One-step solvothermal synthesis of N-doped TiO2 nanoparticles with high photocatalytic activity in the reduction of aqueous Cr（Ⅵ）

N-doped TiO2 （N-TiO2） nanoparticles were synthesized via a one-step low temperature （180℃） solvothermal route, which adopted NH4NO3 as the nitrogen source. The structure, composition, BET specific surface area, and optical properties of the as-synthesized product were characterized by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, N2 adsorption- desorption isotherms, and UV-vis diffuse reflectance spectroscopy. In addition, its photocatalytic properties were tested by the reduction of aqueous Cr（VI） under UV and visible light （x 〉 420 rim） irradiation. It was observed that for the reduction of aqueous Cr（VI）, the as-synthesized N-TiO2 nanoparticles not only exhibited much higher photocatalytic activity than P25 TiO2 under UV light, but also exhibited remarkably high photocatalytic activity under visible light （λ 〉 420 nm）.     

Preparation of mesostructured barium sulfate with high surface area by dispersion method and its characterization

The spherical and cubic mesoporous BaSO(4) particles with high surface area were successfully produced via one-step process through precipitation reaction in aqueous solution of Ba(OH)(2) and H(2)SO(4) with ethylene glycol (n-HOCH(2)CH(2)OH) as a modifying agent. The BaSO(4) nanomaterial revealed that the high surface area and the mesoporous was stable up to 400 degrees C. Agglomerate mesoporous barium sulfate nanomaterials were obtained by the reaction of Ba(2+) and SO(2-)(4) with ethylene glycol aqueous solution. The ethylene glycol was used to control the BaSO(4) particle size and to modify the surface property of the particles produced from the precipitation. The dried and calcined mesoporous BaSO(4) nanomaterials were characterized by X-ray diffraction (XRD), BET surface area and N(2) adsorption-desorption isotherm, scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared resonance (FTIR) and thermogravimetric analysis (TGA). The as-prepared mesoporous dried BaSO(4) possesses a high BET surface area of 91.56 m(2) g(-1), pore volume of 0.188 cm(3) g(-1) (P/P(0)=0.9849) and pore size of 8.22 nm. The SEM indicates that the morphology of BaSO(4) nanomaterial shows shell like particles up to 400 degrees C, after that there is drastically change in the material due to agglomeration. Synthesis of mesoporous BaSO(4) nanomaterial is of significant importance for both sulphuric acid decomposition and oxidation of methane to methanol.     

Self assembled 12-tungstophosphoric acid-silica mesoporous nanocomposites as proton exchange membranes for direct alcohol fuel cells

A highly ordered inorganic electrolyte based on 12-tungstophosphoric acid (H(3)PW(12)O(40), abbreviated as HPW or PWA)-silica mesoporous nanocomposite was synthesized through a facile one-step self-assembly between the positively charged silica precursor and negatively charged PW(12)O(40)(3-) species. The self-assembled HPW-silica nanocomposites were characterized by small-angle XRD, TEM, nitrogen adsorption-desorption isotherms, ion exchange capacity, proton conductivity and solid-state (31)P NMR. The results show that highly ordered and uniform nanoarrays with long-range order are formed when the HPW content in the nanocomposites is equal to or lower than 25 wt%. The mesoporous structures/textures were clearly presented, with nanochannels of 3.2-3.5 nm in diameter. The (31)P NMR results indicates that there are (≡SiOH(2)(+))(H(2)PW(12)O(40)(-)) species in the HPW-silica nanocomposites. A HPW-silica (25/75 w/o) nanocomposite gave an activation energy of 13.0 kJ mol(-1) and proton conductivity of 0.076 S cm(-1) at 100 °C and 100 RH%, and an activation energy of 26.1 kJ mol(-1) and proton conductivity of 0.05 S cm(-1) at 200 °C with no external humidification. A fuel cell based on a 165 μm thick HPW-silica nanocomposite membrane achieved a maximum power output of 128.5 and 112.0 mW cm(-2) for methanol and ethanol fuels, respectively, at 200 °C. The high proton conductivity and good performance demonstrate the excellent water retention capability and great potential of the highly ordered HPW-silica mesoporous nanocomposites as high-temperature proton exchange membranes for direct alcohol fuel cells (DAFCs).     

Preparation of ordered mesoporous SiC from preceramic polymer templated by nanoporous silica

Highly ordered mesoporous SiC materials were prepared by infiltrating viscous liquid preceramic polymer, allylhydridopolycarbosilane, into two types of surface modified nanoporous silica templates: mesoporous silica SBA-15 and mesocellular siliceous foam. The silica templates were subsequently etched off after pyrolysis at 1000 degrees C under nitrogen atmosphere with the resultant formation of ordered mesoporous structures. The mesoporous SiC materials, synthesized from both types of templates possessed high Brunauer-Emmett-Teller (BET) surface areas in the range of 250-260 m(2)/g with pore sizes of 3.4-3.6 nm. The ordered structures of mesoporous SiC were exact inverse replicas of their respective silica templates, as characterized by small angle X-ray diffraction (XRD), transmission electron microscope (TEM) images, and the adsorption-desorption isotherm of nitrogen.     

苯基磺酸官能化中孔硅基材料的制备及催化性能研究

通过溶胶-凝胶法制得了苯基聚硅氧烷, 进一步磺化制备了苯基磺酸官能化的中孔硅基催化材料, 并通过BET, SEM和固体核磁技术对其进行了表征. BET结果表明, 该催化剂比表面积为722 m²/g, 平均孔径为9.06 nm, 孔容0.59 mL/g. ¹³C CPMAS NMR和²⁹Si CPMAS NMR表征显示磺酸基键合于苯环间位, 苯基以共价方式进入无机-有机杂化硅基材料的内部结构. 该固体酸的活性中心磺酸基在表面呈均匀分布, 在芳族羧酸和取代酚的直接酯化反应中表现出优异的催化性能.     

功能化有序介孔碳对重金属离子Cu(II)、Cr(VI)的选择性吸附行为

以三嵌段共聚物F127为模板剂, 酚醛树脂为碳源, 正硅酸乙酯为硅源, 三组分共组装合成介孔碳?氧化 硅纳米复合物, 再经HF去除氧化硅, 得到有序介孔碳(OMC). X射线衍射(XRD)、透射电子显微镜(TEM)、低温 N2吸脱附(BET)等测试表明, 所得样品具有高度有序的介孔结构, 比表面积和孔容分别为1330 m²·g^-1和2.13 cm³·g^-1, 平均孔径6.4 nm. 对其先氧化、后氯化、再胺化, 得到不同胺基接枝量的胺化介孔碳(C-NH₂(m), m为加入的乙二胺的质量(g)). 傅里叶变换红外(FT-IR)光谱表征结果证实, 胺基官能团成功接枝到有序介孔碳表面.TEM测试表明介孔碳的有序孔道结构得到了较好的保持. 以有序介孔碳、胺化介孔碳作吸附剂对Cu(II)、Cr(VI)进行选择性吸附研究. 结果表明: 功能化修饰前, 样品对Cu(II)、Cr(VI)饱和吸附量分别为213.33、241.55 mg·g^-1; 修饰后饱和吸附量可分别达到495.05、68.21 mg·g^-1. 功能化介孔碳表现了较强的选择性吸附Cu(II)的能力.     

Cr或V掺杂的HMS在甲酸溶液中的光催化产氢性能研究

本文以过渡金属离子M(M代表Cr或V)掺杂为改性手段,通过改变掺杂量,合成了一系列分子筛光催化剂M(x)-HMS(x代表M/Si摩尔投料比)。用X-射线荧光光谱(XRF)、低温 N2 吸附-脱附、X-射线衍射(XRD)和紫外-可见吸收漫反射光谱(UV-vis)对M(x)-HMS进行了表征和分析。以高压汞灯为光源,以甲酸分解产氢为探针反应,研究了M(x)-HMS的光催化性能,发现Cr(x)-HMS和V(x)-HMS的产氢速率随组成变化呈双峰规律(均在x＝0.01和0.05时出现两个极大值),并从光催化剂的组成和结构角度给予了解释。以过渡金属离子M (M代表Cr或V)掺杂为改性手段, 通过改变掺杂量, 合成了一系列分子筛光催化剂M(x)-HMS (x代表M/Si投料摩尔比). 用X射线荧光光谱(XRF)、低温N₂吸附-脱附、X射线衍射(XRD)、紫外-可见吸收漫反射光谱(UV-vis)、高分辨透射电子显微镜(HRTEM)和X射线能量散射谱(EDXS)对M(x)-HMS进行了表征和分析. 以高压汞灯为光源, 以甲酸分解产氢为探针反应, 研究了M(x)-HMS的光催化性能, 发现Cr(x)-HMS和V(x)-HMS的产氢速率随组成变化呈双峰规律(均在x＝0.01和0.05时出现两个极大值), 并从光催化剂的组成和结构角度给予了解释.     

二元阴阳离子表面活性剂法合成介孔氧化硅囊泡

以十二烷基磺酸钠(SDS)和十六烷基三甲基溴化铵(CTAB)为表面活性剂, 在SDS与CTAB的摩尔比为1.0~2.3时, 以正硅酸乙酯(TEOS)为硅源, 在氨水-水体系中于68℃下合成介孔氧化硅囊泡. 通过透射电子显微镜(TEM)、 X射线衍射仪(XRD)、 热重分析仪(TGA)和氮气吸附-脱附实验仪对合成的产物进行表征. 结果表明, 合成的产物为介孔氧化硅囊泡聚集体, 孔径约为4 nm, 样品的Brunauer-Emmett-Teller(BET)比表面积为826 m²/g. 对介孔氧化硅囊泡的形成机理做了初步探讨.     

Synthesis of Mesostructured Iron Oxides with Potential As(V) Adsorption Application

Mesostructured iron oxides(MIOs) were nanocasted from a plugged hexagonal templated silica(PHTS) with a Brunauer-Emmett-Teller(BET) surface area of 694 m²/g. Results of X-ray diffraction(XRD), transmission electron microscopy(TEM) and N₂ adsorption-desorption suggest that the nanocasted MIOs are synthetic hematite(α-Fe₂O₃) with a wormhole-like mesoporous network. As(V) adsorption test shows that the selected MIO—MIO-500(calcinated at 500℃) with a BET surface area of 82 m²/g has a maximum adsorption capacity of 5.39 mg/g for As(V), which is 2.5 times as large as that of natural hematite adsorbent. The study suggests that MIOs could be potentially used as the adsorbent of As(V) in wastewater.     

以MCM-22为原料合成高水热稳定性的介孔材料

以合成的微孔分子筛MCM-22为原料,将其与表面活性剂及氢氧化钠一起回流溶解,再调节溶液的pH值至7～9, 使MCM-22转化为高水热稳定性的介孔材料. 所得介孔材料具有蠕虫状的均匀孔道,骨架中不含有MCM-22的微观结构单元. 该介孔材料至少含有18%的表面活性剂,经823 K焙烧脱除表面活性剂后,其孔径为2 2 nm, 比表面积为 1 038 m2/g, 孔容为0 97 cm3/g. 焙烧后的介孔材料具有非常高的水热稳定性,经沸水回流100 h后其比表面积为896 m2/g, 孔容为0 90 cm3/g, 孔径为2 1 nm, 即使经过300 h的回流,该材料仍能保持698 m2/g的比表面积和0 90 cm3/g的孔容. 固体 29Si MAS NMR结果表明,该介孔材料的高水热稳定性与其高表面缩合度有关.     

Evaluation of microstructures and properties of bulk mesoporous silica

Synthesis of mesoporous MCM-type bulks prepared by hydrothermal hot-pressing (HHP) method using MCM-type mesoporous powder was attempted. Scanning electron microscopy (SEM), bulk density measurement, N₂ adsorption-desorption isotherms and formaldehyde adsorption test have been employed to characterize the bulky products. As a result, we succeeded in preparing a dense and strong mesoporous bulks with high BET over 1000 m²/g through the hydrothermal hot-pressing method under appropriate conditions.     

放射孔二氧化硅及其核壳结构的制备与表征

室温下以十六烷基三甲基溴化铵(CTAB)为模板剂, 正硅酸乙酯(TEOS)为硅源, 氨水(质量分数25%)为催化剂, 在水-乙醇-乙醚作共溶剂的体系中以氨基化的实心二氧化硅(NH₂-sSiO₂)为添加剂, 制备了放射孔二氧化硅及其核壳结构(sSiO₂@rSiO₂). 通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)、小角X射线衍射(XRD)、氮气吸附-脱附实验和孔径分布测定对其进行了表征和分析. 结果表明, 合成的产物为0.4~1 μm的球形粒子, 球上存在多级放射状孔道结构, 孔径从3 nm到几十纳米的多级孔径并存, 样品的Brunauer-Emmett-Teller(BET)比表面积为996 m²/g. 最后对放射孔二氧化硅的形成机理及核壳结构的影响因素进行了初步探讨.     

高温水热合成具有超低介电常数的规则介孔氧化硅材料

分别以高分子三嵌段共聚物P123(PEO₂₀-PPO₇₀-PEO₂₀)和F127(PEO₁₀₆-PPO₇₀-PEO₁₀₆)为模板剂, 通过高温水热法制备了具有超低介电常数的规则介孔氧化硅材料(OMSs). 当合成温度达到200℃时, 得到的产物仍可保持规则的介孔结构. X射线衍射和氮气吸附结果表明, OMSs系列材料具有规则的二维六方或体心立方介孔结构、 大的比表面积和孔容及均一的孔径分布. ²⁹Si MAS NMR分析表明, OMSs与低温(100℃)合成产物相比具有更高的骨架缩合度, 从而具有优异的水热稳定性. 由于具有大的孔容和高的骨架缩合度, OMSs表现出了超低的介电常数. 以P123为模板剂, 200℃下合成的OMS的介电常数可达1.31. OMSs作为一类稳定的超低介电常数材料, 对于绝缘材料的发展具有潜在的应用价值.     

Synthesis of carbon-coated, porous and water-dispersive Fe3O4 nanocapsules and their excellent performance for heavy metal removal applications

Porous Fe(3)O(4)@C nanocapsules with a diameter of about 120 nm (about 50 nm cavity) were synthesized by combining a sacrificial template method with solvothermal treatment. The N(2) adsorption-desorption isotherms reveals their mesoporous structure and large BET surface area (159.8 m(2) g(-1)). The magnetic investigation indicates their superparamagnetic nature and high saturation magnetization (55.93 emu g(-1)). The nanocapsules also exhibit negative zeta potential (-27.59 mV) and possess carboxyl groups on the outer carbon layer, which keeps them highly dispersive in aqueous solution and provides a chelating function for metal ions. The heavy metals removal test demonstrates the excellent affinity of nanocapsules, the high efficiency for different metals (>90%), 79 mg g(-1) adsorption capacity for Pb(2+) and ultrafast removal process (Pb(2+), 99.57% within 1 minute). Protected by a porous carbon layer, the nanocapsules display excellent acidic resistance and adsorption properties even in an acidic solution (pH = 3). Moreover, the metal ions can be easily adsorbed and desorbed through manipulating the pH value for adsorbent regeneration and heavy metal recycling.     

氧化钨介孔材料的制备与表征

以介孔二氧化硅(KIT-6)为硬模板, 硅钨酸为钨源, 用硬模板法制备WO3-SiO2复合材料, 再利用HF除去二氧化硅, 得到了介孔三氧化钨材料. 用X射线衍射(XRD)、能量扩散X射线(EDX)、高分辨透射电镜(HRTEM)、N2吸附-脱附等表征手段, 对制备复合材料的物料比、煅烧温度以及不同分散剂等条件进行了考察. 结果表明, 硅钨酸与硅介孔的物料比(m(WO3)/m(SiO2))在3:1到4:1之间, 在600-750 ℃下煅烧, 能制备结构较好的介孔氧化钨. 乙醇和蒸馏水为分散剂时, 用乙醇为分散剂所得的介孔WO3材料具有更高的比表面积和孔体积.     

Three-dimensional low symmetry mesoporous silica structures templated from tetra-headgroup rigid bolaform quaternary ammonium surfactant

Two kinds of highly ordered mesoporous silica materials (FDU-11, FDU-13) with novel three-dimensional (3-D) tetragonal and orthorhombic structures were synthesized by using tetra-headgroup rigid bolaform quaternary ammonium surfactant [(CH(3))(3)NCH(2)CH(2)CH(2)N(CH(3))(2)CH(2)(CH(2))(11)OC(6)H(4)C(6)H(4)O(CH(2))(11)CH(2)N(CH(3))(2)CH(2)CH(2)CH(2)N(CH(3))(3).4Br] (C(3-12-12)(-)(3)) as a template under alkaline conditions. High-resolution transmission electron microscopy (HRTEM), small-angle X-ray scattering (SAXS), and X-ray diffraction (XRD) show that mesoporous silica FDU-11 has primitive tetragonal P4/mmm structure with cell parameters a = b = 8.46 nm, c = 5.22 nm, and c/a ratio = 0.617. N(2) sorption isotherms show that calcined FDU-11 has a high BET surface area of approximately 1490 m(2)/g, a uniform pore size of approximately 2.72 nm, and a pore volume of approximately 1.88 cm(3)/g. Mesoporous silica FDU-13 has primitive orthorhombic Pmmm structure. The cell parameters are a = 9.81, b = 5.67, and c = 3.66 nm. N(2) sorption isotherms show that calcined FDU-13 has a high BET surface area of 1210 m(2)/g, a uniform mesopore size of approximately 1.76 nm, and a large pore volume of approximately 1.83 cm(3)/g. Such low symmetries for 3-D mesostructures (tetragonal and orthorhombic system) have not been observed before even in amphiphilic liquid crystals, which maybe resulted from an oblate aggregation of the bolaform surfactant and its strong electrostatic interaction with inorganic precursor. A probable mechanism has been proposed for the formation of such a 3-D low symmetrical mesostructure. These results will further extend the synthesis of mesoporous materials and may open up new opportunities for their new applications in catalysis, separation, and nanoscience.     

Synthesis of ordered mesoporous silica membrane on inorganic hollow fiber

This paper reports on a new method for the preparation of mesoporous silica membranes on alumina hollow fibers. A surfactant-silica sol is filled in the lumen of an alpha-alumina hollow fiber. The filtration technique combined with an evaporation-induced self-assembly (EISA) process results in the formation of a continuous ordered mesoporous silica layer on the outer side of alpha-alumina hollow fibers. X-ray diffraction (XRD), transmission electron microscopy (TEM), and nitrogen isothermal adsorption measurements reveal that these membranes possess hexagonal (P6mm) mesostructures with pore diameters of 4.48 nm and BET surfaces of 492.3 m(2) g(-1). Scanning electron microscopy (SEM) studies show that the layers are defect free and energy-dispersive spectroscopy (EDS) mapping images further confirm the formation of continuous mesoporous silica layer on the outer side of alpha-alumina hollow fibers. Nitrogen and hydrogen permeance tests show that the membranes are defect free.     

Green preparation of hollow mesoporous silica nanosphere inside-loaded gold nanoparticles and the catalytic activity

In this work, an active nano-catalyst with gold nanoparticles loaded in hollow mesoporous silica nanospheres (HMSNs/Au) was prepared by a one-pot sol-gel method, in which gold ions were loaded in hollow mesoporous silica spheres followed by sodium alginate reduction. The characterization of the HMSNs/Au were determined by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), N₂ adsorption–desorption isotherms (BET). The high catalytic activity of HMSNs/Au, denoted as apparent turn-over frequency (TOF), was detected by UV-Vis spectrophotometer for the catalytic reduction of 4-nitrophenol (74.5 h^?1) and 2-nitrophenol (108.7 h^?1) in the presence of sodium borohydride solution due to the small gold nanoparticles size and overall exposure of active sites. It is expected that this ecofriendly approach to prepare inorganic composited nanoparticles as high active catalysts based on hollow mesoporous materials was a promising platform for loading noble metal nanoparticles.     

High performance of phosphonate-functionalized mesoporous silica for U(VI) sorption from aqueous solution

The renaissance of nuclear energy promotes increasing basic research on the separation and enrichment of nuclear fuel associated radionuclides. Herein, we report the first study for developing mesoporous silica functionalized with phosphonate (NP10) as a sorbent for U(VI) sorption from aqueous solution. The mesoporous silica was synthesized by co-condensation of diethylphosphatoethyltriethoxysilane (DPTS) and tetraethoxysilane (TEOS), using cationic surfactant cetyltrimethylammonium bromide (CTAB) as the template. The synthesized silica nanoparticles were observed to possess a mesoporous structure with a uniform pore diameter of 2.7 nm, and to have good stability and high efficiency for U(VI) sorption from aqueous solution. A maximum sorption capacity of 303 mg g(-1) and fast equilibrium time of 30 min were achieved under near neutral conditions at room temperature. The adsorbed U(VI) can be easily desorbed by using 0.1 mol L(-1) HNO(3), and the reclaimed mesoporous silica can be reused with no decrease of sorption capacity. In addition, the preconcentration of U(VI) from a 100 mL aqueous solution using the functionalized mesoporous silica was also studied. The preconcentration factor was found to be as high as 100, suggesting the vast opportunities of this kind of mesoporous silica for the solid-phase extraction and enrichment of U(VI).     

A Novel,Efficient and Facile Method for the Template Removal from Mesoporous Materials

A new catalytic-oxidation method was adopted to remove the templates from SBA-1 5 and MCM-4 1 me- soporous materials via Fenton-like techniques under microwave irradiation. The mesoporous silica materials were treated with different Fenton agents based on the template＇s property and textural property. The samples were cha- racterized by powder X-ray diffraction（XRD） measurement, N2 adsorption-desorption isotherms, infrared spectro- scopy, 29Si MAS NMR and thermo gravimetric analysis（TGA）. The results reveal that this is an efficient and facile approach to the thorough template-removal from mesoporous silica materials, as well as to offering products with more stable structures, higher BET surface areas, larger pore volumes and larger quantity of silanol groups.