金属离子掺杂硅胶吸附剂的性能与结构表征

以陶瓷纤维纸为基材,钴盐、铝盐或钛盐为改性剂,顺次经水玻璃、酸性盐溶液浸渍共沉积制得金属离子掺杂硅胶吸附剂。采用扫描电镜、多孔介质空隙分析仪、光电子能谱仪表征改性吸附剂组成、表面形貌、孔径大小及分布;用程序升温脱附谱,热失重分析仪等检测材料的脱附性能及热稳定性。结果表明:金属离子掺杂硅胶均匀分布在陶瓷纤维纸表面及其空隙中;经掺杂后的硅胶,其吸附性能、Brunauer-Emmett-Teller(BET)比表面积、孔容、平均孔径明显增加。改性硅胶的BET表面积、饱和吸附量及热稳定性按照铝掺杂硅胶、钛掺杂硅胶、钴掺杂硅胶及硅胶的顺序递减。     

陶瓷基Al3+掺杂硅胶吸附剂材料的制备与性能

陶瓷纤维纸经水玻璃、铝盐及其它添加剂顺次浸渍得到新型陶瓷基Al^3 掺杂硅胶吸附剂材料。探讨浸渍条件对材料吸附性能的影响;反应的优化条件为：水玻璃质量分数26．6％,铝盐质量分数为10％,反应温度60℃。由于铝替代硅进入硅胶网络,红外光谱显示Si-OH对称伸缩振动峰由968cm^-1移至Si(Al)-OH的954cm^-1;扫描电镜图表明Al^3 掺杂硅胶能较好地分布在陶瓷纤维表面及其孔隙中;X射线能谱(EDS)揭示材料表面微区Al^3 的存在与含量;多孔介质孔隙分析显示材料起吸附作用的主要为中孔。由于Al^3 掺杂,新型材料的吸附性能、耐热性能及机械强度等均优于同等条件下反应生成的硅胶。     

硅胶负载F掺杂TiO_2的制备与性能评价

利用水热法,以硅胶为载体、以Ti（SO4）2为钛源、NaF为氟源制备了具有良好性能的＂硅胶负载氟掺杂二氧化钛＂（FTS）光催化剂。考察了氟投加量、焙烧温度及钛硅比对光催化活性的影响。利用X射线晶体粉末衍射（XRD）,比表面积分析（BET）和紫外可见漫反射光谱（DRS）等表征手段对样品进行表征。结果表明,氟投加量为30%、钛硅比为1/1、焙烧温度为200℃时制备的FTS具有最佳的光催化活性,其比表面积为81.40 m2/g。氟掺杂二氧化钛（FT）经硅胶负载后,其表面孔结构发生了变化,并且热稳定性增加。苯酚降解实验表明：与FT相比,FTS以0.53 g/g的二氧化钛含量却体现更高光催化活性。     

第一性原理计算Al原子及空位掺杂6H-SiC的电子结构和磁性能

基于密度泛函理论的第一性原理,研究了6H-SiC的不同掺杂体系如碳空位(V_C)掺杂体系、硅空位(V_(Si))掺杂体系及(Al,V_(Si))共掺杂体系的电子结构和磁性。结果表明:单独的V_C或V_(Si)掺杂体系具有微弱的磁性,而(V_C,V_(Si))共掺杂体系呈现出强烈的磁性,其原因归结于V_C和V_(Si)之间强烈的耦合效应,致使碳原子附近的空位产生强烈的自旋极化。虽然在Al原子单独掺杂6H-SiC的体系中没有发现磁性,但是(Al, V_(Si))共掺杂体系具有明显的磁性,表明磁性并非源于Al原子的3p轨道,而是来源于C原子的2p轨道。研究结果为6H-SiC在稀磁半导体自旋电子器件上的潜在应用提供理论依据。     

Fe/SiO2核壳复合粒子表面的XPS谱研究

采用XPS技术研究了Fe/SiO2核壳复合粒子的表面化学成分和电子结构。结果表明,表面化学成分仅由Si和O元素组成,表面Si存在4种电子结构,表面O存在5种电子结构。表面硅4种电子结构的Si2p电子结合能及归属为:102.91eV(51.18%)为Q4硅[Si(OSi)4],102.15eV(23.23%)为Q3硅[Si(OSi)3OH],103.98eV(18.70%)为Q2硅[Si(OSi)2(OH)2],101.35eV(6.89%)为Q1硅[Si(OSi)(OH)3];表面氧5种电子结构的O1s电子结合能及归属为:532.85eV(52.07%)为Q4硅基团中的氧,531.80eV(19.93%)为Q3硅基团中的氧,533.90eV(17.09%)为Q2硅基团中的氧,534.75eV(7.65%)为Q1硅基团中的氧,530.55eV(3.26%)为与金属铁核相互作用的氧。531.80和530.55eV的氧原子数(19.93% 3.26%=23.19%)与102.15eV的硅原子数(23.23%)非常相近,这不仅表明与金属铁核相互作用的表面氧为Q3硅基团中的氧,而且说明表面氧与金属铁核相互作用后O1s电子结合能会因为Fe给电子能力较大而降低。     

TS-1分子筛骨架钛分布的DFT理论研究

采用密度泛函理论的B3LYP-D3方法,在6-31G(d,p)基组水平上研究了钛硅分子筛TS-1的骨架钛分布最佳替代位置。通过计算12个T位上的取代能,发现最易发生取代的位置是T10位,其次是T1、T9和T11位。Ti替代Si之后,Ti-O键长明显大于Si-O键长,增加范围为0.137～0.155?,中心原子的NPA电荷明显降低。前线轨道分析表明,HOMO-LUMO的能级差在Ti替代后都有所降低,分子筛活性明显提升。     

钛改性硅胶块体吸附剂除湿性能研究

采用浸渍沉积法制得钛改性硅胶块体吸附剂.对块体吸附剂的孔结构进行表征;考察了改性硅胶吸附剂动、静态除湿性能以及在吸附/脱附过程中湿度场、温度场的变化.结果表明,改性后的硅胶,其微孔、中孔孔径有所减少,而孔容和比表面显著增大;钛改性硅胶的吸附性能好于硅胶,而脱附能力劣于硅胶;由于钛改性硅胶产生更多的吸附热,吸附时出口气流温度略高于硅胶,而脱附时正好相反.     

SiO2掺杂稳定ZrO2界面Si-O-Zr键形成的量子化学研究

依据SiO2掺杂稳定ZrO2溶液中可能存在的各种生长基元及界面反应产物的团簇模型,利用密度泛函理论计算获得了各团簇的结构参数、原子的Mulliken电荷分布、红外活性振动光谱和反应的Gibbs自由能。理论红外光谱分析证实了SiO2／ZrO2界面Si-O-Zr键的形成,同时发现460cm^-1左右的特征峰不应归为链状Si-O-Si键的振动．而应是环状Si—O—Si键的振动光谱。此外,Mulliken电荷分布和热力学研究表明：SiO2掺杂稳定的ZrO2四方到单斜相变温度和相变临界尺寸的增加是由于界面Si—O—Zr键的形成降低了与邻近锆配位羟基氧的电荷所致。     

氧化铝对硅酸的吸附去除机理

探讨了氧化铝对水体中硅酸的吸附去除潜力、影响因素及机理。结果表明,pH 4～8时吸附量随pH、吸附剂投加量的增大而增加,说明氧化铝具有吸附去除硅酸的能力。吸附过程符合Langmuir吸附等温模式,最大吸附量达39.82 mg/g。结合~(27)Al MAS NMR与SEM-EDX分析,氧化铝吸附硅酸的机理是通过硅酸分子与氧化铝中4配位的铝发生化学反应,硅原子取代原来Al—O—Al键上的铝原子形成Al—O—Si键而被固定在氧化铝表面。     

表面接枝法合成Si掺杂介孔SO42-/TiO2

以工业硫酸钛液水解得到的介孔偏钛酸为载体,正硅酸乙酯(TEOS)为浸渍剂,采用表面接枝法制备了Si掺杂的介孔SO42/TiO2.通过X射线衍射(XRD)、N2吸附-脱附、X射线光电子能谱(XPS)和傅立叶-红外光谱(FT-IR)对焙烧产物进行表征,考察了超声波和微波外场对浸渍过程的影响以及Si提高介孔TiO2热稳定性的机制.结果表明,掺杂Si形成的Ti-O-Si键对介孔TiO2的孔结构起到支持作用,阻止晶粒长大和提高锐钛矿向金红石矿的相变温度,使SO4-2稳定的介孔Ti2的热稳定性提高,在700℃焙烧后仍保持138 m2/g的比表面积;超声波和微波场强化了浸渍过程,大大缩短了浸渍时间,促进Si在内外表面的分布.     

Silica–Titania mixed Oxides: Si–O–Ti Connectivity, Coordination of Titanium, and Surface Acidic Properties

A series of SiO₂–TiO₂ mixed oxides was prepared by the sol–gel route, and the influence of several important preparation parameters (Ti precursors, content, and calcination temperature) on the Si–O–Ti connectivity, coordination of titanium and surface acidity has been studied using various analytical techniques. The solids obtained were largely amorphous and characterized by Ti enrichment on surfaces with low titanium content; however, the addition of titanium greater than 50 mol% into the SiO₂ matrix led to significant phase separation of crystalline anatase. The Ti atoms are tetrahedrally coordinated with Si/Ti ratios higher than 10 and gradually enter into octahedral positions in the silica matrix with further increase in the titanium content. High-temperature treatment can break Si–O–Ti linkages and eliminate hydroxyl groups, resulting in a decrease in acid site density.     

Textural and Structural Properties of Mesoporous Silica Synthesized Under Refluxing Conditions

Mesoporous silica with pore sizes of 3–6 nm has been synthesized under refluxing and autogenous pressure conditions of hydrothermal synthesis from precursor gels having different alkaline pH. The mesoporous silica prepared is characterized by powder X-ray diffraction, nitrogen adsorption-desorption measurement and scanning electron microscopy. Thermal stability has been tested by XRD analysis of mesoporous silica after thermal treatment at 823 K, 6 h; 1023 K, 1 h and 1223 K, 1 h. The results indicate that the mesoporous silica prepared under refluxing condition from precursor gel of pH 11 has large surface area (ca.1103 m² g^{− 1}) and pore volume (ca. 0.868 cm³ g^{− 1}) and is thermally stable at 1223 K. The surface area, pore volumes and pore wall thickness increase as the pH of the precursor gel is increased for refluxing condition of synthesis. The comparison of textural properties revealed that the refluxing condition is advantageous over autogenous pressure condition for obtaining mesoporous silica with higher surface area (852 m² g^{− 1}), pore volume (0.894 cm³ g^{− 1}) and pore diameter > 4 nm with wall thickness of 1.59 nm, when synthesized from precursor gel of pH 9.2. The ²⁹Si NMR spectra showed that a great part of the Si atoms exists as silanol groups. The mesoporous silica made at the lower pH (9.2) under refluxing conditions have more condensed framework. In calcined mesoporous silica, the proportion of partly condensed silica (Q³) is higher than fully condensed silica (Q⁴).     

Preparation and characterization of epoxy resin modified with alkoxysilane‐ functionalized poly(urethane‐imide) by the sol–gel process

The sol–gel process has been frequently employed for preparation of high performance silica/polymer composites. In this paper, novel sol–gel precursor triethoxysilane‐terminated poly(urethane‐imide) (PUI‐Si), combining the advantages of polyurethane (PU) and polyimide, was synthesized and characterized. Then PUI‐Si was incorporated into the epoxy resin matrix to prepare a series of EP/PUI‐Si organic‐inorganic hybrids through an in situ sol–gel process and crosslinking reactions. The thermal stability of EP/PUI‐Si hybrids was evaluated by thermogravimetric analysis and the results show that the PUI‐Si could significantly improve the thermal properties of epoxy resin. The initial decomposition temperature of composites with 50 wt% PUI‐Si reached 347.1 °C, 157.3 °C higher than that of neat epoxy resin. Furthermore, the tensile strength and breaking elongation can also be clearly improved by adding a suitable amount of PUI‐Si. Similarly, the water contact angle increased to 97.4° with 70 wt% PUI‐Si, showing a hydrophobic surface. The morphology was investigated by transmission electron microscopy and the results reveal that the silica particles are smaller than 20 nm and have a strong interaction with the epoxy resin matrix, resulting in the above‐mentioned high performance properties. Copyright © 2011 Society of Chemical Industry     

Chromic titanate catalysts for high-melt-index polyethylene by the particle-form process

A novel thermal activation procedure for ethylene polymerization catalysts made from silica, a chromium compound, and a titanium ester greatly increases the melt index of the polyethylene product under commericla polymerization conditions in comparison with conventional air activation. The novel activation has two steps. The first is heating under a reducing gas atmosphere (N₂ + CO). The second step is partial oxidation at a lower temperature for a shorter time. The size of the melt index increase is related to the average oxidation number of the chromium, but oxidized chromium can be reduced and the effect persists with less intensity. Additionally, the magnitude of the effect is dependent upon gas flow rates during activation and prior chemical and thermal history of the chromium–silica combination. Since titanium is required for the two-step activation to be effective in increasing melt index, titanium atoms have a critical influence on the catalyst active sites. An experiment with tetraethoxysilane added to the catalyst shows that titanium and chromium atoms must be next nearest neighbors (separated by oxygen atoms).     

新型高效复合吸附剂开发及系统仿真

针对一种新型高效复合吸附剂开展了吸附性能实验研究,并假想将该复合吸附剂装填于一固体吸附式空调样机吸附床内进而开展仿真研究。对比研究表明该复合吸附剂不但具有比硅胶强得多的吸附能力,而且再生温度较低。装填该复合吸附剂的吸附式空调不但可以获得比装填纯硅胶时高得多的比制冷功率SCP,而且系统性能系数COP也明显高于纯硅胶系统。     

Morphology of titania coatings on silica gel

Control of the hydrolysis and condensation of soluble precursors of titanium is shown to yield oxide coatings of well-defined morphology. A ``smooth' coating, consisting of patches of titania on silica, causes only a small increase in the surface area, from 130 m<sup>2</sup>/g for the uncoated silica gel to 154 m<sup>2</sup>/g. On the other hand, the ``rough' coating, which consists of 3 nm diameter titania particles dispersed over the silica surface, results in an increase in the BET surface area to 350 m²/g. The specific titania surface area was determined via isopropanol dehydration activity and was found to be comparable to the BET surface area indicating that the titania phase is responsible for the increase in surface area. Small angle X-ray scattering (SAXS) and transmission electron microscopy (TEM) provide definitive evidence for the coating morphology while X-ray photoelectron spectroscopy (XPS) was used to determine the dispersion of the titania. The supported titania maintains its surface area upon calcination at temperatures up to 873 K while unsupported titania looses much of its surface area. Also demonstrated in this work is a novel preparation method using titanium bis-ammonium lactato dihydroxide (TALH), a water soluble precursor. This revised version was published online in July 2006 with corrections to the Cover Date.     

Preparation and anticorrosive properties of hybrid coatings based on epoxy‐silica hybrid materials

A series of sol‐gel derived organic–inorganic hybrid coatings consisting of organic epoxy resin and inorganic silica were successfully synthesized through sol‐gel approach by using 3‐glycidoxypropyl‐trimethoxysilane as coupling agent. Transparent organic–inorganic hybrid sol‐gel coatings with different contents of silica were always achieved. The hybrid sol‐gel coatings with low silica loading on cold‐rolled steel coupons were found much superior improvement in anticorrosion efficiently. The as‐synthesized hybrid sol‐gel materials were characterized by Fourier‐transformation infrared spectroscopy, ²⁹Si‐nuclear magnetic resonance spectroscopy and transmission electron microscopy. Effects of the material composition of epoxy resins along with hybrid materials on the thermal stability, Viscoelasticity properties and surface morphology were also studied, respectively. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Composites prepared from silica gel and furfuryl alcohol with p-toluenesulfphonic acid as the catalyst

Summary Composites of furfuryl alcohol and silica gel or Aerosil were prepared using p-toluenesulphonic acid as catalyst at room temperature. The molar ratio furfuryl alcohol/p-toluensulphonic acid was varied between 64.7 and 10. The surface of silica gel was partially coated when composite was prepared with the lower quantity of acid while the use of the higher proportion of acid produces the start of particle agglutination. The thickness of the polymer layer completely coating the surface of the composites ranged between around 10 to 39 ?. Preliminary results suggest that composites could be used as adsorbent of organic pollutants from water.     

Preceramic organoboron–silicon polymers

Several boron-containing organosilicon polymers were synthesized from a sodium-coupling reaction of silicon and boron halides with and without alkyl halide in hydrocarbon solvents. The B–Si preceramic polymers were characterized using techniques such as IR, UV, and NMR spectrometry, gel permeation chromatography, elemental analysis, molecular weight measurement, and thermal analyses (TGA, DSC, DTA, and TMA). The chemical structures of the preceramic polymers were postulated based on the analytical results. Black ceramic materials were obtained from the precursor polymers upon thermal degradation at temperatures above 1000°C in an inert atmosphere. The precursor polymers had a ceramic yield of up to 70%. Thermogravimetric analysis of the ceramic material in air at a flow rate of 100 mL/min showed it was stable up to 1000°C with little weight gain or loss. Several methods were used to characterize the ceramic materials: XRD, solid NMR, high-temperature DTA, elemental analysis, and acid digestion. The analyses indicated that the ceramic materials comprised a mixture of silicon carbide (SiC), silicon borides (SiB₄, SiB₆), and amorphous Si–B–C ceramics, with small amounts of silica and free silicon.