Selective removal of 2,4-dichlorophenoxyacetic acid from water by molecularly-imprinted amino-functionalized silica gel sorbent

A molecularly-imprinted amino-functionalized sorbent for selective removal of 2,4-dichlorophenoxyacetic acid （2,4-D） was prepared by a surface imprinting technique in combination with a sol-gel process. The 2,4-D-imprinted amino-functionalized silica sorbent was characterized by FT-IR, nitrogen adsorption and static adsorption experiments. The selectivity of the sorbent was investigated by a batch competitive binding experiment using an aqueous 2,4-D and 2,4-dichlorophenol （2,4-DCP） mixture or using an aqueous 2,4-D and 2,4- dichlorophenylacetic acid （DPAC） mixture. The largest selectivity coefficient for 2,4-D in the presence of 2,4-DCP was found to be over 18, the largest relative selectivity coefficient between 2,4-D and 2,4-DCP over 9. The static uptake capacity and selectivity coefficient of the 2,4-D-imprinted functionalized sorbent are higher than those of the non-imprinted sorbent. The imprinted functionalized silica gel sorbent offered a fast kinetics for the extraction/stripping of 2,4-D, 73% of binding capacity （200 mg/L 2,4-D onto 20 mg of imprinted sorbent） was obtained within 5 min and the adsorbed 2,4-D can be easily stripped by the mixture solution of ethanol and 6 mol/L HC1 （V：V =1：1）. In a test of five extraction/stripping cycles, the adsorption capacity of the sorbent was all above 93% of that of the fresh sorbent. Experimental result showed the potential of molecularly-imprinted amino-functionalized sorbent for selective removal of 2,4-D.

Preparation of organically functionalized silica gel as adsorbent for copper ion adsorption

A novel adsorbent （AMPS-silica） was synthesized by bounding AMPS （2-acrylamido-2-methylpropanesulfonic acid） onto silica surface, which functioned with γ-methacryloxypropyltrimethoxysilane reagent. The adsorbent was characterized by nitrogen adsorption/desorption measurement, thermogravimetric analysis （TGA） and potentiometric titration analysis. The TGA result indicated that the surface modification reactions introduced some organic functional groups onto the surface of silica. The surface area of AMPSsilica was 389.7 m2/g. The adsorbent was examined for copper ion removal in series of batch adsorption experiments. Results showed that the adsorption of Cu2＋ onto AMPS-silica was pH dependent, and the adsorption capacity increased with increasing pH from 2 to 6. The adsorption kinetics showed that Cu^2＋ adsorption was fast and the data fitted well with a pseudo secondorder kinetic model. The adsorption of Cu^2＋ onto AMPS-silica obeyed both Freundlich and Langmuir isotherms, with r^2 = 0.993 and r^2 = 0.984, respectively. The maximum Cu^2＋ adsorption capacity was 19.9 mg/g. The involved mechanism might be the adsorption through metal binding with organic functional groups such as carboxyl, amino and sulfonic groups. Cu^2＋ loaded on AMPS-silica could be desorbed in HNO3 solution, and the adsorption properties remain stable after three adsorption-desorption cycles.

Effects of Functionalized Silica Nanoparticles on Characteristics of Nanocomposites PES Cation Exchange Membranes

Nanocomposite cation exchange membranes（CEMs） were prepared by adding various loadings of functionalized silica nanoparticles to the sulfonated polyethersulfone（s PES） polymeric matrix. The silica nanoparticles were functionalized by mercaptopropyl（F1, IEC=0）, propylsulfonic acid（F2, IEC= 2.71）, and sulfonic acid（F3, IEC=2.84）. The properties of prepared membranes were investigated by varying the loadings of functionalized silica nanoparticles. Applying functionalized nanoparticles provides additional ion exchange groups and enhances water contents as well as conductivities and permselectivities of the membranes. The maximum IEC of 1.9 meq.g^-1 was obtained for the membrane having 3 wt% F3 nanoparticles and the maximum conductivity of 0.237 S·cm^-1 was achieved for the membrane having 2 wt% F3 nanoparticles, which were 19.6% and 64% higher than the corresponding values for s PES membrane, respectively. The excellent properties of the nanocomposite cation-exchange membranes make them appropriate candidates for electrodialysis and desalination processes.

Novel one-pot synthesis of 4H-chromene derivatives using amino functionalized silica gel catalyst

A simple, efficient, and environmentally benign method for the synthesis of 4H-chromene derivatives was developed using well ordered and recoverable amino functionalized silica gel as a base catalyst. The 4H-chromene derivatives were obtained in short time and excellent yield （87%-96%） by three component reaction of aldehydes, malononitrile and cyclic 1,3-diketones in water at 70 ℃.

On-line solid-phase extraction using alizarin violet functionalized silica gel for determination of trace lead in environmental samples and wastewater by sequential injection spectrophotometry

Trace of Pb(Ⅱ) has been on-line separated and enriched from environmental samples and wastewater by using the self-made alizarin violet functionalized silica gel micro-column coupling with a sequential injection sampling technology. The determination is based on the color reaction of Pb(Ⅱ) with iodide and crystal violet to form an ionic association complex in the presence of polyvinyl alcohol and hydrochloric acid. The use of the microcolumn can prevent the interference of most familiar metal ions, and therefore improve the selectivity and sensitivity of this analytical technique. The proposed method was used for the determination of Pb(Ⅱ) in environmental samples and wastewater. No statistically significant difference was observed between the results determined by the present method and atomic absorption spectrometry.

SYNTHESIS OF CATALYSIS BY THE FUNCTIONALIZATION OF SILICA AND ITS APPLICATIONS

Hybrid organic-inorganic silica materials containing organic functional groups have been preparedby the reaction of activated silica with a silane coupling reagent such as N-(2-aminoethyl)3-aminopropyltrimethoxysilane. The hybrid silica was further modified by organic compounds having abifunctional group. These modified hybrid silicas were used as catalysts for various nucleophilic reactions.And also, these were complexed with metallic ions for use as catalysts for oxygen oxidation of hydrocarbons.

Functionalization of Silica Surface with UV-Active Molecules by Multivalent Organosilicon Spacer

Immobilization of active molecules by attachment onto solid surfaces is a well-established practice in many processes and applications. Silica micro- and nano-particles are attractive candidates as support for active molecules as a result of a combination of desirable properties. The present study deals with grafting of a functional UV active molecule onto silica surfaces via hydrosilylation reactions using multivalent organosilicon spacers. Different types of organosilicon precursors based on dimethylsiloxysilanes containing multiple SiH groups were used as spacers between vinyl-modified silica surface and the benzotriazole UV-absorber (UVA). Firstly, the surface of silica was modified with vinyltrimetoxsisilane coupling agent. The UVA molecules were attached to the silica-vinyl by a two-step procedure involving hydrosilylation reaction. The successful grafting was confirmed by FTIR, TGA and UV-Vis characterization. More than fivefold increase in UVA loading was found for the MH30 multifunctional spacer, which contains approximately 75 SiH groups per molecule, when compared to a four-functional spacer. Furthermore a branched, bulky six-functional spacer is preferred over a linear spacer of the same functionality. UV activity of functionalized silica was studied by UV-Vis spectroscopy, indicating that the immobilization of UVA onto silica surface has not altered its UV absorbance properties.

Proton-Exchange Sulfonated Poly （ether ether ketone） （SPEEK）/SiOx-S Composite Membranes in Direct Methanol Fuel Cells

A sulfonated poly（ether ether ketone） （SPEEK） membrane with a fairly high degree of sulfonation （DS） can swell excessively and even dissolve at high temperature. To solve these problems, insolvable functionalized silica powder with sulfonic acid groups （SiOx-S） was added into the SPEEK matrix （DS = 55.1%） to prepare SPEEK/ SiOx-S composite membranes. The decrease in both the swelling degree and the methanol permeability of the membranes was a dose-dependent result of addition of the SiOx-S powder. Pure SPEEK membrane swelled 52.6% at 80℃, whereas the SPEEK/SiOx-S （15%, by mass） membrane swelled only 27.3% at the same temperature. From room temperature to 80℃, all SPEEK/SPEEK/SiOx-S composite membranes had methanol permeability of about one order of magnitude lower than that ofNafion115. Compared with pure SPEEK membranes, the addition of the SiOx-S powder not only leads to higher proton conductivity, but also increases the dimensional stability at higher temperatures, and greater proton conductivity can be achieved at higher temperature. The SPEEK/SiO4-S （20%, by mass） membrane could withstand temperature up to 145℃, at which in 100% relative humidity （RH） its proton conductivity exceeded slightly that of Nafion 1 15 membrane and reached 0.17 S·cm^-1, while pure SPEEK membrane dissolved at 90℃. The SPEEK/SiOx-S composite membranes are promising for use in direct methanol fuel cells because of their good dimensional stability, high proton conductivity, and low methanol permeability.

Preparation of Functionalized Porous Silica by Ultrasonic Technique for the Methylation Reaction of Phenol with Dimethyl Carbonate

Porous silica modified with -（CH2）3NH2 （primary amine）, -（CH2）3NHCH2CH2NH2 （secondary/primary amine） and -（CH2）3N-cycl-（CH2）4 （tertiary amine） were synthesized by ultrasonic technique under mild conditions. The samples were characterized by BET, elemental analysis and TG, showing that the organosilane moieties were grafted onto the surface of porous silica by covalent bond. The structure of the organosilane moieties and ultrasonic treatment time were all significant for the quantities of grafted amino groups. The samples exhibited promising catalytic properties towards the methylation reaction of phenol with dimethyl carbonate （DMC）. The methylation reaction with the modified samples featured high selectivity at high conversion. The samples were subjected to utilization for a few recycles without obvious loss of activity to indicate that ultrasonic technique was effective for the preparation of organically modified porous silica catalysts.

A facile method for preparing thiocyanato-functionalized porous silica nanospheres

In this study, we present a facile method to prepare thiocyanato-functionalized porous silica nanospheres. Thiocyanato functionalized silica shells were coated on positively charged cetyltrimethylammonium bromide （CTAB） micelles via hydrolysis and condensation of （3-thiocyanatopropyl）triethoxysilane （TCPTES）, the CTAB cores were removed subsequently to form thiocyanato-functionalized porous sil- ica nanospheres. We demonstrate that the contents of the thiocyanato groups within the functionalized porous silica nanosphere frameworks gradually diminished as a function ofhydrothermal treatment time at 100~C until complete removal, confirmed by TGA and FTIR spectra. The data indicate that extended operation at relatively elevated temperatures may lead to the decomposition of the thiocyanato functional groups. In addition, at a lower CTAB concentration （0.0009 M）, non-porous thiocyanato functionalized sil- ica nanospheres were formed. However, increasing the CrAB concentration to 0.01 M resulted in porous nanospheres inferring that a CTAB concentration threshold is needed to form thiocyanato-functionalized porous silica nanospheres.