High-Throughput Synthesis of Zeolitic Imidazolate Frameworks and Application to CO ₂ Capture

Abstract

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 degrees 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 approximately 83 liters of CO2 at 273 kelvin under ambient pressure.

Microporous metal-organic framework with potential for carbon dioxide capture at ambient conditions

“…The regeneration energy cost to utilize these porous materials for CO 2 capture by the implementation of temperature swing adsorption, pressure swing adsorption (PSA) and vacuum swing adsorption is significantly lower than the abovementioned alkanolamine technology. More importantly, the rapid development over the past decade in this research field to target some porous MOFs for their extremely high uptake of CO 2 at high pressure 11,12 and to immobilize functional sites, such as open metal sites [13][14][15][16][17][18][19][20][21][22][23] , -NH 2 and -OH organic sites into the pore surfaces to enhance their interactions and thus enforce their efficient CO 2 separation selectivity have principally ensured the feasibility of porous MOFs for CO 2 capture [24][25][26][27][28][29][30][31][32][33][34][35][36][37][38] .…”

In situ crystal growth of zeolitic imidazolate frameworks (ZIF) on electrospun polyurethane nanofibers

“…Particularly, ZIF-8 is one of the most interesting structures first synthesized by Yaghi's group. 5 In recent years, the design of the hierarchical ZIF-8 nanostructure has attracted the attention of many scientists. For instance, continuous and compact ZIF-8 membranes using α-Al 2 O 3 , 6 polyethersulfone 7 or titania 8 as supports have shown high selectivity to mixed gases.…”

Modelling a Linker Mix‐and‐Match Approach for Controlling the Optical Excitation Gaps and Band Alignment of Zeolitic Imidazolate Frameworks

“…For each composition, the lowest‐energy mixed configuration is significantly stable with respect to the separated pure phases (by 0.2–0.4 eV per formula unit, see Supporting Information), which indeed suggests they should be able to form experimentally. It is known that mixed‐linker ZIFs can be synthesized solvothermally, via the reaction of equimolar amounts of the two protonated linkers with the divalent metal nitrate; this has been demonstrated by Yaghi et al.,16 who reported the formation of structures with ordered distributions of linkers 17. Figure 2 c shows the HOCO and LUCO levels for the most stable mixed ZIFs with compositions Zn(fIm)(nIm) and Zn(mIm)(nIm).…”