High-Throughput Synthesis of Zeolitic Imidazolate Frameworks and Application to CO2 Capture

Center for Reticular Chemistry at California NanoSystems Institute, Department of Chemistry and Biochemistry, University of California at Los Angeles, 607 East Charles E. Young Drive, Los Angeles, CA 90095, USA.
Science (Impact Factor: 33.61). 03/2008; 319(5865):939-43. DOI: 10.1126/science.1152516
Source: PubMed


A high-throughput protocol was developed for the synthesis of zeolitic imidazolate frameworks (ZIFs). Twenty-five different
ZIF crystals were synthesized from only 9600 microreactions of either zinc(II)/cobalt(II) and imidazolate/imidazolate-type
linkers. All of the ZIF structures have tetrahedral frameworks: 10 of which have two different links (heterolinks), 16 of
which are previously unobserved compositions and structures, and 5 of which have topologies as yet unobserved in zeolites.
Members of a selection of these ZIFs (termed ZIF-68, ZIF-69, and ZIF-70) have high thermal stability (up to 390°C) and chemical
stability in refluxing organic and aqueous media. Their frameworks have high porosity (with surface areas up to 1970 square
meters per gram), and they exhibit unusual selectivity for CO2 capture from CO2/CO mixtures and extraordinary capacity for storing CO2: 1 liter of ZIF-69 can hold ∼83 liters of CO2 at 273 kelvin under ambient pressure.

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Available from: Hiroyasu Furukawa, Oct 13, 2015
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    • "There is good agreement between the simulated and experimentally obtained patterns, as well as with the literature [12] [27]. The reference patterns were obtained via simulation from the crystallographic information files supplied by the Cambridge Crystallographic Data Centre, who in turn were provided the files from Huang [1] and Banerjee [4]. The anomalies in the experimental patterns (2h < 4°) are due to the reflections from the sample holder. "
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    ABSTRACT: Although a considerable amount of the research is focussed in carbon capture specifically towards flue gas separations, another area that is of interest is CO2/CH4 separation for the natural gas industries. It is believed that 40 % of the world’s reserves of natural gas are sour, and these gas reserves are typically left unexploited due to their high CO2 content and the costs associated with separation and transport. One recent class of adsorbents, metal organic frameworks (MOFs) has been advocated as potential candidates for CO2 removal from natural gas at high pressure. This can be attributed to their high CO2 capacities, which could be exploited in high pressure separations. In this work we synthesised ZIFs -8, -14 and -71 and measured CO2 and CH4 isotherms over a range of temperatures and pressures. The CO2 capacity for these materials at 303 K and 45 bar(a) was in the order of ZIF-8 (9.1 molkg-1) > ZIF-71 (8.1 molkg-1) > ZIF-14 (5.0 molkg-1). The CH4 loading at 303 K and 100 bar(a) was in the order of ZIF-8 (6.8 molkg-1) > ZIF-14 (4.8 molkg-1) > ZIF-71 (4.4 molkg-1). The ideal selectivity of these materials for a 15 %mol CO2, 85 %mol CH4 feed mixture at 100 bar(a) and 303 K was found to be 5.6 for ZIF-8, 4.5 for ZIF-14 and 13 for ZIF-71. This isotherm data was then used to design and simulate a pressure swing adsorption process for CO2/CH4 separation.
    Chemical Engineering Journal 05/2015; 280. DOI:10.1016/j.cej.2015.04.090 · 4.32 Impact Factor
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    • "Therefore, to deal with the problem of global warming, the storage and separation of carbon dioxide gas from the atmosphere is currently a serious challenge. To date, many types of sorbents have been proposed as potential sorbents for carbon dioxide, including metal–organic frameworks [2] [3] [4] [5], zeolitic imidazolate frameworks [6] [7], microporous organic polymers [8] [9], mesoporous silicas [10] [11], and porous carbons [12] [13]. These materials generally possess high specific surface area and permanent porosity, which make them highly competitive in carbon dioxide uptake. "
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    ABSTRACT: We developed a facile method to obtain bulk quantities of three-dimensional porous materials through hydrothermal treatment of aqueous graphene oxide (GO) dispersion at different temperatures. The morphology and textural properties of hydrothermally reduced GO (HRGO) were characterized by scanning electron microscopy, X-ray diffraction, and nitrogen adsorption-desorption measurements. X-ray photoelectron spectroscopy, Raman spectroscopy, and infrared spectroscopy were used to analyze their chemical properties. The as-prepared HRGO not only exhibited three-dimensional porous network structure, but also possessed high specific surface area and large pore volume. Controllable surface functionalities on graphene sheets and textural properties enabled the HRGO to show an excellent carbon dioxide capture performance. The HRGO prepared at 100 degrees C exhibited higher carbon dioxide adsorption capacity (2.4 mmol g(-1) at 1.0 bar and 273 K) than those of the other two porous materials prepared at 80 and 120 degrees C. It was found that in addition to textural properties, the excellent adsorption performance can also be ascribed to various surface interactions between carbon dioxide and HRGO, including acid-base interaction, polar interaction, and hydrogen bonding. This study can be helpful to the development of porous materials for carbon dioxide uptake and separation.
    Carbon 02/2015; 82:590-598. DOI:10.1016/j.carbon.2014.11.014 · 6.20 Impact Factor
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    • "Supported porous layers are of interest for various potential applications as separation membranes, chemical sensors, and optical and electrical devices. Zeolitic imidazolate frameworks (ZIFs) constructed from tetrahedral building blocks, in which each bivalent metal cation (e.g., Zn, Co) joins four imidazole-derived ligands to form neutral open framework structures adopting zeolite topologies , [1] [2] [3] have been recognized as promising candidates for use in membrane-based liquid and gas separations [4] [5] [6]. So far, diverse synthesis protocols have been used to prepare polycrystalline ZIF membranes, including in situ and secondary seeded growth techniques along with others. "
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    ABSTRACT: Zeolitic imidazolate frameworks (ZIFs) have received attention for membrane separation applications due to their zeolite-like permanent porosity and tunable uniformly-sized micropores. Although aqueous room temperature synthesis has apparently opened up environmental friendly and efficient ways to synthesize ZIFs, it poses challenges for membrane preparation including unavoidable homogeneous nucleation. Many ZIF membranes prepared in an aqueous system are based on conventional secondary seeded growth techniques for zeolite membranes in spite of well-recognizing that the coordination chemistry of ZIFs is fundamentally different from the covalent chemistry of zeolites. In this study, we first applied a support-surface activation approach to promote heterogeneous nucleation followed by crystal growth in the aqueous system. Continuous well-intergrown ZIF-8 membranes were successfully grown on α-alumina porous support using zinc acetate and showed relatively-high hydrogen permeance of 6.9×10−7 mol/m2 s Pa with corresponding ideal separation selectivity of 13.6 for the hydrogen/methane. The competitive interaction between the coordination of constructing framework and zinc–acetate interaction by carboxylate functionality of acetate anions is essential to control heterogeneous nucleation and membrane growth. Avoiding the seeding process and reducing the use of organic solvents can provide potential for improving a reproducible, scalable, and commercializable process configuration for membrane preparation.
    Journal of Membrane Science 12/2014; 472:29–38. DOI:10.1016/j.memsci.2014.08.038 · 5.06 Impact Factor
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