纳米TiO2-SiO2复合氧化物的制备与性质

采用溶胶-凝胶结合CO2超临界干燥方法制备了比表面积大、热稳定性好的纳米TiO2-SiO2复合氧化物.考察了原料组成和焙烧温度对复合氧化物比表面积、热稳定性和酸性的影响,通过加氢脱硫反应考察了该复合氧化物作为加氢精制催化剂载体的可行性.结果表明,采用该方法制备的复合氧化物为纳米颗粒,在n(Ti)/n(Si)=1时,其比表面积和孔容最大;与纯TiO2相比,引入SiO2明显提高了复合氧化物的热稳定性和晶型稳定性;以此复合氧化物为载体的加氢精制催化剂具有很好的低温脱硫活性,TiO2-SiO2复合氧化物载体的酸性特征影响了催化剂的加氢脱硫活性.     

CeO2-SiO2复合氧化物的制备表征及其负载Pd催化活性的研究

以硝酸铈和正硅酸乙酯为原料, 采用溶胶凝胶超临界流体干燥法制备了不同CeO2含量的一系列复合氧化物. 利用物理吸附仪, XRD, IR等手段对复合氧化物的织构和结构进行了表征, 结果表明 采用该法可制备高比表面积的CeO2-SiO2复合氧化物, 随着CeO2含量的增加, 复合氧化物的比表面积逐渐降低; CeO2的结晶逐渐完善. 最后对5CS复合氧化物负载Pd的催化活性进行了初步研究, 发现其具有CO低温氧化活性.     

V2O5-MoO3-SiO2表面复合氧化物催化剂的制备与表征

采用表面改性法制备了V2O5-SiO2,MoO3-SiO2,V2O5-MoO3-SiO2复合氧化物催化剂,并用TPR和IR技术研究了催化剂的表面结构及V=O,M0=O的活性,同时用化学吸附IR技术研究了催化剂样品对异丁烷的化学吸附性能.实验结果表明:这些复合氧化物催化剂对异丁烷都有较高的化学吸附能力;SiO2能缓解表面Lewis碱位V=O和Mo=O的氧化能力,有利于选择氧化.     

TiOx(x＜2)表面修饰Ni/TiO2-SiO2催化顺酐液相选择加氢合成γ-丁内酯

以TiO2-SiO2复合氧化物气凝胶为载体,制备了一系列Ni/TiO2-SiO2催化剂,并采用N2物理吸附-脱附、H2程序升温还原/脱附、X射线衍射及原位漫反射傅里叶变换红外光谱等技术对催化剂进行了表征,考察了载体中钛含量对催化剂结构、表面性质及其催化顺酐液相选择加氢合成γ-丁内酯反应性能的影响.结果表明,较小的Ni0...     

Ni/SiO_2、Ni/TiO_2-SiO_2催化剂上顺酐液相选择加氢合成γ-丁内酯

通过溶胶-凝胶方法结合超临界干燥技术制备了SiO2和TiO2-SiO2复合氧化物气凝胶载体,采用等体积浸渍法制备了Ni/SiO2和Ni/TiO2-SiO2催化剂,运用BET、H2-TPR、XRD、TEM及FT-IR等手段对催化剂进行了表征,并考察了催化剂在顺酐液相选择加氢合成γ-丁内酯反应中的催化性能.结果表明,Ni/TiO2-SiO2催化剂中Ti-O-Si键的形成增强了NiO与载体的相互作用,促进了NiO在载体表面的分散,得到了晶粒较小的活性Ni0物种,表现出高的加氢活性,在H2压力5.0 MPa、反应温度240℃、反应时间6 h的条件下,顺酐转化率为100%,γ-丁内酯的选择性达94.7%.     

TiO2-SnO2复合凝胶的结构表征及其吸附与光催化性能研究

采用溶胶-凝胶法制备了TiO2-SnO2复合凝胶,利用XRD、UV、IR谱对其结构进行了表征,研究了复合凝胶的组成对水、乙醇、丙酮、氨水蒸气平衡吸附量的影响,以苯酚溶液为模拟污染物测定了复合凝胶的光催化降解能力.实验结果表明,组成为n(TiO2)∶SnO2=80%∶20%的复合凝胶具有最强的吸附和光催化活性,对水蒸气、乙醇、丙酮气体的吸附以及对苯酚溶液的光催化降解能力均高于其它组成的复合凝胶.     

CeO2-TiO2复合氧化物的制备、表征及其对CO氧化的催化性能

采用溶胶-凝胶法制备了一系列不同n(Ce)/n(Ti)的CeO2-TiO2复合氧化物,对复合氧化物的物相结构、形貌特征、比表面积和氧化还原性质进行了表征,并考察了复合氧化物对CO氧化反应的催化性能.结果表明,n(Ce)/n(Ti)>0.10时,复合氧化物为无定形结构;n(Ce)/n(Ti)=0.10~0.30时,复合氧化物失去CeO2和TiO2各自的特征,形成CeO2-TiO2固溶体,具有较大的比表面积.CeO2-TiO2复合氧化物本身对CO氧化反应的催化活性不如TiO2或CeO2的高,但Pd/CeO2-TiO2比Pd/TiO2或Pd/CeO2具有更高的催化活性.     

TiO2–ZrO2的表征及其异丙醇催化转化性能

用共沉淀法制备了TiO2-ZrO2复合氧化物. 采用N2吸附、XRD、TEM、NH3和CO2吸附量热、NH3吸附红外对TiO2-ZrO2体系的结构及酸碱性等进行了表征. 结果表明: 与单纯的氧化物相比, 形成的复合氧化物为无定形物相, 有介孔结构, 表面积明显提高, 可达218 m2·g-1; 初始吸附热差别不大, 但具有更多的表面B酸位; 随着TiO2掺入量的增大, 复合氧化物表面碱位减少. 异丙醇催化转化, 在无氧条件下, ZrO2、TiO2和TiO2-ZrO2复合氧化物上丙烯的选择性大于90%, 说明这些氧化物具有强的表面酸性; 在有氧条件下, ZrO2和TiO2丙酮的选择性达到70%～85%, 主要体现为氧化还原性; 而在复合氧化物上丙烯选择性增大到70％左右, 丙酮的选择性下降为30%左右, 表明生成的复合氧化物表面上的氧化还原性削弱, 酸性增强.     

TiO_2-SiO_2纳米粒子的合成及二级散射光谱法测定核糖核酸

采用溶胶-凝胶法制备了TiO2-SiO2纳米粒子.通过X-射线衍射谱、透射电子显微镜等对纳米粒子进行了表征.研究了TiO2-SiO2纳米粒子与核糖核酸(RNA)的相互作用,建立了基于纳米粒子与RNA吸附反应,二级散射光谱法测定痕量RNA的新方法.方法的线性范围是0.005～5 mg/L; 检出限为1.46 μg/L.方法用于RNA合成样品的测定,回收率为99.4%～103.9%;相对标准偏差为019%～0.24%.     

TiO2-SiO2光催化纸业废水有色有机物的降解

研究了TiO2-SiO2混合氧化物对纸业废水中有色有机物的吸附与光催化降解效率．常温下．TiO2对纸业废水中有色有机物的吸附符合Freundlich模型，Qe=0．239Ce^0.791。TiO2-SiO2混合氧化物对纸业废水中有色有机物的吸附与光催化降解效率与催化剂样品的组成有关，光催化降解效率也与TiO2-SiO2表面总酸量有关．     

Vibrational structure of titanium silicate catalysts. A spectroscopic and theoretical study.

A thorough analysis of the vibrational features of the titanium silicalite-1 (TS-1) catalyst is presented, based on quantitative IR measurements, Raman and resonant Raman experiments, quantitative XANES, and quantum chemical calculations on cluster and periodic models. The linear correlation of the intensity of the IR and Raman bands located at 960 and 1125 cm(-1) and the XANES peak at 4967 eV with the amount of tetrahedral Ti are quantitatively demonstrated. Raman and resonant Raman spectra of silicalite and TS-1 with variable Ti content are presented, showing main features at 960 and 1125 cm(-1) associated with titanium insertion into the zeolite framework. The enhancement of the intensity of the 1125 cm(-1) feature and the invariance of the 960 cm(-1) feature in UV-Raman experiments, are discussed in terms of resonant Raman selection rules. Quantum chemical calculations on cluster models Si[OSi(OH)(3)](4) and Ti[OSi(OH)(3)](4) at the B3LYP/6-31G(d) level of theory provide the basis for the assignment of the main vibrational contributions and for the understanding of Raman enhancement. The resonance-enhanced 1125 cm(-1) mode is unambiguously associated with a totally symmetric vibration of the TiO(4) tetrahedron, achieved through in-phase antisymmetric stretching of the four connected Ti-O-Si bridges. This vibration can also be described as a totally symmetric stretching of the four Si-O bonds pointing toward Ti. The resonance enhancement of this feature is explained in terms of the electronic structure of the Ti-containing moiety. Asymmetric stretching modes of TO(4) units show distinct behavior when (i) T is occupied by Si as in perfect silicalite, (ii) T is occupied by Ti as in TS-1, or (iii) the oxygen atom belongs to an OH group, such as in terminal tetrahedra of cluster models and in real defective zeolites. Asymmetric SiO(4) and TiO(4) stretching modes appear above and below 1000 cm(-1), respectively, when they are achieved through antisymmetric stretching of the T-O-Si bridges, and around 800 cm(-1) (in both SiO(4) and TiO(4)) when they involve symmetric stretching of the T-O-Si units. In purely siliceous models, the transparency gap between the main peaks at 800 and 1100 cm(-1) contains only vibrational features associated with terminal Si-OH groups, while in Ti-containing models it contains also the above-mentioned asymmetric TiO(4) modes, which in turn are strongly coupled with Si-OH stretching modes. Calculations on periodic models of silicalite and TS-1 free of OH groups using the QMPOT embedding method correctly reproduce the transparency gap of silicalite and the appearance of asymmetric TiO(4) vibrations at 960 cm(-1) in TS-1. Finally, we demonstrate, for the first time, that the distortion of the tetrahedral symmetry around Ti caused by water adsorption quenches the UV-Raman enhancement of the 1125 cm(-1) band.     

SO42-/TiO2-SiO2的制备及对甲基橙的光催化降解

0 引言 水中难降解有机物的治理已成为当今重要的环境问题,对新型高效水处理剂的需求也愈加迫切。多相光催化氧化已成为国内外治理污水的新技术,但常规二氧化钛半导体光催化剂的量子效率     

掺钛熔石英TiO2—SiO2缺陷的ESCA研究

高纯熔石英中掺杂TiO_2可使其具有低热膨胀或无膨胀性及特殊的紫外吸收,以实现能量转换,提高红外发射率,因而对其结构研究已受到关注,我们曾用Raman光谱研究了其结构与光谱特性,本文用光电子能谱(ESCA)探讨不同TiO_2含量的熔石英中网络缺陷与钛的配位结构变化。     

Reactivity of sub 1 nm supported clusters: (TiO2)n clusters supported on rutile TiO2 (110)

Metal oxide clusters of sub-nm dimensions dispersed on a metal oxide support are an important class of catalytic materials for a number of key chemical reactions, showing enhanced reactivity over the corresponding bulk oxide. In this paper we present the results of a density functional theory study of small sub-nm TiO(2) clusters, Ti(2)O(4), Ti(3)O(6) and Ti(4)O(8) supported on the rutile (110) surface. We find that all three clusters adsorb strongly with adsorption energies ranging from -3 eV to -4.5 eV. The more stable adsorption structures show a larger number of new Ti-O bonds formed between the cluster and the surface. These new bonds increase the coordination of cluster Ti and O as well as surface oxygen, so that each has more neighbours. The electronic structure shows that the top of the valence band is made up of cluster derived states, while the conduction band is made up of Ti 3d states from the surface, resulting in a reduction of the effective band gap and spatial separation of electrons and holes after photon absorption, which shows their potential utility in photocatalysis. To examine reactivity, we study the formation of oxygen vacancies in the cluster-support system. The most stable oxygen vacancy sites on the cluster show formation energies that are significantly lower than in bulk TiO(2), demonstrating the usefulness of this composite system for redox catalysis.     

多重射流燃烧反应制备的TiO2/ SiO2纳米复合颗粒的形态和结构

TiO₂-SiO₂ nanocomposite particles were prepared in premixed H₂ / Air flame, and the morphology and structure of these nanocomposites were characterized by FTIR, XRD, TEM and HRTEM. The morphology of SiO₂ / TiO₂ nanocomposites was different from that of pure TiO₂ or SiO₂ nanoparticles, and the chemical bond of Ti-O-Si was found in the nanocomposites indicating that the TiO₂ / SiO₂ nanocomposites were not merely a physical mixture of TiO₂ and SiO₂. TiO₂ nanocrystalline grains with sizes of 1～2 nm were homogeneously dispersed in the amorphous SiO₂ matrix when TiCl₄ and SiCl₄ were mixed at molecular level in the flame. The particle size and rutile content decreased with increasing of SiO₂ molar ratio.     

FTIR spectroscopic study of titanium-containing mesoporous silicate materials

The surface acidity of different mesoporous titanium-silicates, such as well-organized hexagonally packed Ti-MMM, Ti-MMM-2, Ti-SBA-15, and amorphous TiO(2)-SiO(2) mixed oxides (aerogels and xerogels), was studied by means of FTIR spectroscopy of CO adsorbed at 80 K and CD(3)CN adsorbed at 293 K. The surface hydroxyl groups of mesoporous titanium-silicates with 2-7 wt % Ti revealed a Br?nsted acidity slightly higher to that of pure silicate. TiO(2)-SiO(2) xerogels revealed the highest Br?nsted acidity among the titanium-silicates studied. CO adsorption revealed two additional sites on the surface in comparison to pure silicate, characterized by nu(CO) from 2185 (high pressure) to 2178 (low pressure) cm(-1) and from 2174 (high pressure) to 2170 (low pressure) cm(-1). These bands are due to CO adsorbed on isolated titanium cations in the silica surrounding or having one Ti(4+) cation in their second coordination sphere and due to CO interactions with Ti-OH groups, respectively. CD(3)CN adsorption similarly revealed the existence of two additional sites, which were not detected for pure silicate: at 2289 cm(-1) due to CD(3)CN interaction with titanol groups and from 2306 (low pressure) to 2300 (high pressure) cm(-1) due to acetonitrile interaction with isolated framework titanium cations with probably one Ti(4+) cation in their second coordination shell. The spectroscopic results are compared with computational data obtained on cluster models of titanium-silicate with different titanium content. According to the IR data, the Ti accessibility on the surfaces for mesoporous titanium-silicates with similar Ti loading (2 wt %) was found to fall in the order TiO(2)-SiO(2) aerogel approximately TiO(2)-SiO(2) xerogel > Ti-MMM approximately Ti-MMM-2 > Ti-SBA-15. This order (except TiO(2)-SiO(2) xerogel) correlates with the catalytic activity found previously for titanium-silicates in 2,3,6-trimethylphenol oxidation with H(2)O(2).     

Ti-Si mixed oxides prepared by polymer in situ sol-gel chemistry with the aid of CO2

A method to prepare titania-silica binary oxides is proposed in this work. In this route, inorganic precursors tetraethyl orthosilicate (TEOS) and titanium isopropoxide (TIP) were simultaneously or sequentially impregnated into a polypropylene (PP) matrix using supercritical carbon dioxide as a swelling agent and carrier. Hydrolysis and condensation reaction of the precursors confined in a polymer network were induced by treating the composites in 1 mol.dm(-3) (1 M) HCl. Then the PP matrix was decomposed at higher temperature, and titania-silica binary oxides were obtained. The mixed oxides were characterized by X-ray diffraction and Raman, FTIR, and X-ray photoelectron spectroscopy. It was demonstrated that the structure of the oxides depended strongly on the procedure to impregnate the precursors. The simultaneous method, in which the TEOS and TIP were simultaneously impregnated into a PP matrix, resulted in mixed oxides with highly dispersed titanium oxide species in the SiO2 matrix, while the sequential method produced the mixed oxide with separate SiO2 and TiO2 phases which were connected by Ti-O-Si bands at the interface. The method described in this work provides a new route to control the texture of TiO2-SiO2 mixed oxide simply by the impregnation sequence.     

Enhanced photocatalytic degradation of C.I. Basic Violet 2 using TiO2-SiO2 composite nanoparticles

In this report, TiO(2) -SiO(2) composite nanoparticles were prepared by the thermal hydrolysis method using titanium tetrachloride and tetraethylorthosilicate as TiO(2) and SiO(2) precursors, respectively. The prepared nanoparticles were characterized by X-ray powder diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), nitrogen adsorption/desorption and UV-Vis diffuse reflectance spectroscopy (DRS). The results indicated that, in comparison with pure TiO(2), TiO(2)-SiO(2) composite nanoparticles had a higher thermal stability, which prevents phase transformation from anatase to rutile. In addition, the TiO(2)-SiO(2) nanoparticles had a higher specific surface area, larger pore volume, greater band gap energy and smaller crystallite size. Thus, the surface area of TiO(2)-40% SiO(2) composite nanoparticles was about 17 times higher than that of pure TiO(2) nanoparticles. The photocatalytic activity of TiO(2)-SiO(2) composite nanoparticles in the photodegradation of C.I. Basic Violet 2 was investigated. The photodegradation rate of Basic Violet 2 using TiO(2)-40% SiO(2) nanoparticles calcined at 600°C was much faster than that using pure TiO(2) and Degussa P25 TiO(2) by 10.9 and 4.3 times, respectively. The higher photoactivity of the TiO(2)-SiO(2) composite nanoparticles was attributed to their higher surface area, larger pore volume, greater band-gap energy and smaller crystallite size compared with pure TiO(2).     

Raman spectroscopic study of the tellurite minerals: rajite and denningite

Tellurites may be subdivided according to formula and structure. There are five groups based upon the formulae (a) A(XO3), (b) A(XO3).xH2O, (c) A2(XO3)3.xH2O, (d) A2(X2O5) and (e) A(X3O8). Raman spectroscopy has been used to study rajite and denningite, examples of group (d). Minerals of the tellurite group are porous zeolite-like materials. Raman bands for rajite observed at 740, and 676 and 667 cm(-1) are attributed to the nu1 (Te2O5)(2-) symmetric stretching mode and the nu3 (TeO3)(2-) antisymmetric stretching modes, respectively. A second rajite mineral sample provided a more complex Raman spectrum with Raman bands at 754 and 731 cm(-1) assigned to the nu1 (Te2O5)(2-) symmetric stretching modes and two bands at 652 and 603 cm(-1) are accounted for by the nu3 (Te2O5)(2-) antisymmetric stretching mode. The Raman spectrum of dennigite displays an intense band at 734 cm(-1) attributed to the nu1 (Te2O5)(2-) symmetric stretching mode with a second Raman band at 674 cm(-1) assigned to the nu3 (Te2O5)(2-) antisymmetric stretching mode. Raman bands for rajite, observed at (346, 370) and 438 cm(-1) are assigned to the (Te2O5)(2-)nu2 (A1) bending mode and nu4 (E) bending modes.