有序介孔炭的合成及液相有机大分子吸附性能研究

分别采用有序介孔氧化硅SBA-15和NaY分子筛为硬模板合成了系列有序介孔炭OMC和微孔炭CFY. N₂静态吸附测试表明, 所合成的介孔炭具有丰富的介孔结构和集中的介孔分布. 以亚甲基蓝为探针分子, 研究其在有序介孔炭OMC和微孔炭CFY上的吸附行为. 研究结果表明, 有序介孔炭中大于3.5 nm的大介孔孔容是决定亚甲基蓝吸附容量和吸附速率的关键因素. 吸附动力学理论研究表明, 准二级动力学方程可以很好地描述亚甲基蓝分子在介孔炭上吸附动力学行为.     

NPE在有序介孔炭上的吸附行为研究

采用有序介孔硅为硬模板制备了具有不同孔径的有序介孔炭(OMCs). 氮气吸附测试表明, 有序介孔炭具有丰富的介孔表面和集中的介孔分布. 以壬基酚聚氧乙烯醚(NPE)为探针分子, 研究了大分子酚类在有序介孔炭上的吸附行为. 吸附研究表明, NPE在有序介孔炭上的吸附满足Langmuir吸附模型. 孔结构分析表明, 大于1.5 nm的孔的表面积是决定NPE吸附量的关键因素, 而有序介孔炭的最可几孔径决定吸附速率的大小. 与吸附量相比, 吸附速率更容易受环境温度的影响. 动力学研究表明, NPE在有序介孔炭上的吸附满足准二级动力学方程.     

Adsorption of bulky molecules of nonylphenol ethoxylate on ordered mesoporous carbons

Ordered mesoporous carbons (OMCs) with varying pore sizes were prepared using ordered mesoporous silica SBA-15 as hard templates. The OMCs possess abundant mesopores with narrow pore size distribution, on which the adsorption behavior of bulky molecules of nonylphenol ethoxylate (NPE) were investigated. The isotherms of NPE on OMCs can be fitted by Langmuir adsorption model, evidenced by the adsorption data. The surface area of the pores larger than 1.5 nm is a crucial factor to the adsorption capacity of NPE, whereas the most probable pore diameter of OMCs is crucial to the adsorption rate of NPE. The adsorption temperature has more significant effects on adsorption rate than the adsorption capacity. Theoretical studies show that the adsorption kinetics of NPE on OMCs can be depicted with the pseudo-second-order kinetic model. In addition, thermodynamic parameters of adsorption were evaluated based on the equilibrium constants related to the equilibrium of adsorption at different temperatures.     

NPE在有序介孔炭上的吸附行为研究

采用有序介孔硅为硬模板制备了具有不同孔径的有序介孔炭(OMCs). 氮气吸附测试表明, 有序介孔炭具有丰富的介孔表面和集中的介孔分布. 以壬基酚聚氧乙烯醚(NPE)为探针分子, 研究了大分子酚类在有序介孔炭上的吸附行为. 吸附研究表明, NPE在有序介孔炭上的吸附满足Langmuir吸附模型. 孔结构分析表明, 大于1.5 nm的孔的表面积是决定NPE吸附量的关键因素, 而有序介孔炭的最可几孔径决定吸附速率的大小. 与吸附量相比, 吸附速率更容易受环境温度的影响. 动力学研究表明, NPE在有序介孔炭上的吸附满足准二级动力学方程.     

孔径渐变的有序介孔炭的合成及电化学应用

以SBA-15为模板,硼酸为孔道扩张剂,蔗糖为碳源制备了一系列孔径渐变的有序硼杂介孔炭材料,并研究了其电化学电容性能。氮气静态吸附测试表明,当硼酸物质的量分数从0%增大到75%时,介孔炭的孔径从3.3nm增大至8.1nm,并保持有序的介孔结构。电化学测试表明,在KOH电解液中,硼杂介孔炭比电容明显高于未掺杂硼有序介孔炭,孔道有序性和孔径大小共同影响了炭材料的电容性能。当硼酸物质的量分数为50%时,炭材料的比电容性能最优。     

Effect of pore packing defects in 2-d ordered mesoporous carbons on ionic transport

Ordered mesoporous materials show great importance in energy, environmental, and chemical engineering. The diffusion of guest species in mesoporous networks plays an important role in these applications, especially for energy storage, such as supercapacitors based on ordered mesoporous carbons (OMCs). The ion diffusion behavior in two different 2-D hexagonal OMCs was investigated by using cyclic voltametry and electrochemical impedance spectroscopy. In addition, transmission electron microscopy, small-angle X-ray diffraction, and nitrogen cryosorption methods were used to study the pore structure variations of these two OMCs. It was found that, for the OMC with defective pore channels (termed as pore packing defects), the gravimetric capacitance was greatly decayed when the voltage scan rate was increased. The experimental results suggest that, for the ion diffusion in 2-D hexagonal OMCs with similar mesopore size distribution, the pore packing defect is a dominant dynamic factor.     

Templated Synthesis of Ordered Mesoporous Carbons with Tailored Structures and Morphologies

Due to the excellent biocompatibility and the capability to load and release drugs, ordered mesoporous carbons (OMCs) have been highly prospective and valuable in drug delivery system. In this contribution, synthesis of OMCs with tailored pore sizes from 4.1 to 3.4 nm was achieved by employing SBA‐15 as template and furfuryl alcohol (FA) as carbon precursors. An array of OMCs with controlled structures and morphologies by incipient wetness with FA was analyzed by powder X‐ray diffraction (XRD), nitrogen adsorption, transmission electron microscopy (TEM), and Raman spectroscopy. The resulting carbon replicas retained the hexagonal symmetry of the silica templates SBA‐15 with p6mm space group, although the framework suffered shrinkage in the replicated process. The pore size distribution, uniformity and pore volume of the mesopores in the OMCs were affected by structural properties of the SBA‐15 templates as shown by N₂ sorption and XRD pattern analysis. The process had the advantage that the textural parameters of the obtained OMCs were tunable simply by varying aging temperature of the silica template and the ratio of carbon precursor.     

Pore size distribution of micelle-templated silicas studied by thermoporosimetry using water and n-heptane

Thermoporosimetry, i.e., DSC measurements of melting point depression of water and heptane confined in mesopores, has been used for determination the pore size distribution of several mesoporous silicas synthesized with the use of micelle templates. Porosity of these materials was additionally characterized by low-temperature nitrogen adsorption and quasi-equilibrated thermodesorption of nonane. The pore size distributions obtained using the water thermoporosimetry were similar to those determined using the other methods, but the pore size values found for the narrow pore materials were underestimated by ca 1?nm. Too large pore sizes obtained for the wide pore silica from heptane thermoporosimetry were attributed to nonlinear dependence of the melting point depression on the reciprocal of the pore size.     

Kinetics of polydopamine film deposition as a function of pH and dopamine concentration: Insights in the polydopamine deposition mechanism

Highly ordered mesoporous carbon functionalized with carboxylate groups and magnetic nanoparticles has been successfully synthesized. By oxidative treatment using (NH(4))(2)S(2)O(8) and H(2)SO(4) mixed solution, numerous hydrophilic groups were created in the mesopores without destroying the ordered mesostructure of CMK-3. Through the in situ reduction in Fe(3+), magnetic nanoparticles were successfully introduced into the mesopores, resulting in the multifunctional mesoporous carbon Fe-CMK-3. The obtained hybrid carbon material possesses ordered mesostructure, high Brunauer-Emmett-Teller (BET) surface area up to 1013 m(2)/g, large pore volume of about 1.16 cm(3)/g, carboxylic surface, and excellent magnetic property. When used as an adsorbent, Fe-CMK-3 exhibits excellent performances for removing toxic organic compounds from waster-water, with a high adsorption capacity, an extremely rapid adsorption rate, and an easy magnetically separable process. In the case of requiring emergency removal of large amount of organic pollutants in aqueous, the hybrid carbon adsorbent would be an ideal choice.     

Engineering macroporous composite materials using competitive adsorption in particle-stabilized foams

Slow crystallization and growth rate at room temperature in the presence of surfactant micelles is a new strategy used to synthesize hierarchical Na-A zeolites. The observed structure of the hierarchical materials was consistent with a two stage growth mechanism. During the early stage of the gel evolution, miniature zeolite gel particles were formed and assembled around surfactant (cetyltrimethylammonium bromide - CTAB) micelles. In a second stage, the slow mass transformation into crystalline phase and the low growth rate of the formed crystallites retained the CTAB micelles within the crystallization domain. After the removal of CTAB templates, the products showed large mesopores which were attributed to the interstitial voids between the aggregated zeolite nanocrystallites. The size of the mesopores can be further expanded by using linear hydrocarbons as swelling agents. The influences of the added amount of the hydrocarbons and the length of the hydrocarbon chains on the mesopore size were examined. The effects of the aging period and the concentration of CTAB in the synthesis mixture on the pore size distribution were also investigated. The colloidal suspension of the synthesized zeolite showed negative zeta potential throughout the entire range of pH. The mesoporous Na-A zeolite synthesized in this work showed higher ethylene adsorption capacity as compared to the conventional microporous Na-A zeolite. XRD, DLS, SEM, N(2) adsorption-desorption at 77K, TEM, (29)Si NMR and FTIR techniques were used to characterize the hierarchical Na-A zeolite.     

Synthesis of mesoporous carbons using ordered and disordered mesoporous silica templates and polyacrylonitrile as carbon precursor

Mesoporous carbons were synthesized from polyacrylonitrile (PAN) using ordered and disordered mesoporous silica templates and were characterized using transmission electron microscopy (TEM), powder X-ray diffraction, nitrogen adsorption, and thermogravimetry. The pores of the silica templates were infiltrated with carbon precursor (PAN) via polymerization of acrylonitrile from initiation sites chemically bonded to the silica surface. This polymerization method is expected to allow for a uniform filling of the template with PAN and to minimize the introduction of nontemplated PAN, thus mitigating the formation of nontemplated carbon. PAN was stabilized by heating to 573 K under air and carbonized under N2 at 1073 K. The resulting carbons exhibited high total pore volumes (1.5-1.8 cm3 g(-1)), with a primary contribution of the mesopore volume and with relatively low microporosity. The carbons synthesized using mesoporous templates with a 2-dimensional hexagonal structure (SBA-15 silica) and a face-centered cubic structure (FDU-1 silica) exhibited narrow pore size distributions (PSDs), whereas the carbon synthesized using disordered silica gel template had broader PSD. TEM showed that the SBA-15-templated carbon was composed of arrays of long, straight, or curved nanorods aligned in 2-D hexagonal arrays. The carbon replica of FDU-1 silica appeared to be composed of ordered arrays of spheres. XRD provided evidence of some degree of ordering of graphene sheets in the carbon frameworks. Elemental analysis showed that the carbons contain an appreciable amount of nitrogen. The use of our novel infiltration method and PAN as a carbon precursor allowed us to obtain ordered mesoporous carbons (OMCs) with (i) very high mesopore volume, (ii) low microporosity, (iii) low secondary mesoporosity, (iv) large pore diameter (8-12 nm), and (v) semi-graphitic framework, which represent a desirable combination of features that has not been realized before for OMCs.     

Electrochemical Oxidation and Detection of Morphine at Ordered Mesoporous Carbon Modified Glassy Carbon Electrodes

In this work, three ordered mesoporous carbons (OMCs) with different structural parameters were synthesized by a simple variation of the hydrothermal temperature of the silica templates (SBA‐15). X‐ray diffraction and nitrogen adsorption‐desorption results show these OMCs exhibit an ordered 2D hexagonal mesostructure with tunable pore diameter. OMC‐modified glassy carbon electrodes exhibit efficient electrocatalytic reactivity toward oxidation of morphine (MO). The amperometric detection of MO in pH 7.0 phosphate buffered saline at +0.39 V versus Ag/AgCl is the lowest potential reported to‐date. A linear range from 0.2 to 197.6 μM and a detection limit of 0.03 μM MO were obtained.     

Protein adsorption on the mesoporous molecular sieve silicate SBA-15: effects of pH and pore size

A mesoporous molecular sieve silicate, SBA-15, with three pore sizes (38.1 A, 77.3 A, and 240 A) has been synthesized using a non-ionic, tri-block copolymer as a template in a sol-gel method. The effects of synthesis conditions on the pore size and pore-size distribution of this adsorbent have been described. The adsorption of proteins on these crystalline, ordered, materials has been studied. The kinetics of adsorption and equilibrium capacity have been probed with three proteins of different dimensions. The effects of electrostatic interactions and protein size are illustrated. It has been shown that SBA-15 materials can be tailored to show size selectivity for proteins, and very high capacities (450 mg/g) can be obtained. Furthermore, the rates of adsorption are shown to be dependent on the pore size, protein structure and solution pH.     

Organic acid-assisted soft-templating synthesis of ordered mesoporous carbons

A series of soft-templated ordered mesoporous carbons (OMCs) was synthesized by using resorcinol and formaldehyde as carbon precursors, triblock copolymer Pluronic F127 as a soft-template, and an organic acid (acetic, benzoic, citric, oxalic, or succinic) as a polymerization reaction catalyst. The aforementioned organic acids were strong enough to facilitate the formation of ordered mesophases by the block copolymer template used and to catalyze the polymerization reaction of resorcinol and formaldehyde in this template. The use of weak organic acids instead of strong inorganic acids such as HCl eliminated inorganic anions from the reaction environment and resulted in high surface area OMCs. Basically, the resulting carbons showed the surface areas and pore volumes comparable to those reported for the carbons prepared under similar conditions but in the presence of strong inorganic acids. Electron microscopy analysis proved the presence of ordered mesopores, whereas thermogravimetric analysis showed a good thermal stability of these carbons.     

孔道三维相互连通锐钛矿TiO2-SiO2纳米复合介孔材料的制备及其高光催化活性

本文报道一种孔道三维相互连通锐钛矿TiO2-SiO2纳米复合介孔材料的制备.该介孔材料是以两维六方有序结构、直孔道、锐钛矿70TiO2-30SiO2-950纳米复合介孔材料(于950oC晶化2 h)为前驱体, NaOH为SiO2的刻蚀剂,通过“在孔壁内造孔”的方法获得.我们的策略是采用温和的造孔条件,如稀NaOH溶液,合适的温度与固/液比等.采用X射线衍射(XRD),透射电镜(TEM)和低温N2吸附等技术对样品的介孔结构进行了系统表征.结果表明,墙内孔的密度非常高,孔径均一(平均尺寸3.6 nm),且在三维网络高度连通原孔道,但介孔结构仍保持其完整性.锐钛矿纳米晶粒的结晶度和大小在墙内造孔前后基本保持不变.该材料光催化降解罗丹明B(0.303 min–1)与亚甲基蓝(0.757 min–1)的活性相当高,此活性分别是其母体材料的5.1和5.3倍,甚至是Degussa P25光催化剂的16.5和24.1倍.这充分表明三维连通孔道结构对活性的大幅提高起了关键作用.孔道三维连通式锐钛矿TiO2-SiO2纳米复合介孔材料对上述污染物展现出意想不到的高降解活性,显著高于迄今已报道的金属氧化物基介孔材料对上述污染物的降解活性.更重要的是,该光催化剂具有相当高的稳定性和重复使用性.相信,本方法将为具有超高性能的孔道三维相互连通其它金属氧化物基介孔材料的制备铺平了道路.
　　小角XRD结果表明,母体材料的孔道是两维六方有序结构,在孔壁内造孔之后,样品原有的介孔结构仍保持其规整性.宽角XRD结果显示,二氧化钛的晶相是锐钛矿,晶粒尺寸为10.8 nm.造新孔之后,锐钛矿纳米晶粒的结晶度和大小与母体样品的相比变化不大. TEM结果显示,母体样品的孔壁内没有孔.孔道是两维六方有序排列的直孔道,孔径大小均一(平均尺寸4.1 nm).高分辨透射电镜(TEM)观察揭示,锐钛矿纳米晶粒(平均大小11.3 nm)在孔壁内随机排列,并与无定形SiO2纳米颗粒相互连接,相间共存,形成类似“砖块?水泥砂浆”砌成的孔壁,这种独特的复合骨架结构赋予其很高的稳定性.当一些SiO2纳米颗粒被去除之后, TEM观察显示,孔壁内有密集分布的孔,这些孔取向随机,并在三维方向连通原孔道,但介孔骨架结构仍保持其完整性.墙内孔的大小范围很窄(3.1?4.3 nm),平均大小为3.6 nm.高分辨TEM观察显示,锐钛矿晶粒大小与母体材料内的相比基本未变.上述结果与XRD结果一致.低温N2吸附表征结果显示,母体样品内只有一种孔道,孔径为4.0 nm.去除部分SiO2后的样品内有两种孔道,孔径分别是3.4和4.1 nm.这些结果与TEM的观察吻合.罗丹明B与亚甲基蓝在造孔前后样品内扩散速率评价结果显示,其在三维连通孔道内的扩散速率很高,大约是其母体材料内的5倍以上.这表明相互连通的孔道网络结构非常有利于客体分子在其内扩散.光催化降解性能评价结果显示,罗丹明B与亚甲基蓝在相互连通孔道内降解的速率相当高,分别是其在不连通孔道内的5.1和5.3倍.这充分证明孔道三维相互连通对活性的大幅提高起了关键作用.我们对材料的稳定性和重复使用性作了评价,经过10次循环使用孔道三维相互连通锐钛矿TiO2-SiO2纳米复合介孔材料,其吸附与光催化降解罗丹明B的性能变化不大.这充分证明本文制备的孔道连通复合介孔材料的性能是相当稳定的和可重复使用的.该方法可用于制备具有超高性能的孔道三维相互连通其它金属氧化物基介孔材料,如Nb2O5, Ta2O5等.     

ZSM-5 monolith of uniform mesoporous channels

A ZSM-5 monolith of uniform mesopores(meso-ZSM-5) was synthesized with the template method using carbon aerogel of uniform mesopores of great pore volume. The pore size distribution determined by N2 adsorption showed the presence of mesopores with an average pore width of 11 nm and micropores with an average pore width of 0.51 nm. Field emission scanning electron micrograph observation revealed the presence of uniform mesopores. X-ray diffraction and FT-IR provided evidence that the synthesized meso-ZSM-5 monolith has a highly crystalline ZSM-5 structure.     

介孔二氧化钛的合成及其对甲基橙降解的光催化活性

以十六烷基三甲基溴化铵为模板剂,通过水解钛酸正丁酯合成了介孔二氧化钛分子筛,探讨了合成条件的影响。采用X射线粉末衍射(XRD)、红外光谱(FT-IR)、透射电子显微镜(TEM)和N2吸附-脱附等技术对介孔二氧化钛的晶相、结构、形貌、比表面积和孔径分布进行了表征。实验结果表明:得到的介孔二氧化钛分子筛的孔径为4-4.3nm,用抽提的方法去除模板剂得到的介孔二氧化钛的比表面积比焙烧的要高。以甲基橙为模型污染物,检验了所合成介孔二氧化钛的光催化性质。     

Synthesis of large-pore SBA-15 silica using poly(ethylene oxide)-poly(methyl acrylate) diblock copolymers

Poly(ethylene oxide)-poly(methyl acrylate) diblock copolymers with narrow molecular weight distributions were synthesized using atom transfer radical polymerization. The copolymers were used as micellar templates for the synthesis of mesoporous silicas. The products were characterized using small-angle X-ray scattering, transmission electron microscopy (TEM) and nitrogen adsorption. The obtained silicas exhibited two-dimensional hexagonal structures of cylindrical mesopores, and thus can be classified as SBA-15 silicas. In some cases, the size of ordered domains was very small. The (100) interplanar spacings were 13–17 nm, depending on the size of the diblock copolymer used and on the synthesis conditions. Nitrogen adsorption showed that the silicas exhibited specific surface areas of 350–800 m² g⁻¹, pore volumes ∼1 cm³ g⁻¹, and narrow pore size distributions. The BJH (nominal) pore diameters were up to ∼20 nm, but actual diameters of cylindrical pores are expected to be somewhat smaller. In many cases, the mesopores exhibited constrictions.     

介孔C/SiO2粉体的制备及对阳离子型染料的吸附

采用吸附法处理染料废水需要合适的吸附剂。利用溶剂蒸发自组装法,以甲阶酚醛树脂为碳源、介孔SiO2粉体为载体制备介孔C/SiO2粉体,表征所制C/SiO2粉体的结构,研究C/SiO2粉体对阳离子型染料亚甲基蓝和阳离子红X-GRL的吸附性能,并与相同条件下制备的非负载的多孔C粉体以及介孔SiO2载体进行比较。结果表明,介孔C/SiO2粉体的孔窗口为11~18 nm,比表面积为303 m2.g-1,比孔容为1.11 cm3.g-1;C/SiO2粉体对这两种染料吸附量均高于C粉体和SiO2载体;在pH≤10的范围内,吸附量随pH值增大而显著提高。     

Post-treatment and characterization of novel luminescent hybrid bimodal mesoporous silicas

A novel luminescent hybrid bimodal mesoporous silicas (LHBMS) were synthesized via grafting 1,8-Naphthalic anhydride into the pore channels of bimodal mesoporous silicas (BMMs) for the first time. The resulting samples were characterized by powder X-ray diffraction (XRD), N₂ adsorption/desorption measurement, Fourier transform infrared spectroscopy (FT-IR), Transmission electron microscopy (TEM), UV-vis absorption spectroscopy, and Photoluminescence spectroscopy (PL). The results show that 1,8-Naphthalic anhydride organic groups have been successfully introduced into the mesopores of the BMMs and the hybrid silicas are of bimodal mesoporous structure with the ordered small mesopores of around 3 nm and the large mesopores of uniform intra-nanoparticle. The excellent photoluminescent performance of LHBMS has a blue shift compared to that of 2-[3-(triethoxysilyl) propyl-1 H-Benz [de]isoquinoline-1, 3(2 H)-dione, suggesting the existence of the quantum confinement effectiveness.