Silica materials recovered from photonic industrial waste powder: its extraction, modification, characterization and application

This study explored the possibility of recovering waste powder from photonic industry into two useful resources, sodium fluoride (NaF) and the silica precursor solution. An alkali fusion process was utilized to effectively separate silicate supernatant and the sediment. The obtained sediment contains purified NaF (>90%), which provides further reuse possibility since NaF is widely applied in chemical industry. The supernatant is a valuable silicate source for synthesizing mesoporous silica material such as MCM-41. The MCM-41 produced from the photonic waste powder (PWP), namely MCM-41(PWP), possessed high specific surface areas (1082 m²/g), narrow pore size distributions (2.95 nm) and large pore volumes (0.99 cm³/g). The amine-modified MCM-41(PWP) was further applied as an adsorbent for the capture of CO₂ greenhouse gas. Breakthrough experiments demonstrated that the tetraethylenepentamine (TEPA) functionalized MCM-41(PWP) exhibited an adsorption capacity (82 mg CO₂/g adsorbent) of only slightly less than that of the TEPA/MCM-41 manufactured from pure chemical (97 mg CO₂/g adsorbent), and its capacity is higher than that of TEPA/ZSM-5 zeolite (43 mg CO₂/g adsorbent). The results revealed both the high potential of resource recovery from the photonic solid waste and the cost-effective application of waste-derived mesoporous adsorbent for environmental protection.     

Preparation of high nickel-containing MCM-41-type mesoporous silica via a modified direct synthesis method

A method with modifying tetraethyl orthosilicate (TEOS) with nickel species has been developed for the synthesis of mesoporous silica with high nickel content (11.8 wt.% of Ni or even higher). With the method, MCM-41-type materials were obtained with high BET surface area reaching 868 m²/g and pore volume up to 0.73 cm³/g. The materials were characterized by means of X-ray powder diffraction, transmission electron microscopy, energy dispersive X-ray spectroscopy, N₂ adsorption, Fourier transform infrared and X-ray photoelectron spectroscopy. Nickel species were incorporated into the silica frameworks. The mesostructures still remain after activation using H₂ at 773 K.     

Tunable adsorption behavior of silica materials in the removal of dense non-aqueous phase liquids

Mesoporous silica material has dual characteristics including adsorption of organic contaminants and transport through the sediments, making it an ideal material as a platform for zerovalent iron particles in the in situ remediation of dense non-aqueous phase liquids such as trichloroethylene. In this paper, tunable adsorption behavior of silica materials was quantitatively investigated by batches of equilibrium experiments. Significant enhancement in adsorption capacity was observed on mesoporous organo-silica particles as a consequence of the functionalization of particle surface from hydrophilicity to hydrophobicity. The fact that there is a wide difference in adsorption capacities between the non-functionalized mesoporous silica (MCM-41) and the alkyl-functionalized mesoporous silica prompted a study to control adsorption levels by simply adjusting the amount of methyl triethoxysilane (MTES) precursor in a mixture of MTES and tetramethoxysilane. In comparison with the most commonly used adsorbent activated carbon, the higher yield of adsorbent of 83 ± 2.6% was observed for mesoporous methyl silica particles. Particle characterizations were performed by means of X-ray powder diffraction, transmission electron microscopy, scanning electron microscopy, Brunauer–Emmett–Teller, thermogravimetric analysis and Fourier transform infrared measurements.     

Ultrasonic-assisted synthesis and magnetic studies of iron oxide/MCM-41 nanocomposite

Iron oxide nanoparticles were stabilized within the pores of mesoporous silica MCM-41 amino-functionalized by a sonochemical method. Formation of iron oxide nanoparticles inside the mesoporous channels of amino-functionalized MCM-41 was realized by wet impregnation using iron nitrate, followed by calcinations at 550 °C in air. The effect of functionalization level on structural and magnetic properties of obtained nanocomposites was studied. The resulting materials were characterized by powder X-ray diffraction (XRD), high-resolution transmission electron microscopy and selected area electron diffraction (HRTEM and SAED), vibrating sample and superconducting quantum interface magnetometers (VSM and SQUID) and nitrogen adsorption–desorption isotherms measurements. The HRTEM images reveal that the most of the iron oxide nanoparticles were dispersed inside the mesopores of silica matrix and the pore diameter of the amino-functionalized MCM-41 matrix dictates the particle size of iron oxide nanoparticles. The obtained material possesses mesoporous structure and interesting magnetic properties. Saturation magnetization value of magnetic iron oxide nanopatricles stabilized in MCM-41 amino-functionalized by in situ sonochemical synthesis was 1.84 emu g⁻¹. An important finding is that obtained magnetic nanocomposite materials exhibit enhanced magnetic properties than those of iron oxide/MCM-41 nanocomposite obtained by conventional method. The described method is providing a rather short preparation time and a narrow size distribution of iron oxide nanoparticles.     

Novel phenol capturer derived from the as-synthesized MCM-41

Novel phenol-capturer was prepared by modifying the as-synthesized mesoporous silica MCM-41 with tetraethylenepentamine (TEPA), not only saving the energy and time for removal of template, but also opening the way to utilize the micelles for adsorption. Once the organic modifier was distributed in the template micelle of MCM-41 to form a web within the mesoporous channel, the composite could adsorb more phenols in gas stream than activated carbon for the first time. With an unwanted high adsorption capacity, this mesoporous silica-amine composite represented potential application for trapping phenols, especially in tobacco smoke to protect environment.     

2-Mercaptothiazoline modified mesoporous silica for mercury removal from aqueous media

Mesoporous silicas (SBA-15 and MCM-41) have been functionalized by two different methods. Using the heterogeneous route the silylating agent, 3-chloropropyltriethoxysilane, was initially immobilized onto the mesoporous silica surface to give the chlorinated mesoporous silica Cl-SBA-15 or Cl-MCM-41. In a second step a multifunctionalized N, S donor compound (2-mercaptothiazoline, MTZ) was incorporated to obtain the functionalized silicas denoted as MTZ-SBA-15-Het or MTZ-MCM-41-Het. Using the homogeneous route, the functionalization was achieved via the one step reaction of the mesoporous silica with an organic ligand containing the chelating functions, to give the modified mesoporous silicas denoted as MTZ-SBA-15-Hom or MTZ-MCM-41-Hom. The functionalized mesoporous silicas were employed as adsorbents for the regeneration of aqueous solutions contaminated with Hg (II) at room temperature. SBA-15 and MCM-41 functionalized with MTZ by the homogeneous method present good mercury adsorption values (1.10 and 0.7mmolHg (II)/g of silica, respectively). This fact suggests a better applicability of such mesoporous silica supports to extract Hg (II) from aqueous solutions. In addition, it was observed the existence of a correlation between mercury adsorption with pore size and volume since, SBA-15 with lower areas and higher pore sizes functionalized with sterically demanding ligands, show better adsorption capacities than functionalized MCM-41.     

Co3O4 doped over SBA 15: excellent adsorbent materials for the removal of methyleneblue dye Pollutant

Nanosized cobalt oxide particles are incorporated into SBA 15 mesoporous silica materials and are effectively used for the first time as adsorbent materials for aquatic dye pollutant removal. Cobalt is found to exist in its Co₃O₄ spinel structure as evident from FTIR and X-ray diffraction studies. The best weight ratio of metal loading to show excellent adsorption of methyleneblue is found to be 10 wt% Co over the support. There, Co₃O₄ spinel nanoparticles lie inside the pores of mesoporous silica. Further increase in the percentage of metal loading decreases the adsorption capacity which may be due to the agglomeration of nanoparticles over the silica support as evident from TEM photographs. Cobalt-doped systems of the present study, having good adsorption capacity of methyleneblue, are prepared via impregnation of cobalt nitrate over SBA 15 in aqueous medium. Here, we introduce a new SBA 15-based system for the fast removal of aquatic dye pollutants which is highly economical for industrial applications.     

Preparation of SnO2 nanoparticles by hard template method for high selectivity gas sensors

In this paper, SnO2 nanoparticles were synthesized by the impregnation method with SnCl2 x 2H2O as the inorganic precursor and mesoporous silica MCM-41 as the hard template. The physical and chemical properties of the products were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The SnO2 nanoparticles grew into the ordered channels of MCM-41. After removing the silica template, the products exhibited good rutile structure. The gas sensing properties of the SnO2 nanoparticles were also studied. The results indicated that these SnO2 nanoparticle sensors showed high selectivity towards ethanol.     

Synthesis of MCM-41 nanoparticles from stem of common reed ash silica and their application as substrate in electrooxidation of methanol

In this work, stem of common reed ash (SCRA) is introduced as a new source of silica in the preparation of mesoporous materials. Mesoporous silicate MCM-41 nanoparticles were synthesized hydrothermally using sodium silicate prepared from SCRA as a silica source. The characterization of MCM-41was carried out by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), N\(_{2}\) adsorption/desorption (BET) and transmission electron microscopy (TEM). SEM shows that MCM-41 nanoparticles are sphere-like with size in the range of 30–50 nm with some degree of agglomeration. TEM image of the synthesized sample shows the open framework structure of MCM-41. A type IV isotherm can be observed from adsorption/desorption curves, which is the characteristic of mesoporous materials. The prepared MCM-41 nanoparticles were used as substrate to facilitate the oxidation of methanol through the modification with an electroactive species. The modification was achieved by impregnation of MCM-41 pores with \(\hbox {Ni}^{2+}\) ions (Ni-doped MCM-41). A modified carbon paste electrode (CPE) was prepared by mixing Ni-doped MCM-41 with carbon paste (NiMCM-41CPE). Cyclic voltammetry of NiMCM-41CPE shows an increment in current density of methanol oxidation in comparison with CPE in alkaline solution. Moreover, a decrease in the overpotential of methanol oxidation occurred on the surface of modified electrode. The effects of some parameters such as scan rate and methanol concentration are also investigated on the behaviour of NiMCM-41CPE. Also, the heterogeneous electron transfer rate for the catalytic reaction (k) of methanol is calculated.     

树枝状纤维形二氧化硅纳米粒子的研究进展

与传统二氧化硅介孔材料相比, 树枝状纤维形二氧化硅纳米粒子(Dendritic Fibrous Nano-silica, DFNS), 特别是具备三维中心辐射状孔道和多级孔结构的球形DFNS拥有较高的比表面积、较大的孔体积、较高的孔渗透性和粒子内表面更易接触性等优点。客体物质(如极小的纳米粒子)能够沿着中心辐射状孔道进行负载和/或输送, 甚至与化学改性所得内部活性位点发生反应。因此, DFNS是一种富有前景的载体平台, 可以用来构筑新型纳米催化剂、吸附剂、基因/蛋白质/药物的递送系统等。大量研究表明: 球形DFNS与生俱来的结构优势使其能够作为MCM-41和SBA-15的理想替代材料。但是, DFNS领域依旧存在很多需要探讨的问题。因此, 本文主要归纳分析DFNS的结构特征、常用结构模型、新型结构和实时应用。希望能够给予材料和化学科学家一些参考, 促进DFNS的蓬勃发展。     

A novel application of mesoporous silica material for extraction of pesticides

The mesoporous silica material MCM-41 was prepared by the sol-gel method and characterized using X-ray diffraction (XRD), N₂ adsorption-desorption and thermogravimetric analysis. The material was tested for extraction of trichlorfon, pyrimethanil, tetraconazole, thiabendazole, imazalil and tebuconazole from mango fruit, with analysis using gas chromatography-mass spectrometry (GC/MS). In experiments carried out in triplicate, at a 1.0 mg/kg concentration level, recoveries using the MCM-41 sorbent were in the range 73-103%. Comparison of MCM-41 with commercially available silica gel showed that MCM-41 was a similar extracting phase for the pesticides investigated with a significant cost advantage over this conventional material.     

Phosphate adsorption on aluminum-coordinated functionalized macroporous–mesoporous silica: Surface structure and adsorption behavior

In this study, Al(III)-coordinated diamino-functionalized macroporous–mesoporous silica was synthesized and characterized by X-ray diffraction, N₂ adsorption–desorption, Fourier transform infrared spectroscopy, scanning and transmission electron microscopy. Because of well-defined and interconnecting macroporous–mesoporous networks, the resulting adsorbent (MM-SBA) exhibited a significantly better phosphate adsorption performance and faster removal rate, as compared with the mesoporous adsorbent (M-SBA). Based on the Freundlich and Langmuir models, the phosphate adsorption capacity and the maximum adsorption capacity of MM-SBA were 7.99 mg P/g and 23.59 mg P/g, respectively. In the kinetic study of MM-SBA, over 95% of its final adsorption capacity reached in the first 1 min; whereas that of M-SBA was less than 79%.     

有序介孔氧化硅孔道氧化锰团簇组装研究

以有序介孔氧化硅MCM-41为主体材料,通过浸渍法及后续热处理工艺,在孔道中组装氧化锰的团簇粒子,并对其进行结构表征。通过XRD、HR—TEM、XPS及N2吸附表明氧化锰的团簇粒子已经成功组装到MCM-41有序孔道中。通过对不同孔径有序介孔材料的氧化锰团簇粒子的组装,表明随着孔道中组装量的增加,350nm附近光致发光强度增强,吸收边发生红移,同时1000nm附近吸收带宽化。     

The investigation of MCM-48-type and MCM-41-type mesoporous silica as oral solid dispersion carriers for water insoluble cilostazol

Objective: To explore the suitable application of MCM-41 (Mobil Composition of Matter number forty-one)-type and MCM-48-type mesoporous silica in the oral water insoluble drug delivery system.

Methods: Cilostazol (CLT) as a model drug was loaded into synthesized MCM-48 (Mobil Composition of Matter number forty-eight) and commercial MCM-41 by three common methods. The obtained MCM-41, MCM-48 and CLT-loaded samples were characterized by means of nitrogen adsorption, thermogravimetric analysis, ultraviolet-visible spectrophotometry, scanning electron microscopy, transmission electron microscopy, differential scanning calorimetry and powder X-ray diffractometer.

Results: It was found that solvent evaporation method was preferred according to the drug loading efficiency and the maximum percent cumulative drug dissolution. MCM-48 with 3D cubic pore structure and MCM-41 with 2D long tubular structure are nearly spherical particles in 300–500?nm. Nevertheless, the silica carriers with similar large specific surface areas and concentrating pore size distributions (978.66?m²/g, 3.8?nm for MCM-41 and 1108.04?m²/g, 3.6?nm for MCM-48) exhibited different adsorption behaviors for CLT. The maximum percent cumulative drug release of the two CLT/silica solid dispersion (CLT-MCM-48 and CLT-MCM-41) was 63.41% and 85.78% within 60?min, respectively; while in the subsequent 12?h release experiment, almost 100% cumulative drug release were both obtained. In the pharmacokinetics aspect, the maximum plasma concentrations of CLT-MCM-48 reached 3.63?mg/L by 0.92?h. The AUC_0–∞ values of the CLT-MCM-41 and CLT-MCM-48 were 1.14-fold and 1.73-fold, respectively, compared with the commercial preparation.

Conclusion: Our findings suggest that MCM-41-type and MCM-48-type mesoporous silica have great promise as solid dispersion carriers for sustained and immediate release separately.     

New mesoporous silica/carbon composites by in situ transformation of silica template in carbon/silica nanocomposite

Hard template-based fabrication of mesoporous carbon unavoidably goes through the removal process of the template to generate template-free carbon replica, including troublesome disposal of template waste often accompanied by toxic etchant, which not only increases the fabrication cost of materials but also raises serious environmental concerns. As a novel strategy to overcome such problem, a direct in situ synthesis approach using silica waste in carbon/silica nanocomposite as a silica source and cetyltrimethylammonium bromide as a porogen under basic condition is reported in this study for the generation of a new composite composed of mesoporous MCM-41 silica and hollow carbon capsule. The resultant MCM-41/carbon capsule composite offers a 3-D interconnected multimodal pore system, which discloses a wide pore range of ordered uniform mesopores (ca 2.3?nm) resulting from MCM-41 silica and disordered uniform mesopores (ca 3.8?nm) and macropores (ca 300?nm) from hollow mesoporous carbon, respectively. The composite has a high specific surface area (ca 909?m²/g) and large pore volume (ca 0.73?cm³/g). The in situ transformation approach of silica waste into valuable mesoporous silica is considered as a promising scalable route for efficient new multi-functional composites useful for a wide range of applications such as adsorption of volatile organic compounds and radioactive wastes produced in a nuclear facility.     

Influence of mesoporous fillers with PP-g-MA on flammability and tensile behavior of polypropylene composites

The effect of mesoporous silica MCM-41 and SBA-15 as a synergistic agent on the flame retardancy of intumescent flame retardant polypropylene composites (PP-IFR) were studied, and the IFR system mainly consisted of the ammonium polyphosphate (APP) as an acid source and blowing agent, pentaerythriol (PER) as a carbonization agent. The mesoporous MCM-41 and SBA-15 were incorporated into flame retardant formulation at four different concentrations (1, 3, 5, 8 wt.%) to investigate the synergism between the flame retardant materials. A synergistic effect in flame retardancy was best when a suitable amount of SBA-15 was used in combination with APP and PER.     

Recycling of glass in synthesis of MCM-48 mesoporous silica as catalyst support for Ni<Subscript>2</Subscript>O<Subscript>3</Subscript> photocatalyst for Congo red dye removal

Glass was successfully recycled in the synthesis of mesoporous silica MCM-48 which was used as catalyst support for nickel oxide photocatalyst. The resulted products were evaluated using X-ray diffraction, scanning electron microscope and UV–Vis spectrophotometer. The precipitated nickel oxide is of Ni₂O₃ form and loading of it onto MCM-48 resulted in a reduction in the band gap energy from about 3.66 eV to about 2.4 eV. The role of MCM-48 as catalyst support for Ni₂O₃ in enhancing the adsorption capacity and photocatalytic properties of nickel oxide was evaluated through series of equilibrium studies and photocatalytic degradation of Congo red dye under visible light. Using of glass-based MCM-48 as catalyst support for Ni₂O₃ showed enhancing the adsorption capacity by 31.3 and 14.8% higher than the adsorption capacity of Ni₂O₃ and MCM-48, respectively. Also, the photocatalytic degradation percentage increased by about 67.3% relative to the Ni₂O₃ degradation percentage. The nature of MCM-48/Ni₂O₃ adsorption mechanism is chemisorption and occurs in multilayer form throughout the heterogeneous surface of the composite. The using of MCM-48 as support for Ni₂O₃ photocatalyst enhanced the adsorption capacity through increasing the total surface area. The loading process resulted in fixing of the Ni₂O₃ particles throughout the porous structure which producing more exposed active photocatalyst sites and active adsorption sites for the incident photons as well as preventing the nickel oxide particles from agglomeration. Based on the obtained results, supporting of Ni₂O₃ particles onto MCM-48 is promising active centers for the degradation of Congo red dye molecules.     

钛掺杂对介孔硅材料结构性能的影响

在室温碱性条件下合成了Ｔｉ掺杂的介孔硅材料ＭＣＭ－４１,借助ＸＲＤ,ＩＲ、ＨＲＥＭ和Ｎ２吸附等分析手段,探讨了Ｔｉ掺杂量对介孔材料结构和性能的影响。结果表明：掺杂的Ｔｉ离子可以进行Ｓｉ骨架,并生成Ｓｉ－Ｏ－Ｔｉ键。     

用稻壳灰为硅源合成有序介孔二氧化硅材料的研究

用稻壳灰为硅源,用十六烷基三甲基溴化铵作为模板剂,在酸性或碱性条件下均成功地合成了有序介孔SiO2材料MCM-41.利用XRD、N2吸附曲线、SEM、TEM等测试方法分别对稻壳灰及介孔SiO2样品进行了表征.结果表明,稻壳灰为非晶体,呈粒状的多孔结构,其比表面积为250m2/g;在酸性条件下合成的MCM-41具有周期性规则排列的介孔结构,最可几孔径为2.4nm,比表面积为1100m2/g.     

Mesoporous silica nanoparticles inhibit cellular respiration

We studied the effect of two types of mesoporous silica nanoparticles, MCM-41 and SBA-15, on mitochondrial O 2 consumption (respiration) in HL-60 (myeloid) cells, Jurkat (lymphoid) cells, and isolated mitochondria. SBA-15 inhibited cellular respiration at 25-500 microg/mL; the inhibition was concentration-dependent and time-dependent. The cellular ATP profile paralleled that of respiration. MCM-41 had no noticeable effect on respiration rate. In cells depleted of metabolic fuels, 50 microg/mL SBA-15 delayed the onset of glucose-supported respiration by 12 min and 200 microg/mL SBA-15 by 34 min; MCM-41 also delayed the onset of glucose-supported respiration. Neither SBA-15 nor MCM-41 affected cellular glutathione. Both nanoparticles inhibited respiration of isolated mitochondria and submitochondrial particles.