聚苯乙烯胶晶模板法制备三维有序大孔SiO2材料

以聚苯乙烯微球(polystyrene microsphere)自然沉积形成的胶体晶体作模板,将以正硅酸甲酯制备的SiO2溶胶填充到模板间隙中,原位形成凝胶,最后通过焙烧除去模板,得到三维有序大孔SiO2.通过SEM检测,观察到六方和四方2种有序的大孔排列方式.大孔孔径及孔径收缩率分别为240nm和19%.2种排列中,大孔之间由小窗口连通,构成三维有序大孔结构.XRD显示,制备的3DOM材料由无定形SiO2组成.     

胶体晶体模板法制备三维有序排列的大孔SiO2材料

将粒径为480 nm的聚苯乙烯微球离心组装为胶体晶体模板,以正硅酸乙酯为硅源配制SiO₂溶胶并填充到模板间隙,原位形成凝胶,最后通过焙烧去除模板,得到三维有序大孔（3DOM）SiO₂。通过SEM检测,大孔以六方有序的方式排列,其孔径及孔径收缩率分别为360 nm和25％。大孔之间由小窗口连通,构成内部三维交联的大孔网络。低温N₂吸附测试表明,大孔孔壁上存在中孔孔隙,其中在3～4 nm有一集中的孔分布。XRD显示,制备的3DOM材料由无定形SiO₂组成。     

聚苯乙烯胶体晶体模板制备及在3DOM-SiO_2材料制备中应用

通过创新的方法制备聚苯乙烯（PS）胶体晶体,成功的制备出粒径在255nm左右的PS胶体晶体,并阐述了乳化剂用量对PS胶体晶体有序性排列的影响。用此PS胶体晶体为模板制备3DOM-SiO2材料,通过扫描电镜与透射电镜观察,SiO2大孔材料的孔径收缩率为10%左右,并且大孔SiO2在大面积范围内排列整齐有序,孔壁均匀致密光滑,是典型的三维有序大孔结构,3DOM-SiO2材料整体上呈面心立方体结构。     

具有介孔孔壁的三维有序大孔氧化铝的制备与表征

以260 nm的聚苯乙烯胶体微球组装的胶体晶体作为模板,采用硝酸铝为原料制备了γ晶相的三维有序大孔(3DOM)Al2O3。首先将Al(NO3)3.9H2O溶解在体积分数70%的甲醇溶液中并填充到胶体晶体模板中,然后取出模板室温干燥,再用质量分数10%的稀氨水浸泡并干燥,最后经550℃焙烧3 h得到3DOMAl2O3。所得材料具有三维有序的大孔孔道,大孔之间由小窗口连通,构成内部交联的大孔网络。3DOMAl2O3孔壁由10 nm左右的Al2O3纳米粒子组成,形成丰富的介孔孔隙,并使材料构成大孔/介孔多级孔道体系,材料的BET比表面积达到315 m2/g。     

三维有序大孔材料的制备及在催化领域的应用

三维有序大孔材料具有均一、有序的大孔结构,制备3DOM材料主要以胶体晶体模板法为主;综述了以胶体晶体模板;技术制备金属、金属氧化物、聚合物、碳材料等各类三维有序大孔材料的方法,从制备和催化应用两方面介绍了三维有序大孔材料的研究进展;评述了三维有序大孔材料多孔结构应用于催化领域的优势,并对其中的不足提出了加以改善的措施.     

前驱体对合成3DOM SiO2材料微观结构的影响

以自然沉积的聚苯乙烯(PS)胶体晶体为模板,分别以正硅酸乙酯(TEOS)的醇盐溶液和溶胶溶液为前驱体对PS模板进行填充,通过煅烧除去模板,得到了三维有序大孔(3DOM) SiO2材料.由SEM照片观察发现,当以TEOS的醇盐溶液为前驱体时,获得的3DOM SiO2结构不易控制,缺陷较多.而以TEOS的溶胶溶液为前驱体时获得的3DOM SiO2结构良好,孔径大小均匀,排列整齐,可以看成是PS模板的逆复制,说明前驱体溶液的选择对3DOMSiO2材料的微观结构有显著的影响.XRD分析显示,制备的3DOM SiO2孔壁为无定形结构.     

有序大孔二氧化硅微球的制备研究

采用乳液聚合法合成了单分散改性聚苯乙烯（PS）乳胶粒,利用PS乳胶粒自组装制得胶体晶体（“蛋白石”）微球,通过溶胶-凝胶模板法制备了有序大孔SiO2（“反蛋白石”）微球,通过SEM对改性PS乳胶粒、胶体晶体微球和有序大孔SiO2微球表面形貌进行了表征。结果表明,改性PS乳胶粒呈单分散性,粒径为317 nm;胶体晶体微球表面PS乳胶粒排列有序;有序大孔SiO2微球表面呈有序多孔,其孔呈六边形,孔径分布均一,约为200 nm。     

贯通有序大孔SnO2气敏材料的制备及气敏性能

以聚苯乙烯（PS）微球为模板,氧化锡（SnO₂）纳米晶为骨架,采用颗粒模板法成功制备了贯通有序大孔SnO₂气敏材料。改变PS微球的粒径,可以调节大孔SnO₂气敏材料的大孔孔径,本文以平均粒径约284nm和356nm的PS微球制备了大孔孔径分别约为200nm和260nm的贯通有序大孔SnO₂气敏材料。对制备的样品进行了热重、X射线衍射、扫描电子显微镜和氮气吸附脱附分析。结果表明：大孔排列高度有序,孔道贯通,孔壁由SnO₂纳米晶构成。制备的大孔SnO₂气敏材料不仅具备大孔-介孔-微孔结构,而且具有大的比表面积,具备优异的气敏性能。气敏测试结果表明孔径为200nm和260nm的贯通有序大孔SnO₂在280℃的工作温度下对300mL/L的乙醇气体的灵敏度为145、245,分别是无大孔SnO₂纳米晶的2.2倍、3.7倍。     

三维有序大孔氧化物催化剂的制备及应用

三维有序大孔氧化物具有均匀有序的大孔孔道、较高的孔容以及骨架组成的多样性等。主要介绍了三维有序大孔氧化物的结构、制备过程及应用进展。详细阐述了单分散微球的制备及改性、胶体晶体模板的制备、前驱体的制备及填充以及胶体晶体模板的去除。简单综述了近年来三维有序大孔氧化物在环境催化、石油化工、光催化及生物催化领域的应用研究,并对未来三维有序大孔氧化物的发展做了总结和展望。     

以聚苯乙烯为模板制备有序大孔氧化铝

采用少皂乳液聚合法成功制备了单分散的聚苯乙烯微球,以微球自组装后的聚苯乙烯胶体晶体为大孔模板,铝溶胶为前驱体填充模板,干燥焙烧除去模板后制备了氧化铝载体。用激光粒度仪、扫描电镜、X射线衍射和氮气吸脱附对聚苯乙烯胶体晶体和氧化铝载体进行了表征。结果表明:少皂乳液聚合法制备的聚苯乙烯微球具有粒径较小(100~350 nm)、单分散性好(0.005)、收率高(约80%)等优点;自组装的胶体晶体呈规则有序排列,微球表面光滑洁净,并以此为模板成功制备了具有三维有序结构的、大孔孔径可调的氧化铝材料。     

Controlled fabrication of nanosized TiO2 hollow sphere particles via acid catalytic hydrolysis/hydrothermal treatment

TiO₂ hollow spheres of controlled size were synthesized by combined acid catalytic hydrolysis and hydrothermal treatment, which involves the deposition of an inorganic coating of TiO₂ on the surface of carbon spheres prepared by a hydrothermal method and subsequent removal of the carbon spheres by calcination in air. The obtained TiO₂ hollow spheres were characterized by scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and powder X-ray diffraction. The results revealed that the size and surface morphology of the TiO₂ hollow spheres can be controlled by adjusting the concentration of the aqueous solution of glucose used to produce the template carbon spheres. Increasing the concentration of the glucose solution increased the average diameter of the TiO₂ hollow spheres from 190 to 300 nm. TiO₂ hollow spheres prepared using a glucose solution with a concentration of 0.7 mol/L are uniform in size with a diameter of 220 nm and shell thickness of 28 nm. The phenol removal rate of the sample prepared by calcination at 600 °C is 1.35 times higher than that of TiO₂ made by the same method without using the carbon template.     

Facile preparation and unique H2 adsorption behavior of three-dimensional novel Pt–Ru hollow sphere assemblies

Three-dimensional long range ordered hollow Pt–Ru sphere assemblies were prepared using a sacrificial three-dimensionally ordered macroporous (3DOM) carbon template. Metallic salts, such as a mixture of RuCl₃ with H₂PtCl₆ were infiltrated into the carbon template, and a reduced Pt–Ru phase was produced on the surface of the 3DOM carbon template by a borohydride reduction reaction. The sacrificial template was then burnt off in air at 650 °C. The diameter of the hollow Pt–Ru spheres could be tailored using a different pore size 3DOM carbon template. Assemblies with an outer diameter of 550 nm showed high BET surface area of 584.3 m²/g. In addition, a high hydrogen adsorption stoichiometry (>0.5 H/M) was obtained on the Pt–Ru sphere assemblies, which indicated that most of the metal atoms on the surface were exposed.     

Fabrication & characterization of macroporous CdSe nanostructure via colloidal crystal templating with electrodeposition method

Large area ordered arrays of macroporous Cadmium Selenide (CdSe) nanostructure, which possesses high refractive index and negligible absorption in the visible spectrum critical for the realization of photonic band gaps, was prepared via colloidal templating by galvanostatic electrodeposition. This work investigates the effect of electrodeposition parameters on the macroporous CdSe nanostructure. Field Emission Scanning Electron Microscope (FESEM) images showed two and three dimensional porous structures, consisting of interconnected close-packed arrays of pores. For CdSe thin film of thickness less than 1/3 of the diameter of a polystyrene sphere, it showed a monolayer of circular pores. As for film thickness close to the diameter of the sphere, the pores adopted irregular rounded triangular shapes. When the film thickness was more than one layer of the colloidal polystyrene template, the pores were spherical and had the same diameter as the polystyrene spheres. X-ray Diffraction (XRD) showed that the CdSe films prepared had a cubic structure with nanometer grain size, which was smaller than the diameter of the template spheres as well as the diameter of the interconnected channels. A range of 45–70 nm thick CdSe films with > 90% optical transmittance showed that there was negligible absorption at wavelength of 750 nm. In addition, the CdSe thin film exhibited a band gap energy of 2.07 eV, blue-shifted from the characteristic 1.7 eV of CdSe. This blue-shift characteristic of the deposited CdSe film further indicated that it was nanocrystalline which is potentially useful in photonic applications.     

Fabrication & characterization of macroporous CdSe nanostructure via colloidal crystal templating with electrodeposition method

Large area ordered arrays of macroporous Cadmium Selenide (CdSe) nanostructure, which possesses high refractive index and negligible absorption in the visible spectrum critical for the realization of photonic band gaps, was prepared via colloidal templating by galvanostatic electrodeposition. This work investigates the effect of electrodeposition parameters on the macroporous CdSe nanostructure. Field Emission Scanning Electron Microscope (FESEM) images showed two and three dimensional porous structures, consisting of interconnected close-packed arrays of pores. For CdSe thin film of thickness less than 1/3 of the diameter of a polystyrene sphere, it showed a monolayer of circular pores. As for film thickness close to the diameter of the sphere, the pores adopted irregular rounded triangular shapes. When the film thickness was more than one layer of the colloidal polystyrene template, the pores were spherical and had the same diameter as the polystyrene spheres. X-ray Diffraction (XRD) showed that the CdSe films prepared had a cubic structure with nanometer grain size, which was smaller than the diameter of the template spheres as well as the diameter of the interconnected channels. A range of 45–70 nm thick CdSe films with > 90% optical transmittance showed that there was negligible absorption at wavelength of 750 nm. In addition, the CdSe thin film exhibited a band gap energy of 2.07 eV, blue-shifted from the characteristic 1.7 eV of CdSe. This blue-shift characteristic of the deposited CdSe film further indicated that it was nanocrystalline which is potentially useful in photonic applications.     

A Novel Route for Preparation of Hollow Carbon Nanospheres Without Introducing Template

A newly developed route for the synthesis of hollow carbon nanospheres without introducing template under hydrothermal conditions was reported. Hollow carbon nanospheres with the diameter of about 100 nm were synthesized using alginate as reagent only. Many instruments were applied to characterize the morphologies and structures of carbon hollow nanospheres, such as XRD, TEM, and Raman spectroscopy. The possible formation and growth mechanism of carbon hollow spheres were discussed on the basis of the investigation of reaction influence factors, such as temperature, time, and content. The findings would be useful for the synthesis of more materials with hollow structure and for the potential use in many aspects. The loading of SnO₂ on the surface of carbon hollow spheres was processed, and its PL property was also characterized.     

Large pore heavy oil processing catalysts prepared using colloidal particles as templates

Macroporous FCC catalyst and macroporous HDS catalyst were prepared using polystyrene spheres as template. The size of the macropores can be tailored by controlling the size of template. The BET surface area and the pore volume of the macroporous catalysts are larger than those of catalysts prepared without template, and the more template used, the larger the surface area and pore volume obtained. When the same amount of template was used, the smaller diameter template produced a catalyst with larger surface area and pore volume. The increments in surface area and pore volume of the catalysts were greater than those predicted from the geometry of the template, indicating particle template could inhibit the shrinkage of the catalyst during drying. When used as heavy oil FCC catalysts and heavy oil HDS catalyst, the prepared macroporous catalysts are much more active than catalysts prepared without the template.