溶胶-凝胶模板法制备三维有序大孔TiO_2微球

采用无皂乳液聚合方法自制的单分散聚苯乙烯(PS)微球乳液为原料,并以PS微球自组装制备了有序胶体晶体模板("蛋白石"),采用溶胶-凝胶模板法制备了三维有序大孔TiO2微球("反蛋白石"),其孔呈六边形,孔径分布均一,约为200 nm,运用SEM,XRD对其形貌特征及晶型进行表征。结果表明,采用表面含有羧基的单分散聚苯乙烯微球及高的硅油粘度制得的模板有序度高;控制煅烧温度可以改变有序大孔TiO2微球的晶型,当煅烧温度为500℃时,其晶型为锐钛型,当煅烧温度为700℃时,其晶型则为金红石型。     

三维有序大孔炭材料的制备及其应用

综述了三维有序大孔(3DOM)炭材料的制备及应用.3DOM炭材料的制备方法主要有胶晶模板法、炭气凝胶法、聚合物热解法,其中胶晶模板法是最有效的方法.还归纳了3DOM炭材料在光子晶体、电极材料、催化剂及催化剂载体、生物材料以及模板等方面的应用研究.     

双模板作用下3DOM ZnO/ZrO2-TiO2（P123）的制备及表征

同时在聚苯乙烯(PS)微球和三嵌段共聚物EO20PO70EO20(P123)双模板剂作用下,经溶胶-凝胶及煅烧后处理的方法制备了三维有序大孔(3DOM)复合材料ZnO/ZrO2-TiO2(P123)。通过X射线衍射(XRD)、傅里叶-红外光谱(FT-IR)、扫描电子显微镜配合X射线能量色散谱仪(SEM-EDS)和N2吸附-脱附测定等测试手段对其元素组成、晶型结构、表面形貌以及表面物理化学性质等进行了表征。结果显示,经PS微球和P123双模板处理后的复合材料3DOM ZnO/ZrO2-TiO2(P123)主要晶型结构为锐钛矿,同时,三维空间的大孔结构排列规则、整齐而有序,其大孔平均直径约为100 nm,且复合材料的BET比表面积高达202.8 m2/g,大孔孔壁的介孔孔径分布也更加均一。     

Preparation of three-dimensional ordered macroporous SiCN ceramic using sacrificing template method

Three-dimensional (3D) long range well ordered macroporous SiCN ceramics were prepared by infiltrating sacrificial colloidal silica templates with the low molecular weight preceramic polymer, polysilazane. This was followed by a thermal curing step, pyrolysis at 1250 °C in a N₂ atmosphere, and finally the removal of the templates by etching with dilute HF. The produced macroporous SiCN ceramics showed high BET surface areas (pore volume) in the range 455 m²/g (0.31 cm³/g)–250 m²/g (0.16 cm³/g) with the pore sizes of 98–578 nm, which could be tailored by controlling the sizes of the sacrificial silica spheres in the range 112–650 nm. The sphere-inversed macropores were interconnected by 50 ± 30 nm windows and 3–5 nm mesopores embedded in the porous SiCN ceramic frameworks, which resulted in a trimodal pore size distribution. The surface of the achieved porous SiCN ceramic was then modified by Pt–Ru nanoparticle depositing under mild chemical conditions.     

Keggin结构三维有序大孔PMo_(12)-SiO_2材料的制备与表征

以三维有序大孔SiO2为载体,采用等体积浸渍法将Keggin结构的12-磷钼酸(PMo12)固载化,制备了三维有序大孔PMo12-SiO2材料,利用IR、TG-DTA、XRD、SEM及低温N2吸附等测试手段对制备的样品进行了表征。结果表明,负载后磷钼酸的热稳定性显著提高,经500℃焙烧后,其Keggin结构依然保持;负载后,样品具有三维有序的大孔结构;磷钼酸以微晶形式高度分散在载体的孔隙中,其对孔隙的填充作用使载体的比表面积由125.4 m2/g下降到24.4 m2/g。     

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。     

微乳法制备纳米氧化锆及其结构分析

以四水合硫酸锆为原料,通过油酸/正丁醇/氨水体系制备纳米ZrO2。运用热重-差热分析、红外光谱分析、X射线衍射、激光粒度分布、透射电子显微镜等手段对产物的结构和形态进行了表征。实验结果表明,所合成的ZrO2为四方晶型,产物的形状为球形,粒径在20 nm左右。红外光谱测试结果表明,随着煅烧温度的升高,Zr─O─Zr键的吸收频率产生红移;随着微乳体系中氨水浓度的增大,所制备样品的Zr─O─Zr键的吸收频率产生红移,ZrO2的粒径增大。     

Preparation of ordered macroporous platinum and palladium powders

Ordered macroporous platinum and palladium metal powders were prepared with a combination of silica template and hydrogen reduction methods. The effects of species of metal precursor and calcination of silica templates on the structure of final metal powders were investigated. Precursor of platinum or palladium was infiltrated into closely packed silica templates prepared from tetraethyl orthosilicate and vacuum dried at room temperature following hydrogen reduction to obtain metal–silica complexes. After the removal of the silica templates from the complexes by hydrofluoric acid treatment, metal powders were obtained. Ordered macroporous platinum and palladium powders were obtained by using hydrogen hexachloroplatinate (IV) hexahydrate with uncalcined silica template and palladium (II) chloride with calcined templates, respectively. Composition analyses indicated that silica templates were completely removed from the ordered metal powder. Sizes of the voids in the ordered macroporous metal powders were controlled in the range of 240–520 nm corresponding to those of the silica spheres used.     

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。     

Preparation and characterization of three-dimensionally ordered macroporous syndiotactic poly(p-methylstyrene)

Three-dimensionally ordered macroporous(3DOM) syndiotactic poly(p-methylstyrene) (sPPMS) with pore size 170 nm was fabricated by means of silica templates using (dbm)₂Ti(OPh)₂/MAO catalytic system. The resulting polymers were characterized by SEM, ¹³C NMR, DSC and GPC. The results indicated that the 3DOM sPPMS were highly syndiotactic. GPC curves showed that the 3DOM sPPMS possessed lower Mn and broader MWD compared with bulk one. Meanwhile, DSC results revealed that three 3DOM sPPMS exhibited crystalline form II, and bulk sPPMS form III.     

Synthesis of three-dimensional ordered macroporous TiO2, Gd/TiO2 and their photocatalytic activity

In this paper, three-dimensional ordered macroporous (3DOM) TiO₂ and Gd/TiO₂ materials were synthesized by colloidal crystal templating process. The obtained samples were analyzed by field-emission scanning electron microscope, transmission electron microscopy, X-ray diffraction, diffuse reflectance spectra and Brunauer–Emmett–Teller method. The photocatalytic activity of various samples was evaluated by degradation of methyl orange in aqueous solution under UV and visible light irradiation. At the same time, Degussa P25 (a commercial Titania) powders were used for comparison. The results indicated that 3DOM Gd/TiO₂ samples showed a significant shift in the onset absorption towards the longer wavelength compare to pure 3DOM TiO₂, and displayed excellent photocatalytic activity under both UV and visible light irradiation.     

简述胶晶模板法制备三维有序大孔炭材料

三维有序大孔炭(3DOM)材料是近年来刚刚兴起的多孔材料领域一项重要研究课题。3DOM大孔炭材料不仅具有多孔材料的一般特点,还具有孔结构排列周期性强、孔径分布窄、大孔尺寸均匀可调,且具有较大的孔径、较高的表面积等一系列特点,在新型催化、吸附分离、电极材料等方面都具有潜在的应用价值。本文总结了近年来胶晶模板法制备三维有序大孔炭材料,分别从模板的制备、碳源的选择以及到最终大孔炭的制备三个方面加以总结概述。     

反向化学沉淀法制备纳米ZrO_2超细粉体

以ZrOCl2.8H2O和NH3.H2O为原料,采用反向化学沉淀、有机物共沸蒸馏法制备超细ZrO2,用XRD、TEM、BET等技术研究粉体的组合结构、晶粒大小、比表面和孔径分布情况。结果表明,纳米ZrO2超细粉体由单斜和四方晶相组成,透射电镜分析提示产物粒径在10~20 nm;样品经400℃焙烧4 h后粉体的比表面积为115.64 m2/g,平均孔径为6.375 nm,总孔容为0.369 mL/g。该粉体具有高比表面性,可用于工业催化剂的载体。     

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。     

Preparation of ZrO2 beads by an improved micro-droplet spray forming process

Monodisperse ZrO₂ ceramic beads with size larger than 1 mm have been prepared by an improved micro-droplet spray forming process, through which a compressor and a dispenser were employed to produce droplets continuously. Furthermore, the slurry recipe and drying temperature have been optimized to enhance the sphericity and smoothness of the beads. The sintered ZrO₂ ceramic beads present promising mechanical performance, including a relative density of 84.6%, a crush strength of 256.2 ± 36.6 N as well as a Vickers hardness of 1344.4 ± 58.3 HV. Such procedure reveals great potential in mass production of ceramic beads.     

Preparation,characterization and growth mechanism of ZrO2 nanosheets

High quality single-crystal zirconia nanosheets were successfully prepared via molten salt method, using solvothermally synthesized product as precursor. The effects of heat treatment temperature and soaking time on the phase composition and morphology of samples were investigated by X-ray diffraction, Fourier transform infrared spectroscopy, Thermal analyzer, Raman spectrometer, Field-emission scanning electron microscope and Transmission electron microscope. The results show that zirconia nanosheets with a thickness of 60–80 nm and a width-thickness ratio up to 13 could be obtained by using NaCl and Na₃PO₄ as composite salts at 900 °C for 5 h. The precursors containing Zr–OH and Zr–O bonds have relatively high activity, which is beneficial to crystal growth. In addition, the as-prepared nanosheets with exposed (001) plane are monoclinic-structured and show no distinct defect. The growth behavior of particles during dissolution-recrystallization process is analogous to self-focusing mechanism. The preparation method can be extended to wet-chemical synthesis of other nanomaterials.     

Preparation and characterization of three-dimensional nanostructured macroporous bacterial cellulose/agarose scaffold for tissue engineering

We fabricated a three-dimensional nanostructured macroporous bacterial cellulose scaffold (3D BC scaffold) and a three-dimensional nanostructured macroporous bacterial cellulose/agarose scaffold (3D BC/A). Results of scanning electron microscopy (SEM) and mercury intrusion porosimeter showed that both the 3D BC and the 3D BC/A have interconnected macropores characterized by nanofibrous pore walls (The diameter of the dominant pores was about 100 μm and ranges from <1 μm to >1,000 μm). 3D BC/A also has high surface area (80 ± 5 m²/g) and sufficient porosity (88.5 ± 0.4%) compare with 3D BC (surface area: 92.81 ± 2.02 m²/g; porosity 90.42 ± 0.24%). 3D BC/A do support C5.18 cell and hBMSC attachment, proliferation evaluated with SEM, confocal microscopy and cell proliferation assay. Furthermore, 3D/ABC has enhanced mechanical property (ultimate compressive strength: 26.26 ± 4.6 kPa, Young’s modulus: 39.26 ± 5.72 kPa)) than that 3D/BC has (ultimate compressive strength: 7.04 ± 2.34 kPa, Young’s modulus: 10.76 ± 3.52 kPa). Overall, the 3D BC/A scaffold had more potential than 3D BC scaffold for using as a scaffold for tissue engineering and tissue repair applications.     

Preparation and characterization of pore wall‐functionalized three‐dimensionally ordered macroporous syndiotactic polystyrene

A versatile method for the modification of three‐dimensionally ordered macroporous (3DOM) highly syndiotactic polystyrene via chloromethylation at the pore walls has been demonstrated. This was followed by reaction with dimethylamine to establish a versatile approach to functionalization of such macroporous polymers. High syndiotacticity of 3DOM sPS is necessary for maintenance of the morphology of the original ordered pore structure after chloromethylation. The relative content of chloromethyl groups was shown to be 1.89 mmol/g3DOM sPS by TG‐titration. The functionalized 3DOM sPS was characterized by SEM, FT‐IR, and DSC to demonstrate that chloromethylation had occurred at the pore walls and that the dimethylamino moiety had replaced the chlorine atom of the chloromethyl group. DSC examination of the modified polymer indicated that the crystallinity of 3DOM sPS is little affected by functionalization. Thus the excellent properties of sPS are retained by the functionalized material. POLYM. ENG. SCI., 2009. © 2008 Society of Plastics Engineers     

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.