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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    • "Zheng and co-workers integrated metal carboxylates and boron imidazolates to prepare a novel family of BIFs called MC-BIFs [12]. Amongst these materials, MC-BIF-2H exhibits extraordinary volumetric capacity for storing CO 2 (81 L/L at 273 K and ambient pressure), comparable to that previously reported for a highly porous ZIF-69 (83 L/L) [13]. Zhang et al. developed a new strategy for the design of zeolite-type MOFs. "

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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.
    The 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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