Morphology Design of Porous Coordination Polymer Crystals by Coordination Modulation

Umemura, Ayako; Diring, Stéphane; Furukawa, Shuhei; Uehara, Hiroki; Tsuruoka, Takaaki; Kitagawa, Susumu

doi:10.1021/ja204233q

Cited by 409 publications

(315 citation statements)

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“…20,21 However, the application of this method is, to date, limited to a framework system that intrinsically has a rather fast nucleation process. 2225 This is because the coordination modulation tends to decelerate the nucleation kinetics and helps to grow crystals larger.…”

Section: 18mentioning

confidence: 99%

“…19 This rather coordination chemistry approach allows us to control both crystallization kinetics and thermodynamics by simply altering the concentration of modulators, which affords the control of crystal size and morphology in nano and meso scales, and to synthesize highly crystalline materials. 20,21 However, the application of this method is, to date, limited to a framework system that intrinsically has a rather fast nucleation process. 2225 This is because the coordination modulation tends to decelerate the nucleation kinetics and helps to grow crystals larger.…”

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Formation of Nanocrystals of a Zinc Pillared-layer Porous Coordination Polymer Using Microwave-assisted Coordination Modulation

et al. 2012

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Nanocrystals of three-dimensional pillared-layer type porous coordination polymers, [Zn 2 (ndc) 2 (dabco)] n , were fabricated by microwave-assisted coordination modulation, and its morphology was controlled by changing the modulator concentration. Adsorption measurement supported that the crystallinity and intrinsic porosity were maintained even for nanosized crystals, comparable to the corresponding micrometer-sized bulk powder crystals.Porous coordination polymers (PCPs) or metalorganic frameworks (MOFs) assembled from organic ligands and inorganic joints have been widely investigated due to their potential application in gas storage, adsorptive separation, catalysis, and molecular sensing. 16 Such properties have been traditionally improved by designing functional organic ligands or inorganic clusters and/or by controlling the overall framework topology. Besides these molecular level functionalizations, methodologies to miniaturize the crystal size of PCPs to mesoscale and nanoscale regimes have been recently developed. 79 Thanks to the enhancement of crystal surface contribution or the shortened total diffusion path of resulting nanosized PCP crystals, the crystal downsizing can be recognized as a novel strategy to tune the porous properties. 79 In addition, the fabrication of PCP nanocrystals gives a further opportunity for applications in electronics and biomedicine. 1013 The key to control crystal sizes of PCPs is to regulate the nucleation kinetics in the crystallization process; rapid nucleation gives small crystals and slow kinetics gives large crystals. 14 The simplest method to produce PCP nanocrystals is to use microwave heating, which induces a rapid nucleation, however, simultaneously results in the production of poor crystalline materials, which significantly decrease the porosity. 15,16 On the other hand, the other approach known as microemulsion requires undesired surfactants that might change the porosity of PCPs. 17,18As an alternative method, we recently proposed a novel fabrication protocol, so-called coordination modulation, by changing the coordination equilibrium at the crystal interfaces during the crystallization process, through competitive interactions originating from an additive (modulator) with the same chemical functionality as linker ligands.19 This rather coordination chemistry approach allows us to control both crystallization kinetics and thermodynamics by simply altering the concentration of modulators, which affords the control of crystal size and morphology in nano and meso scales, and to synthesize highly crystalline materials. 20,21 However, the application of this method is, to date, limited to a framework system that intrinsically has a rather fast nucleation process. 2225 This is because the coordination modulation tends to decelerate the nucleation kinetics and helps to grow crystals larger. Therefore, the framework system with slow nucleation kinetics, which grows as a large single crystal, is not suitable.Here we show that the microwave-assisted coordination ...

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Section: 18mentioning

confidence: 99%

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Formation of Nanocrystals of a Zinc Pillared-layer Porous Coordination Polymer Using Microwave-assisted Coordination Modulation

et al. 2012

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“…[ 24 ] It has been that demonstrated that the geometric shape of a MOF is determined by the relative growth rates of each crystal facet, which are inversely proportional to the attachment energy of a defi ned growth unit on crystal facets, similar to atoms as units in metal nanocrystal growth. [ 25 ] Therefore, adjusting the growth rates of different crystal facets should be applicable for the growth of low-dimensional MOFs, e.g., using growth-blocking agents to inhibit the crystal growth in certain directions. [ 26,27 ] As one of the most important MOFs, HKUST-1 (i.e., Cu 3 (BTC) 2 (H 2 O) 3 , where the parent molecule of BTC 3− linker is H 3 BTC (1,3,5-benzenetricarboxylic acid, see Scheme 1 )), has been widely studied since it was fi rst reported in 1999.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Functionalization of Oriented Metal–Organic‐Framework Nanosheets: Toward a Series of 2D Catalysts

Zhan

Zeng

2016

Adv Funct Materials

237

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3268 wileyonlinelibrary.com inorganic nodes in MOFs can be intrinsic active sites for catalysis, e.g., copperbased MOFs have been demonstrated as an excellent solid Lewis acid catalyst for a few reactions; [ 4,7 ] (ii) extrinsic functional species (e.g., nanoparticles) can be introduced to MOFs structure, either on the external surfaces or inside the bulks or shells of MOFs. Various catalytic nanoparticles have been successfully incorporated into different MOFs matrices, including Au, Ag, Pt, Cu, or their combination etc.; [8][9][10] and (iii) MOFs also serve as solid precursors for metal or metaloxide catalysts due to their high metal density within the frameworks and easy transformation. Many porous transition metal oxides, such as CuO, Cu 2 O, Mn 2 O 3 , Mn 3 O 4 , Co 3 O 4 , and ZnO among others, have been derived through thermolysis under controlled atmospheres. [11][12][13][14][15][16] For example, porous CuO hollow architectures with perfect octahedral shape were prepared by annealing HKUST-1 precursor in fl owing air. [ 12 ] Moreover, zeolitic imidazolate framework-67 (ZIF-67) was used to design and generate Co 3 O 4 or structurally more complex Co 3 O 4 /NiCo 2 O 4 . [ 13,14 ] Although increasing research attention has been paid to the catalytic applications of MOFs, to our knowledge, shapes of the studied MOFs are mostly followed in 3D isotropic polyhedrons (i.e., high symmetric MOF crystals with sizes greater than 100 nm), and the catalytic systems derived from MOFs with anisotropic shapes such as nanofi bers or nanosheets with a dimension(s) less than 10 nm have seldom been explored.Similar to many inorganic nanomaterials, tailoring of size and shape is essential to customize MOFs for specifi c applications according to the principle of "structure dictates function." [ 17 ] Although a fi ne control over the size and size-distribution of MOFs has been realized, e.g., in the range of 100 nm to several micrometers, [ 18 ] fashioning MOFs into desired shapes for specifi c applications remain to be challenging. Nevertheless, several attempts to the architectural control of MOFs shapes have recently appeared in the literature, ranging from 1D, 2D to 3D nanostructures. [ 19,20 ] For example, nanosheets of MOFs as molecular sieving membranes for gas separation have been made in two recent reports, [ 21,22 ] which achieved much higher separation selectivity than MOFs in other

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“…Experiments to understand the crystallization processes of MOFs will enable us to partially control their sizes and shapes by controlling the recrystallization conditions. [19] This prompted us to fabricate a polyhedral polymer network in a wide range of sizes using a cross-linking reaction inside the MOFs. In a previous report, we demonstrated the formation of a polymer gel from a MOF by cross-linking of the organic linkers in the crystalline state of the MOF using an in situ click reaction of the azidemodified MOF, with external multifunctional cross-linkers with four acetylene moieties.…”

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Nano‐ and Microsized Cubic Gel Particles from Cyclodextrin Metal–Organic Frameworks

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Morphology Design of Porous Coordination Polymer Crystals by Coordination Modulation

Cited by 409 publications

References 70 publications

Formation of Nanocrystals of a Zinc Pillared-layer Porous Coordination Polymer Using Microwave-assisted Coordination Modulation

Formation of Nanocrystals of a Zinc Pillared-layer Porous Coordination Polymer Using Microwave-assisted Coordination Modulation

Synthesis and Functionalization of Oriented Metal–Organic‐Framework Nanosheets: Toward a Series of 2D Catalysts

Nano‐ and Microsized Cubic Gel Particles from Cyclodextrin Metal–Organic Frameworks

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