Surface modified mesoporous silica polymer nanocomposites for adsorption of dyes from aqueous solution

Functionalized mesoporous silica nanocomposites were synthesized via in situ radical polymerization of vinyl monomers (vinylcarbazole, vinyl imidazole and vinyl sulphonic acid) and characterized for adsorption of dyes from aqueous solution. Physicochemical characterization (PXRD, SEM, adsorption studies etc.) of the functionalized nanocomposites showed the presence of mesoporous nature of the nanocomposites. Different adsorption parameters such as adsorption weight, adsorption time, temperature, pH etc., were optimized for adsorption of dyes under environmental friendly conditions. The adsorption studies showed 96.8 and 80.49 % removal for cationic and anionic dyes respectively. Adsorption kinetics of the dyes on the functionalized nanocomposites can be well depicted theoretically by using pseudo-second-order kinetic model.     

Preparation and properties of poly(dimethyl siloxane)–colloidal silica/functionalized colloidal silica nanocomposites

Aqueous spherical colloidal silica (CS) particles with a diameter of 15 ± 5 nm were modified with three different types of monofunctional silane coupling agents to prepare functionalized colloidal silica (FCS) particles. The effects of the surface chemistry of the FCS were studied as a function of the CS/FCS loading in the poly(dimethyl siloxane) (PDMS) polymer. The prepared PDMS–CS/FCS composites were investigated for their physical properties both in the cured and uncured states. The extent of filler–filler and filler–polymer interactions was found to vary with the type of functionalizing agent used to treat the surface of the CS. The filler–filler interaction appeared to be predominant in the PDMS–CS composites, and improved filler–polymer interaction was indicated in the case of the PDMS–FCS composites. The composites containing CS treated with methyltrimethoxysilane exhibited relatively better optical and mechanical properties compared to the other PDMS–FCS composites. This study highlighted the importance of judiciously choosing functionalizing agents to achieve PDMS–FCS composites with predetermined optical and mechanical properties. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Removal of aqueous toxic Hg(II) by functionalized mesoporous silica materials

BACKGROUND: Hg(II) is one of the most toxic metals and has received particular attention in environmental pollution. Hg(II) pollution is common in water sources, so rapid and efficient methods must be developed for its removal from water samples. Mesoporous silica (MS) is an ideal adsorbent due to its high surface area and biocompatibility. The efficiency and selectivity of MS adsorbents can be improved by surface modification. RESULTS: A new sorbent for trace Hg(II) removal was developed by grafting 1‐(3‐carboxyphenyl)‐2‐thiourea (CPTU) onto SBA‐15 mesoporous silica. The optimum pH range for Hg(II) adsorption was 3‐7 and the maximum static adsorption capacity was 64.5 mg g^?1. An enrichment factor of 150 was obtained with a relative standard deviation < 1.5% (n = 8). Common coexisting ions did not interfere with the adsorption of Hg(II) under optimal conditions. Quantitative recovery was achieved by stripping with a mixed solution of 1 mol L^?1 HCl and 5% CS(NH₂)₂. Efficient adsorption capacity of the recycled material could still be maintained at a level of 95% at the 7th cycle. CONCLUSION: 1‐(3‐carboxyphenyl)‐2‐thiourea functionalized SBA‐15 mesoporous silica was synthesized and applied for Hg(II) removal from water samples with high efficiency and selectivity. Copyright © 2012 Society of Chemical Industry     

Design of NiS/CNTs nanocomposites for visible light driven catalysis and antibacterial activity studies

The outstanding photocatalytic activity of metal sulphide based photocatalysts have much attention in environmental remediation due to utilization of wide spectrum range. In present paper, the photocatalytic activity of NiS and NiS-CNTs (carbon nanotubes) nanocomposite has been investigated. The hydrothermal technique was used for synthesis of NiS and NiS/CNTs nanocomposite. Structural elucidation of NiS and NiS/CNTs nanocomposite was conducted by X-ray diffraction (XRD) and Fourier transform infra-red (FTIR) techniques. These characterization techniques verified the formation and purity of samples as extra peaks of impurities were not observed in the obtained data. Scherer formula was used to examine the crystallite size of NiS NPs and NiS/CNTs reported that 9.5 nm and 10.2 nm are sizes of NiS and NiS/CNTs respectively. Scanning electron microscopic (SEM) analysis revealed the reduction in the aggregation of NiS and improved the surface area to assist the redox reactions due to presence of CNTs. Current-voltage (I–V) measurements studied the electrical behaviour of photocatalysts. Optical measurements of synthesized samples were analysed by UV–Visible spectrophotometry. The improvement in bandgap energy of nanocomposite was main reason of excellent photocatalytic activity. About 96% degradation of methylene blue was recorded via NiS/CNTs nanocomposite within 50 min. Photocatalytic performance of nanocomposite is faster than individual metal sulphide due to production of more free radicals, Ni–S–C bond development, surface defects and availability of more reaction sites. These features improved the photocatalytic activity of NiS/CNTs and provide an evidence to use carbon nanotubes for the formation of metal sulphide nanocomposites. Antibacterial property of sample was investigated by four Gram negative bacteria (Proteus vulgaris, Klebsiella pneumonia, Escherichia coli and Pseudomonas aeruginosa) and one Gram positive bacteria (Staphylococcus aureus) at different concentrations using disc diffusion method. The possible mechanism for degradation of Methylene blue under UV–Visible illuminations has been discussed. The upgraded degradation of methylene blue by NiS/CNTs nanocomposite supported that it is promising material for treatment of wastewater.     

Chain flexibility effect on the refractive index grating of fully functionalized carbazole/DO3/epoxy polymer

The photorefractive (PR), photoconductive, and holographic characteristics of 3‐amino‐9‐ethyl carbazole (AEC)/dispersed orange 3 (DO3)/diepoxy main chain copolymers are investigated to study the relationship between the structure and properties. The recorded pattern exhibits good fringe contrast with the resolution 20 μm in the recorded hologram. The formation rate of refractive index grating (PR grating) can be speeded up by applying an electric field or changing comonomer structure or monomer composition. Faster PR response can be achieved by incorporating aliphatic diepoxy with longer chain length or increasing the concentration of the charge transport moieties, while more nonlinear optical (NLO) segment (DO3) in the copolymer results in higher diffraction efficiency. The dark decay rate of the PR film at room temperature depends on the dark conductivity and steric interaction between the NLO chromophores and the polymer matrix. However, the latter shows greater influence on the dark decay at elevated temperature. More charge transport segment increases the dark conductivity and it leads to higher dark decay rate. The diffracted signals of polymers synthesized from the diepoxy comonomers containing longer soft chain exhibit slower dark decay at room temperature, but drop sharply as the temperature get higher. In comparison with experimentally measured dark decay at elevated temperature, thermal stimulated current spectroscopy is a more sensitive tool than differential scanning calorimetry diagrams to evaluate what temperature a sharp dark decay of the PR signal will occur. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1321–1333, 1999     

Inorganic silica functionalized with PLLA chains via grafting methods to enhance the melt strength of PLLA/silica nanocomposites

The low melt strength greatly limits the application of PLA as biodegradable package materials produced by film blowing method. Modified silica nanoparticles are introduced into PLA matrix to solve this problem in this study. To build Poly (l-lactide) nanocomposites successfully, two kinds of convenient and efficient methods are conducted to synthesize well-defined topological PLLA grafted SiO₂ nanoparticle. One is the ring-opening of l-lactide (Grafting from), and another is nucleophilic addition reaction (Grafting to). The structure, molecular weight of grafted PLLA chains, grafting density, and the thermal decomposition behavior of the nanoparticles prepared by different methods are characterized. By varying the contents of the initiator SiO₂ and the molecular weight of the reacted PLA chains, high density-low molecular weight PLLA grafted SiO₂ are obtained in “grafting from” while high molecular weight-low grafting density PLLA grafted SiO₂ are synthesized in “grafting to”. It is exactly in good agreement with the theoretic model. The spatial distribution of nanoparticles as well as the interaction force between nanoparticles and matrix is critical important to structuring bionanocomposites with desirable properties. So the two kinds of synthesized nanoparticles are introduced into PLA matrix in our contribution to evaluate these two factors, respectively. The TEM and SEM results both reveal the uniform dispersion of nanoparticles after modified. While the extension and shear rheology results show that the long grafted chains covalently connected on the surface of the silica via “grafting to” contribute more to enhance the melt strength of PLA. Meanwhile, stabilized PLA nanocomposites films with modified silica via “grafting to” method are successfully blown base on these researches. The research in this work constitutes a robust way to design melt-strengthen PLA/SiO₂ nanocomposites.     

Synthesis and application of amine functionalized silica mesoporous magnetite nanoparticles for removal of chromium(VI) from aqueous solutions

In this research, novel nanoparticles of Kit-6 mesoporous silica magnetite were synthesized with 9.6 nm pore diameter and 241.68 m² g^?1 surface area. The synthesized mesoporous magnetite nanoparticles (MMNPs) were functionalized with amine groups. Scanning electron microscopy, powder X-ray diffraction, Fourier transform infrared spectroscopy and nitrogen adsorption–desorption method confirmed the morphology and structure of the synthesized nanoparticles. The amine functionalized MMNPs were used for sorption of toxic chromate ions from aqueous samples. The effect of various experimental parameters (four factors at three levels) on the sorption efficiency of Cr(VI) was studied and optimized via Taguchi L₉ (3⁴) orthogonal array experimental design. At optimum conditions, the sorption of the Cr(VI) was best described by a pseudo second-order kinetic model with R² = 0.9999 and q_eq = 129.8 mg g^?1, suggesting chemisorption mechanism. Adsorption data were fitted well to the Langmuir isotherm and the synthesized sorbent showed complete ion removal with 185.2 mg g^?1sorption capacity.     

Mesoporous silica/polyphosphoric acid (SBA-15/PPA) nanocomposites for acylation of naphthalene

Silica-polyphosphoric acid nanocomposites (SBA/PPA) were synthesized via direct and post-functionalization of ordered mesoporous SBA-15 materials with PPA. The catalytic studies for acylation of naphthalene in the liquid phase showed very high selectivity of 2-acylated product (A) over direct functionalized SBA/PPA nanocomposites.     

(Re)processing effects on linear low-density polyethylene/silica nanocomposites

A linear low density polyethylene matrix was melt compounded with a given amount (2 vol.%) of both untreated (hydrophilic) and surface treated (hydrophobic) fumed silica nanoparticles with the aim to investigate the influence of the time under processing conditions on the microstructure and thermo-mechanical properties of the resulting materials. Crosslinking reactions induced by thermal processing caused a remarkable increase of the melt viscosity, as revealed by the melt flow index values of both neat matrix and nanocomposites. Thermal oxidation of the matrix was slightly reduced by the introduction of fumed silica nanoparticles, especially for long compounding times. Differential scanning calorimetry evidenced how silica nanoparticles had a nucleating effect on the matrix, while both the melting temperature and the relative crystallinity were decreased by the compounding process. Nanosilica addition promoted a general improvement of the tensile properties, that progressively decreased with the processing time.     

Polymer-derived mesoporous Ni/SiOC(H) ceramic nanocomposites for efficient removal of acid fuchsin

In this paper, magnetic porous Ni-modified SiOC(H) ceramic nanocomposites (Ni/SiOC(H)) were successfully prepared via a template-free polymer-derived ceramic route, which involves pyrolysis at 600 °C of nickel-modified allylhydridopolycarbosilane (AHPCS-Ni) precursors synthesized by the reaction of allylhydridopolycarbosilane (AHPCS) with nickel(II)acetylacetonate (Ni(acac)₂). The resultant Ni/SiOC(H) nanocomposites are comprised of in-situ formed nanoscaled Ni socialized with small amounts of NiO and nickel silicides embedded in the amorphous SiOC(H) matrix. The materials show ferromagnetic behavior and excellent magnetic properties with the saturation magnetization in the range of 1.71–7.08 emu g⁻¹. Besides, the Ni/SiOC(H) nanocomposites are predominantly mesoporous with a high BET surface area and pore volume in the range of 253–344 and 0.134–0.185 cm³ g⁻¹, respectively. The measured porosity features cause an excellent adsorption capacity towards a template dye acid fuchsin with the adsorption capacity Q_t at 10 min of 80.7–85.8 mg g⁻¹ and the Q_e at equilibrium of 123.8–129.8 mg g⁻¹.     

Removal of Ni(II), Cd(II), and Pb(II) from a ternary aqueous solution by amino functionalized mesoporous and nano mesoporous silica

In the present study, the application for the removal of Ni(II), Cd(II) and Pb(II) ions from aqueous solution by using mesoporous silica materials, namely, MCM-41, nanoparticle of MCM-41, NH₂-MCM-41 (amino functionalized MCM-41) and nano NH₂-MCM-41 was investigated. Suitable adsorbents preparation techniques were developed in the laboratory. The effects of the solution pH, metal ion concentrations, adsorbent dosages, and contact time were studied. It was found that NH₂-MCM-41 showed the highest uptake for metal ions in aqueous solution. The results indicated that the adsorption of Ni(II), Cd(II) and Pb(II) ions on the surface of the adsorbent was increased with increasing solution pH. The experimental data were analyzed using the Langmuir and Freundlich equations. Correlation coefficients were determined by analyzing each isotherm. It was found that the Langmuir equation showed better correlation with the experimental data than the Freundlich. According to the parameters of the Langmuir isotherm, the maximum adsorption capacity of NH₂-MCM-41 for Ni(II), Cd(II) and Pb(II) was found to be 12.36, 18.25 and 57.74 mg/g, respectively. The kinetic data of adsorption reactions and the evaluation of adsorption equilibrium parameters were described by pseudo-first-order and pseudo-second-order equations. The synthesized solid sorbents were characterized by Fourier transform infrared (FT-IR) spectrometry, X-ray diffraction (XRD), scanning electron microscopy (SEM) and nitrogen sorption measurements.     

Controlling the pitch length of helical mesoporous silica (HMS)

The effects of synthesis conditions including the co-structure directing agent (CSDA)/amphiphile molar ratio, reaction temperature, and pH value on the pitch length of the helical mesoporous silicas (HMSs) have been comprehensively investigated. It has been found that the external diameter of the HMS rod increased with increasing CSDA/amphiphile molar ratio, reaction temperature, and pH value, while the pitch length increased linearly with increasing diameter of the HMS rod in a settled condition. The driving force for the formation of HMS has been considered to be the 2d-hexagonally-ordered propeller-like micelles with moment M₀ which can be related to the pitch length (p) and diameter (d) of the micelle (). The shorter pitch length of the micelle would give rise to a strong moment for the hexagonally-stacked rods in the same micelle diameter, and vice versa with a longer pitch length. It was shown that the moment of the propeller-like micelle was not significantly changed by varying the TMAPS/SDS molar ratio or the pH value, but obviously affected by the reaction temperature.     

Photoluminescence studies of stilbene laser dye incorporated mesoporous silica nanoparticle (MSN) with sulphur dioxide

Photoluminescence spectra of different concentration of laser grade dye stilbene dye solution and stilbene incorporated in mesoporous silica nanoparticle (MSN) had been studied and compared to determine maximum quantum yield. High quantum yield was obtained for 10^?3 M concentration stilbene incorporated MSN. This stilbene incorporated MSN silica is shown to give a fluorescence response to gaseous sulphur dioxide, with a response time of a few seconds and fluorescence emission intensity is proportional to the sulphur dioxide concentration, which are desirable properties for gas sensing. These features together make this MSN material very promising for optical sensing applications.     

Aminopropyl-modified mesoporous silica nanospheres for the adsorption of Cr(VI) from water

Journal of Porous Materials - Aminopropyl-functionalized mesoporous silica spherical particles were obtained through post-synthetic route. The suitability of this material as an adsorbent for heavy...     

Thermodynamics,kinetics, and isotherms studies for gold(III) adsorption using silica functionalized by diethylenetriaminemethylenephosphonic acid

A novel hybrid material silica gel chemically modified by diethylenetriaminemethylenephosphonic acid GH-D-P has been developed and characterized. The results of the adsorption thermodynamics and kinetics of the as-synthesized GH-D-P for Au(III) showed that this high efficient inorganic–organic hybrid adsorbent had good adsorption capacity for Au(III), and the best interpretation for the experimental data was given by the Langmuir isotherm equation, the maximum adsorption capacity for Au(III) is 357.14 mg/g at 35 °C. Moreover, the study indicated the adsorption kinetics of GH-D-P could be modeled by the pseudo-second-order rate equation wonderfully, and the adsorption thermodynamic parameters ΔG, ΔH and ΔS were −20.43 kJ mol⁻¹, 9.17 kJ mol⁻¹, and 96.24 J K⁻¹ mol⁻¹, respectively. Therefore, the high adsorption capacity make this hybrid material have significant potential for Au(III) uptake from aqueous solutions using adsorption method.     

Chitosan/poly(dimethylaminoethylmethacrylate-co-hydroxyethylacrylate) based semi-IPN hydrogels and silver nanocomposites: Synthesis,evaluation of amoxicillin release studies,and antibacterial studies

To fabricate new smart materials that can deliver both the pharmaceutically active molecules and metal nanoparticles, we have formulated chitosan-based semi-IPN hydrogels and their silver nanocomposites (Ag NCs) along with amoxicillin (AMX). Semi-IPN hydrogels and their Ag NCs were synthesized from chitosan, dimethylamino ethyl methacrylate and 2-hydroxyethyl methacrylate via simple-free radical polymerization method and reducing with NaBH₄. The resultant formulations were evaluated for in vitro release of AMX, anti-bacterial studies and DNA cleavage studies. The hydrogels with AMX-derived silver nanoparticles (Ag NPs) show better ability to cleave DNA and anti-microbial activity than individual AMX and Ag NPs.     

Physicochemical properties of poly(ethylene oxide)-based composite polymer electrolytes with a silane-modified mesoporous silica SBA-15

Mesoporous silica SBA-15 was surface-modified by γ-glycidoxypropyltrimethoxy silane (GPTMS), and novel poly(ethylene oxide) (PEO)-based composite polymer electrolytes (CPE) using the silane-modified SBA-15 (SBA-15-GPTMS) as filler were prepared and characterized. The results of the low-angle X-ray diffraction (XRD) patterns and Fourier-transform infrared (FT-IR) spectroscopy indicated that GPTMS has been successfully attached to the surface of SBA-15 with a high degree of mesoscopic hexagonal pore structure. The incorporation of SBA-15-GPTMS in the PEO-LiClO₄ matrix effectively reduced the PEO crystallinity and obviously improved the conductivity and electrochemical stability of the CPEs. The CPE with 10 wt.% SBA-15-GPTMS provided the highest conductivity among all the tested CPEs, about 2-3 orders of magnitude higher than that of the PEO-LiClO₄ matrix below the melting temperature of PEO. The reasons that the CPEs using SBA-15-GPTMS as filler showed higher conductivity than that with SBA-15 were discussed.     

Development of a cashew nut shell liquid (CNSL)‐based polymer for antibacterial activity

A biobased polymer derived from cashew nut shell liquid (CNSL) as a renewable resource was investigated for use as an antibacterial material. CNSL is a mixture of aromatics containing cardanol as the main component and cardol and 2‐methylcardol as minor components. CNSL composition analyses showed that the minor components (i.e., cardol and 2‐methylcardol) in CNSL had higher contents of unsaturated structures than cardanol. These higher unsaturated contents promoted the thermal polymerization in the preparation of an epoxy CNSL prepolymer (ECNP). The biobased polymer film was fabricated by the reaction of amine compounds and ECNP without any organic solvent. The ECNP film took less than 2.0 h to reach a hardened dry condition at room temperature because of the crosslinking reaction between epoxy and amine groups. The antibacterial activities of the biobased polymer against Escherichia coli and Staphylococcus aureus were evaluated. CNSL showed antibacterial activity against S. aureus, whereas epoxy CNSL and ECNP alone showed no significant antibacterial activity against E. coli or S. aureus. This indicated that the antibacterial activity was based on the phenolic and catechol hydroxyl groups of CNSL. In addition, a biobased polymer film derived from CNSL and diamine showed antibacterial activity against both E. coli and S. aureus, even with alcohol conditioning. This suggested that the antibacterial activity was certainly fixed in the structure of the ECNP‐based polymers after the standard antisepsis treatment in medical facilities. Therefore, this biobased polymer could be useful in antibacterial materials as a coating and resin for health care applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42725.