticles were systematically investigated. It was found that, to some extent, the SiO₂ particle size increased linearly with the increase of ammonia or water content, as well as the decrease of reaction temperature, while nearly kept constant with the increase of tetraethyl orthosilicate (TEOS). Based upon the results, an empirical formula has been developed to model/predict the particle size of the SiO₂ nanoparticles over a wide range of various reaction conditions.