Exploration of molecular dynamics during transient sorption of fluids in mesoporous materials

In recent years, considerable progress has been made in the development of novel porous materials with controlled architectures and pore sizes in the mesoporous range. An important feature of these materials is the phenomenon of adsorption hysteresis: for certain ranges of applied pressure, the amount of a molecular species adsorbed by the mesoporous host is higher on desorption than on adsorption, indicating a failure of the system to equilibrate. Although this phenomenon has been known for over a century, the underlying internal dynamics responsible for the hysteresis remain poorly understood. Here we present a combined experimental and theoretical study in which microscopic and macroscopic aspects of the relaxation dynamics associated with hysteresis are quantified by direct measurement and computer simulations of molecular models. Using nuclear magnetic resonance techniques and Vycor porous glass as a model mesoporous system, we have explored the relationship between molecular self-diffusion and global uptake dynamics. For states outside the hysteresis region, the relaxation process is found to be essentially diffusive in character; within the hysteresis region, the dynamics slow down dramatically and, at long times, are dominated by activated rearrangement of the adsorbate density within the host material.     

络合水热法合成介孔SnO2简

二氧化锡（SnO2）作为一种n型宽禁带半导体氧化物材料,广泛用于有机物催化、固态电子器件和锂离子电池电极材料领域。介孔SnO2具有较大的比表面积和纳米级有序孔道,与周围介质之间存在更强的相互作用力,可提高其在气敏传感器、催化反应中的应用效率。本文以SnCl4·5H2O为锡源,P123为模板剂,采用络合水热法合成了具有金红石结构的介孔二氧化锡,并考察了pH值、表面活性剂和添加剂等因素对介孔结构形成的影响;采用X射线衍射、透射电镜、荧光光谱等手段综合分析了产物的结构、形貌、成分及光学性质。结果表明所制备的介孔SnO2具有蠕虫状孔结构,表面积大,孔径集中分布在2～8 nm。合成的样品具有良好的光学性能,在光学材料领域具有应用前景。     

Video imaging of walking myosin V by high-speed atomic force microscopy

The dynamic behaviour of myosin V molecules translocating along actin filaments has been mainly studied by optical microscopy. The processive hand-over-hand movement coupled with hydrolysis of adenosine triphosphate was thereby demonstrated. However, the protein molecules themselves are invisible in the observations and have therefore been visualized by electron microscopy in the stationary states. The concomitant assessment of structure and dynamics has been unfeasible, a situation prevailing throughout biological research. Here we directly visualize myosin V molecules walking along actin tracks, using high-speed atomic force microscopy. The high-resolution movies not only provide corroborative 'visual evidence' for previously speculated or demonstrated molecular behaviours, including lever-arm swing, but also reveal more detailed behaviours of the molecules, leading to a comprehensive understanding of the motor mechanism. Our direct and dynamic high-resolution visualization is a powerful new approach to studying the structure and dynamics of biomolecules in action.     

不同粒径高度有序的介孔二氧化硅纳米材料（MSNs）的制备与表征

通过调解正硅酸乙酯(TEOS)和NH₃·H₂O的加入量,  采用共沉淀法可控地制备了一系列不同粒径（80~320 nm）, 且具有规则孔道结构的介孔二氧化硅纳米材料（MSNs）, 并利用小角X射线衍射（SAXRD）、 透射电镜（TEM）、 扫描电镜(SEM)及N2[KG-*3]吸附 脱附等方法对产物进行表征. 实验结果表明: 合成的样品均具有高度有序的孔道结构, 为典型的MCM 41介孔二氧化硅纳米材料; 采用合成后水热处理方法可提高材料的有序性和稳定性.     

Direct imaging of the pores and cages of three-dimensional mesoporous materials

Mesostructured composite materials, with features ranging from 20 to 500 A in size, are obtained by the kinetically controlled competitive assembly of organic and inorganic species into nanostructured domains. Short-range order is limited, and long-range order is determined by weak forces such as van der Waals or hydrogen-bonding. Three-dimensional mesoporous materials obtained by removing the organic phase are of particular interest for applications such as catalysis and chemical sensing or separation, for which structural features such as cavity shape, connectivity and ordered bimodal porosity are critical. But atomic-scale structural characterization by the usual diffraction techniques is challenging for these partially ordered materials because of the difficulty in obtaining large (> 10 microm) single crystals, and because large repeat spacings cause diffraction intensities to fall off rapidly with scattering angle so that only limited small-angle data are available. Here we present a general approach for the direct determination of three-dimensional mesoporous structures by electron microscopy. The structure solutions are obtained uniquely without pre-assumed models or parametrization. We report high-resolution details of cage and pore structures of periodically ordered mesoporous materials, which reveal a highly ordered dual micro- and mesoscale pore structure.     

一种合成大孔径SBA-15介孔分子筛的新方法

通过加入无机盐硝酸铵辅助合成大孔径介孔分子筛SBA-15,用小角X-射线粉末衍射(SAXS)、透射电子显微镜(TEM)、N_2吸附脱附等手段对分子筛进行了表征.结果表明:合成的大孔径分子筛SBA-15具有高度有序的介孔结构,孔径约12 nm,比表面积894 m~2·g~(-1),孔容为2.6 cm~3·g~(-1);不加硝酸铵则不能得到具有高有序度的介孔材料.     

无机介孔材料在第三代电化学生物传感器中的应用研究

无机介孔材料是一种孔直径在2,50nm的多孔材料。这种材料具有结构规则,机械性能高、化学和热能稳定性好等特点。近年来,随着材料合成技术的提高,不断有新型高负载能力和生物相容性好的介孔材料被开发出来。同时,实验表明,无机介孔材料是固载生物大分子的良好载体。利用无机介孔材料固载氧化还原蛋白质并结合其的直接电子转移,为我们提供了一种新的构建第三代生物传感器的方法。基于无机介孔材料的特点及氧化还原蛋白质的直接电子转移,所构建的第三代电化学生物传感器有望具有较传统电化学传感器更好的性能。将介孔材料分为二氧化硅基和非二氧化硅基2大类,描述了无机介孔材料在第三代电化学生物传感器中的应用。     

Synthesis and characterization of chiral mesoporous silica

Chirality is widely expressed in organic materials, perhaps most notably in biological molecules such as DNA, and in proteins, owing to the homochirality of their components (d-sugars and l-amino acids). But the occurrence of large-scale chiral pores in inorganic materials is rare. Although some progress has been made in strategies to synthesize helical and chiral zeolite-like materials, the synthesis of enantiomerically pure mesoporous materials is a challenge that remains unsolved. Here we report the surfactant-templated synthesis of ordered chiral mesoporous silica, together with a general approach for the structural analysis of chiral mesoporous crystals by electron microscopy. The material that we have synthesized has a twisted hexagonal rod-like morphology, with diameter 130-180 nm and length 1-6 micro m. Transmission electron microscopy combined with computer simulations confirm the presence of hexagonally ordered chiral channels of 2.2 nm diameter winding around the central axis of the rods. Our findings could lead to new uses for mesoporous silica and other chiral pore materials in, for example, catalysis and separation media, where both shape selectivity and enantioselectivity can be applied to the manufacturing of enantiomerically pure chemicals and pharmaceuticals.     

Synthesis and characterization of wormhole-like mesoporous Ce0.6Zr0.35Y0.05O2 solid solutions

Nanoparticles of Ce0.6Zr0.35Y0.05O2 (CZY) solid solution have been prepared by the CTAB (hexadecyl-trimethyl ammonium bromide), CTAB-EG (ethylene glycol) templating, and CTAB-EG-NaCl (in which the pores of the precursor synthesized by the CTAB-EG method is filled by a certain amount of NaCl) method, respectively. The physical properties of these materials were characterized by means of tech-niques such as X-ray diffraction (XRD), high resolution scanning electron microscopy (HRSEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), and N2 adsorp-tion-desorption measurements. The CZY samples synthesized by the above three methods display wormhole-like mesoporous morphology and cubic crystal structures. The materials are narrow in pore size distribution (averaged pore diameter = 5.3―7.1 nm), high in surface areas (95―119 m2/g), and large in pore volumes (0.16―0.18 cm3/g). It has been demonstrated that the introduction of NaCl is capable of retaining the pore structures of solid nanomaterials at high-temperature calcination.     

外场操控单分子的电子转移动力学特性

研究单分子的电子转移动力学特性并进行可靠的量子操控是应用单分子于量子信息领域的先决条件.利用电场改变单分子与周围电子受体之间的库仑势垒,操控PMMA聚合物薄膜中的染料SR单分子的电子转移,发现分子荧光对电场响应存在增强效应.将电流引入染料SR单分子/ITO半导体纳米粒子系统中,观察到了电流操控下的单分子荧光强度熄灭效应,电子转移率达到91％.     

Surface PEGylation of hollow mesoporous silica nanoparticles via aminated intermediate

A hybrid of organic/inorganic system, hollow mesoporous silica nanoparticles functionalized with poly(ethylene glycol), was synthesized in the presence of coupling agent and aminated ends. Doxorubicin (DOX) was used as a model drug to evaluate the effect of PEGylation on the loading capacity and release pattern of the system. Characterization with transmission electron microscopy (TEM) and scanning electron microscopy (SEM), X-ray diffraction (XRD), nitrogen adsorption-desorption, thermogravimetric analysis (TGA) and Fourier transformed infrared (FTIR) confirmed the PEG conjugation, as well as the amorphous mesoporous nature of the synthesized particles. Due to the capping effect of PEG molecules over the pores in the silica structure, the synthesized system was able to retain higher amount of cargo and establish a controlled manner when releasing.     

介孔硅铝酸盐材料的合成、 表征及催化应用

采用NaOH调节体系的pH值, 通过改变造孔剂柠檬酸的加入量, 制备了一系列新型介孔硅铝酸盐材料, 并利用X射线衍射(XRD)、 透射电镜(TEM)和N₂吸附脱附等进行表征, 同时分析了不同柠檬酸加入量对材料孔结构的影响.  结果表明： 合成材料具有蠕虫状内交联的介孔结构,   具有较强的酸性; 柠檬酸与铝物质的量比为13的样品在苯酚与叔丁醇烷基化反应中具有较高的催化活性和对2,4-二叔丁基苯酚（2,4-DTBP）的选择性; 较高的苯酚转化率和对2,4-DTBP的选择性主要归因于催化剂较强的酸性和较大的介孔孔径.     

多孔氧化镍纳米片的制备及其磁性能研究

采用水热合成法制备了大孔径和小孔径两种多孔氧化镍纳米片.采用透射电子显微镜(TEM)、扫描电子显微镜(SEM)、X射线衍射仪(XRD)、全自动比表面及孔隙度分析仪以及超导量子相干磁强计等对它们的形貌、晶体结构、比表面积以及磁性能进行了表征,并且探讨了这两种不同孔径氧化镍纳米片的形成机制.研究结果显示:这两种多孔NiO纳米片在55 K和300 K温度下都呈现类铁磁性,而小孔径NiO纳米片显示具有更高的饱和磁化强度,这可能是由于小孔径氧化镍纳米片拥有较大的开孔密度和比表面积,表面缺陷增多导致其表面自旋无序度增加,超反铁磁性效应更加显著.     

铝合金阳极氧化膜的微观结构分析

使用透射电镜观察了铝合金阳极氧化膜的微观结构,发现了阳极氧化膜的阻挡层与多孔层以及独特的六解形胞孔结构,氧化膜胞孔的孔道沿氧化膜表面向铝合金基体方向呈收缩趋势,这与阳极氧化过程中电压升高对多孔结构生长的影响有关。结合阳极氧化膜生长环境以及氧化膜的生长模型,探讨了氧化膜多孔结构的生长方式。     

磁性FeNi合金/石墨化介孔碳纳米复合材料的合成及其在染料吸附中的应用

以介孔SBA-15为模板,金属硝酸盐作为磁性FeNi合金纳米颗粒前驱物,采用纳米铸造法合成出一系列磁性FeNi合金/石墨化介孔碳纳米复合材料.利用X射线衍射仪(XRD)、N₂吸附-脱附仪(BET)、电感耦合等离子体质谱仪、透射电子显微镜(TEM)、振动样品磁强计(VSM)和热重分析仪(TG)等对合成物进行表征.结果发现,试验得到的纳米复合材料具有一致的介孔结构,高含量的磁性FeNi合金纳米晶体(尺寸大约是3~6 nm)均匀分散在石墨介孔碳模型的壁上,此介孔材料具有高的比表面积(360.3~431.9 m²·g^-1),大孔体积(0.558~0.718 cm³·g^-1)和高饱和磁化强度(18.2~42.1 emu·g^-1).基于以上特性,研究了材料对于水中染料的吸附性能.结果发现,当染料浓度为50 mg·L^-1时,材料对其去除率接近100%,同时在外加磁场存在时,悬浮液可以很好地实现固液分离.因此,磁性FeNi合金/石墨化介孔碳纳米复合材料在去除废水中的染料方面可以作为高效和可循环使用的吸附剂.     

Carboxyl-modified hierarchical wrinkled mesoporous silica supported TiO2 nanocomposite particles with excellent photocatalytic performances

Titanium dioxide (TiO₂) is a common photocatalyst for organic pollutants degradation. However, in practical application, the poor adsorption capacity of pure TiO₂ seriously impeded its efficiency in the degradation of organic molecules. In this work, a series of hierarchical wrinkle mesoporous silica supported TiO₂ nano-composite particles (TiO₂ @WMS-COOH) were successfully prepared. Thanks to their high surface areas, large pore volumes and mesoporous structures, these materials showed high adsorption capacity and excellent photocatalytic performance towards dye molecules, which is comparable to or even better than commercial catalyst P25. Moreover, their photocatalytic efficiency can be further enhanced by increasing the calcination temperature during preparation process. Therefore it can be concluded that the TiO₂ @WMS-COOH particles may find promising applications in the photodegradation of organic pollutants.     

球形氧化镍粉末对乙醇的电催化性能的研究

通过水热-热分解法制备球形介孔氧化镍粉末,并采用X射线衍射、扫描电镜、透射电镜和比表面积仪对氧化镍粉末的形貌和结构进行表征;通过循环伏安法、计时电流法和电化学阻抗谱的测试,系统研究该种粉末在碱性介质中对乙醇的电催化氧化活性.结果表明：所得到的氧化镍粉末为球形,比表面积为35 m2·g-1,平均孔径为15.88 nm;该粉末对乙醇具有良好的催化活性,氧化电流随乙醇浓度和扫描速率的增大而增大,在0.60 V电位下保持1000 s,球形多孔氧化镍对乙醇氧化催化的电流衰减率为0.075%,稳定性比较好.循环伏安法、计时电流法和电化学阻抗谱测试表明,球形介孔NiO/玻碳电极( NiO/GCE)对乙醇的催化氧化反应机理为扩散控制.     

制备介孔复合环境材料的酸洗刻蚀工艺

探索了一种制备介孔复合环境材料的方法--破坏式造孔与有机复合相结合,使最终产品可大量吸附污染水体中的各种污染物并具有一定的杀菌功能.该方法通过酸洗刻蚀,达到了去除原材料中的杂质和刻蚀孔径的目的,所制备的中间产品24h吸湿率为原材料的2倍,染料吸附量为原材料的1.6倍.     

Biotemplated fabrication of hierarchical mesoporous CeO2 derived from diatom and its application for catalytic oxidation of CO

Hierarchically hollow nanostructures have been the focus of numerous studies due to their prominent physicochemical properties that differ significantly from bulk materials and their potential for extensive applications. We present a novel diatom-based scaffold for the synthesis of hierarchically biomorphic CeO2 with special porous structure via incorporating Ce ions into the frustule. Scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and nitrogen adsorption-desorption measure- ments were adopted to characterize the products. Owing to its unique hierarchical structure and periodic meso-macro scale features, the obtained CeO2 exhibits high catalytic activity in CO oxidation. This facile strategy may design a new way towards replicating desired biological structures for metal oxide catalyst in other potential applications.     

孔径可调的介孔磷酸铈的合成

采用中性表面活性剂十八胺为模板剂、硫酸铈为铈源，在水热条件下合成具有介孔结构的磷酸铈。通过X-射线衍射、透射电镜、高倍透射电镜和液氮吸附手段对介孔磷酸铈的介观结构、微观形貌和孔道结构进行了表征。结果表明，该材料是的有序的层状相介孔，层间距为2～3nm。产物主晶相为结晶性良好的单斜晶系的独居石磷酸铈，次晶相为正交晶系的磷酸铈。调整无机铈源与表面活性剂的摩尔比，实现磷酸铈介孔孔径在5.5～9.8nm之间可调。该介孔材料的最大比表面积高达113m²/g，孔体积为0.25mL/g。