PICA法合成介孔二氧化硅研究

以硅酸钠为硅源,在酸性条件下,通过尿素和甲醛的缩聚反应,用诱导聚合胶体团聚法(PICA)制备出单分散脲醛/SiO2复合微球,并经高温煅烧制得介孔二氯化硅。通过X射线衍射(XRD)、氮气脱吸附、透射电镜(TEM)和高分辨透射电镜(HRTEM)等手段对介孔二氧化硅进行了表征。结果表明,通过PICA法制得的介孔二氧化硅有序性好,孔径较大、孔壁较厚、孔径分布均匀。     

Templating synthesis of ordered mesoporous carbon particles

This research reports the synthesis of spherical ordered mesoporous carbon particles using mesoporous silica particles as a template. The silica particles with ordered cubic and lamellar mesostructures were synthesized from an aerosol-assisted self-assembly process using block copolymer surfactants as the structural directing agent. Infiltrating the pores of the silica particles with a sucrose solution followed by carbonization, and silica removal results in mesoporous carbon particles with replicated mesostructures. The particles were characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), and nitrogen sorption techniques.     

以阳离子Gemini表面活性剂为模板合成介孔氧化硅

以阳离子Gemini表面活性剂——双十六烷基三甲基溴化铵[C16H33N+(CH3)2(CH2)2N+(CH3)2C16H33].2Br-(G16-2-16)为模板剂,正硅酸乙酯为硅源,在n(SiO2)∶n(G16-2-16)∶n(NH3)∶n(H2O)=1∶0.1∶9∶110的条件下,在弱碱性环境中用水热法合成了平均孔径3.1 nm、比表面积906.71 m2/g、孔容0.93 cm3/g、具有二维六角结构且高度有序的介孔氧化硅MCM-41。采用小角XRD、高分辨透射电镜(HRTEM)、N2吸附-脱附分析和热重-微分热重法(TG-DTG)对其结构进行了考察,分析了不同模板剂浓度对材料结构有序度的影响。结果表明,n(G16-2-16)/n(TEOS)=0.1时,合成的材料有序度最高。     

Effects of fluoride ion on the formation of earthworm‐like mesoporous silica

In a strong acidic environment, ordered earthworm‐like mesoporous silica has been synthesized with CTAB templating and fluoride ion (F^?) as a counterion. The synthesized products were characterized by small‐angle X‐ray diffraction (SXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N₂ adsorption‐desorption isotherms, and Fourier‐transform infrared spectroscopy (FTIR). The effects of F/Si mole ratio on the morphology, surface area, and the pore size of the sample were discussed. It was found that a F/Si mole ratio at 0.083 induced the formation of 3D hexagonal mesophase, whereas higher F/Si mole ratios led to the formation of 2D hexagonal mesoporous silica, the optimum molar ratio of F/Si for the formation of delicate earthworm‐like mesoporous silica was observed at 0.250. The effects of the F/Si mole ratio, surfactant chain length, acid concentration, and shear flow on morphology were also studied.     

Effect of Counterions on Synthesis of Mesoporous Silica by the Route of Template

Mesoporous silica materials with ordered hexagonal and parallel-arranged pore channel have been synthesized using cetyl trimethylammonium bromide as a template and Na₂SO₄ as counterions. Their ordered mesostructures were characterized by infrared spectroscopy, X-ray diffraction patterns, scanning electron microscopy, transmission electron microscopy, and nitrogen sorption analysis. The effects of Na₂SO₄ concentration on variations of morphology, specific surface area, and pore size were discussed; the results show that a high concentration of Na₂SO₄ induces the formation of crystal threads with a "tubules-within-tubule" structure, and also leads to mesoporous silica materials with spherical, fabaceous, sheet-like, or prismatic shapes. The results also show that a high concentration of Na₂SO₄ can make the pore size decrease, but cannot change pore wall thickness, demonstrating the stability of the hexagonal-shaped pores.     

Template Synthesis of Three-Dimensional Cubic Ordered Mesoporous Carbon With Tunable Pore Sizes

Three-dimensional cubic ordered mesoporous carbons with tunable pore sizes have been synthesized by using cubic Ia3d mesoporous KIT-6 silica as the hard template and boric acid as the pore expanding agent. The prepared ordered mesoporous carbons were characterized by powder X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and nitrogen adsorption–desorption analysis. The results show that the pore sizes of the prepared ordered mesoporous carbons with three-dimensional cubic structure can be regulated in the range of 3.9–9.4 nm. A simplified model was proposed to analyze the tailored pore sizes of the prepared ordered mesoporous carbons on the basis of the structural parameters of the silica template.     

Synthesis and characterization of porous media produced by a sol-gel method

Mesoporous silica materials were synthesized by sol-gel method using tetraethoxysilane (TEOS) as precursors and surfactants i.e., cetyltrimethyl ammonium bromide (CTAB), sodium dodecyl sulfate (SDS), and polyoxyethylene cetyl ether (Brij 56) as templates. Surfactant templates were completely removed by calcination to form mesoporous structure. The effects of type and amount of surfactants on the characteristics of samples were studied. The textural characteristics such as surface area, pore volume, pore size, and pore size distribution were determined by nitrogen sorption isotherms. Fourier transform infrared (FTIR) spectroscopy was employed to qualitatively identify the chemical functionality and to confirm the removal of surfactant template. Scanning electron microscope (SEM) and transmission electron microscope (TEM) were used to directly observe surface morphology and mesoporous structure, respectively. The adsorption capacity of the synthesized adsorbent for toluene vapor was examined. We found that the pore volume and pore size of mesoporous materials affected the adsorption capacity. The sample prepared with high content of CTAB under basic condition (pH ∼7) yielded large pore volumes and pore sizes and subsequently possessed the high adsorption capacity for toluene vapor.     

弱酸性条件下SBA-16型二氧化硅介孔材料的合成与表征

引言 有序介孔材料由于具有较大的比表面积、均一可调的孔径(2～50 nm)、规则可控的形貌、较高的热稳定性和耐水解性等性能,在分离、吸附、催化、生物材料、信息材料、碳纳米管制备等领域有着广泛应用[1-3].     

Mesoporous silica MCM-41 with rod-shaped morphology: Synthesis and characterization

A new synthesis route has been established to prepare highly pure mesoporous silica material (Si-MCM-41) with rod-like morphology. To improve the stability and to bring about the long range ordering in the mesoporous material, a series of tetra-alkylammonium salts has been employed in the new procedure in addition to the surfactant, cetyl-trimethylammonium bromide. The mesoporous silica materials have been characterized by small-angle X-ray diffraction (SAX), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N₂ sorption and solid state ²⁹Si NMR measurements. The XRD study revealed that an excellent long range structural ordering of mesoporous material can be achieved using tetra-butylammonium bromide as a promoter. SEM study showed that rod-shaped single crystal like particles were formed in hydrothermal synthesis. TEM study revealed the presence of hexagonal voids on the face of the rod-shaped particles while nitrogen sorption study establishes the mesoporosity of the material. A high degree of cross-linking of -Si-O-Si- networks in the mesoporous silica has been evidenced in ²⁹Si NMR study.     

水热条件下CuMCM-41介孔分子筛的合成与表征

以硅酸钠(Na2SiO3·9H2O)、氯化铜(CuCl2·6H2O)等无机盐为原料,十六烷基三甲基溴化铵为模板剂,通过水热法合成CuMCM-41介孔分子筛.分别采用X射线粉末衍射、红外光谱、透射电子显微镜和N2吸附-脱附等技术,对产物的晶相、结构、形貌、比表面积和孔径分布进行了表征.同时研究金属铜添加量与比表面积、孔径之间的关系.结果表明:合成出的4种不同铜含量的CuMCM01介孔分子筛,其比表面积最高可达1032.41m2/g,平均孔径在3.4～4.0 nm之间.随着介孔分子筛中掺杂的金属铜含量的增加,介孔分子筛的比表面积变小、介孔有序性变差.当原料配比增加到n(SiO2):n(CuO)=1:0.2时,合成出的CuMCM-41介孔分子筛有序性很差.     

A combination of hard and soft templating for the fabrication of silica hollow microcoils with nanostructured walls

Hollow silica microcoils have been prepared by using functionalized carbon microcoils as hard templates and surfactant or amphiphilic dye aggregates as soft templates. The obtained materials have been characterized by electron and optical microscopy, nitrogen sorption and small angle X-ray scattering. The obtained hollow microcoils resemble the original hard templates in shape and size. Moreover, they have mesoporous walls (pore size ≈ 3 nm) with some domains where pores are ordered in a hexagonal array, originated from surfactant micelles. The obtained silica microcoils also show preferential adsorption of cationic fluorescent dyes. A mechanism for the formation of silica microcoils is proposed.     

Preparation of Mesoporous Silica Using Amphoteric Surfactant Potassium and Sodium N-Dodecyl Glycine Template

Mesoporous silica with hexagonal structure and Pm     n cubic structure with an ordered and parallel arranged pore channel has been synthesized using potassium N -dodecyl glycine and sodium N -dodecyl glycine as template, respectively. Their ordered mesostructures were characterized by infrared spectroscopy, small X-ray diffraction patterns, SEM, transmission electron muicroscopy, and nitrogen sorption analysis.     

MCM-41介孔碳材料的合成及其电化学性能研究

该文以十六烷基三甲基溴化铵（CTAB）为模板剂,可溶性淀粉(Starch)为碳源,通过软模板法一步合成了高度有序的介孔碳材料。通过热重分析（TG）、X-射线衍射（XRD）、N2吸附-脱附和透射电子显微镜（TEM）等对材料的结构进行了表征。结果表明：当模板剂与可溶性淀粉质量比为m(CTAB):m(Starch)=1.0：1.5,650 ℃焙烧碳化3 h,并用氢氟酸去除二氧化硅后,所得到的MCM-41有序介孔碳材料（OMC-650）的比表面积为985 m2/g,平均孔径为孔径分布均匀,平均孔径为2.5 nm。XRD和TEM分析表明,OMC-650具有典型的MCM-41结构特征,有序性良好。以OMC-650作为工作电极,氧化汞为参比电极,铂为辅助电极,用6 M•L-1 KOH做电解液,测其比电容为150 F/g,且经过1000次循环后,其比电容仍为138 F/g,为原电容的92%,说明所合成的材料具有良好的电容稳定性。     

Preparation of spherical MCM-41 molecular sieve at room temperature: Influence of the synthesis conditions in the structural properties

A rapid and facile synthesis route to obtain mesoporous MCM-41 silica at room temperature under basic conditions using as template cetyltrimethylammonium bromide (CTAB) is reported. The synthesis variables such as reaction time, molar ratios of CTAB/TEOS and H₂O/ethanol in the initial gel composition were studied. Samples were characterized by X-ray diffraction, nitrogen adsorption–desorption analyses, scanning electron microscopy and transmission electron microscopy. It was found that reaction conditions affect the quality of the MCM-41 silica. This silica can be prepared at short periods of time, and it exhibited a uniform size and spherical morphology.     

以聚乙二醇/十六烷基三甲基溴化铵为模板剂制备MCM-41分子筛

通过将聚乙二醇(PEG)直接引入MCM-41分子筛合成模板剂十六烷基三甲基溴化铵溶液中,经脱洗和焙烧处理得到厚孔壁有序介孔材料.选用X射线衍射(xRD)、透射电子显微镜(TEM)和等温吸附(BET)对样品进行了表征,结果显示,添加PEG的合成产物孔壁厚度增加,孔壁厚度可达1.45 nm,孔径尺寸和比表面积减小,有序性降低,低相对分子质量PEG的添加有助于厚孔壁产物生成.     

Ordered mesoporous sulfated silica-zirconia materials with high zirconium contents in the structure

A series of mesoporous sulfated silica-zirconia materials with various Si/Zr molar ratios (2.0–5.0) have been prepared using tri-block copolymer as a template, which were characterized by X-ray diffraction, TEM, nitrogen adsorption, UV-Vis diffuse reflectance spectroscopy, infrared spectroscopy, thermal gravimetric analysis, and catalytic reactions. XRD patterns displayed that ordered mesoporous sulfated silica-zirconia materials were obtained when the molar ratio of Si/Zr was not less than 4.0 (ZrSiS-4 and ZrSiS-5). When the molar ratio of Si/Zr was less than 4.0, the samples had a separated phase of amorphous sulfated zirconia (ZrSiS-2 and ZrSiS-3). Furthermore, TEM images (ZrSiS-4 and ZrSiS-5) revealed that the mesostructure of these materials were highly ordered. N₂ adsorption (ZrSiS-4 and ZrSiS-5) exhibited typical IV adsorption isotherms and uniform pore distribution. UV-Vis reflectance and IR spectra suggested (ZrSiS-4 and ZrSiS-5) that Zr atoms were incorporated into the walls of mesoporous silica. Cracking reactions of cumene and 1,3,5-triisopropylbenzene (TIPB) showed that, the ordered mesoporous sulfated silica-zirconia materials were very active in acidic catalytic reactions, especially for the cracking of large molecules.     

空心鼓状多级孔钛硅氧化物的合成及氧化-吸附脱硫性能研究

燃料油中的含硫化合物燃烧后会形成SO _x 排放到空气中,不仅引起环境污染,而且危害人类健康。因此,温和条件下的超深度脱硫技术已成为众多科研工作者关注的焦点。以表面活性剂-聚电解质形成的介观复合物为模板,成功合成了空心鼓状含钛多级孔结构二氧化硅材料。通过小角X射线衍射（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、氮气吸附-脱附以及紫外-可见光谱表征发现,所得到的含钛二氧化硅材料具有立方Pm-3n有序介观相态、多级介孔结构和较高骨架钛含量。由于多级介孔结构和丰富骨架钛活性位点的存在,该二氧化硅在室温下表现出优良的氧化脱硫催化活性和稳定性。此外,含钛二氧化硅对强极性氧化产物砜具有明显的吸附作用,实现了氧化-吸附一步法脱硫。     

Morphological control of mesoporous silica SBA-15 synthesized at low temperature without additives

Fiber-like or rod-like mesoporous SBA-15 silicas with different lengths and diameter of macrostructures and pore diameter could be synthesized by the self-assembly of silica-surfactant (commonly used Pluronic P123 (EO₂₀-PO₇₀EO₂₀) as a structure-directing agent) through careful control of the synthetic temperature and stirring time without any additives. X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM), and nitrogen adsorption–desorption isotherms are used to characterize these mesoporous silica materials. Compared with those reports on conventional SBA-15, our work is focused on one-step synthesis and the morphological control of ordered mesoporous silica synthesized at low temperature under low concentration of P123 (0.67 wt%) without the addition of inorganic salts, where pre-hydrolyzed silica species may favor the self-assembly of silica-polymer hybrid micelles. Moreover, the pore diameter of fiber-like SBA-15 synthesized at 40 °C is slightly smaller than that of conventional SBA-15, revealing that the average micellar radius of P123 micelles in this low concentration of P123 solution was almost same as that for the conventional synthesis of SBA-15.     

微波法合成Cu-MCM-41介孔分子筛的研究

以硅酸钠、氯化铜等无机盐为原料,十六烷基三甲基溴化铵(CTAB)为模板剂,通过微波辐射方法合成不同铜含量的Cu-MCM-41介孔分子筛。分别采用X射线粉末衍射(XRD)、透射电子显微镜(TEM)和N2吸附-脱附等技术对产物的晶相、结构、形貌、比表面积和孔径分布进行表征。结果表明,通过微波辐射方法成功地合成出含有不同孔径的Cu-MCM-41介孔分子筛。随着原料配比中n(CuO)∶n(S iO2)(摩尔比)的增加,介孔分子筛的比表面积和孔体积变小,介孔有序性变差。     

Uniform and ordered periodic mesoporous organosilica thin films by a facile solution growth approach

We demonstrate a novel solution growth method for synthesis of uniform and ordered periodic mesoporous organosilica (PMO) thin films on substrate. The approach is simple and facile, in which a substrate is immersed into a solution containing 1,2-bis(triethoxysilyl)ethane (BTSE) precursor, cetyltrimethylammonium bromide (CTAB) surfactant template, ammonia catalyst, ethanol, and decane. The precursors are hydrolyzed, cross-linked by ammonia catalyst, and assembled with the surfactant on the substrate to form highly ordered hexagonal mesostructures. The obtained mesoporous silica films possess substrate-size-dependent dimension, uniform and tunable thickness (30–100 nm), and ethane group incorporated frameworks. The obtained PMO films have been characterized by field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), and grazing incidence small-angle X-ray scattering (GISAXS). The film thickness can be easily controlled by adjusting the reaction temperature. A formation mechanism of the ethane-bridged PMO films via CTAB directed sol–gel process is further proposed.