Novel mesoporous composites based on natural rubber and hexagonal mesoporous silica: Synthesis and characterization

The present study is the first report on the synthesis and characterization of mesoporous composites based on natural rubber (NR) and hexagonal mesoporous silica (HMS). A series of NR/HMS composites were prepared in tetrahydrofuran via an in situ sol–gel process using tetraethylorthosilicate as the silica precursor. The physicochemical properties of the composites were characterized by various techniques. The effects of the gel composition on the structural and textural properties of the NR/HMS composites were investigated. The Fourier-transform infrared spectroscopy (FTIR) and ²⁹Si magic angle spinning nuclear magnetic resonance (²⁹Si MAS NMR) results revealed that the surface silanol groups of NR/HMS composites were covered with NR molecules. The powder X-ray diffraction (XRD) and transmission electron microscopy (TEM) data indicated an expansion of the hexagonal unit cell and channel wall thickness due to the incorporation of NR molecules into the mesoporous structure. NR/HMS composites also possessed nanosized particles (∼79.4 nm) as confirmed by scanning electron microscopy (SEM) and particle size distribution analysis. From N₂ adsorption–desorption measurement, the NR/HMS composites possessed a high BET surface area, large pore volume and narrow pore size distribution. Further, they were enhanced hydrophobicity confirmed by H₂O adsorption–desorption measurement. In addition, the mechanistic pathway of the NR/HMS composite formation was proposed.     

Direct synthesis of Cr-MCM-48-like large pore mesoporous silica

Chromium-substituted MCM-48-like large pore mesoporous silica with average pore size up to 10 nm was directly synthesized by using P123 (EO₂₀PO₇₀EO₂₀) as a template, n-butanol as an assistant, and chromic nitrate nonahydrate as a chromium source. The Cr species was doped by simply adjusting the pH of the synthesis system with ammonia from strong acid to nearly neutral after crystallization for 24 h. The Si/Cr ratios in the initial gel ranged from 10 to 80, and the actual weight percentage of Cr was analyzed by ICP. XRD pattern, high-resolution TEM, and N₂ adsorption–desorption isotherm were employed to investigate the pore structure properties of these materials. The results showed that all the samples had Ia3d cubic structure and the pore channels were highly ordered. UV–vis, wide-angle XRD, and ESR spectra revealed that at lower Cr content (Si/Cr > 30), only Cr (VI) and Cr(V) species existed in the mesoporous framework, and at higher Cr content, Cr (III) species appeared.     

Gelatin-assisted porous expansion of mesoporous silica

In this study, we report the pore expansion effect of gelatin, a common amphoteric biological protein, on the hexagonal mesoporous silica materials. Tetraethyl orthosilicate (TEOS) was used as silica source and the nonionic surfactant P123 (EO₂₀PO₇₀EO₂₀) as template. The microstructure characters of products were investigated by low-angle X-ray diffraction (LAXRD), transmission electron microscope (TEM), and N₂ adsorption–desorption measurements. The results show that the products prepared with gelatin have the mild expansion ratios of 29–39% and 5–22% in pore diameter and pore volume, respectively. The specific surface area of products ranges from 445 to 590 m² g⁻¹. Moreover, it is revealed that the presence of gelatin did not change the intact 2D-hexagonal mesoporous structure of materials. The ultraviolet–visible absorption spectroscopy (UV–Vis) analysis indicates that there is an interaction between the oxygen atoms of P123 and gelatin molecules. The pore expansion may be because the gelatin can interact with the hydrophilic sides of P123 micelles via hydrogen bonds interaction, which is different from the reported pore expansion mechanisms for other systems.     

Synthesis and characterization of Ti-SBA-16 ordered mesoporous silica composite

Ti-SBA-16 mesoporous silica with a cubic Im3m structure has been successfully synthesized through prehydrolysis of a silica precursor in the presence of a tri-block copolymer F127 under acidic condition. X-ray diffraction (XRD) shows that the highly ordered mesostructure was maintained even at the high loading of titanium up to 5.5 (bulk molar ratio SiO₂/TiO₂). UV–vis and Raman spectroscopy reveal that the titanium species was highly dispersed in the silica framework with tetrahedral coordinate and octahedral coordinate, respectively. N₂-adsorption data exhibit that the BET surface, pore size and pore volume were maintained with an increase of titanium species loading for this cubic Im3m mesoporous composite. SEM image shows its amorphous morphology. The synthesis of mesoporous TiO₂-containing SBA-16 composite with a cubic Im3m structure will open new applications for catalysts.     

Synthesis of 3-dimensional mesoporous silica using a di-block copolymer template

Exploring polymeric surfactants as templates for synthesizing ordered mesoporous silicas has become increasingly important for both academic interests and industrial applications. In this work, we employed C₁₆EO₄₀, a di-block copolymer polyethylene-poly(ethylene oxide), as template in an attempt to synthesize a modified 3-dimensional wormhole mesoporous silicas (WMS-39). In addition, various synthesizing conditions were investigated, including pre-hydrolysis time of TEOS, reaction temperatures and the ratios of TEOS to template. The products were characterized using powder XRD, TEM, ²⁹Si MAS NMR and nitrogen adsorption measurements. The characteristics of as-synthesized mesoporous silica were compared with SBA-15, a highly ordered mesoporous silica, prepared using non-ionic tri-block copolymers of poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) as templates. The WMS-39 materials have a BET surface area of 600–970 m²/g and narrowly distributed pore diameter around 3.9 nm. The morphology of WMS-39 was found to be wormhole framework as indicated in TEM diagrams. Thermal transformation of the as-synthesized mesoporous materials were carefully analyzed with TGA/DTA. Findings obtained from this work enable us to propose a modified assembly mechanism of mesoporous silicas.     

Synthesis of mesoporous structured hydroxyapatite particles using yeast cells as the template

In this study, hydroxyapatite (HAp) particles with mesoporous structure have been synthesized from calcium hydroxide and di-ammonium hydrogen phosphate using yeast cells as the template. The characterization methods such as X-ray diffraction (XRD), Fourier transform infrared spectrograph (FTIR), N₂ adsorption–desorption isotherms (NADI), transmission electron microscopy (TEM) and field emission scanning electron microscopy (FESEM) were used for determination of the particles structure (particle size, structural evolution and morphology). The results show that HAp particles with mesoporous structure could be produced. The size of HAp particles was approximately hundreds of nanometer. The pore width of HAp particles was in the range of 2.0–40 nm and the maximum centered around 4.5 nm.     

Cu(II) complexes imobilized on functionalized mesoporous silica as catalysts for biomimetic oxidations

Mesoporous HMS silica was synthesized and functionalized with 3-aminopropyl-triethoxysilane (APTES) by a post-synthesis method. HMS and NH₂-HMS supports were used for immobilization of two Cu(II) biomimetic complexes ([Cu(acac)(phen)(H₂O)](ClO₄), [Cu(acac)(Me₂bipy)](ClO₄)) or laccase enzyme. Mesoporous structure of the support; functionalization of silica surface, structure of ligands, and Cu complexes; and their immobilization were evidenced by XRD analysis, N₂ adsorption–desorption, SEM microscopy, TGA-DTA, IR and UV–Vis spectroscopy, and elemental analysis. The results confirm the structural integrity of the mesoporous hosts and successful anchoring of the metal complexes over the supports. For comparison, copper-substituted mesoporous silica (Cu-HMS) by using dodecylamine as structure-directing agent was also synthesized. All the synthesized materials were tested for their catalytic activity on the oxidation of 4-aminoantipyridine, 2,2′-azinobis (3-ethyl-benzothiazoline)-sulfonic acid (ABTS) with air, as well as in liquid phase oxidation of anisole and phenol with hydrogen peroxide. In order to verify the complex biomimetic activity, the Trametes versicolor laccase was immobilized by adsorption in the same supports.     

One-pot synthesis of ordered mesoporous carbon–silica nanocomposites templated by mixed amphiphilic block copolymers

Mixed amphiphilic block copolymers of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO–PPO–PEO) and polydimethylsiloxane-poly(ethylene oxide) (PDMS–PEO) have been successfully used as co-templates to prepare ordered mesoporous polymer–silica and carbon–silica nanocomposites by using phenolic resol polymer as a carbon precursor via the strategy of evaporation-induced self-assembly (EISA). The ordered mesoporous materials of 2-D hexagonal (p6m) mesostructures have been achieved, as confirmed by small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM), and nitrogen-sorption measurements. Experiments show that using PDMS–PEO as co-template can enlarge the pore sizes and reduce the framework shrinkage of the materials without evident effect on the specific surface areas. Ordered mesoporous carbons can then be obtained with large pore sizes of 6.7 nm, pore volumes of 0.52 cm³/g, and high surface areas of 578 m²/g. The mixed micelles formed between the hydrophobic PDMS groups and the PPO chains of the F127 molecules should be responsible for the variation of the pore sizes of the resulting mesoporous materials. Through the study of characteristics of mesoporous carbon and mesoporous silica derived from mother carbon–silica nanocomposites, we think mesoporous carbon–silica nanocomposites with the silica-coating mesostructure can be formed after the pyrolysis of the PDMS–PEO diblock copolymer during surfactant removal process. Such method can be thought as the combination of surfactant removal and silica incorporation into one-step. This simple one-pot route provides a pathway for large-scale convenient synthesis of ordered mesostructured nanocomposite materials.     

The size modulation of hollow mesoporous carbon spheres synthesized by a simplified hard template route

Hollow mesoporous carbon spheres (HMCSs) have been prepared by a simplified replication route from a solid silica core/mesoporous silica shell aluminosilicate (SCMS-Al) template, which was synthesized by directly incorporating aluminum species into the mesoporous framework during template synthesis. The size of HMCSs can be tuned between 80 and 470 nm by simply changing the diameters of SCMS-Al. The HMCSs have uniform mesopores with a narrow pore size distribution (3.4-4.1 nm), and high surface area, (890-1150 m²/g) and total pore volumes (0.75-1.15 cm³/g). The techniques of N₂ sorption isotherms, TEM, EDX and SEM were used to characterize the as-synthesized spheres.     

Direct synthesis of mesoporous Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> through citric acid-assisted solid thermal decomposition

A simple and inexpensive approach to synthesizing mesoporous Fe₃O₄ is developed by using citric acid-assisted solid thermal decomposition of ferric nitrate. The structure and magnetic property of mesoporous Fe₃O₄ were characterized by XRD, FT–IR, N₂ adsorption–desorption isotherms, TEM, and vibrating sample magnetometer. It was shown that the decomposition of citric acid results in the formation of the mesoporous structure and narrow pore-size distribution. The reducing atmosphere which created by the decomposition of the ferric nitrate–citric acid complex caused the partial reduction of Fe(III) to Fe(II) and in turn the formation of Fe₃O₄. Moreover, the strength of the coordination between carboxyl group and Fe³⁺ also affected the phase composition of the iron oxides.     

Synthesis of mesoporous hydroxyapatite nanoparticles using a template-free sonochemistry-assisted microwave method

A facile template-free sonochemistry-assisted microwave method was successfully developed for the synthesis of mesoporous hydroxyapatite nanoparticles (MHN) in a short time. The prepared MHN were characterized by means of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), and N₂ adsorption–desorption isotherms. TEM images showed a clear rod-like morphology with length of 50–100 nm and width of about 20 nm. XRD and FTIR indicated a typical hydroxyapatite phase with high crystallinity. N₂ adsorption–desorption isotherms revealed an irregular mesoporous structure. Judging from the values calculated from N₂ isotherms, the specific surface area and pore volume obviously decreased after the sintering process. In a typical example, the specific surface area, pore volume, and pore size of MHN before and after calcination were 79.74 m²/g, 0.46 cm³/g, 2.7 nm and 45.41 m²/g, 0.22 cm³/g, 2.8 nm, respectively. In addition, MHN could be synthesized in a period of time as short as 10 min. Further investigation indicated that microwave radiation played a dominant role in the emergence of mesoporous structure, while ultrasound irradiation acted as a supporting role. Based on the above results, a possible mechanism of formation of mesoporous hydroxyapatite has been proposed.     

Mesoporous silica obtained by polycondensation of octahydridooctasilsesquioxane

Mesoporous silica, due to its porosity and morphological features, have been considered a fascinating material for many technological applications. In this report, we describe the preparation of a structurally stable mesoporous silica material using octahydridooctasilsesquioxane (T₈ ^H). The structure and properties of final samples were determined by XRD, FT-IR, and TEM methods. Structural analysis has shown that the siliceous material is amorphous but mesoporous. BET surface area, pore volumes, and pore size distribution were measured using nitrogen sorption methods—data were collected from the adsorption branch using BJH method for mesopores and t-plot method for micropores. It was found that the cage-type structure of T₈ ^H molecules and the process conditions determine the specific morphology of the cross-linked products. Completely inorganic, mesoporous silica of a narrow pore distribution was obtained. It was found that the materials have large surface area and pores in the meso range (2–5 nm). The amount of mesopores and the characteristic surface area of the prepared samples strongly depended on the reaction conditions.     

NaY/MCM-48复合分子筛的合成与表征

以微孔分子筛NaY为内核, 合成一种中微孔复合分子筛NaY/MCM-48. 通过XRD、SEM、TEM、IR、N_2吸附脱附和TPD等手段对复合材料进行了表征, 此外对复合材料的水热稳定性进行了考察. 研究结果表明, 复合材料同时具有中孔分子筛MCM-48和微孔NaY型沸石的特点, 并且和纯MCM-48分子筛相比孔壁增厚, 孔径变大; 与纯中孔分子筛MCM-48相比, 复合分子筛的酸性明显增强, 并且水热稳定性提高. DFT计算其孔径分布主要集中于1.2和3.2nm.     

Preparation of highly ordered Fe-SBA-1 and Ti-SBA-1 cubic mesoporous silica via sol-gel processing of silatrane

Silatrane prepared from fumed silica and triethanolamine (TEA) was used as a precursor for the sol-gel synthesis of M-SBA-1 (M = Fe and Ti) at room temperature using cetyltrimethylammonium bromide as a template, and dilute solutions of ferric chloride and titanium glycolate as metal sources. Powder X-ray diffraction (XRD) showed the mesoporous materials to be well-ordered cubic structures, while N₂ adsorption/desorption measurements yielded high surface areas. Diffuse reflectance UV-visible spectroscopy demonstrated that iron (Fe³⁺) and titanium (Ti⁴⁺) were incorporated in the framework of the calcined materials to loadings of 6 wt.% Fe and 10 wt.% Ti without perturbing the ordered mesoporous structure.     

Controlled release of phenytoin for epilepsy treatment from titania and silica based materials

Template technique was used to obtain well ordered nanostructured materials: mesoporous silica and nanostructured titania tubes. This technique permits the synthesis of solids with controlled mesoporosity, where a large variety of molecules that have therapeutic activity can be hosted and further released to specific sites. In this work phenytoin (PH), a drug used in epilepsy treatment, was loaded in ordered mesoporous silica (SBA 15) and nanostructured titania tubes (TiO₂). The pure materials and those containing PH were characterized by X-ray diffraction, FTIR spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy (SEM) and N₂ adsorption–desorption at 77 K. In order to determine the loading capacity of the antiepileptic drug on these silica- and titania-based materials, the loading and release of PH was investigated using UV–vis spectroscopy. Tubular structures were found for the titania samples, for which the X-ray diffractograms showed to be formed by anatase and rutile phases. On the other hand, an amorphous phase was found in the silica sample. A highly ordered hexagonal structure of 1D cylindrical channels was also observed for this material. Loaded PH showed a good stability inside the used materials as observed by spectroscopy analysis. The adsorption and desorption of PH are faster in nanostructured TiO₂ tubes than in mesoporous silica matrix.     

Electrochemical capacitance study on Co<Subscript>3</Subscript>O<Subscript>4</Subscript> nanowires for super capacitors application

One-dimensional Co₃O₄ nanowires have been prepared by utilizing the ordered mesoporous silica material SBA-15 as template. The results of transmission electron microscope (TEM) and N₂ adsorption–desorption characterizations show that the Co₃O₄ nanowires possess a uniform size and a large Brunauer-Emmett-Teller (BET) surface area. Its electrochemical performance was investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) techniques in various concentration of KOH solution. This nanomaterial shows a small resistance, a high specific capacitance (SC), and a strong cyclic stability. The maximal SC value of 373 F·g⁻¹ was obtained in 6 M electrolyte under the scan speed of 3 mV·s⁻¹ at the first CV cycle. After 500 CV cycles, the SC value is about 90% of the original value. It is considered that the short path of ion transfer given by nanomaterial brought on the great pseudo capacitance performance.     

Steam-assisted crystallization of TPA+-exchanged MCM-41 type mesoporous materials with thick pore walls

Hierarchical MCM-41/MFI composites were synthesized through ion-exchange of as-made MCM-41 type mesoporous materials with tetrapropylammonium bromide and subsequent steam-assisted recrystallization. The obtained samples were characterized by powder X-ray diffraction (XRD), UV–vis diffuse reflectance spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis, FT-IR, ¹H–¹³C CP/MAS and nitrogen adsorption–desorption. The XRD patterns show that the MCM-41/MFI composite possesses both ordered MCM-41 phase and zeolite MFI phase. SEM and TEM images indicate that the recrystallized materials retained the mesoporous characteristics and the morphology of as-made mesoporous materials without the formation of bulky zeolite, quite different from the mechanical mixture of MCM-41 and MFI structured zeolite. Among others, lower recrystallization temperature and the introduction of the titanium to the parent materials are beneficial to preserve the mesoporous structure during the recrystallization process.     

Effect of calcination temperature on the textural properties and photocatalytic activities of highly ordered cubic mesoporous WO3/TiO2 films

Highly organized cubic mesoporous WO3/TiO2 films were successfully prepared by evaporation-induced self-assembly (EISA) process, employing triblock copolymer as template. The characterization results by XRD, SEM, TEM, UV-Vis. spectrophotometry, and nitrogen adsorption-desorption isotherms reveal that the mesoporous films are made up of well-defined 3-D cubic (lm3m space group) mesoporous structure and nanocrystalline anatase frameworks with high surface area, uniform pore sizes and excellent optical transparency. Photocatalytic properties of the mesoporous WO3/TiO2 films in decomposing gaseous 2-propanol to CO2 were analyzed as a function of calcinations temperature. The highest photocatalytic activity was obtained for the films calcined at 450 degrees C, which possess an appropriate crystallinity and relevant ordering of mesoporous structure. It was found that that long-range ordering of mesopores is one of the important factors in determining the photocatalytic degradation of gaseous organics.     

Fabrication and textural characterization of nanoporous carbon electrodes embedded with CuO nanoparticles for supercapacitors

Abstract

We introduce a novel strategy of fabricating nanoporous carbons loaded with different amounts of CuO nanoparticles via a hard templating approach, using copper-containing mesoporous silica as the template and sucrose as the carbon source. The nature and dispersion of the CuO nanoparticles on the surface of the nanoporous carbons were investigated by x-ray diffraction (XRD), high-resolution scanning electron microscopy (HRSEM) and high-resolution transmission electron microscopy (HRTEM). XRD results reveal that nanoporous carbons with embedded CuO nanoparticles exhibit a well-ordered mesoporous structure, whereas the nitrogen adsorption measurements indicate the presence of excellent textural characteristics such as high surface area, large pore volume and uniform pore size distribution. The amount of CuO nanoparticles in the nanochannels of the nanoporous carbon could be controlled by simply varying the Si/Cu molar ratio of the mesoporous silica template. Morphological characterization by SEM and TEM reveals that high-quality CuO nanoparticles are distributed homogeneously within the nanoporous carbon framework. The supercapacitance behavior of the CuO-loaded nanoporous carbons was investigated. The material with a small amount of CuO in the mesochannels and high surface area affords a maximum specific capacitance of 300 F g^-1 at a 20 mV s^-1 scan rate in an aqueous electrolyte solution. A supercapacitor containing the CuO-loaded nanoporous carbon is highly stable and exhibits a long cycle life with 91% specific capacitance retained after 1000 cycles.     

介孔SiO2孔道结构对聚酰胺反渗透复合膜性能的影响

在界面聚合过程中,通过添加改进水热方法制备的球形介孔SiO2纳米材料,制备了改性的聚酰胺反渗透复合膜。使用扫描电镜、X射线衍射和氮气吸附-脱附等手段对制备的介孔SiO2纳米材料进行表征;采用反渗透膜评价装置、原子力显微镜、扫描电镜(SEM)和静态接触角仪器等手段对复合膜的性能和结构进行测试和表征;并对比了相同粒径大小的实心SiO2和介孔SiO2对膜渗透性能的影响。结果证明:成功合成了一种具有孔径分布均匀、粒径均一、比表面积较大、分散性较好的介孔SiO2纳米球形颗粒;SEM表征结果证实纳米材料在膜表面分布均匀,膜表面亲水性能提高,粗糙度变大;膜性能测试结果证实了介孔SiO2的添加使得膜在维持较高截留率的前提下,具有更高的水通量;同时,通过对比相同尺寸的实心SiO2作为添加材料,证实了介孔SiO2的孔道结构更有利于水分子的传输。当介孔SiO2添加质量为0.06%时,水通量由23L/(m2·h)提高至39L/(m2·h),对氯化钠的截留仍然维持在98%以上。