Magneto-Optical Properties of Silica Gel Containing Magnetite Fine Particles

The magnetic composite materials that consist of transparent matrix and magnetic fine particles are expected to have large residual magnetization and coercive force because of their fine magnetic domain structure, and also to show magneto-optical effects. Silica gels containing magnetite (Fe₃O₄) fine particles were prepared by sol-gel method. The magnetic, optical and magneto-optical properties of the composites were investigated by measurements of magnetization curves, UV-visible spectra and Faraday rotation in visible range. The saturation magnetization of the composite was almost as same as that expected from the amount of magnetite fine particles in it. Although the composites had large and broad absorption at around 400 nm, they still maintained their transparency. The origins of decrement of transparency attributed to the optical absorption of magnetite and scattering due to magnetite fine particles. The whole composites showed positive Faraday rotation under external static magnetic field due to the large contribution of diamagnetic silica gel matrix. Magnetite contributed negative Faraday rotation with maximum at around 470–480 nm to the magneto-optical spectra of the composites.     

Freezing and Melting of Water Confined in Silica Nanopores

In nanosized pores, liquid water can be thermodynamically stable down to temperatures well below the limit of homogeneous nucleation of bulk water (～235 K). Studies of water in such pores therefore offer an opportunity to reveal the anomalous behavior of deeply supercooled water. Herein we focus on recent studies of the limits of freezing and melting of water in the cylindrical pores of ordered mesoporous silicas with pore diameters in the range of 2–10 nm, based on vapor sorption measurements, calorimetric studies, NMR spectroscopy and cryoporometry, and neutron diffraction studies.     

Preparation and adsorption property of novel inverse-opal hierarchical porous N-doped carbon microspheres

The design of pore structure is the key factor for the performance of porous carbon spheres.In this wo rk,novel micron-sized colloidal crystal microspheres consisting of fibrous silica(F-SiO_2) nanoparticles are firstly prepared by water-evapo ration-induced self-assembly of F-SiO_2 nanoparticles in the droplets of an inverse emulsion system to be used as sacrificial templates.Acrylonitrile(AN) was infiltrated in the voids of the F-SiO_2 colloidal crystal microspheres,and in-situ induced by ~(60)Co y-ray to polymerize into polyacrylonitrile(PAN).After the PAN-infiltrated F-SiO_2 colloidal crystal microspheres were carbonized and etched with HF solution,novel micron-sized inverse-opal N-doped carbon(IO-NC) microspheres consisting of hollow carbon nanoparticles with a hierarchical macro/meso-porous inner surface were obtained.The IO-NC microspheres have a specific surface area as high as 266.4 m~2/g and a molar ratio of C/N of 5.They have a good dispersibility in water,and show a high adsorption capacity towards rhodamine B(RhB) up to 137.28 mg/(g microsphe re).This work offers a way to obtain novel micron-sized hierarchical macro/meso-porous N-doped carbon microspheres,which opens a new idea to prepare high-performance hierarchical porous carbon materials.     

担载型铱催化剂上CO吸附量热和红外光谱研究

分别对Al2O3和SiO2担载的不同含量铱(Ir)催化剂进行了H2程序升温还原、CO微量吸附量热和红外研究.结果表明,还原后,Ir/Al2O3上存在金属态Ir0和氧化态Irδ 两种物种,CO在催化剂表面主要以线式和孪生吸附态存在,测量的CO吸附热为两种吸附形式的平均吸附热.提高还原温度和Ir担载量,Ir/Al2O3表面CO线式吸附物种的比例增加,从而导致CO吸附热值的升高.而在Ir/SiO2上Ir物种主要为金属态Ir0,CO吸附都以线式吸附为主,在所考察的条件下CO吸附热随Ir担载量和还原温度的变化不明显。     

A facile synthesis of highly water-soluble, core–shell organo-silica nanoparticles with controllable size via sol–gel process

A series of highly water-soluble organo-silica nanoparticles, ranging from 2 to 10 nm in diameter, were synthesized by the cohydrolysis and copolycondensation reactions. ω-methoxy(polyethyleneoxy)propyltrimethoxysilane (PEG6-9) and hydroxymethyltriethoxysilane (HMTEOS) mixtures were catalyzed by sodium hydroxide in the presence of surfactant benzethonium chloride (BTC) with various ratios of PEG6-9/HMTEOS at room temperature. The synthesized organo-silica nanoparticles possess a core–shell structure with a core of organo-silica resulting from HMTEOS and a monolayer shell of PEG6-9. The chemo-physical characteristics of the particles were studied by gel permeation chromatography (GPC), Fourier transform infrared (FTIR) spectroscopy, ²⁹Si nuclear magnetic resonance (NMR), dynamic light scattering (DLS), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The molecular weight and particle size of the particles increased with increasing HMTEOS molar ratios. The richest HMTEOS composition for the water-soluble particles was found to be HMTEOS:PEG6-9 = 80:20, where the particles had a 6 nm diameter core and a 0.8 nm thick shell. We propose that these water-soluble organo-silica nanoparticles will be suitable for biomedical applications.     

The Effects of Intramolecular Hydrogen Bonding on the Reaction of Phenols with Epoxide in the Presence of Nano Calcium Carbonate

The reaction of phenols and dihydroxybenzenes with epoxide in the presence of nano CaCO₃ was studied. Catechol could react with epoxide and gave monochlorohydrin derivative; other dihydroxybenzenes and monomeric phenols had no reaction under the same conditions. The reaction of catechol with epoxide did not occur when nano CaCO₃ was replaced by a normal one. These were attributed to the strong interaction between nano CaCO₃ and the substrate as catechol possessed intrahydrogen bond and excess active hydrogen, which can induce the intramolecular proton transfer via the intramolecular hydrogen bond and promote the reaction of hydroxyl and epoxide. This is an example revealing the unique role of the hydrogen bond played in chemical reactions.     

Adsorbents and columns in analytical high-performance liquid chromatography: a perspective with regard to development and understanding

A brief historical survey is presented on the evaluation of silica adsorbents in analytical HPLC. The theory of analytical HPLC is mostly still being based on the height equivalent to a theoretical plate concept and the van Deemter equation that was derived from gas phase adsorption involving a linear adsorption isotherm and fast mass transfer kinetics. One can obviously wonder whether the use of the van Deemter equation is relevant and valid for the evaluation of the performance of HPLC systems, where most often the liquid solutes involve charged molecules in electrolytes and in very many cases the adsorbates are macromolecules having diffusion coefficients of small magnitude. Instead of the van Deemter equation, a multi-scale modelling approach that involves microscopic and macroscopic dynamic non-linear mass-transfer-rate models should be employed. Furthermore, advanced experimental methods for the characterisation of porous media and the distribution of the density of immobilised active sites (e.g., ligands) on surfaces as well as microscopic pore-network modelling and molecular dynamics modelling and simulation methods could be used for the design of novel adsorbents whose porous structures and immobilised active sites would provide effective mass transport and adsorption rates for realising efficient separations as well as high dynamic capacities when larger throughputs are required.     

Efficient Multi‐component Synthesis of Highly Substituted Imidazoles Utilizing P2O5/SiO2 as a Reusable Catalyst

Phosphorus pentoxide supported on silica gel (P₂O₅/SiO₂) has been used as an efficient and reusable catalyst for the one‐pot pseudo four‐component synthesis of 2,4,5‐trisubstituted imidazoles from benzil or benzoin, aldehydes, and ammonium acetate. It was also used for four‐component preparation of 1,2,4,5‐tetrasubstituted imidazoles from benzil or benzoin, aldehydes, primary amine, and ammonium acetate under thermal solvent‐free conditions. The remarkable features of this new procedure are high conversions, cleaner reaction, simple experimental and work‐up procedures and also the catalyst can be easily separated from the reaction mixture and reused several times without any loss of its activity.     

The flow-through silica as the matrix to immobilize gold nanoparticles for HPLC applications

In the present study, the flow-through silica, featured with hierarchical pores, i.e., tunable mesopores and penetrable macropores, was attempted as the chromatographic stationary phase matrix to immobilize gold nanoparticles (AuNPs). It was first modified by mercapto groups (named as SiO₂-SH), and then by AuNPs (named as SiO₂-S-Au). Thanks to the characteristic macropores, the column backpressure of SiO₂-S-Au was comparable to SiO₂-SH, which effectively overcame the difficulty of high column backpressure upon the nanoparticles were introduced to the chromatographic matrix. Both the reversed-phase and hydrophilic interaction liquid chromatographic performance were observed on these two columns but with different selectivities. Hydrophobic, hydrophilic, hydrogen bond and electrostatic interactions between the SiO₂-S-Au stationary phase and analytes could contribute to the retention. The SiO₂-S-Au column showed excellent aqueous compatibility by “Stop-flow” test with the relative standard deviations (RSD) of analyte’s k (capacity factor) values from 0.59% to 2.88%. The reproducibility of SiO₂-S-Au was acceptable with RSDs of analyte’s k values in the range of 3.13%-5.03%. In addition, compared with the SiO₂-SH column, the SiO₂-S-Au column had better separation performance and selectivity. The results demonstrated that the flow-through silica was a promising matrix for nanoparticles with low backpressure and different selectivities.