Macroporous metal–organic framework microparticles with improved liquid phase separation

Ahmed, Adham; Hodgson, Nicola; Barrow, Michael; Clowes, Rob; Robertson, Craig M.; Steiner, Alexander; McKeown, Paul; Bradshaw, Darren; Myers, Peter; Zhang, Haifei

doi:10.1039/c4ta00138a

Cited by 87 publications

(71 citation statements)

References 43 publications

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“…This type of particle has been applied to the fast HPLC separation of peptides and proteins [22][23][24][25] . Modification of the Stöber method with tetraethyl orthosilicate (TEOS) as the silica precursor and adding polyvinyl alcohol plus cetyltrimethylammonium bromide lead to the production of monodisperse, porous silica microspheres.…”

Section: Core-shell Particles Methods Of Preparationmentioning

confidence: 99%

Core–Shell, Ultrasmall Particles, Monoliths, and Other Support Materials in High-Performance Liquid Chromatography

Tanaka¹,

McCalley

2015

Anal. Chem.

154

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Section: Core-shell Particles Methods Of Preparationmentioning

confidence: 99%

Core–Shell, Ultrasmall Particles, Monoliths, and Other Support Materials in High-Performance Liquid Chromatography

Tanaka¹,

McCalley

2015

Anal. Chem.

154

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“…hollow boxes vs. rhombic dodecahedra) may result advantageous for applications in chromatography (e.g. improving the separation of substances) [8] and in heterogeneous catalysis. [17,18] Also, as already observed in MFI zeolites, [19] etched porous morphologies may show changes in the adsorption/desorption rates because of the change in the number of defects present on the crystal surface.…”

Section: Introductionmentioning

confidence: 99%

“…[5,6] Inspired by similar results with zeolites, this strategy has enabled researchers to prepare hierarchical MOF crystals and/or create macropores on the MOF crystal surfaces. [7,8] However, to date, no one has demonstrated the ability to rationally and post-synthetically control the anisotropic etching of a porous MOF crystal in function of its crystal planes, to shape it into different morphologies.…”

mentioning

confidence: 99%

Post‐Synthetic Anisotropic Wet‐Chemical Etching of Colloidal Sodalite ZIF Crystals

et al. 2015

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Controlling the shape of metal-organic framework (MOF) crystals is important for understanding their crystallization and useful for myriad applications. However, despite the many advances in shaping of inorganic nanoparticles, post-synthetic shape control of MOFs and, in general, molecular crystals remains embryonic. Herein we report using a simple wet-chemistry process at room temperature to control the anisotropic etching of colloidal ZIF-8 and ZIF-67 crystals. Our work enables uniform reshaping of these porous materials into unprecedented morphologies, including cubic and tetrahedral crystals, and even hollow boxes, via acid-base reaction and subsequent sequestration of leached metal ions. Etching tests on these ZIFs reveal that etching occurs preferentially in the crystallographic directions richer in metal-ligand bonds; that, among these directions, the etching rate tends to be faster on the crystal surfaces of higher dimensionality; and that the etching can be modulated by adjusting the pH of the etchant solution. KeywordsMetal-Organic Frameworks; Zeolitic-Imidazolate Frameworks; anisotropic etching; hollow particles; porosity Chemical etching is an ancient fabrication method that was used by metal and glass craftsmen to obtain sophisticated surface designs. With the advent of controlling the etching orientation at the microscale and nanoscale, anisotropic wet-chemical etching has become highly useful for shaping many materials for diverse applications.[1,2] For example, the anisotropic wet-chemical etching of single-crystal silicon in the presence of a base is essential in microelectronics manufacturing.[1] Anisotropic etching can also be applied to preparation of metal nanocrystals from oxidative species and coordination ligands, for which it enables unprecedented morphologies and complexities, and unique physical properties.[2] Here, we introduce the concept of anisotropic wet-chemical etching for metal-organic frameworks (MOFs)-specifically, for the zeolitic-imidazolate framework (ZIF) subfamily. Figure S1).[9] Recently, several studies have shown that the crystal growth of ZIF-8 starts with formation of cubes exposing six {100} facets, which gradually evolve into truncated rhombic dodecahedra exposing six {100} and twelve {110} facets, and finally, into the thermodynamically more stable rhombic dodecahedra, in which only the twelve {110} facets are exposed ( Figure 1a). [10,11] Figure 1a illustrates the different exposed crystallographic planes for the cubes and for the truncated and non-truncated rhombic dodecahedra. As shown in this figure, each crystal shape has different exposed crystallographic planes, and each crystallographic plane, a distinct chemical composition. In ZIF-8, {100} and {211} planes contain several Zn-2-MIM linkages, whereas the {110} and {111} planes do not contain any of these linkages ( Figure 1b).By exploiting the aforementioned differences, we devised a method for anisotropic wet etching of colloidal crystals of isostructural ZIF-8 and ZIF-67. Our approach combines ...

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“…This is particularly important in view of recent advances in microfabrication technologies which facilitate the fabrication of porous media comprising of ordered pillar arrays [8,10], three dimensional ordered hierarchical porous materials [9]. Since available techniques provide the designer with the flexibility of forming multiscale pore geometry of various shapes and patterns, one has the opportunity to optimize chromatography column and reactor design and significantly improve the process performance.…”

Section: Introductionmentioning

confidence: 99%

“…with tunable pore geometry and pore size, such as core-shell particle packs [6,7], array of pillars with porous shell [8], metalorganic frameworks with tunable macropore size [9], nanopillar array [10,11], porous graphitic carbon [12].…”

Section: Introductionmentioning

confidence: 99%

Predictive model of solute transport with reversible adsorption in spatially periodic hierarchical porous media

Yan

Wang

Li³

2015

Journal of Chromatography A

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Macroporous metal–organic framework microparticles with improved liquid phase separation

Abstract: Macroporous HKUST-1 crystalline particles are prepared by solvothermal modification and exhibit improved liquid chromatographic separation.

Cited by 87 publications

References 43 publications

Core–Shell, Ultrasmall Particles, Monoliths, and Other Support Materials in High-Performance Liquid Chromatography

Core–Shell, Ultrasmall Particles, Monoliths, and Other Support Materials in High-Performance Liquid Chromatography

Post‐Synthetic Anisotropic Wet‐Chemical Etching of Colloidal Sodalite ZIF Crystals

Predictive model of solute transport with reversible adsorption in spatially periodic hierarchical porous media

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