| 1. |
- Cho, Hae Sung, et al.
(author)
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Directing the Distribution of Potassium Cations in Zeolite-LTL through Crown Ether Addition
- 2017
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In: Crystal Growth & Design. - : American Chemical Society (ACS). - 1528-7483 .- 1528-7505. ; 17:9, s. 4516-4521
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Journal article (peer-reviewed)abstract
- We discover that the crystal morphology of zeolite-LTL could be modified by crown ether (21-crown-7, CE), where CE decreases the aspect ratio of zeolite-LTL while increasing the nucleation of domains on the (0001) face and hindering their growth along the c-axes. Moreover, the study using scanning electron microscopy supports that the ratio between the rates for generation of cancrinite columns and bridging cancrinite columns on the {10 (1) over bar0} face remains constant among the LTL frameworks with different amounts of CE molecules. In addition, X-ray diffraction analysis shows that potassium cations redistribute into pore cavities (t-lil) from cancrinite cages (t-can) and t-ste cages by the strong interactions between potassium and CE as the amount of CE molecules is increased. Additionally, Monte Carlo simulations clarify that stabilization of the t-lil cage via the redistribution of potassium cations at high CE concentration is attributed to the dominant effect in the crystal morphology changes observed. To understand the catalytic and adsorption properties of zeolites, it is important to investigate their structure/property relationships. Especially, studying the morphology of an anisotropic zeolite crystals has been of great interest because of the strong influence on controlling its properties. Thus, morphological control of the material with a particular crystallographic direction is highly desirable to obtain maximum properties for applications.
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| 2. |
- Cho, Hae Sung, et al.
(author)
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Extra adsorption and adsorbate superlattice formation in metal-organic frameworks
- 2015
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In: Nature. - : Springer Science and Business Media LLC. - 0028-0836 .- 1476-4687. ; 527:7579, s. 503-U193
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Journal article (peer-reviewed)abstract
- Metal-organic frameworks (MOFs) have a high internal surface area and widely tunable composition(1,2), which make them useful for applications involving adsorption, such as hydrogen, methane or carbon dioxide storage(3-9). The selectivity and uptake capacity of the adsorption process are determined by interactions involving the adsorbates and their porous host materials. But, although the interactions of adsorbate molecules with the internal MOF surface(10-17) and also amongst themselves within individual pores(18-22) have been extensively studied, adsorbate-adsorbate interactions across pore walls have not been explored. Here we show that local strain in the MOF, induced by pore filling, can give rise to collective and long-range adsorbate-adsorbate interactions and the formation of adsorbate superlattices that extend beyond an original MOF unit cell. Specifically, we use in situ small-angle X-ray scattering to track and map the distribution and ordering of adsorbate molecules in five members of the mesoporous MOF-74 series along entire adsorption-desorption isotherms. We find in all cases that the capillary condensation that fills the pores gives rise to the formation of 'extra adsorption domains'-that is, domains spanning several neighbouring pores, which have a higher adsorbate density than non-domain pores. In the case of one MOF, IRMOF-74-V-hex, these domains form a superlattice structure that is difficult to reconcile with the prevailing view of pore-filling as a stochastic process. The visualization of the adsorption process provided by our data, with clear evidence for initial adsorbate aggregation in distinct domains and ordering before an even distribution is finally reached, should help to improve our understanding of this process and may thereby improve our ability to exploit it practically.
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| 3. |
- Cho, Hae Sung, et al.
(author)
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Study of Argon Gas Adsorption in Ordered Mesoporous MFI Zeolite Framework
- 2012
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In: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 116:48, s. 25300-25308
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Journal article (peer-reviewed)abstract
- An ordered mesoporous MFI zeolite material (Meso-MFI) was prepared by using CMK-type mesoporous carbons as a hard template. The Meso-MFI exhibits both structural and adsorption differences compared to the conventional bulk MFI zeolite. To study the argon (Ar) adsorption process in Meso-MFI, an in situ gas adsorption powder X-ray diffraction (XRD) analysis was performed using synchrotron X-ray source. Structural rearrangement of the mesoporous MFI zeolite upon Ar adsorption at low temperature (83 K) was intensively studied together with Ar adsorption process in Meso-MFI. We observed that a structural transition of the Meso-MFI zeolite framework from monoclinic (P2(1)/n) to orthorhombic (Pnma) occurred at around 126 Pa at 83 K. Positions of Ar atoms are determined as a function of the Ar gas pressure through Rietveld refinement of powder XRD data. Ar atoms are observed at straight channels, sinusoidal channels, and the intersection of these channels at low pressure. As gas pressure increases, Ar atoms in the pore intersection are pulled off from the intersection toward the straight and sinusoidal channels. The pore shape of the straight channel is changed accordingly with the amount of adsorbed Ar atoms within the pores from circular to oval. These results indicate that Ar adsorption induces not only continuous rearrangement of framework atoms but also symmetry change in the Meso-MFI. A molecular simulation study combined with Rietveld refinement of in situ XRD data provided a full understanding of the adsorption process of Ar in Meso-MFI.
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| 4. |
- Garcia-Bennett, Alfonso E, et al.
(author)
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Bicontinuous Cubic Mesoporous Materials with Biphasic Structures
- 2011
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In: Chemistry - A European Journal. - : Wiley. - 0947-6539 .- 1521-3765. ; 17:48, s. 13510-13516
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Journal article (peer-reviewed)abstract
- The replication of amphiphilic systems within an inorganic silica matrix allows the study of the fundamental properties of mesostructural changes, that is, kinetic and structural parameters. Herein we report a detailed study of the transition between cubic bicontinuous mesostructure with space groups Ia$\bar 3$d and Pn$\bar 3$m symmetry, which are associated with the minimal G and D surfaces, respectively. The transition may be induced through micellar swelling of the anionic amphiphilic surfactant N-lauroyl alanine by trimethylbenzene. Rich kinetic behaviour is observed and has been exploited to prepare particles with biphasic structures. Transmission electron microscopy evidence indicates that there is epitaxial growth from one mesostructure to the other involving the [111] and [110] orientations of the Ia$\bar 3$d and Pn$\bar 3$m symmetry structures, respectively. From kinetic studies, we show that the formation of the Ia$\bar 3$d mesophase is preceded by a hexagonal phase (plane group p6mm) and an epitaxial relationship has been observed involving the sixfold or $\bar 3$ axis orientations of both structures. Our data suggests that the Pn$\bar 3$m mesostructure is kinetically stable at low temperatures whereas the Ia$\bar 3$d mesostructure is the more stable structure after prolonged periods of hydrothermal treatment. We present evidence from transmission electron microscopy and small-angle X-ray diffractograms and also electron crystallography modelling of the unit cells at particular points in the structural change.
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| 5. |
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| 6. |
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| 7. |
- Gu, Dong, et al.
(author)
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Growth of Single-Crystal Mesoporous Carbons with Im(3)over-barm Symmetry
- 2010
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In: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 22:16, s. 4828-4833
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Journal article (peer-reviewed)abstract
- Highly ordered mesoporous carbon FDU-16 rhombic dodecahedral single crystals with body-centered cubic structure (space group Im (3) over barm) have been successfully synthesized by employing an organic-organic assembly of triblock copolymer Pluronic F127 (EO106PO70EO106) and phenol/formaldehyde resol in basic aqueous solution. Synthetic factors (including reaction time, temperature, and stirring rate) are explored for controlling the formation of rhombic dodecahedral single crystals. The optimal stirring rate and the reaction temperature are 300 +/- 10 rpm and similar to 66 degrees C, respectively. High-resolution scanning electron microscopy (HRSEM), scanning transmission electron microscopy (STEM), and ultramicrotomy are applied to study the fine structures of the carbon single crystals. The mesopores are arranged in body-centered cubic symmetry throughout the entire particle. Surface steps are clearly observed in the {110} surface, which suggests a layer-by-layer growth of the mesoporous carbon FDU-16 single crystals. Cryo-SEM results from the reactant solution confirm the formation of resol/F127 unit micelles, further supporting the layer-by-layer growth process. The mesoporous carbon FDU-16 single crystals grow up to the final size of 2-4 mu m within 2 days. These findings may have consequences for the growth mechanism of other carbon materials in aqueous solution; moreover, the high-quality single crystals also have potential applications in nanodevice technologies.
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| 8. |
- Han, Lu, et al.
(author)
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Electron Crystallography
- 2014
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In: Structure from Diffraction Methods. - Chichester : John Wiley & Sons. - 9781118695708 - 9781119953227 ; , s. 201-258
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Book chapter (peer-reviewed)abstract
- A transmission electron microscope (TEM) can provide an electron diffraction pattern on the back focal plane of the objective lens and can supply real-space information through images on the image plane. X-ray crystallography, using X-ray diffraction (XRD) with either a powder or a single-crystal diffractometer, is the most precise and most popular method of structural analysis. However, structure determination by powder XRD has its limitations. Due to this, electron crystallography (EC), which is the focus of this chapter, is the only possible technique by which to solve/characterise the crystal structure. The chapter discusses the relationship between crystal structure and TEM images. It describes in detail, the various materials including 1D atomistic crystal, solved by EC methods. The chapter also discusses other TEM techniques such as high-angle annular dark-field imaging (HAADF) and electron tomography.
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| 9. |
- Han, Lu, et al.
(author)
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Evolution of Packing Parameters in the Structural Changes of Silica Mesoporous Crystals : Cage-Type, 2D Cylindrical, Bicontinuous Diamond and Gyroid, and Lamellar
- 2011
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In: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 133, s. 11524-11533
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Journal article (peer-reviewed)abstract
- Cage-type, two-dimensional (2D) cylindrical hexagonal (C), bicontinuous diamond (D), bicontinuous gyroid (G), and one-dimensional (1D) lamellar (L) structures of silica mesoporous crystals (SMCs) were obtained by using the anionic surfactant N-stearoyl-L-glutamic acid (C(18)GluA) as a template in the presence of the nonionic surfactant C(16)(EO)(10) (Brij-56). The mesostructures were controlled by the organic/inorganic interface curvature change induced by Brij-56. A synthesis-field diagram showed that the mesostructure changed in the sequence cage-type -> C -> intergrowth of C and D -> intergrowth of C and G -> D -> G -> L with increase of the amount of Brij-56. Mixed micelles were formed by the anionic and nonionic surfactants, the packing parameter g of which increased with increasing the addition amount of nonionic surfactant and the reaction temperature. The local g parameter was obtained from electron crystallography reconstruction results by calculating mean curvatures and Gaussian curvatures from the equi-electrostatic potential surface. The intergrowth of C and D and two kinds of intergrowth of C and G are also discussed.
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| 10. |
- Han, Lu, et al.
(author)
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Silica-Based Nanoporous Materials
- 2014
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In: Zeitschrift für Anorganische und Allgemeines Chemie. - : Wiley. - 0044-2313 .- 1521-3749. ; 640:3-4, s. 521-536
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Research review (peer-reviewed)abstract
- Ordered nanoporous structures are among the most fascinating and industrially important materials currently in use. The archetypal zeolite material has now been joined by an eclectic array of new structures that exhibit porosity over a wide range of length scales and with order/disorder expressed in a multitude of ways. This raises the bar in terms of characterization and extends a real challenge to the scientific community to fully understand the properties and potential future applications of such materials. In this review we discuss the importance of modern microscopy tools combined with diffraction in this endeavour and show how the details of even the most complex quasi-crystalline nanoporous architectures can be elucidated. We show by using the appropriate spherical aberration (C-s) corrections in scanning transmission electron microscopy it is possible to decipher all the individual silicon and aluminum atoms in a zeolite structure. Automated routines for using large electron diffraction datasets for crystal structure determination of nanocrystals is described making the need for large single crystal synthesis less-and-less important. The power of complementary combinations of surface tools such as atomic force microscopy and high-resolution scanning electron microscopy is discussed to elucidate crystal growth mechanisms. For mesoporous materials synthesized from self-organized organic mesophases electron microscopy reveals the details of the complex hierarchy of porosity so crucial for the functional performance of the structure.
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