Ligand‐Directed Strategy for Zeolite‐Type Metal–Organic Frameworks: Zinc(<scp>II</scp>) Imidazolates with Unusual Zeolitic Topologies

Huang, Xiao‐Chun; Lin, Yan‐Yong; Zhang, Jie‐Peng; Chen, Xiaoming

doi:10.1002/anie.200503778

Cited by 1,634 publications

(963 citation statements)

References 38 publications

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“…Notably, the decomposition of Sr-ABDC was at a higher temperature than that observed for ZIF-8, another widely studied MOF material with the decomposition temperature at approximately 380°C. [47][48][49] The weight losses observed in Mg-ABDC and Co-ABDC at temperatures below 100°C are due to the evaporation of surface-adsorbed DMF, methanol and moisture. The decompositions of these frameworks were completed at temperatures of 370°C, 500°C and 575°C for Co-ABDC, Sr-ABDC, Mg-ABDC, respectively.…”

Section: Morphology Of M-abdc (M = Mg Co Sr)mentioning

confidence: 99%

Synthesis and characterization of three amino-functionalized metal–organic frameworks based on the 2-aminoterephthalic ligand

Yang

Lin

et al. 2015

Dalton Trans.

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The incorporation of Lewis base sites and open metal cation sites into metal-organic frameworks (MOFs) is a potential route to improve selective CO 2 adsorption from gas mixtures. In this study, three novel amino-functionalized metal-organic frameworks ( solvothermal reactions of 2-aminoterephthalic acid (H 2 ABDC) with magnesium, cobalt and strontium metal centers, respectively. Single-crystal structure analysis showed that Mg-ABDC and Co-ABDC were isostructural compounds comprising two-dimensional layered structures. The Sr-ABDC contained a three-dimensional motif isostructural to its known Ca analogue. The amino-functionalized MOFs were characterized by powder X-ray diffraction, thermal gravimetric analysis and N 2 sorption. The CO 2 and N 2 equilibrium adsorption capacities were measured at different temperatures (0 and 25°C). The CO 2 /N 2 selectivities of the MOFs were 396 on Mg-ABDC, 326 on Co-ABDC and 18 on Sr-ABDC. Both Mg-ABDC and Co-ABDC exhibit high heat of CO 2 adsorption (>30 kJ mol −1 ). The Sr-ABDC displays good thermal stability but had a low adsorption capacity resulting from narrow pore apertures.

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Section: Morphology Of M-abdc (M = Mg Co Sr)mentioning

confidence: 99%

Synthesis and characterization of three amino-functionalized metal–organic frameworks based on the 2-aminoterephthalic ligand

Yang

Lin

et al. 2015

Dalton Trans.

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“…In ZIF-8 the pores have diameter of 11.6 Å with an aperture of 3.4 Å. Other characteristics of the ZIFs include low density, high thermal and chemical stability, periodicity and systematic variation of pore size and porosity [14][15][16] . In terms of gas separation ZIF-8 has been studied in a great number of applications due to its aperture size that lies in the size range of the kinetic diameter of various gases including CO 2 , CH 4 and N 2 .…”

Section: Introductionmentioning

confidence: 99%

Ultem®/ZIF-8 Mixed Matrix Membranes for Gas Separation: Transport and Physical Properties

2016

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Mixed matrix membranes are promising options for improving gas separation processes. Zeolitic imidazolate frameworks (ZIFs) have a porous structure similar to conventional zeolites, being capable in principle of separating gases based on their differences in kinetic diameter while offering the advantage of having a partial organic character. This partial organic nature improves the compatibility between the sieve and the polymer, and a combination of the mentioned characteristics makes these hybrid materials interesting for the preparation of mixed matrix gas separation membranes. In this context the present work reports the preparation of Ultem  /ZIF-8 mixed matrix membranes and their permeabilities to pure CO 2 , N 2 and CH 4 gases. A significant increase in permeability with increase in CO 2 /N 2 selectivity was observed for the mixed matrix systems as compared to the properties of the neat Ultem  . Sorption results allowed to speculate that the ZIF-8 framework is not completely stable dimensionally, what influences the separation process by allowing gases with higher kinetic diameter than its nominal aperture to be sorbed and to diffuse through the crystal. Sorption and diffusion selectivities indicate that the higher separation performance of the mixed matrix membranes is governed by the diffusion process associated with the influence of gas molecule´s geometry.

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“…However, these materials are relatively dense (nonporous) and͞or low-symmetry structures. Only very recently, Zn(II) IMs having symmetrical porous structures analogous to zeolites were reported (10). Two of the aforementioned compounds are included, as zeolitic IM framework (ZIF)-7 and -8, among the library of ZIFs we report here (Fig.…”

mentioning

confidence: 99%

Exceptional chemical and thermal stability of zeolitic imidazolate frameworks

Park

Côté

et al. 2006

Proc. Natl. Acad. Sci. U.S.A.

6,443

314

5,102

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Twelve zeolitic imidazolate frameworks (ZIFs; termed ZIF-1 to -12) have been synthesized as crystals by copolymerization of either Zn(II) (ZIF-1 to -4, -6 to -8, and -10 to -11) or Co(II) (ZIF-9 and -12) with imidazolate-type links. The ZIF crystal structures are based on the nets of seven distinct aluminosilicate zeolites: tetrahedral Si(Al) and the bridging O are replaced with transition metal ion and imidazolate link, respectively. In addition, one example of mixed-coordination imidazolate of Zn(II) and In(III) (ZIF-5) based on the garnet net is reported. Study of the gas adsorption and thermal and chemical stability of two prototypical members, ZIF-8 and -11, demonstrated their permanent porosity (Langmuir surface area ‫؍‬ 1,810 m 2 ͞g), high thermal stability (up to 550°C), and remarkable chemical resistance to boiling alkaline water and organic solvents.catalysis ͉ hydrogen storage ͉ metal-organic frameworks ͉ porosity ͉ zeolites A large segment of the global economy ($350 billion) is based on the use of crystalline microporous zeolites in petrochemical cracking, ion-exchange for water softening and purification, and in the separation of gases (1). Zeolite structures are composed of tetrahedral Si(Al)O 4 units covalently joined by bridging O atoms to produce Ͼ150 different types of framework (2). A long-standing challenge is to incorporate transition metal ions and organic units within their pores and, more desirably, to do so as an integral part of the zeolite framework. This ability would be useful in many catalytic applications because the pores would be lined with a high concentration of ordered transition metal sites whose electronic and steric properties can be tailored by functionalization of the organic links. However, the vision of achieving such a zeolite that combines these features remains largely unrealized. Here, we outline a general synthesis of structures having zeolite framework topologies in which all tetrahedral atoms are transition metals, and all bridging ones are imidazolate (IM) units.Imidazole can lose a proton to form IM, 1. In examining the dense-phases Co(IM) 2 and Zn(IM) 2 , whose structures are based on nets of linked CoN 4 or ZnN 4 tetrahedra (3, 4), we noticed that IM bridges make an M-IM-M angle, 1, close to 145°, which is coincident with the Si-O-Si angle, 2, which is preferred and commonly found in many zeolites (see Scheme 1). We believed that it should be possible under the right conditions to prepare metal IMs adopting open-framework zeolite structures. Indeed, a number of relatively new Fe(II) (5), Co(II) (6, 7), Cu(II) (8), and Zn(II) (9) IM compounds have structures that are based on zeolite-like tetrahedral nets. However, these materials are relatively dense (nonporous) and͞or low-symmetry structures. Only very recently, Zn(II) IMs having symmetrical porous structures analogous to zeolites were reported (10). Two of the aforementioned compounds are included, as zeolitic IM framework (ZIF)-7 and -8, among the library of ZIFs we report here (Fig. 1).** The focus of th...

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Ligand‐Directed Strategy for Zeolite‐Type Metal–Organic Frameworks: Zinc(II) Imidazolates with Unusual Zeolitic Topologies

Cited by 1,634 publications

References 38 publications

Synthesis and characterization of three amino-functionalized metal–organic frameworks based on the 2-aminoterephthalic ligand

Synthesis and characterization of three amino-functionalized metal–organic frameworks based on the 2-aminoterephthalic ligand

Ultem®/ZIF-8 Mixed Matrix Membranes for Gas Separation: Transport and Physical Properties

Exceptional chemical and thermal stability of zeolitic imidazolate frameworks

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