MOF-5/n-Bu4NBr: an efficient catalyst system for the synthesis of cyclic carbonates from epoxides and CO2 under mild conditions
TL;DR: In this paper, the coupling reaction of CO2 with propylene oxide (PO) to produce propylene carbonate (PC) catalyzed by MOF-5 (metal-organic frameworks) in the presence of quaternary ammonium salts was studied in different conditions.
About: This article is published in Green Chemistry.The article was published on 2009-07-06. It has received 400 citations till now. The article focuses on the topics: Cycloaddition & Propylene oxide.
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TL;DR: This review provides a comprehensive account of significant progress in the design and synthesis of MOF-based materials, including MOFs, MOF composites and MOF derivatives, and their application to carbon capture and conversion.
Abstract: Rapidly increasing atmospheric CO2 concentrations threaten human society, the natural environment, and the synergy between the two. In order to ameliorate the CO2 problem, carbon capture and conversion techniques have been proposed. Metal–organic framework (MOF)-based materials, a relatively new class of porous materials with unique structural features, high surface areas, chemical tunability and stability, have been extensively studied with respect to their applicability to such techniques. Recently, it has become apparent that the CO2 capture capabilities of MOF-based materials significantly boost their potential toward CO2 conversion. Furthermore, MOF-based materials’ well-defined structures greatly facilitate the understanding of structure–property relationships and their roles in CO2 capture and conversion. In this review, we provide a comprehensive account of significant progress in the design and synthesis of MOF-based materials, including MOFs, MOF composites and MOF derivatives, and their application to carbon capture and conversion. Special emphases on the relationships between CO2 capture capacities of MOF-based materials and their catalytic CO2 conversion performances are discussed.
1,378 citations
TL;DR: This review covers advances in the MOF field from the past three years, focusing on applications, including gas separation, catalysis, drug delivery, optical and electronic applications, and sensing.
Abstract: Metal-organic frameworks (MOFs) represent a new class of hybrid organic-inorganic supramolecular materials comprised of ordered networks formed from organic electron donor linkers and metal cations. They can exhibit extremely high surface areas, as well as tunable pore size and functionality, and can act as hosts for a variety of guest molecules. Since their discovery, MOFs have enjoyed extensive exploration, with applications ranging from gas storage to drug delivery to sensing. This review covers advances in the MOF field from the past three years, focusing on applications, including gas separation, catalysis, drug delivery, optical and electronic applications, and sensing. We also summarize recent work on methods for MOF synthesis and computational modeling.
1,193 citations
TL;DR: In this paper, structural and chemical features of state-of-the-art metal-organic frameworks for their application in the entire carbon cycle of capturing, purifying and transforming CO 2 into valuable products are described.
Abstract: This Review details the structural and chemical features of state-of-the-art metal–organic frameworks for their application in the entire carbon cycle of capturing, purifying and transforming CO 2 into valuable products.
966 citations
TL;DR: The cobalt-coordinated conjugated microporous polymers can also simultaneously function as heterogeneous catalysts for the reaction of CO2 and propylene oxide at atmospheric pressure and room temperature, wherein the polymers demonstrate better efficiency than a homogeneous salen-cobalt catalyst.
Abstract: Conjugated microporous polymers are a new class of porous materials with an extended π-conjugation in an amorphous organic framework. Owing to the wide-ranging flexibility in the choice and design of components and the available control of pore parameters, these polymers can be tailored for use in various applications, such as gas storage, electronics and catalysis. Here we report a class of cobalt/aluminium-coordinated conjugated microporous polymers that exhibit outstanding CO2 capture and conversion performance at atmospheric pressure and room temperature. These polymers can store CO2 with adsorption capacities comparable to metal-organic frameworks. The cobalt-coordinated conjugated microporous polymers can also simultaneously function as heterogeneous catalysts for the reaction of CO2 and propylene oxide at atmospheric pressure and room temperature, wherein the polymers demonstrate better efficiency than a homogeneous salen-cobalt catalyst. By combining the functions of gas storage and catalysts, this strategy provides a direction for cost-effective CO2 reduction processes.
649 citations
TL;DR: In this paper, the advantages and limitations of MOFs as catalysts are summarized and fundamental issues to be addressed about their potential applications, including shape-selective and bifunctional catalysis, and quantifying reaction/transport processes in MOFs, identifying catalytic sites, and determining intrinsic catalytic reaction rates.
Abstract: Metal organic frameworks (MOFs) have drawn wide attention as potential catalysts, offering high densities of catalytic sites in high-area porous solids, some with stabilities at high temperatures. The field is at an early stage, characterized by numerous discoveries and novel demonstrations of catalytic properties associated with the crystalline structures of MOFs, but applications of MOFs as catalysts are still lacking. In this perspective we summarize advantages and limitations of MOFs as catalysts and fundamental issues to be addressed about their potential applications. MOF framework compositions and pore structures can strongly influence catalytic performance, allowing, for example, shape-selective and bifunctional catalysis, but research is needed to quantify reaction/transport processes in MOFs, identify catalytic sites, and determine intrinsic catalytic reaction rates. Progress is hindered by the lack of understanding of the heterogeneity of MOFs, with catalytic sites sometimes being in structures...
529 citations
References
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TL;DR: The aim is to present the state of the art chemistry and physics of and in the micropores of porous coordination polymers, and the next generation of porous functions based on dynamic crystal transformations caused by guest molecules or physical stimuli.
Abstract: The chemistry of the coordination polymers has in recent years advanced extensively, affording various architectures, which are constructed from a variety of molecular building blocks with different interactions between them. The next challenge is the chemical and physical functionalization of these architectures, through the porous properties of the frameworks. This review concentrates on three aspects of coordination polymers: 1). the use of crystal engineering to construct porous frameworks from connectors and linkers ("nanospace engineering"), 2). characterizing and cataloging the porous properties by functions for storage, exchange, separation, etc., and 3). the next generation of porous functions based on dynamic crystal transformations caused by guest molecules or physical stimuli. Our aim is to present the state of the art chemistry and physics of and in the micropores of porous coordination polymers.
9,661 citations
TL;DR: Metal-organic framework (MOF-5), a prototype of a new class of porous materials and one that is constructed from octahedral Zn-O-C clusters and benzene links, was used to demonstrate that its three-dimensional porous system can be functionalized with the organic groups and can be expanded with the long molecular struts biphenyl, tetrahydropyrene, pyrene, and terphenyl.
Abstract: A strategy based on reticulating metal ions and organic carboxylate links into extended networks has been advanced to a point that allowed the design of porous structures in which pore size and functionality could be varied systematically. Metal-organic framework (MOF-5), a prototype of a new class of porous materials and one that is constructed from octahedral Zn-O-C clusters and benzene links, was used to demonstrate that its three-dimensional porous system can be functionalized with the organic groups –Br, –NH2, –OC3H7, –OC5H11, –C2H4, and –C4H4 and that its pore size can be expanded with the long molecular struts biphenyl, tetrahydropyrene, pyrene, and terphenyl. We synthesized an isoreticular series (one that has the same framework topology) of 16 highly crystalline materials whose open space represented up to 91.1% of the crystal volume, as well as homogeneous periodic pores that can be incrementally varied from 3.8 to 28.8 angstroms. One member of this series exhibited a high capacity for methane storage (240 cubic centimeters at standard temperature and pressure per gram at 36 atmospheres and ambient temperature), and others the lowest densities (0.41 to 0.21 gram per cubic centimeter) for a crystalline material at room temperature.
6,922 citations
TL;DR: In this article, an organic dicarboxylate linker is used in a reaction that gives supertetrahedron clusters when capped with monocarboxyates.
Abstract: Open metal–organic frameworks are widely regarded as promising materials for applications1,2,3,4,5,6,7,8,9,10,11,12,13,14,15 in catalysis, separation, gas storage and molecular recognition. Compared to conventionally used microporous inorganic materials such as zeolites, these organic structures have the potential for more flexible rational design, through control of the architecture and functionalization of the pores. So far, the inability of these open frameworks to support permanent porosity and to avoid collapsing in the absence of guest molecules, such as solvents, has hindered further progress in the field14,15. Here we report the synthesis of a metal–organic framework which remains crystalline, as evidenced by X-ray single-crystal analyses, and stable when fully desolvated and when heated up to 300?°C. This synthesis is achieved by borrowing ideas from metal carboxylate cluster chemistry, where an organic dicarboxylate linker is used in a reaction that gives supertetrahedron clusters when capped with monocarboxylates. The rigid and divergent character of the added linker allows the articulation of the clusters into a three-dimensional framework resulting in a structure with higher apparent surface area and pore volume than most porous crystalline zeolites. This simple and potentially universal design strategy is currently being pursued in the synthesis of new phases and composites, and for gas-storage applications.
6,778 citations
6,030 citations
TL;DR: The synthesis of a homochiral metal–organic porous material that allows the enantioselective inclusion of metal complexes in its pores and catalyses a transesterification reaction in an enantiOSElective manner is reported.
Abstract: Inorganic zeolites are used for many practical applications that exploit the microporosity intrinsic to their crystal structures. Organic analogues, which are assembled from modular organic building blocks linked through non-covalent interactions, are of interest for similar applications. These range from catalysis, separation and sensor technology to optoelectronics, with enantioselective separation and catalysis being especially important for the chemical and pharmaceutical industries. The modular construction of these analogues allows flexible and rational design, as both the architecture and chemical functionality of the micropores can, in principle, be precisely controlled. Porous organic solids with large voids and high framework stability have been produced, and investigations into the range of accessible pore functionalities have been initiated. For example, catalytically active organic zeolite analogues are known, as are chiral metal-organic open-framework materials. However, the latter are only available as racemic mixtures, or lack the degree of framework stability or void space that is required for practical applications. Here we report the synthesis of a homochiral metal-organic porous material that allows the enantioselective inclusion of metal complexes in its pores and catalyses a transesterification reaction in an enantioselective manner. Our synthesis strategy, which uses enantiopure metal-organic clusters as secondary building blocks, should be readily applicable to chemically modified cluster components and thus provide access to a wide range of porous organic materials suitable for enantioselective separation and catalysis.
3,598 citations