From porous AlPO 4 to porous BIFs Reported here are a family of crystalline materials based on boron imidazolate frameworks (BIFs). It is demonstrated that the synthetic method, which is based on the crosslinking of various pre-synthesized boron imidazolates by monovalent cations (Li + and Cu + ), is capable of generating a large variety of open frameworks ranging from the 4-connected zeolitic sodalite type to the 3-connected chiral (10,3)-a type.
While it is not uncommon to form chiral crystals during crystallization, the formation of bulk porous homochiral materials from achiral building units is rare. Reported here is the homochiral crystallization of microporous materials through the chirality induction effect of natural alkaloids. The resulting material possesses permanent microporosity and has a uniform pore size of 9.3Å.
Under diverse and dramatically different chemical environments, including organic solvents, an ionic liquid, and a deep eutectic solvent, a series of porous anionic framework materials that contain size-tunable, ion-exchangeable extraframework organic cations have been prepared. Even though a large fraction of the pore space is occupied with charge-balancing cations, some of these materials exhibit a very high gas uptake capacity (e.g., 70.6 cm(3)/g for CO(2) at 1 atm and 273 K), suggesting that the charged anionic framework and extraframework cations may help to enhance the gas adsorption.
From a basic tetrahedral Cu(4)I(4) cluster, a new MTN-type cluster-organic framework (COZ-1) containing giant 6(4)5(12) and 5(12) cages was successfully constructed. The 6(4)5(12) cage has an inner diameter of 2.6 nm and a large pore volume of 9.2 nm(3); these tetrahedral Cu(4)I(4) clusters with bulky size offer new opportunities for not only the formation of 4-connected zeotype structures but also the integration of porosity and photoluminescent properties from both the cluster and the framework.
Metal-organic zeolites (MOZs) are an important branch of metal-organic frameworks (MOFs) and combine the advantages of zeolites and MOFs, such as high surface area and porosity as well as the exceptional stability of zeolites, which would have a significant impact on catalysis chemistry, inorganic chemistry, coordination chemistry, materials science and other areas. In this review, we focus on the recent advances in MOZs with a brief outline of the most prominent examples. In particular, we highlight the basic principles of the design and synthesis approaches toward the construction of MOZs. Obeying the principle of charge matching, tuning tetrahedral metal centers, using enlarged tetrahedral building units as clusters, introducing functional groups into ligands, and combining traditional inorganic TO sites in MOZs enable the final materials with diverse topological structures to exhibit superior performance for various applications, such as gas sorption/separation, catalysis, enantio-selectivity, luminescence, etc.
Traditional semiconducting metal oxide-based gas sensors are always limited on low surface areas and high operating temperatures. Considering the high surface area and high stability of zeolitic imidazolate framework (ZIF), ZIF-67 (surface area of 1832.2 m(2) g(-1)) was first employed as a promising formaldehyde gas sensor at a low operating temperature (150 °C), and the gas sensor could detect formaldehyde as low as 5 ppm. This work develops a new promising application approach for porous metal-organic frameworks.
Crystalline porous materials with diverse chemical compositions (e.g., inorganic porous materials, inorganic-organic hybrid frameworks, and covalent organic frameworks) and framework topologies have been intensively studied in the past 60 years.[1] They have wide applications in fields such as heterogeneous catalysis, gas storage, and separation.[2] Moreover, some currently emerging areas related to health, energy use, and environmental conservation and remediation are still looking for the development of new porous materials. [3][4][5] Zeolites are among the most well known porous materials because of their typical 4-connected open frameworks with TO 4 (T = Si 4+ , Al 3+ , or P 5+ etc.) building blocks and outstanding catalytic or gas separation properties. [6,7] Recently, the search for new zeolite-like structures was extended to metal-organic frameworks (MOFs), and these explorations in part produced a variety of zeolitic imidazolate frameworks (ZIFs) ). [8][9][10][11] The rich chemistry associated with the organic imidazolate building blocks in ZIFs leads to some exceptional properties, such as large surface area and high gas uptake capacities.[12] A question that emerges is: "Are there material with properties intermediate of those of zeolites and ZIFs?". It is true that there is a hybrid state that remains unknown to date.In this work, we were seeking to integrate compositional and structural features of zeolites and ZIFs by combining TO 4 tetrahedra with zinc-imidazolate units. Such a combination is trusted to bear both merits of zeolites and ZIFs, for example, possession of catalytic active TO 4 sits of zeolites and high porosity of ZIFs. Herein, we report this kind of hybrid zeolitic imidazolate framework [denoted HZIFs; general formula: M 4 (im) 6 TO 4 ] with catalytically active TO 4 (T = Mo 6+ or W 6+ ) building blocks and high thermal stability (up to 550 8C), which presents a new class of porous materials filling the gap between zeolites and ZIFs.The HZIFs reported herein are constructed from two kinds of tetrahedral building blocks and contain two kinds of connectivity, and combine structural features of both zeolites and ZIFs (Scheme 1). The TO 4 or WO 4 2À anions, and 2-methylimidazolate (2-mim) under solvothermal conditions. Both compounds were structurally characterized by single-crystal X-ray diffraction and found to be isostructural. They crystallize in the same cubic space group Im " 3 3m and have neutral three-dimensional frameworks Zn 4 (2-mim) 6 TO 4 ·x(solvent) (HZIF-1Mo: T = Mo; HZIF-1W: T = W) containing structurally disordered solvent molecules. In each structure, the tetrahedral TO 4 unit bonds to four Zn centers and the tetrahedral geometry of each Zn center is completed by three 2-mim ligands (Scheme 1 c). The whole framework topology is identified as the 4-connected net with symbol sdt, [13] which is still unknown in both zeolites and ZIFs. A prominent structural feature of this sdt-type framework is to interconnect the truncated octahedral cages of 36 ] by the inorganic Mo...
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