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Journal ArticleDOI

The Chemistry and Applications of Metal-Organic Frameworks

30 Aug 2013-Science (American Association for the Advancement of Science)-Vol. 341, Iss: 6149, pp 1230444-1230444

TL;DR: Metal-organic frameworks are porous materials that have potential for applications such as gas storage and separation, as well as catalysis, and methods are being developed for making nanocrystals and supercrystals of MOFs for their incorporation into devices.
Abstract: Crystalline metal-organic frameworks (MOFs) are formed by reticular synthesis, which creates strong bonds between inorganic and organic units. Careful selection of MOF constituents can yield crystals of ultrahigh porosity and high thermal and chemical stability. These characteristics allow the interior of MOFs to be chemically altered for use in gas separation, gas storage, and catalysis, among other applications. The precision commonly exercised in their chemical modification and the ability to expand their metrics without changing the underlying topology have not been achieved with other solids. MOFs whose chemical composition and shape of building units can be multiply varied within a particular structure already exist and may lead to materials that offer a synergistic combination of properties.
Citations
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Journal ArticleDOI
Zhichao Hu1, Benjamin J. Deibert1, Jing Li1Institutions (1)
TL;DR: This review intends to provide an update of work published since then and focuses on the photoluminescence properties of MOFs and their possible utility in chemical and biological sensing and detection.
Abstract: Metal–organic frameworks (MOFs) are a unique class of crystalline solids comprised of metal cations (or metal clusters) and organic ligands that have shown promise for a wide variety of applications Over the past 15 years, research and development of these materials have become one of the most intensely and extensively pursued areas A very interesting and well-investigated topic is their optical emission properties and related applications Several reviews have provided a comprehensive overview covering many aspects of the subject up to 2011 This review intends to provide an update of work published since then and focuses on the photoluminescence (PL) properties of MOFs and their possible utility in chemical and biological sensing and detection The spectrum of this review includes the origin of luminescence in MOFs, the advantages of luminescent MOF (LMOF) based sensors, general strategies in designing sensory materials, and examples of various applications in sensing and detection

3,042 citations


Journal ArticleDOI
Bao Yu Xia1, Ya Yan1, Nan Li1, Hao Bin Wu1  +2 moreInstitutions (1)
11 Jan 2016-Nature Energy
Abstract: Oxygen electrocatalysis is of great importance for many energy storage and conversion technologies, including fuel cells, metal–air batteries and water electrolysis. Replacing noble metal-based electrocatalysts with highly efficient and inexpensive non-noble metal-based oxygen electrocatalysts is critical for the practical applications of these technologies. Here we report a general approach for the synthesis of hollow frameworks of nitrogen-doped carbon nanotubes derived from metal–organic frameworks, which exhibit higher electrocatalytic activity and stability for oxygen reduction and evolution than commercial Pt/C electrocatalysts. The remarkable electrochemical properties are mainly attributed to the synergistic effect from chemical compositions and the robust hollow structure composed of interconnected crystalline nitrogen-doped carbon nanotubes. The presented strategy for controlled design and synthesis of metal–organic framework-derived functional nanomaterials offers prospects in developing highly active electrocatalysts in electrochemical energy devices. Precious metals are efficient oxygen electrocatalysts but suffer from poor stability and high cost. Now, nitrogen-doped carbon nanotubes derived from metal–organic frameworks are shown to have activity and durability comparable to that of Pt/C catalysts.

1,513 citations


Journal ArticleDOI
Bayrammurad Saparov1, David B. Mitzi1Institutions (1)
04 Apr 2016-Chemical Reviews
TL;DR: This review will explore beyond the current focus on three-dimensional (3-D) lead(II) halide perovskites, to highlight the great chemical flexibility and outstanding potential of the broader class of 3-D and lower dimensional organic-based perovSKite family for electronic, optical, and energy-based applications as well as fundamental research.
Abstract: Although known since the late 19th century, organic–inorganic perovskites have recently received extraordinary research community attention because of their unique physical properties, which make them promising candidates for application in photovoltaic (PV) and related optoelectronic devices. This review will explore beyond the current focus on three-dimensional (3-D) lead(II) halide perovskites, to highlight the great chemical flexibility and outstanding potential of the broader class of 3-D and lower dimensional organic-based perovskite family for electronic, optical, and energy-based applications as well as fundamental research. The concept of a multifunctional organic–inorganic hybrid, in which the organic and inorganic structural components provide intentional, unique, and hopefully synergistic features to the compound, represents an important contemporary target.

1,478 citations


Journal ArticleDOI
TL;DR: The achieved ultrahigh oxygen evolution activity and strong durability, with superior performance in comparison to the state-of-the-art noble-metal/transition-metal and nonmetal catalysts, originate from the unique nanowire array electrode configuration and in situ carbon incorporation, which lead to the large active surface area, enhanced mass/charge transport capability, easy release of oxygen gas bubbles, and strong structural stability.
Abstract: Hybrid porous nanowire arrays composed of strongly interacting Co3O4 and carbon were prepared by a facile carbonization of the metal–organic framework grown on Cu foil. The resulting material, possessing a high surface area of 251 m2 g–1 and a large carbon content of 52.1 wt %, can be directly used as the working electrode for oxygen evolution reaction without employing extra substrates or binders. This novel oxygen evolution electrode can smoothly operate in alkaline solutions (e.g., 0.1 and 1.0 M KOH), affording a low onset potential of 1.47 V (vs reversible hydrogen electrode) and a stable current density of 10.0 mA cm–2 at 1.52 V in 0.1 M KOH solution for at least 30 h, associated with a high Faradaic efficiency of 99.3%. The achieved ultrahigh oxygen evolution activity and strong durability, with superior performance in comparison to the state-of-the-art noble-metal/transition-metal and nonmetal catalysts, originate from the unique nanowire array electrode configuration and in situ carbon incorporati...

1,453 citations


References
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Journal ArticleDOI
Omar M. Yaghi1, Michael O'Keeffe2, Nathan W. Ockwig1, Hee K. Chae1  +3 moreInstitutions (3)
12 Jun 2003-Nature
TL;DR: This work has shown that highly porous frameworks held together by strong metal–oxygen–carbon bonds and with exceptionally large surface area and capacity for gas storage have been prepared and their pore metrics systematically varied and functionalized.
Abstract: The long-standing challenge of designing and constructing new crystalline solid-state materials from molecular building blocks is just beginning to be addressed with success. A conceptual approach that requires the use of secondary building units to direct the assembly of ordered frameworks epitomizes this process: we call this approach reticular synthesis. This chemistry has yielded materials designed to have predetermined structures, compositions and properties. In particular, highly porous frameworks held together by strong metal-oxygen-carbon bonds and with exceptionally large surface area and capacity for gas storage have been prepared and their pore metrics systematically varied and functionalized.

7,384 citations


"The Chemistry and Applications of M..." refers background in this paper

  • ...These materials are constructed by joining metal-containing units [secondary building units (SBUs)] with organic linkers, using strong bonds (reticular synthesis) to create open crystalline frameworks with permanent porosity (1)....

    [...]

  • ...MOF-1001 [Zn4O(BPP34C10DA)3; BPP34C10DA = 4,4′-(2,5,8,11,14,16,19,22,25,28decaoxa-1,15(1,4)-dibenzenacyclooctacosaphane1(2),1(5)-diylbis(ethyne-2,1-diyl))dibenzoate] uses periodic crown ether receptors attached to the architectural framework; this endows the pore with active domains capable of molecular recognition of highly disordered guests in a stereoelectronically controlled fashion (Fig....

    [...]

  • ...works inwhich single atomswere linked by ditopic coordinating linkers (1)....

    [...]


Journal ArticleDOI
Mohamed Eddaoudi1, Jaheon Kim1, Nathaniel L. Rosi1, David T. Vodak1  +3 moreInstitutions (2)
18 Jan 2002-Science
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.

6,376 citations


"The Chemistry and Applications of M..." refers background in this paper

  • ...changing its underlying topology) in the design of MOFs with ultrahigh porosity and unusually large pore openings (5)....

    [...]

  • ...One of the smallest isoreticular structures of MOF-5 is Zn4O(fumarate)3 (34); one of the largest is IRMOF-16 [Zn4O(TPDC)3; TPDC 2– = terphenyl-4,4′′-dicarboxylate] (5) (fig....

    [...]


Journal ArticleDOI
JeongYong Lee1, Omar K. Farha1, John M. Roberts1, Karl A. Scheidt1  +2 moreInstitutions (1)
TL;DR: A critical review of the emerging field of MOF-based catalysis is presented and examples of catalysis by homogeneous catalysts incorporated as framework struts or cavity modifiers are presented.
Abstract: A critical review of the emerging field of MOF-based catalysis is presented. Discussed are examples of: (a) opportunistic catalysis with metal nodes, (b) designed catalysis with framework nodes, (c) catalysis by homogeneous catalysts incorporated as framework struts, (d) catalysis by MOF-encapsulated molecular species, (e) catalysis by metal-free organic struts or cavity modifiers, and (f) catalysis by MOF-encapsulated clusters (66 references).

6,356 citations


"The Chemistry and Applications of M..." refers background in this paper

  • ...MOFs can be used to support homogeneous catalysts, stabilize short-lived catalysts, perform size selectivity, and encapsulate catalysts within their pores (70)....

    [...]


Journal ArticleDOI
18 Nov 1999-Nature
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.

5,961 citations


"The Chemistry and Applications of M..." refers background in this paper

  • ...A major advance in the chemistry of MOFs came in 1999 when the synthesis, x-ray singlecrystal structure determination, and low-temperature, low-pressure gas sorption properties were reported for the first robust and highly porousMOF,MOF-5 (13)....

    [...]


Book
01 Jan 1945-

5,801 citations


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No. of citations received by the Paper in previous years
YearCitations
202260
20211,591
20201,505
20191,347
20181,131
2017966