Effect of Microstructure on Electrorheological Property for Pure TiO2 Particle Material

Pure titanium dioxide （TiO2） particle materials were prepared by hydrolyzing titanium tetrachloride （TiCl4）. The microstructures of these materials were determined by X-ray diffraction （XRD）, accelerated surface area and porosimetry apparatus （BET）, and transmission electron microscopy （TEM）. The TiO2 materials obtained by calcinations under different temperatures distinctly revealed different microstructures in crystal structure type, surface area, pore size, pore volume and grain size. The relationship between the microstructure of the TiO2 materials and their electrorheological （ER） activity was investigated. Anatase titania particles have better ER performance than rutile titania particles. Amorphous TiO2 materials display higher ER activity than the crystalline titania materials. A large pore volume can be more advantageous in improving the ER effect of a particle material.     

掺碳二氧化钛的制备和其电流变性质

采用十二烷基胺 (DDA)作模板合成了二氧化钛颗粒 ,并在氮气流中以不同温度碳化制出了掺碳的二氧化钛。掺碳的二氧化钛的结构由透射电子显微镜 (TEM )、氮气吸附 -解吸等温线、XPS等表征。掺碳二氧化钛颗粒的电镜照片显示有不规则孔 ,粒径大小为 130～ 2 0 0nm。氮气吸附 -解吸等温线表明 :这些有着IV型等温线的颗粒存在介孔。XPS分析显示碳主要分布在粒子的表面。掺碳的二氧化钛粉末分散在石蜡油中形成无水电流变液 ,表现出很强的电流变效应。DDA和二氧化钛的物质的量比在 0 .0 5～ 0 .10并在 6 73K碳化的掺碳二氧化钛表现出很强的电流变效应 ,主要是因为在粒子表面的碳有合适的电导率     

有机模板剂对合成纳米TiO_2结构影响规律的研究

以钛酸四丁酯为前驱体,乙醇为溶剂,采用溶胶-凝胶法制备纳米二氧化钛。选择P123作为模板剂考察了不同n(P123)/n(Ti)对TiO2织构性能以及晶粒尺寸的影响。采用碳化的方法使有机物在氩气气氛中高温焙烧后形成的炭层对孔道起支撑作用,防止孔道的塌陷并得到高度晶化的二氧化钛,同时考察了碳化温度和不同模板剂对二氧化钛织构性能的影响规律。结合X射线衍射(XRD)、N2吸附脱附、热分析(TG/DSC)表征手段得到以下结论:物质的量比在0～0.030范围内,P123含量的增加有利于晶粒尺寸的减小和比表面积的增大;碳化过程提高了TiO2的热稳定性,随着碳化温度的升高TiO2比表面积变化不大;P123、PEG2000、CTAB 3种模板剂中P123得到的样品性能最好。     

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.     

Vapor-phase photo-oxidation of methanol over nanosize titanium dioxide clusters dispersed in MCM-41 host material part 1: synthesis and characterization

Nanosize clusters of titania were dispersed in mesoporous MCM-41 silica matrix with the help of the incipient wet-impregnation route, using an isopropanol solution of titanium isopropoxide as precursor. The clusters thus formed were of pure anatase phase and their size depended upon the titania loading. In the case of low (< 15 wt %) loadings, the TiO2 particles were X-ray and laser-Raman amorphous, confirming very high dispersion. These particles were mostly of < or = 2 nm size. On the other hand, larger size clusters (2-15 nm) were present in a sample with a higher loading of approximately 21 wt %. These particles of titania, irrespective of their size, exhibited an absorbance behavior similar to that of bulk TiO2. Powder X-ray diffraction, N2-adsorption and transmission electron microscopy results showed that while smaller size particles were confined mostly inside the pore system, the larger size particles occupied the external surface of the host matrix. At the same time, the structural integrity of the host was maintained even though some deformation in the pore system was noticed in the case of the sample having highest loading. The core level X-ray photoelectron spectroscopy results revealed a + 4 valence state of Ti in all the samples. A positive binding energy shift and the increase of the width of Ti 2p peaks were observed, however, with the decrease in the particle size of supported titania crystallites, indicative of a microenvironment for surface sites that is different from that of the bulk.     

TiCl4-O2体系高温反应制备超细TiO2光催化材料的研究

高温管式气溶胶反应器中,利用ＴｉＣｌ４气相氧化制备超细ＴｉＯ２光催化材料,研究了停留时间和反应温度对粒子形态的影响。结果表明ＴｉＯ２粒度随停留时间延长和反应温度升高而增大;金红石相含量随停留时间延长而增加;当反当温度１３００℃时,粒子中金红石含量出现最大值。以偶氮染料活性艳红Ｘ－３Ｂ为模拟废水,考察粒子光催化活性。光催化活性与粒径和晶型等形态指标有关。等效粒径３６．４ｎｍ,金红石含量１８．９７％Ｔ     

A two-step sol-gel method for synthesis of nanoporous TiO2

This article reports a study of the effects of synthesis parameters on the preparation and formation of mesoporous titania nanopowders by employing a two-step sol-gel method. These materials displayed crystalline domains characteristic of anatase. The first step of the process involved the hydrolysis of titanium isopropoxide in a basic aqueous solution mediated by neutral surfactant. The solid product obtained from step 1 was then treated in an acidified ethanol solution containing the same titanium precursor to thicken the pore walls. Low pH and higher loading of the Ti precursor in step 2 produced better mesoporosity and crystallinity of titanium dioxide polymorphs. The resultant powder exhibited a high surface area (73.8 m2/g) and large pore volume (0.17 cm3/g) with uniform mesopores. These materials are envisaged to be used as precursors for mesoporous titania films as a wide band gap semiconductor in dye-sensitized nanocrystalline TiO2 solar cells.     

介孔TiO2微球水热法合成及在染料敏化太阳能电池中的应用

以Ti(SO4)2为钛源,采用尿素辅助水热法合成了介孔TiO2微球,利用XRD、FESEM和比表面积分析仪对样品的晶型、形貌和比表面积进行分析,探讨了尿素加入量对TiO2微球的颗粒尺寸、比表面积、孔径和孔容的影响。采用刮涂法,用所合成的介孔TiO2微球制备了染料敏化太阳能电池(DSSC)的光阳极,结果表明,尿素用量为1.2g合成的介孔TiO2微球所组装的电池在模拟太阳光的照射下(100mW/cm2,AM1.5),光电转换效率为6.2%,明显高于商用P25纳晶所组装的电池光电转换效率(4.24%)。     

模板法制备介孔TiO2及其光催化性能研究

以十六烷基三甲基溴化铵(CTAB)作为模板剂,钛酸正四丁酯(TBOT)为钛源,异丙醇为溶剂,通过溶胶-凝胶过程合成出介孔TiO2前驱体凝胶后,经老化、焙烧得到了TiO2介孔材料.利用XRD、HR-TEM、TGA、N2的吸附-脱附、BET等方法对材料的结构、形貌、比表面积、孔径分布进行表征.以亚甲基蓝的降解为模型反应,对其催化性能进行评价并与商品DegussaP-25进行比较.实验结果表明,比表面积为137.5m2/g、孔径为8.62nm的锐钛型介孔TiO2具有很高的催化活性.     

Synthesis of TiO2 supported on SBA-15 using different method and their photocatalytic activity

SBA-15 mesoporous materials were successfully prepared by the conventional hydrothermal method and TiO2 nanoparticles were supported on them using different loading methods. The synthesized materials were characterized and their activity as photocatalysts for the decomposition of methylene blue was evaluated. The loading of titanium dioxide on the framework of SBA-15 makes the pore diameter and pore volume decrease compared to that of SBA-15. The chelating method causes the support to have a much better dispersion capacity for TiO2 particles as compared to the other two methods. The TiO2 supported by chelating method showed the highest photocatalytic activity among the photocatalysts prepared by different method.     

Microemulsion-mediated hydrothermal synthesis of photocatalytic TiO2 powders

A reverse microemulsion-mediated hydrothermal route has been employed to synthesize photocatalytic titanium dioxide (TiO2) powders. Nano-crystalline monophasic anatase TiO2 powders were successfully prepared when the microemulsion-derived precursors were hydrothermally treated. The advantage of using this microemulsion mediated hydrothermal route is the significant reduction in reaction time and temperatures as compared with the conventional hydrothermal process. The oil/water emulsion ratio significantly affected the particle sizes of the obtained TiO2 powders. The specific surface area of TiO2 powders was increased with the oil/water ratio, thereby leading to enhanced photocatalytic activity of TiO2 powders. As the hydrothermal temperature was elevated, the morphology of the TiO2 particles changed from a rod-like shape into a polyhedral shape. The variation in microstructures decreased the specific surface area of the TiO2 powders and lowered the photocatalytic activity.     

Catalytic conversion of 1,2-dichlorobenzene over mesoporous V2O5/TiO2 prepared from spray pyrolysis

Mesoporous V2O5/TiO2 particles were prepared by spray pyrolysis and applied to the catalytic oxidation of 1,2-dichlorobenzene (1,2-DCB). Two different precursors (alkoxide and nanoparticles) for the TiO2 support were used to determine the effects on the texture properties and the catalytic activity of the mesoporous V2O5/TiO2 particles. The 5 wt% V2O5/TiO2 particles had the largest surface area (173 m2/g) and 4.7 nm in average pore size. The catalytic activity of the V2O5/TiO2 particles depended strongly on the loading quantity of vanadium, whereas the P25-derived samples showed no significant change in catalytic activity with weight% of vanadium. The surface area of the V2O5/TiO2 particles prepared using the alkoxide precursor was larger than that of the particles prepared using P25 nanoparticles. The P25-derived V2O5/TiO2 particles, however, showed a higher catalytic activity compared with those alkoxide-derived, which is due to the difference in the vanadium quantity exposed to the pore surface. It was confirmed that the 10 wt% V2O5/TiO2 particles prepared by spray pyrolysis had an excellent activity for the oxidation of 1,2-DCB, particularly at temperatures below 300 degrees C.     

Vapor-phase photo-oxidation of methanol over nano-size titanium dioxide clusters dispersed in MCM-41 host material part 2: catalytic properties and surface transient species

We report in this paper on the ultraviolet-assisted vapor-phase oxidation of methanol at room temperature, with the help of nano-size clusters of titanium dioxide dispersed in an MCM-41 silicate matrix. The surface species formed during the adsorption/oxidation of methanol and the transformation that they undergo as a result of ultraviolet irradiation were monitored using in-situ Fourier transform infrared and thermal desorption spectroscopy techniques. Parallel experiments conducted on TiO2/MCM, bulk titania, and pristine MCM-41 samples helped in identifying the individual role of titanium dioxide and host matrix in these processes. The photo-catalytic oxidation of methanol, at concentrations of 0.1 to 1.1 mol% in air, gave rise to formation of CO2 and H2O as products, for both the TiO2/MCM and bulk TiO2 samples. No such reaction occurred on titania-free MCM. Furthermore, the rate of reaction depended upon the TiO2 content of a sample and also on the concentration of methanol in reaction mixture. Thus, the rate of conversion increased progressively with the increase in TiO2 loading from 5 to 21 wt% in TiO2/MCM samples, particularly for the experiments with high concentration of methanol. For low methanol concentration (0.1 mol%) in air, the effect of titania content in MCM was very small. The specific activity (per g of titania) of a sample, on the other hand, showed an inverse relationship with the loading of titanium dioxide in a sample. Infrared and temperature-programmed desorption results revealed that the mode of CH3OH adsorption and the reactivity of the transient species formed during the oxidation process were independent of the size of dispersed titania particles. Thus, the particles of approximately 2-6 nm size, present in TiO2/MCM, exhibited a chemisorption behavior similar to that of the bulk titania. The results of the present study provide strong evidence that the hydroxyl groups, both on the host matrix and at the titania sites, participate independently in the formation of methoxyl groups and at the same time promote the heterogeneous photo-catalytic oxidation of methanol molecules via formation of transient formate groups. Our results also show that the effect of titania crystallite size in the photo-catalytic properties relate mainly to the larger surface area and hence to the enhanced number of chemisorption sites, rather than to the changes in electronic properties.     

Visible light active photocatalytic degradation of bisphenol-A using nitrogen doped TiO2

Nitrogen doped titania was prepared by low temperature sol-gel method using titanium precursor and nitrogen containing bases like triethylamine and tetramethyl ammonium hydroxide compounds. The materials were characterized by XRD, BET, SEM, XPS, DRS-UV, and FT-IR techniques. DRS-UV study substantially indicates shift of the absorption edge of TiO2 to lower energy region. The phase composition, crystallinity, specific surface area, and visible light activity of nitrogen doped titania depend upon the preparation conditions. Photocatalytic degradation of bisphenol-A in aqueous medium was investigated by TiO2 and nitrogen doped TiO2 under visible light irradiation in a batch photocatalytic reactor. The results indicate higher visible light activity for nitrogen doped TiO2 than commercial TiO2 (Degussa P25) for bisphenol-A degradation. The influence of various parameters such as initial concentration of bisphenol-A, catalyst loading and pH was examined for maximum degradation efficiency.     

TiCl4-O2体系高温反应制备超细TiO2光催化材料的研究

高温管式气溶胶反应器中,利用ＴｉＣｌ_４气相氧化制备超细ＴｉＯ_２光催化材料,研究了停留时间和反应温度对粒子形态的影响．结果表明ＴｉＯ_２粒度随停留时间延长和反应温度升高而增大;金红石相含量随停留时间延长而增加,当反应温度１３００℃时,粒子中金红石含量出现最大值．以偶氮染料活性艳红Ｘ－３Ｂ为模拟废水;考察粒子光催化活性．光催化活性与粒径和晶型等形态指标有关,等效粒径３６．４ｎｍ、金红石含量１８９７％ＴｉＯ_２的活性高于商品Ｐ２５和ＳＨ－１．     

Synthesis of TiO2 supported on SBA-15 using chelating method and their photocatalytic decomposition of methylene blue

SBA-15 mesoporous materials were successfully prepared by the conventional hydrothermal method and used as the support for TiO2 loaded SBA-15 photocatalysts. The synthesized materials were characterized by XRD, PL, FT-IR, BET and TEM. We also examined the activity of these materials as photocatalysts for the decomposition of methylene blue. The loading of titanium dioxide on the framework of SBA-15 makes the pore diameter and the pore volume decrease and decreases the surface area compared to that of SBA-15. For the TiO2 loaded SBA-15 photocatalysts, the IR absorption at approximately 960 cm(-1) is commonly accepted as the characteristic vibration of the Ti-O-Si bond. The PL peaks appears at about 410 nm at a loading ratio of less than 5% but moves to 430 nm at higher loading ratios. It was also shown that the excitonic PL signal is proportional to the photocatalytic activity for the decomposition of methylene blue. The photocatalytic activity increases with increasing TiO2 loading ratio, shows a maximum value at 7% TiO2/SBA-15, and then decreases at 10% TiO2/SBA-15.     

Guided self-assembly of nanostructured titanium oxide

A series of nanostructured titanium oxide particles were synthesized by a simple wet chemical method and characterized by means of small-angle x-ray scattering (SAXS)/wide-angle x-ray scattering (WAXS), atomic force microscope (AFM), scanning electron microscope (SEM), transmission electron microscope (TEM), thermal analysis, and rheometry. Tetrabutyl titanate (TBT) and ethylene glycol (EG) can be combined to form either TiO(x) nanowires or smooth nanorods, and the molar ratio of TBT:EG determines which of these is obtained. Therefore, TiO(x) nanorods with a highly rough surface can be obtained by hydrolysis of TBT with the addition of cetyl-trimethyl-ammonium bromide (CTAB) as surfactant in an EG solution. Furthermore, TiO(x) nanorods with two sharp ends can be obtained by hydrolysis of TBT with the addition of salt (LiCl) in an EG solution. The AFM results show that the TiO(x) nanorods with rough surfaces are formed by the self-assembly of TiO(x) nanospheres. The electrorheological (ER) effect was investigated using a suspension of titanium oxide nanowires or nanorods dispersed in silicone oil. Oil suspensions of titanium oxide nanowires or nanorods exhibit a dramatic reorganization when submitted to a strong DC electric field and the particles aggregate to form chain-like structures along the direction of applied electric field. Two-dimensional SAXS images from chains of anisotropically shaped particles exhibit a marked asymmetry in the SAXS patterns, reflecting the preferential self-assembly of the particles in the field. The suspension of rough TiO(x) nanorods shows stronger ER properties than that of the other nanostructured TiO(x) particles. We find that the particle surface roughness plays an important role in modification of the dielectric properties and in the enhancement of the ER effect.     

Low temperature synthesis and visible light driven photocatalytic activity of highly crystalline mesoporous TiO2 particles

Mesoporous TiO2 powder materials with a high crystallinity have been prepared by evaporation induced self assembly (EISA) process using titanium tetraisopropoxide (TTIP) and pluronic P123 surfactant (EO20PO70EO20) as titanium source and structure-directing reagent, respectively. The prepared materials were characterized by low and wide-angle X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), optical absorption, and N2 adsorption-desorption experiments. The crystallinity of the materials was controlled by varying the calcination temperature. The resulting TiO2 materials showed highly crystalline structure with uniform particle size which increases from 11.8 to 23.8 nm with increasing the calcination temperature from 400 to 600 degrees C, respectively, whereas the specific surface area decreases from 125 to 40 m2/g. TEM and XRD results revealed that the calcination temperature of 600 degrees C is the best condition to obtain highly crystalline mesoporous TiO2. The photocatalytic activity of the TiO2 mesoporous materials with different crystallinity and textural parameters has been studied in the decomposition of methylene blue (MB) dye molecules under visible light irradiation. Among the mesoporous TiO2 materials studied, the material with the highest crystallinity, prepared at 600 degrees C, showed the best photocatalytic performance in the decomposition of MB under visible light in a short time.     

TiCl3、TiCl4共水解制备金红石相氧化钛粉体

通过TiCl3、TiCl4共同水解可以制备出金红石相的氧化钛粉体．改变原料浓度可以控制产物的形貌，较高浓度下得到300—500nm的球状颗粒，由许多细小晶粒组成；较低浓度下得到纳米针状颗粒．提高TiCl3的浓度可以使晶粒尺寸有所减小．     

The direct synthesis of mesoporous structured MnO(2)/TiO(2) nanocomposite: a novel visible-light active photocatalyst with large pore size

A series of visible-light-driven mesoporous structured MnO(2)/TiO(2) nanocrystal photocatalysts have been synthesized through a modified sol-gel method, and the N(2) adsorption-desorption isotherm confirms that the mesoporous materials possess large pore size (up to 9.2?nm) and a narrow pore size distribution. X-ray powder diffraction (XRD) analyses and complementary x-ray photoelectron spectroscopy (XPS) measurements reveal that the doping of the transition metal Mn inhibits the growth of TiO(2) anatase nanocrystals and the Mn species are highly dispersed on the surface of TiO(2). The ultraviolet (UV)-vis spectrum demonstrates the excellent adsorption properties of MnO(2)/TiO(2) over the whole region of visible light, which enables this novel photocatalysis material to possess remarkable activity in the photocatalytic degradation of methylene blue under visible light radiation. Moreover, a 'coating mechanism' based on the nucleation of titania nanocrystals along with the interaction between the dopant precursors and titania clusters has been suggested.