Synthesis and Integration of Fe-soc-MOF Cubes into Colloidosomes via a Single-Step Emulsion-Based Approach

Pang, Maolin; Cairns, Amy; Liu, Yunling; Belmabkhout, Youssef; Zeng, Hua Chun; Eddaoudi, Mohamed

doi:10.1021/ja403994u

Cited by 278 publications

(252 citation statements)

References 44 publications

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“…For cubes with cos θ ¼ 0.3, which induce negligible deformations, we do not expect capillary interactions, in agreement with experiments of cubes with cos θ ≈ 0.3 and L ≈ 1 μm [46]. Cubes with such a contact angle tend to assemble into tetragonal, possibly closedpacked structures [47]. More interesting is the case cos θ ¼ 0, where cubes are in the f111g configuration and induce a hexapolar deformation in the height profile of the interface, with three depressions and three rises [see Fig.…”

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confidence: 87%

Self-Assembly of Cubes into 2D Hexagonal and Honeycomb Lattices by Hexapolar Capillary Interactions

2016

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Particles adsorbed at a fluid-fluid interface induce capillary deformations that determine their orientations and generate mutual capillary interactions which drive them to assemble into 2D ordered structures. We numerically calculate, by energy minimization, the capillary deformations induced by adsorbed cubes for various Young's contact angles. First, we show that capillarity is crucial not only for quantitative, but also for qualitative predictions of equilibrium configurations of a single cube. For a Young's contact angle close to 90°, we show that a single-adsorbed cube generates a hexapolar interface deformation with three rises and three depressions. Thanks to the threefold symmetry of this hexapole, strongly directional capillary interactions drive the cubes to self-assemble into hexagonal or graphenelike honeycomb lattices. By a simple free-energy model, we predict a density-temperature phase diagram in which both the honeycomb and hexagonal lattice phases are present as stable states. DOI: 10.1103/PhysRevLett.116.258001 Over a century ago, it had already been observed that submm sized particles strongly adsorb at fluid-fluid interfaces [1,2]. Indeed, a fluid-fluid interface of area A and surface tension γ has a free energy cost γA, and particles can reduce A by adsorbing at the interface. The bonding potential is usually strong enough to allow stable monolayers of particles. Since a pioneering study by Pieranski [3], a lot of interest has been devoted to these quasi-2D systems, which have many applications, e.g., emulsions [4][5][6][7][8][9], coatings [10,11], optics [12], and new material development [13]. Because of the contact angle constraint imposed by Young's Law, an adsorbed particle in general induces deformations in the shape of the fluid-fluid interface. These so-called capillary deformations are responsible for capillary interactions between the adsorbed particles [14,15], which regulate the particle self-assembly at the interface [16][17][18]. These interactions can be tuned by varying, e.g., the particle shape and chemistry [10,[19][20][21], or the curvature of the fluidfluid interface [22][23][24]. Very recent experiments [25][26][27] have shown that adsorbed nanocubes with truncated corners can assemble into graphenelike honeycomb and hexagonal lattices. The origin of these structures is unknown, although ligand adsorption and van der Waals forces between specific facets of the truncated cubes have been suggested [25]. In this Letter, however, we show that generic cubes with homogeneous surface properties generate hexapolar capillary deformations which are largely responsible for the observed structures. Cubes of other materials or dimensions could, therefore, form similar structures.A primary step for understanding adsorbedparticle systems is the study of an isolated particle at a macroscopically flat fluid-fluid interface. Important issues are the equilibrium configuration of the particle at the interface [28][29][30][31] and the adsorption energy [32-34] which depend on the particl...

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confidence: 87%

Self-Assembly of Cubes into 2D Hexagonal and Honeycomb Lattices by Hexapolar Capillary Interactions

2016

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“…18,21 Additionally, CO 2 droplets have been employed as internal cores for the gas-liquid interfacial templating formation of hollow MOFs, 31 and emulsion droplets have been used for the self-assembly of MOF particles at the liquid-liquid interface to form monolayer MOF shells. 30 However, the preparation of hollow MOF 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 3 microparticles in the absence of any add-on template materials via a one-step reaction was barely studied before. 32 Herein, we report the production of unique hollow MOF microparticles without extra template materials.…”

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confidence: 99%

Hollow Metal–Organic Framework Microparticles Assembled via a Self-Templated Formation Mechanism

Lee

Choi

Lee

et al. 2015

Crystal Growth & Design

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Hollow particles are considered to be fascinating materials due to their useful applications and unique properties. Understanding the formation mechanism of hollow structures is critical for their controlled formation. Herein, we demonstrate the fabrication of hollow metal–organic framework (hollow MOF) microparticles via a one-step solvothermal reaction of Zn(NO3)2 and 1,3,5-benzenetricarboxylic acid (H3BTC) without extra template materials. The formation mechanism study of the hollow MOF reveals a unique self-templated formation mechanism consisting of three stages: (1) spherical microparticles are initially formed during the early stage of the reaction, (2) the initially formed spherical microparticles act as self-templates for the growth of new crystalline MOF materials during the middle stage of the reaction, and (3) the initially formed spherical microparticles spontaneously disappear for the formation of hollow MOFs during the late stage of the reaction.

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“…In contrast, Zn-pbdc-7a and Zn-pbdc-8a exhibit very different morphologies.A lthough both spherical and cubic particles are observed (Figure 3), closer examination shows that the spherical solids are intergrown crystalline superstructures with regular facets. [20] We interpret the polycrystalline, spherical superstructures of Zn-pbdc-7a and Zn-pbdc-8a as the result of many individual crystals growing together and partially sharing polymer ligands.T his most likely results from the formation of multiple nucleation sites for IRMOF growth on individual polymer ligand chains and intergrowth of polymer ligand chains during coordination to Zn II . To exclude the possibility that only oligomers or smaller molecular weight species were responsible for MOF formation, arepresentative reaction with pbdc-7a was monitored by 1 Figure S18).…”

Section: Angewandte Zuschriftenmentioning

confidence: 96%

polyMOFs: A Class of Interconvertible Polymer‐Metal‐Organic‐Framework Hybrid Materials

et al. 2015

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Preparation of porous materials from one‐dimensional polymers is challenging because the packing of polymer chains results in a dense, non‐porous arrangement. Herein, we demonstrate the remarkable adaptation of an amorphous, linear, non‐porous, flexible organic polymer into a three‐dimensional, highly porous, crystalline solid, as the organic component of a metal–organic framework (MOF). A polymer with aromatic dicarboxylic acids in the backbone functioned as a polymer ligand upon annealing with ZnII, generating a polymer–metal–organic framework (polyMOF). These materials break the dogma that MOFs must be prepared from small, rigid ligands. Similarly, polyMOFs contradict conventional polymer chemistry by demonstrating that linear and amorphous polymers can be readily coaxed into a highly crystalline, porous, three‐dimensional structure by coordination chemistry.

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Synthesis and Integration of Fe-soc-MOF Cubes into Colloidosomes via a Single-Step Emulsion-Based Approach

Cited by 278 publications

References 44 publications

Self-Assembly of Cubes into 2D Hexagonal and Honeycomb Lattices by Hexapolar Capillary Interactions

Self-Assembly of Cubes into 2D Hexagonal and Honeycomb Lattices by Hexapolar Capillary Interactions

Hollow Metal–Organic Framework Microparticles Assembled via a Self-Templated Formation Mechanism

polyMOFs: A Class of Interconvertible Polymer‐Metal‐Organic‐Framework Hybrid Materials

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