Thermal Diffusivity and Adsorption Kinetics of Silica-Gel/Water

There have been performed experimental measurements of effective thermal conductivity of silica-gel for a stagnant cylindrical fixed bed under transient and steady state conditions in the presence of dry air at different pressures and for different amounts of adsorbed water. The Bauer-Schlünder and Kunii-Smith models have been used to identify the thermal solid conductivity of silica gel pellets from measurements of the conductivity in an adsorbent bed. Sorption rates of water vapor in silica gel were measured using a single-step thermal method by monitoring the sample surface temperature by infrared detection. In order to obtain the mass diffusivity it is necessary to match the numerical solution of the mathematical model to the experimental data.     

Chemical modification of silica-gel with diethylenetriamine via an end-group protection approach for adsorption to Hg(II)

Four kinds of silica-gel supported diethylenetriamine adsorbents with different structures, were prepared by so-called “heterogeneous-direct-amination” (hetero-DA), “homogeneous-direct-amination” (homo-DA), “heterogeneous end-group protection” (hetero-EGP), and “homogeneous end-group protection” (homo-EGP) methods, respectively. The obtained products were named SG-HE-dD, SG-HO-dD, SG-HE-pD and SG-HO-pD, respectively (where SG means silica-gel; HE means heterogeneous, HO means homogeneous, d means direct, p means protected and D means diethylenetriamine). Their structures were characterized by FT-IR, elemental analysis, porous structure analysis and thermogravimetric analysis. The adsorption capabilities of such adsorbents towards Hg(II) were studied and evaluated by static method. SG-HE-pD and SG-HO-pD showed higher performance towards Hg(II) adsorption than corresponding counterparts SG-HE-dD and SG-HO-dD, even though the former two possessed lower contents of diethylenetriamine (DETA). The kinetics data indicated that the adsorption process was governed by the film diffusion and followed pseudo-first-order rate model for SG-HE-dD, SG-HO-dD and SG-HE-pD and pseudo-second-order model for SG-HO-pD. The Langmuir model was applied to fit the experimental equilibrium data for all adsorbents. The end-group protection method exhibited its advantage in preparation of effective adsorbent for metal ions uptake compared to the direct-amination method.     

硅胶固定功能化离子液体的制备及其在HMF合成中的应用

通过氯丙基三甲氧基硅烷将磺基功能化离子液体--N-磺丙基咪唑盐化学键联到微球硅胶上,制得微球硅胶固定化离子液体（IL3）。用FTIR、TG、13C-NMR、SEM、BET及酸度测定等方法对IL3进行了表征,并考察其在果糖脱水合成5-羟甲基糠醛（HMF）过程中的催化性能。研究结果表明：氯丙基三甲氧基硅烷可以将磺基功能化咪唑型离子液体化学键联到微球硅胶上。微球硅胶固定化磺基咪唑离子液体能有效催化果糖脱水生成HMF。在45.4-IL3催化下、乙二醇甲醚(EGME)溶剂中、115℃反应5小时, HMF收率可达82.1％。使用后的催化剂可以方便地循环使用。但随次数增加,HMF收率明显下降。45.4-IL3催化剂循环使用四次后,HMF的收率下降为53.0%。     

呋喃类化合物在离子液体和硅胶负载离子液体中的Diels-Alder反应研

以1-丁基3-甲基咪唑盐作为离子液体阳离子,与三种不同阴离子BF4、PF6、Tf2N组成性质不同的三种离子液体,催化呋喃类和丁炔二羧酸酯之间发生的Diels-Alder反应,合成了一系列化合物,研究了离子液体的催化效果。研究表明,呋喃类化合物的极性越低, Diels-Alder 反应的活性越高。在含硫的呋喃类化合物的反应中,当以 [Bmim]PF6 作为离子液体时,Diels-Alder 反应的产率可达到53%。另外,当 [Bmim]PF6 离子液体被吸附在硅胶表面上时,Diels-Alder的反应产率有所提高。     

硅胶表面扑灭津分子印迹材料的制备及性能表征

以扑灭津为模板分子,在甲苯溶液中经三步反应合成了基于硅胶表面修饰的分子印迹聚合物,并探讨了聚合物制备工艺,验证了聚合物的结构。红外1726cm-1指认印迹膜中的羰基特征峰,元素分析表明印迹材料含碳量18%,N2吸附实验表征印迹膜厚度为0.3nm。应用高效液相色谱-质谱考察了扑灭津和其它3种三嗪农药水溶液中的竞争吸附特性。研究表明:本法制备的表面印迹材料对4种三嗪类农药的吸附均优于参比材料。     

Molecular Imprinting of Cyclodextrin on Silica-Gel Support for the Stationary Phase of High-Performance-Liquid-Chromatography

By copolymerizing acryloyl cyclodextrin (CD) andN,N'-methylenebisacrylamide with vinylated silica-gel in the presence of a template in water,a thin layer of molecularly imprinted CD polymer was immobilized on a porous silica-gel support. This mechanically weak polymer was reinforced by the silica-gel andsuccessfully used as a stationary phase in high-performance-liquid-chromatography (HPLC). When L-Phe-L-Phe was the template, the polymer/silica-gel conjugate retainedL-Phe-L-Phe in the aqueous eluent more strongly than D-Phe-D-Phe. As expected, the D-Phe-D-Phe-imprinted polymer retained D-Phe-D-Phe more strongly than L-Phe-L-Phe. Selective separation of antibiotics was also achieved by thepolymer/silica-gel conjugate. Molecularly imprinted CD polymer, immobilizedon silica-gel, is an eminent stationary phase for HPLC in water.     

Development of TiO<Subscript>2</Subscript> photocatalysts suitable for practical use and their applications in environmental cleanup

Recently, environmental disruption is proceeding on a global scale through the consumption of huge amounts of fossil fuels and the emission of various chemical substances. However, these substances resist bio-treatment. TiO₂ generates electrons and holes by irradiation with light. Most organic micro-pollutants, including dioxins, are decomposed into carbon dioxide and water by the effect of the holes with high oxidative potential. By using such a photocatalytic reaction, various applications are feasible for environmental cleanup. In general, TiO₂ powder has been utilized as photocatalyst, although TiO₂ powder photocatalyst has several disadvantages: (1) it is difficult to handle, (2) photocatalytic reaction is slow and it takes a lot of time for treatment and (3) it is difficult to apply to plastics and textiles, because the photocatalyst decomposes them. We have developed a photocatalyst suitable for practical use and have developed high-activity photocatalysts such as TiO₂ photocatalytic transparent film, photocatalytic silica-gel, apatite-coated TiO₂ photocatalyst usable for plastics and textiles, photocatalytic paper, photocatalytic blue charcoal and photocatalytic oxygen scavenger. The application of these high-activity photocatalysts has been studied in deodorization, anti-bacterial, self-cleaning, anti-stain, water treatment, air purification such as photocatalytic decomposition of dioxins and VOC, and NO _x removal. Now various photocatalytic articles using these new photocatalyst materials are on the market in Japan. Photocatalytic technology can create many valuable products for environmental use all over the world.     

Nanoparticle-Reinforced Silica Gels with Enhanced Mechanical Properties and Excellent pH-Sensing Performance

Silica gels offer excellent wear resistance, high chemical stability, good insulation, and light transmittance, are therefore promising to engineer 2D sensing films. However, their practical applications are greatly hampered by their poor structural stability, low sensitivity, reliability, and repeatability. Incorporation of nanoelements into glasses and ceramics is a promising new pathway to tackle these challenges. Unfortunately, it is difficult to disperse nanoparticles uniformly in any glass and ceramics. Herein, a facile sol–gel approach is applied to synthesize novel silica gel nanocomposites with dispersed nanoparticles (NPs) as additives and thymol blue as an indicator. Titanium dioxide (TiO₂) NPs with a diameter of 5 nm can be dispersed uniformly in the silica gel, with enhanced modulus and hardness (up to 230% and 138%, respectively) and good alkaline resistance. The addition of nanoparticles improves the film's stability, sensitivity, and repeatability of spectral responses (in pH 1–12), and reduces the indicator leakage. The interaction of indicator with silica gel substrate, nanoparticles, and H⁺ is analyzed to elucidate the principle of reversible color change. This novel simplified method to produce glass-like functional materials under much lower temperatures is groundbreaking in materials science and engineering.     

Nucleation of Hydroxyapatite on Silica-Gel: Experiments and Thermodynamic Explanation

Silica-gels prepared from ethanol, TEOS and water, using a hydrochloric acid as catalyst, were slowly dried and heated in air up to 900°C. Plate-like pieces of heat treated silica-gel were used for hydroxyapatite nucleation experiments in a simulated body fluid (SBF) medium since sol-gel processing gives the silica an active surface. The SBF was changed every 3 days.After 9 days in the SBF, hydroxyapatite was observed by SEM on the surface of the silica-gel samples. The presence of hydroxyapatite was confirmed by FTIR. Subsequent growth of hydroxyapatite was evaluated after 12 and 21 days total soaking time in SBF. A thermodynamic analysis was made in order to explain the nucleation and growth of the hydroxyapatite on the silica-gel.     

Solid phase extraction of heavy metals on chemically modified silica-gel with 2-(3-silylpropylimino) methyl)-5-bromophenol in food samples

Trace amounts of Fe³⁺, Pb²⁺, Cu²⁺, Ni²⁺, Co²⁺ and Zn²⁺ ions were efficiently enriched following complexation with silica-gel chemically functionalized with 2-((3-silylpropylimino)methyl)-5-bromophenol. The enriched metal ions efficiently eluted with 6?mL of 4.0?mol?L^?1 nitric acid and their metal contents were determined by flame atomic absorption spectrometry (FAAS). The influences of the analytical parameters and experimental variables on the recoveries of the metal ions under study were investigated and optimized. The method has high sorption preconcentration efficiency even in the presence of various interfering ions. At optimum values of all variables the method is applicable for analysis of real samples with recoveries in the range of 95 to 105% with RSD lower than 4.2% and detection limits between 1.4 and 2.8?µg?L^?1.