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Sample records for metal-organic framework material

  1. Purification of metal-organic framework materials

    SciTech Connect

    Farha, Omar K.; Hupp, Joseph T.

    2012-12-04

    A method of purification of a solid mixture of a metal-organic framework (MOF) material and an unwanted second material by disposing the solid mixture in a liquid separation medium having a density that lies between those of the wanted MOF material and the unwanted material, whereby the solid mixture separates by density differences into a fraction of wanted MOF material and another fraction of unwanted material.

  2. Purification of metal-organic framework materials

    DOEpatents

    Farha, Omar K.; Hupp, Joseph T.

    2015-06-30

    A method of purification of a solid mixture of a metal-organic framework (MOF) material and an unwanted second material by disposing the solid mixture in a liquid separation medium having a density that lies between those of the wanted MOF material and the unwanted material, whereby the solid mixture separates by density differences into a fraction of wanted MOF material and another fraction of unwanted material.

  3. Emerging Multifunctional Metal-Organic Framework Materials.

    PubMed

    Li, Bin; Wen, Hui-Min; Cui, Yuanjing; Zhou, Wei; Qian, Guodong; Chen, Banglin

    2016-10-01

    Metal-organic frameworks (MOFs), also known as coordination polymers, represent an interesting type of solid crystalline materials that can be straightforwardly self-assembled through the coordination of metal ions/clusters with organic linkers. Owing to the modular nature and mild conditions of MOF synthesis, the porosities of MOF materials can be systematically tuned by judicious selection of molecular building blocks, and a variety of functional sites/groups can be introduced into metal ions/clusters, organic linkers, or pore spaces through pre-designing or post-synthetic approaches. These unique advantages enable MOFs to be used as a highly versatile and tunable platform for exploring multifunctional MOF materials. Here, the bright potential of MOF materials as emerging multifunctional materials is highlighted in some of the most important applications for gas storage and separation, optical, electric and magnetic materials, chemical sensing, catalysis, and biomedicine.

  4. Metal-organic framework materials with ultrahigh surface areas

    DOEpatents

    Farha, Omar K.; Hupp, Joseph T.; Wilmer, Christopher E.; Eryazici, Ibrahim; Snurr, Randall Q.; Gomez-Gualdron, Diego A.; Borah, Bhaskarjyoti

    2015-12-22

    A metal organic framework (MOF) material including a Brunauer-Emmett-Teller (BET) surface area greater than 7,010 m.sup.2/g. Also a metal organic framework (MOF) material including hexa-carboxylated linkers including alkyne bond. Also a metal organic framework (MOF) material including three types of cuboctahedron cages fused to provide continuous channels. Also a method of making a metal organic framework (MOF) material including saponifying hexaester precursors having alkyne bonds to form a plurality of hexa-carboxylated linkers including alkyne bonds and performing a solvothermal reaction with the plurality of hexa-carboxylated linkers and one or more metal containing compounds to form the MOF material.

  5. Porous materials: Lining up metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Champness, Neil R.

    2017-02-01

    A new report demonstrates an innovative approach to aligning crystallites of metal-organic frameworks such that thin films are created with oriented channels -- potentially overcoming one of the major barriers to application of these highly topical materials.

  6. Metal-Organic Frameworks as Platforms for Functional Materials.

    PubMed

    Cui, Yuanjing; Li, Bin; He, Huajun; Zhou, Wei; Chen, Banglin; Qian, Guodong

    2016-03-15

    Discoveries of novel functional materials have played very important roles to the development of science and technologies and thus to benefit our daily life. Among the diverse materials, metal-organic framework (MOF) materials are rapidly emerging as a unique type of porous and organic/inorganic hybrid materials which can be simply self-assembled from their corresponding inorganic metal ions/clusters with organic linkers, and can be straightforwardly characterized by various analytical methods. In terms of porosity, they are superior to other well-known porous materials such as zeolites and carbon materials; exhibiting extremely high porosity with surface area up to 7000 m(2)/g, tunable pore sizes, and metrics through the interplay of both organic and inorganic components with the pore sizes ranging from 3 to 100 Å, and lowest framework density down to 0.13 g/cm(3). Such unique features have enabled metal-organic frameworks to exhibit great potentials for a broad range of applications in gas storage, gas separations, enantioselective separations, heterogeneous catalysis, chemical sensing and drug delivery. On the other hand, metal-organic frameworks can be also considered as organic/inorganic self-assembled hybrid materials, we can take advantages of the physical and chemical properties of both organic and inorganic components to develop their functional optical, photonic, and magnetic materials. Furthermore, the pores within MOFs can also be utilized to encapsulate a large number of different species of diverse functions, so a variety of functional MOF/composite materials can be readily synthesized. In this Account, we describe our recent research progress on pore and function engineering to develop functional MOF materials. We have been able to tune and optimize pore spaces, immobilize specific functional groups, and introduce chiral pore environments to target MOF materials for methane storage, light hydrocarbon separations, enantioselective recognitions

  7. Methods for associating or dissociating guest materials with a metal organic framework, systems for associating or dissociating guest materials within a series of metal organic frameworks, thermal energy transfer assemblies, and methods for transferring thermal energy

    DOEpatents

    McGrail, B. Peter; Brown, Daryl R.; Thallapally, Praveen K.

    2016-08-02

    Methods for releasing associated guest materials from a metal organic framework are provided. Methods for associating guest materials with a metal organic framework are also provided. Methods are provided for selectively associating or dissociating guest materials with a metal organic framework. Systems for associating or dissociating guest materials within a series of metal organic frameworks are provided. Thermal energy transfer assemblies are provided. Methods for transferring thermal energy are also provided.

  8. Methods for associating or dissociating guest materials with a metal organic framework, systems for associating or dissociating guest materials within a series of metal organic frameworks, thermal energy transfer assemblies, and methods for transferring thermal energy

    DOEpatents

    McGrail, B. Peter; Brown, Daryl R.; Thallapally, Praveen K.

    2014-08-05

    Methods for releasing associated guest materials from a metal organic framework are provided. Methods for associating guest materials with a metal organic framework are also provided. Methods are provided for selectively associating or dissociating guest materials with a metal organic framework. Systems for associating or dissociating guest materials within a series of metal organic frameworks are provided. Thermal energy transfer assemblies are provided. Methods for transferring thermal energy are also provided.

  9. Metal-organic frameworks as functional, porous materials

    NASA Astrophysics Data System (ADS)

    Rood, Jeffrey A.

    The research presented in this thesis investigates the use of metal carboxylates as permanently porous materials called metal-organic frameworks (MOFs). The project has focused on three broad areas of study, each which strives to develop a further understanding of this class of materials. The first topic is concerned with the synthesis and structural characterization of MOFs. Our group and others have found that the reaction of metal salts with carboxylic acids in polar solvents at elevated temperatures often leads the formation of crystalline MOF materials that can be examined by single crystal X-ray diffraction. Specifically, Chapter 2 reports on some of the first examples of magnesium MOFs, constructed from formate or aryldicarboxylate ligands. The magnesium formate MOF, [Mg3(O2CH) 6] was found to be a permanently porous 3-D material capable of selective uptake and exchange of small molecules. Once the synthesis and structures of some of these materials was known, their physical properties were studied. The magnesium formate MOF, [Mg 3(O2CH)6], was found to be permanently porous and able to reversibly adsorb both N2 and H2 gas. Furthermore, the material was also capable of taking up a variety of organic molecules to form new inclusion compounds that were characterized by XRD studies. Size exclusion was shown for cyclohexane and larger molecules. Chapters 3, 5, and 6 attempt to build off of the synthetic findings reported in Chapter 2. Specifically, the ability of these materials to take up guest molecules is expanded by the attempted synthesis of porous, homochiral MOFs using enantiopure carboxylic acids in the synthesis. It was found that under the appropriate synthetic conditions, both L-tartaric acid and (+)-camphoric acid were robust linkers for the formation of homochiral MOFs. Of the compounds synthesized, the most interesting were the set of compounds, [Zn2(Cam) 2(bipy)⊃3DMF] and [Zn2(Cam)2(apyr)⊃2DMF]. These compounds formed isoreticular cubic

  10. Metal-organic framework materials based on icosahedral boranes and carboranes

    DOEpatents

    Mirkin, Chad A.; Hupp, Joseph T.; Farha, Omar K.; Spokoyny, Alexander M.; Mulfort, Karen L.

    2010-11-02

    Disclosed herein are metal-organic frameworks of metals and boron rich ligands, such as carboranes and icosahedral boranes. Methods of synthesizing and using these materials in gas uptake are disclosed.

  11. Selective Bifunctional Modification of a Non-catenated Metal-Organic Framework Material via 'Click' Chemistry

    SciTech Connect

    Gadzikwa, Tendai; Farha, Omar K.; Malliakas, Christos D.; Kanatzidis, Mercouri G.; Hupp, Joseph T.; Nguyen, SonBinh T.; NWU

    2009-12-01

    A noncatenated, Zn-based metal-organic framework (MOF) material bearing silyl-protected acetylenes was constructed and postsynthetically modified using 'click' chemistry. Using a solvent-based, selective deprotection strategy, two different organic azides were 'clicked' onto the MOF crystals, resulting in a porous material whose internal and external surfaces are differently functionalized.

  12. Metal-organic frameworks as host materials of confined supercooled liquids

    NASA Astrophysics Data System (ADS)

    Fischer, J. K. H.; Sippel, P.; Denysenko, D.; Lunkenheimer, P.; Volkmer, D.; Loidl, A.

    2015-10-01

    In this work, we examine the use of metal-organic framework (MOF) systems as host materials for the investigation of glassy dynamics in confined geometry. We investigate the confinement of the molecular glass former glycerol in three MFU-type MOFs with different pore sizes (MFU stands for "Metal-Organic Framework Ulm-University") and study the dynamics of the confined liquid via dielectric spectroscopy. In accord with previous reports on confined glass formers, we find different degrees of deviations from bulk behavior depending on pore size, demonstrating that MOFs are well-suited host systems for confinement investigations.

  13. Selective Adsorption of Sulfur Dioxide in a Robust Metal-Organic Framework Material.

    PubMed

    Savage, Mathew; Cheng, Yongqiang; Easun, Timothy L; Eyley, Jennifer E; Argent, Stephen P; Warren, Mark R; Lewis, William; Murray, Claire; Tang, Chiu C; Frogley, Mark D; Cinque, Gianfelice; Sun, Junliang; Rudić, Svemir; Murden, Richard T; Benham, Michael J; Fitch, Andrew N; Blake, Alexander J; Ramirez-Cuesta, Anibal J; Yang, Sihai; Schröder, Martin

    2016-10-01

    Selective adsorption of SO2 is realized in a porous metal-organic framework material, and in-depth structural and spectroscopic investigations using X-rays, infrared, and neutrons define the underlying interactions that cause SO2 to bind more strongly than CO2 and N2 .

  14. A Look into PNNL’s New Way of Making Metal Organic Framework Materials (MOFs)

    SciTech Connect

    2016-07-25

    Metal organic framework materials are used in many energy-efficient and green technologies. PNNL researchers may bring their commercial use a step closer to reality by developing a new way to create these materials in larger quantities, better qualities, and more quickly than ever before. This video is a step-by-step look at how our PNNL scientists create MOFs with 80% efficacy.

  15. polyMOFs: A Class of Interconvertible Polymer-Metal-Organic-Framework Hybrid Materials.

    PubMed

    Zhang, Zhenjie; Nguyen, Ha Thi Hoang; Miller, Stephen A; Cohen, Seth M

    2015-05-18

    Preparation of porous materials from one-dimensional polymers is challenging because the packing of polymer chains results in a dense, non-porous arrangement. Herein, we demonstrate the remarkable adaptation of an amorphous, linear, non-porous, flexible organic polymer into a three-dimensional, highly porous, crystalline solid, as the organic component of a metal-organic framework (MOF). A polymer with aromatic dicarboxylic acids in the backbone functioned as a polymer ligand upon annealing with Zn(II), generating a polymer-metal-organic framework (polyMOF). These materials break the dogma that MOFs must be prepared from small, rigid ligands. Similarly, polyMOFs contradict conventional polymer chemistry by demonstrating that linear and amorphous polymers can be readily coaxed into a highly crystalline, porous, three-dimensional structure by coordination chemistry.

  16. Flexibility in metal-organic framework materials: Impact on sorption properties

    NASA Astrophysics Data System (ADS)

    Fletcher, Ashleigh J.; Thomas, K. Mark; Rosseinsky, Matthew J.

    2005-08-01

    Recent years have seen the development of a new class of porous coordination polymers known collectively as metal organic framework materials (MOFs). This review outlines recent progress in understanding how adsorption characteristics of these systems differ from rigid classical sorbents such as activated carbon and zeolites. Gas/vapor adsorption studies for characterization of the porous structures of MOF materials are reviewed and differences in adsorption characteristics based on detailed measurement of equilibrium and dynamical sorption behavior, compared with previous generations of sorbents, are highlighted. The role of framework flexibility and specific structural features, such as windows and pore cavities, within the MOF porous structures are discussed in relation to adsorption mechanisms.

  17. Recent advances in porous polyoxometalate-based metal-organic framework materials.

    PubMed

    Du, Dong-Ying; Qin, Jun-Sheng; Li, Shun-Li; Su, Zhong-Min; Lan, Ya-Qian

    2014-07-07

    Polyoxometalate (POM)-based metal-organic framework (MOF) materials contain POM units and generally generate MOF materials with open networks. POM-based MOF materials, which utilize the advantages of both POMs and MOFs, have received increasing attention, and much effort has been devoted to their preparation and relevant applications over the past few decades. They have good prospects in catalysis owing to the electronic and physical properties of POMs that are tunable by varying constituent elements. In this review, we present recent developments in porous POM-based MOF materials, including their classification, synthesis strategies, and applications, especially in the field of catalysis.

  18. Barcoded materials based on photoluminescent hybrid system of lanthanide ions-doped metal organic framework and silica via ion exchange.

    PubMed

    Shen, Xiang; Yan, Bing

    2016-04-15

    A multicolored photoluminescent hybrid system based on lanthanide ions-doped metal organic frameworks/silica composite host has potential in display and barcode applications. By controlling the stoichiometry of the lanthanides via cation exchange, proportional various lanthanide ions are successfully introduced into metal organic frameworks, whose emission intensity is correspondingly proportional to its amount. The resulting luminescent barcodes depend on the lanthanide ions ratios and compositions. Subsequently, the lanthanide ions located in the channels of metal organic frameworks are protected from any interaction with the environment after the modification of silica on the surface. The optical and thermal stability of the hybrid materials are improved for technological application.

  19. Metal-organic frameworks as competitive materials for non-linear optics.

    PubMed

    Mingabudinova, L R; Vinogradov, V V; Milichko, V A; Hey-Hawkins, E; Vinogradov, A V

    2016-09-26

    The last five years have witnessed a huge breakthrough in the creation and the study of the properties of a new class of compounds - metamaterials. The next stage of this technological revolution will be the development of active, controllable, and non-linear metamaterials, surpassing natural media as platforms for optical data processing and quantum information applications. However, scientists are constantly faced with the need to find new methods that can ensure the formation of quantum and non-linear metamaterials with higher resolution. One such method of producing metamaterials in the future, which will provide scalability and availability, is chemical synthesis. Meanwhile, the chemical synthesis of organized 3D structures with a period of a few nanometers and a size of up to a few millimeters is not an easy task and is yet to be resolved. The most promising avenue seems to be the use of highly porous structures based on metal-organic frameworks that have demonstrated their unique properties in the field of non-linear optics (NLO) over the past three years. Thus, the aim of this review is to examine current progress and the possibilities of using metal-organic frameworks in the field of non-linear optics as chemically obtained metamaterials of the future. The review begins by presenting the theoretical principles of physical phenomena represented by mathematical descriptions for clarity. Major attention is paid to the second harmonic generation (SHG) effect. In this section we compare inorganic single crystals, which are most commonly used to study the effect in question, to organic materials, which also possess the required properties. Based on these data, we present a rationale for the possibility of studying the non-linear optical properties of metal-organic structures as well as describing the use of synthetic approaches and the difficulties associated with them. The second part of the review explicitly acquaints the reader with a new class of materials

  20. Tetratopic phenyl compounds, related metal-organic framework materials and post-assembly elaboration

    DOEpatents

    Farha, Omar K.; Hupp, Joseph T.

    2012-09-11

    Disclosed are tetratopic carboxylic acid phenyl for use in metal-organic framework compounds. These compounds are useful in catalysis, gas storage, sensing, biological imaging, drug delivery and gas adsorption separation.

  1. Tetratopic phenyl compounds, related metal-organic framework materials and post-assembly elaboration

    DOEpatents

    Farha, Omar K; Hupp, Joseph T

    2013-06-25

    Disclosed are tetratopic carboxylic acid phenyl for use in metal-organic framework compounds. These compounds are useful in catalysis, gas storage, sensing, biological imaging, drug delivery and gas adsorption separation.

  2. Metallated metal-organic frameworks

    DOEpatents

    Bury, Wojciech; Farha, Omar K.; Hupp, Joseph T.; Mondloch, Joseph E.

    2017-02-07

    Porous metal-organic frameworks (MOFs) and metallated porous MOFs are provided. Also provided are methods of metallating porous MOFs using atomic layer deposition and methods of using the metallated MOFs as catalysts and in remediation applications.

  3. Imparting biomolecules to a metal-organic framework material by controlled DNA tetrahedron encapsulation.

    PubMed

    Jia, Yongmei; Wei, Benmei; Duan, Ruixue; Zhang, Ying; Wang, Boya; Hakeem, Abdul; Liu, Nannan; Ou, Xiaowen; Xu, Shaofang; Chen, Zhifei; Lou, Xiaoding; Xia, Fan

    2014-08-04

    Recently, the incorporation of biomolecules in Metal-organic frameworks (MOFs) attracts many attentions because of controlling the functions, properties and stability of trapped molecules. Although there are few reports on protein/MOFs composites and their applications, none of DNA/MOFs composite is reported, as far as we know. Here, we report a new composite material which is self-assembled from 3D DNA (guest) and pre-synthesized MOFs (host) by electrostatic interactions and hydrophilic interactions in a well-dispersed fashion. Its biophysical characterization is well analyzed by fluorescence spectroscopy, quartz crystal microbalance (QCM) and transmission electron microscopy (TEM). This new composite material keeps 3D DNA nanostructure more stable than only 3D DNA nanostructure in DI water at room temperature, and stores amounts of genetic information. It will make DNA as a guest for MOFs and MOFs become a new platform for the development of DNA nanotechnology.

  4. Metal-organic Frameworks as A Tunable Platform for Designing Functional Molecular Materials

    PubMed Central

    Wang, Cheng; Liu, Demin

    2013-01-01

    Metal-organic frameworks (MOFs), also known as coordination polymers, represent an interesting class of crystalline molecular materials that are synthesized by combining metal-connecting points and bridging ligands. The modular nature of and mild conditions for MOF synthesis have permitted the rational structural design of numerous MOFs and the incorporation of various functionalities via constituent building blocks. The resulting designer MOFs have shown promise for applications in a number of areas, including gas storage/separation, nonlinear optics/ferroelectricity, catalysis, energy conversion/storage, chemical sensing, biomedical imaging, and drug delivery. The structure-property relationships of MOFs can also be readily established by taking advantage of the knowledge of their detailed atomic structures, which enables fine-tuning of their functionalities for desired applications. Through the combination of molecular synthesis and crystal engineering MOFs thus present an unprecedented opportunity for the rational and precise design of functional materials. PMID:23944646

  5. Separation of C2 Hydrocarbons by Porous Materials: Metal Organic Frameworks as Platform

    SciTech Connect

    Banerjee, Debasis; Liu, Jun; Thallapally, Praveen K.

    2014-12-22

    The effective separation of small hydrocarbon molecules (C1 – C4) is an important process for petroleum industry, determining the end price of many essential commodities in our daily lives. Current technologies for separation of these molecules rely on energy intensive fractional distillation processes at cryogenic temperature, which is particularly difficult because of their similar volatility. In retrospect, adsorptive separation using solid state adsorbents might be a cost effective alternative. Several types of solid state adsorbents (e.g. zeolite molecular sieves) were tested for separation of small hydrocarbon molecules as a function of pressure, temperature or vacuum. Among different types of plausible adsorbents, metal organic frameworks (MOFs), a class of porous, crystalline, inorganic-organic hybrid materials, is particularly promising. In this brief comment article, we discuss the separation properties of different types of solid state adsorbents, with a particular emphasis on MOF based adsorbents for separation of C2 hydrocarbon molecules.

  6. Metal-Organic Frameworks: Literature Survey and Recommendation of Potential Sorbent Materials

    SciTech Connect

    Baumann, T F

    2010-04-29

    Metal-organic frameworks (MOFs) are a special type of porous material with a number of unique properties, including exceptionally high surface areas, large internal pore volumes (void space) and tunable pore sizes. These materials are prepared through the assembly of molecular building blocks into ordered three-dimensional structures. The bulk properties of the MOF are determined by the nature of the building blocks and, as such, these materials can be designed with special characteristics that cannot be realized in other sorbent materials, like activated carbons. For example, MOFs can be constructed with binding sites or pockets that can exhibit selectivity for specific analytes. Alternatively, the framework can be engineered to undergo reversible dimensional changes (or 'breathing') upon interaction with an analyte, effectively trapping the molecule of interest in the lattice structure. In this report, we have surveyed the 4000 different MOF structures reported in the open literature and provided recommendations for specific MOF materials that should be investigated as sorbents for this project.

  7. van der Waals Metal-Organic Framework as an Excitonic Material for Advanced Photonics.

    PubMed

    Milichko, Valentin A; Makarov, Sergey V; Yulin, Alexey V; Vinogradov, Alexandr V; Krasilin, Andrei A; Ushakova, Elena; Dzyuba, Vladimir P; Hey-Hawkins, Evamarie; Pidko, Evgeny A; Belov, Pavel A

    2017-01-23

    Synergistic combination of organic and inorganic nature in van der Waals metal-organic frameworks supports different types of robust excitons that can be effectively and independently manipulated by light at room temperature, and opens new concepts for all-optical data processing and storage.

  8. Creating a Discovery Platform for Confined-Space Chemistry and Materials: Metal-Organic Frameworks.

    SciTech Connect

    Allendorf, Mark D.; Greathouse, Jeffery A.; Simmons, Blake

    2008-09-01

    Metal organic frameworks (MOF) are a recently discovered class of nanoporous, defect-free crystalline materials that enable rational design and exploration of porous materials at the molecular level. MOFs have tunable monolithic pore sizes and cavity environments due to their crystalline nature, yielding properties exceeding those of most other porous materials. These include: the lowest known density (91% free space); highest surface area; tunable photoluminescence; selective molecular adsorption; and methane sorption rivaling gas cylinders. These properties are achieved by coupling inorganic metal complexes such as ZnO4 with tunable organic ligands that serve as struts, allowing facile manipulation of pore size and surface area through reactant selection. MOFs thus provide a discovery platform for generating both new understanding of chemistry in confined spaces and novel sensors and devices based on their unique properties. At the outset of this project in FY06, virtually nothing was known about how to couple MOFs to substrates and the science of MOF properties and how to tune them was in its infancy. An integrated approach was needed to establish the required knowledge base for nanoscale design and develop methodologies integrate MOFs with other materials. This report summarizes the key accomplishments of this project, which include creation of a new class of radiation detection materials based on MOFs, luminescent MOFs for chemical detection, use of MOFs as templates to create nanoparticles of hydrogen storage materials, MOF coatings for stress-based chemical detection using microcantilevers, and "flexible" force fields that account for structural changes in MOFs that occur upon molecular adsorption/desorption. Eight journal articles, twenty presentations at scientific conferences, and two patent applications resulted from the work. The project created a basis for continuing development of MOFs for many Sandia applications and succeeded in securing $2.75 M in

  9. Synthesis and gas adsorption study of porous metal-organic framework materials

    NASA Astrophysics Data System (ADS)

    Mu, Bin

    Metal-organic frameworks (MOFs) or porous coordination polymers (PCPs) have become the focus of intense study over the past decade due to their potential for advancing a variety of applications including air purification, gas storage, adsorption separations, catalysis, gas sensing, drug delivery, and so on. These materials have some distinct advantages over traditional porous materials such as the well-defined structures, uniform pore sizes, chemically functionalized sorption sites, and potential for postsynthetic modification, etc. Thus, synthesis and adsorption studies of porous MOFs have increased substantially in recent years. Among various prospective applications, air purification is one of the most immediate concerns, which has urgent requirements to improve current nuclear, biological, and chemical (NBC) filters involving commercial and military purposes. Thus, the major goal of this funded project is to search, synthesize, and test these novel hybrid porous materials for adsorptive removal of toxic industrial chemicals (TICs) and chemical warfare agents (CWAs), and to install the benchmark for new-generation NBC filters. The objective of this study is three-fold: (i) Advance our understanding of coordination chemistry by synthesizing novel MOFs and characterizing these porous coordination polymers; (ii) Evaluate porous MOF materials for gasadsorption applications including CO2 capture, CH4 storage, other light gas adsorption and separations, and examine the chemical and physical properties of these solid adsorbents including thermal stability and heat capacity of MOFs; (iii) Evaluate porous MOF materials for next-generation NBC filter media by adsorption breakthrough measurements of TICs on MOFs, and advance our understanding about structureproperty relationships of these novel adsorbents.

  10. A porous proton-relaying metal-organic framework material that accelerates electrochemical hydrogen evolution

    PubMed Central

    Hod, Idan; Deria, Pravas; Bury, Wojciech; Mondloch, Joseph E.; Kung, Chung-Wei; So, Monica; Sampson, Matthew D.; Peters, Aaron W.; Kubiak, Cliff P.; Farha, Omar K.; Hupp, Joseph T.

    2015-01-01

    The availability of efficient hydrogen evolution reaction (HER) catalysts is of high importance for solar fuel technologies aimed at reducing future carbon emissions. Even though Pt electrodes are excellent HER electrocatalysts, commercialization of large-scale hydrogen production technology requires finding an equally efficient, low-cost, earth-abundant alternative. Here, high porosity, metal-organic framework (MOF) films have been used as scaffolds for the deposition of a Ni-S electrocatalyst. Compared with an MOF-free Ni-S, the resulting hybrid materials exhibit significantly enhanced performance for HER from aqueous acid, decreasing the kinetic overpotential by more than 200 mV at a benchmark current density of 10 mA cm−2. Although the initial aim was to improve electrocatalytic activity by greatly boosting the active area of the Ni-S catalyst, the performance enhancements instead were found to arise primarily from the ability of the proton-conductive MOF to favourably modify the immediate chemical environment of the sulfide-based catalyst. PMID:26365764

  11. A porous proton-relaying metal-organic framework material that accelerates electrochemical hydrogen evolution

    SciTech Connect

    Hod, Idan; Deria, Pravas; Bury, Wojciech; Mondloch, Joseph E.; Kung, Chung-Wei; So, Monica; Sampson, Matthew D.; Peters, Aaron W.; Kubiak, Cliff P.; Farha, Omar K.; Hupp, Joseph T.

    2015-09-14

    The availability of efficient hydrogen evolution reaction (HER) catalysts is of high importance for solar fuel technologies aimed at reducing future carbon emissions. Even though Pt electrodes are excellent HER electrocatalysts, commercialization of large-scale hydrogen production technology requires finding an equally efficient, low-cost, earth-abundant alternative. Here, high porosity, metal-organic framework (MOF) films have been used as scaffolds for the deposition of a Ni-S electrocatalyst. Compared with an MOF-free Ni-S, the resulting hybrid materials exhibit significantly enhanced performance for HER from aqueous acid, decreasing the kinetic overpotential by more than 200 mV at a benchmark current density of 10 mA cm−2. In conclusion, although the initial aim was to improve electrocatalytic activity by greatly boosting the active area of the Ni-S catalyst, the performance enhancements instead were found to arise primarily from the ability of the proton-conductive MOF to favourably modify the immediate chemical environment of the sulfide-based catalyst.

  12. A porous proton-relaying metal-organic framework material that accelerates electrochemical hydrogen evolution

    DOE PAGES

    Hod, Idan; Deria, Pravas; Bury, Wojciech; ...

    2015-09-14

    The availability of efficient hydrogen evolution reaction (HER) catalysts is of high importance for solar fuel technologies aimed at reducing future carbon emissions. Even though Pt electrodes are excellent HER electrocatalysts, commercialization of large-scale hydrogen production technology requires finding an equally efficient, low-cost, earth-abundant alternative. Here, high porosity, metal-organic framework (MOF) films have been used as scaffolds for the deposition of a Ni-S electrocatalyst. Compared with an MOF-free Ni-S, the resulting hybrid materials exhibit significantly enhanced performance for HER from aqueous acid, decreasing the kinetic overpotential by more than 200 mV at a benchmark current density of 10 mA cm−2. In conclusion, althoughmore » the initial aim was to improve electrocatalytic activity by greatly boosting the active area of the Ni-S catalyst, the performance enhancements instead were found to arise primarily from the ability of the proton-conductive MOF to favourably modify the immediate chemical environment of the sulfide-based catalyst.« less

  13. A porous proton-relaying metal-organic framework material that accelerates electrochemical hydrogen evolution.

    PubMed

    Hod, Idan; Deria, Pravas; Bury, Wojciech; Mondloch, Joseph E; Kung, Chung-Wei; So, Monica; Sampson, Matthew D; Peters, Aaron W; Kubiak, Cliff P; Farha, Omar K; Hupp, Joseph T

    2015-09-14

    The availability of efficient hydrogen evolution reaction (HER) catalysts is of high importance for solar fuel technologies aimed at reducing future carbon emissions. Even though Pt electrodes are excellent HER electrocatalysts, commercialization of large-scale hydrogen production technology requires finding an equally efficient, low-cost, earth-abundant alternative. Here, high porosity, metal-organic framework (MOF) films have been used as scaffolds for the deposition of a Ni-S electrocatalyst. Compared with an MOF-free Ni-S, the resulting hybrid materials exhibit significantly enhanced performance for HER from aqueous acid, decreasing the kinetic overpotential by more than 200 mV at a benchmark current density of 10 mA cm(-2). Although the initial aim was to improve electrocatalytic activity by greatly boosting the active area of the Ni-S catalyst, the performance enhancements instead were found to arise primarily from the ability of the proton-conductive MOF to favourably modify the immediate chemical environment of the sulfide-based catalyst.

  14. A porous proton-relaying metal-organic framework material that accelerates electrochemical hydrogen evolution

    NASA Astrophysics Data System (ADS)

    Hod, Idan; Deria, Pravas; Bury, Wojciech; Mondloch, Joseph E.; Kung, Chung-Wei; So, Monica; Sampson, Matthew D.; Peters, Aaron W.; Kubiak, Cliff P.; Farha, Omar K.; Hupp, Joseph T.

    2015-09-01

    The availability of efficient hydrogen evolution reaction (HER) catalysts is of high importance for solar fuel technologies aimed at reducing future carbon emissions. Even though Pt electrodes are excellent HER electrocatalysts, commercialization of large-scale hydrogen production technology requires finding an equally efficient, low-cost, earth-abundant alternative. Here, high porosity, metal-organic framework (MOF) films have been used as scaffolds for the deposition of a Ni-S electrocatalyst. Compared with an MOF-free Ni-S, the resulting hybrid materials exhibit significantly enhanced performance for HER from aqueous acid, decreasing the kinetic overpotential by more than 200 mV at a benchmark current density of 10 mA cm-2. Although the initial aim was to improve electrocatalytic activity by greatly boosting the active area of the Ni-S catalyst, the performance enhancements instead were found to arise primarily from the ability of the proton-conductive MOF to favourably modify the immediate chemical environment of the sulfide-based catalyst.

  15. Methane storage in metal-organic frameworks.

    PubMed

    He, Yabing; Zhou, Wei; Qian, Guodong; Chen, Banglin

    2014-08-21

    Natural gas (NG), whose main component is methane, is an attractive fuel for vehicular applications. Realization of safe, cheap and convenient means and materials for high-capacity methane storage can significantly facilitate the implementation of natural gas fuelled vehicles. The physisorption based process involving porous materials offers an efficient storage methodology and the emerging porous metal-organic frameworks have been explored as potential candidates because of their extraordinarily high porosities, tunable pore/cage sizes and easily immobilized functional sites. In this view, we provide an overview of the current status of metal-organic frameworks for methane storage.

  16. Minerals with metal-organic framework structures.

    PubMed

    Huskić, Igor; Pekov, Igor V; Krivovichev, Sergey V; Friščić, Tomislav

    2016-08-01

    Metal-organic frameworks (MOFs) are an increasingly important family of advanced materials based on open, nanometer-scale metal-organic architectures, whose design and synthesis are based on the directed assembly of carefully designed subunits. We now demonstrate an unexpected link between mineralogy and MOF chemistry by discovering that the rare organic minerals stepanovite and zhemchuzhnikovite exhibit structures found in well-established magnetic and proton-conducting metal oxalate MOFs. Structures of stepanovite and zhemchuzhnikovite, exhibiting almost nanometer-wide and guest-filled apertures and channels, respectively, change the perspective of MOFs as exclusively artificial materials and represent, so far, unique examples of open framework architectures in organic minerals.

  17. "Clickable" metal-organic framework.

    PubMed

    Goto, Yuta; Sato, Hiroki; Shinkai, Seiji; Sada, Kazuki

    2008-11-05

    We demonstrated the metal-organic framework bearing the azide group in the organic linkers and in situ click reactions with some small alkynes. The XRPD patterns indicated that the click reaction proceeded without any decomposition of the original MOF network. Controlling the organic linkers and incorporation of the azide groups should provide the designer-made MOFs that have controlled molecular cavities with the desired steric dimensions and functionality.

  18. Metal-organic framework templated synthesis of porous inorganic materials as novel sorbents

    DOEpatents

    Taylor-Pashow, Kathryn M. L.; Lin, Wenbin; Abney, Carter W.

    2017-03-21

    A novel metal-organic framework (MOF) templated process for the synthesis of highly porous inorganic sorbents for removing radionuclides, actinides, and heavy metals is disclosed. The highly porous nature of the MOFs leads to highly porous inorganic sorbents (such as oxides, phosphates, sulfides, etc) with accessible surface binding sites that are suitable for removing radionuclides from high level nuclear wastes, extracting uranium from acid mine drainage and seawater, and sequestering heavy metals from waste streams. In some cases, MOFs can be directly used for removing these metal ions as MOFs are converted to highly porous inorganic sorbents in situ.

  19. De novo synthesis of a metal-organic framework material featuring ultrahigh surface area and gas storage capacities.

    PubMed

    Farha, Omar K; Yazaydın, A Özgür; Eryazici, Ibrahim; Malliakas, Christos D; Hauser, Brad G; Kanatzidis, Mercouri G; Nguyen, SonBinh T; Snurr, Randall Q; Hupp, Joseph T

    2010-11-01

    Metal-organic frameworks--a class of porous hybrid materials built from metal ions and organic bridges--have recently shown great promise for a wide variety of applications. The large choice of building blocks means that the structures and pore characteristics of the metal-organic frameworks can be tuned relatively easily. However, despite much research, it remains challenging to prepare frameworks specifically tailored for particular applications. Here, we have used computational modelling to design and predictively characterize a metal-organic framework (NU-100) with a particularly high surface area. Subsequent experimental synthesis yielded a material, matching the calculated structure, with a high BET surface area (6,143 m(2) g(-1)). Furthermore, sorption measurements revealed that the material had high storage capacities for hydrogen (164 mg g(-1)) and carbon dioxide (2,315 mg g(-1))--gases of high importance in the contexts of clean energy and climate alteration, respectively--in excellent agreement with predictions from modelling.

  20. Superhydrophobic perfluorinated metal-organic frameworks.

    PubMed

    Chen, Teng-Hao; Popov, Ilya; Zenasni, Oussama; Daugulis, Olafs; Miljanić, Ognjen Š

    2013-08-07

    Three perfluorinated Cu-based metal-organic frameworks (MOFs) were prepared starting from extensively fluorinated biphenyl-based ligands accessed via C-H functionalization. These new materials are highly hydrophobic: with water contact angles of up to 151 ± 1°, they are among the most water-repellent MOFs ever reported.

  1. Materials design by evolutionary optimization of functional groups in metal-organic frameworks

    PubMed Central

    Collins, Sean P.; Daff, Thomas D.; Piotrkowski, Sarah S.; Woo, Tom K.

    2016-01-01

    A genetic algorithm that efficiently optimizes a desired physical or functional property in metal-organic frameworks (MOFs) by evolving the functional groups within the pores has been developed. The approach has been used to optimize the CO2 uptake capacity of 141 experimentally characterized MOFs under conditions relevant for postcombustion CO2 capture. A total search space of 1.65 trillion structures was screened, and 1035 derivatives of 23 different parent MOFs were identified as having exceptional CO2 uptakes of >3.0 mmol/g (at 0.15 atm and 298 K). Many well-known MOF platforms were optimized, with some, such as MIL-47, having their CO2 adsorption increase by more than 400%. The structures of the high-performing MOFs are provided as potential targets for synthesis. PMID:28138523

  2. Temperature-/pressure-dependent selective separation of CO(2) or benzene in a chiral metal-organic framework material.

    PubMed

    Tan, Yan-Xi; He, Yan-Ping; Zhang, Jian

    2012-08-01

    Presented here is a chiral microporous metal-organic framework material with a three-fold interpenetrating diamond-type structural topology and interesting properties for selective separation. The material has a high storage capacity for CO(2) gas (4.23 mmol g(-1) at 273 K and 1 bar) and shows fantastic temperature-dependent selectivity for CO(2) over N(2). Moreover, this multifunctional material, which has a rich π system, can selectively adsorb benzene over cyclohexane at low pressure (0.05 bar) at 298 K.

  3. Experimental Evidence Supported by Simulations of a Very High H2 Diffusion in Metal Organic Framework Materials

    NASA Astrophysics Data System (ADS)

    Salles, F.; Jobic, H.; Maurin, G.; Koza, M. M.; Llewellyn, P. L.; Devic, T.; Serre, C.; Ferey, G.

    2008-06-01

    Quasielastic neutron scattering measurements are combined with molecular dynamics simulations to extract the self-diffusion coefficient of hydrogen in the metal organic frameworks MIL-47(V) and MIL-53(Cr). We find that the diffusivity of hydrogen at low loading is about 2 orders of magnitude higher than in zeolites. Such a high mobility has never been experimentally observed before in any nanoporous materials, although it was predicted in carbon nanotubes. Either 1D or 3D diffusion mechanisms are elucidated depending on the chemical features of the MIL framework.

  4. Experimental Evidence Supported by Simulations of a Very High H{sub 2} Diffusion in Metal Organic Framework Materials

    SciTech Connect

    Salles, F.; Maurin, G.; Jobic, H.; Koza, M. M.; Llewellyn, P. L.; Devic, T.; Serre, C.; Ferey, G.

    2008-06-20

    Quasielastic neutron scattering measurements are combined with molecular dynamics simulations to extract the self-diffusion coefficient of hydrogen in the metal organic frameworks MIL-47(V) and MIL-53(Cr). We find that the diffusivity of hydrogen at low loading is about 2 orders of magnitude higher than in zeolites. Such a high mobility has never been experimentally observed before in any nanoporous materials, although it was predicted in carbon nanotubes. Either 1D or 3D diffusion mechanisms are elucidated depending on the chemical features of the MIL framework.

  5. Minerals with metal-organic framework structures

    PubMed Central

    Huskić, Igor; Pekov, Igor V.; Krivovichev, Sergey V.; Friščić, Tomislav

    2016-01-01

    Metal-organic frameworks (MOFs) are an increasingly important family of advanced materials based on open, nanometer-scale metal-organic architectures, whose design and synthesis are based on the directed assembly of carefully designed subunits. We now demonstrate an unexpected link between mineralogy and MOF chemistry by discovering that the rare organic minerals stepanovite and zhemchuzhnikovite exhibit structures found in well-established magnetic and proton-conducting metal oxalate MOFs. Structures of stepanovite and zhemchuzhnikovite, exhibiting almost nanometer-wide and guest-filled apertures and channels, respectively, change the perspective of MOFs as exclusively artificial materials and represent, so far, unique examples of open framework architectures in organic minerals. PMID:27532051

  6. Metal-organic framework nanosheets in polymer composite materials for gas separation

    PubMed Central

    Seoane, Beatriz; Miro, Hozanna; Corma, Avelino; Kapteijn, Freek; Llabrés i Xamena, Francesc X.; Gascon, Jorge

    2014-01-01

    Composites incorporating two-dimensional nanostructures within polymeric matrices hold potential as functional components for several technologies, including gas separation. Prospectively, employing metal-organic-frameworks (MOFs) as versatile nanofillers would notably broaden the scope of functionalities. However, synthesizing MOFs in the form of free standing nanosheets has proven challenging. We present a bottom-up synthesis strategy for dispersible copper 1,4-benzenedicarboxylate MOF lamellae of micrometer lateral dimensions and nanometer thickness. Incorporating MOF nanosheets into polymer matrices endows the resultant composites with outstanding CO2 separation performance from CO2/CH4 gas mixtures, together with an unusual and highly desired increment in the separation selectivity with pressure. As revealed by tomographic focused-ion-beam scanning-electron-microscopy, the unique separation behaviour stems from a superior occupation of the membrane cross-section by the MOF nanosheets as compared to isotropic crystals, which improves the efficiency of molecular discrimination and eliminates unselective permeation pathways. This approach opens the door to ultrathin MOF-polymer composites for various applications. PMID:25362353

  7. Gas adsorption and structural diversity in a family of Cu(II) pyridyl-isophthalate metal-organic framework materials

    NASA Astrophysics Data System (ADS)

    Gould, Jamie A.; Athwal, Harprit Singh; Blake, Alexander J.; Lewis, William; Hubberstey, Peter; Champness, Neil R.; Schröder, Martin

    2017-01-01

    A family of Cu(II)-based metal-organic frameworks (MOFs) has been synthesized using three pyridyl-isophthalate ligands, H2L1 (4'-(pyridin-4-yl)biphenyl-3,5-dicarboxylic acid), H2L2 (4''-(pyridin-4-yl)-1,1':4',1''-terphenyl-3,5-dicarboxylic acid) and H2L3 (5-[4-(pyridin-4-yl)naphthalen-1-yl]benzene-1,3-dicarboxylic acid). Although in each case the pyridyl-isophthalate ligands adopt the same pseudo-octahedral [Cu2(O2CR)4N2] paddlewheel coordination modes, the resulting frameworks are structurally diverse, particularly in the case of the complex of Cu(II) with H2L3, which leads to three distinct supramolecular isomers, each derived from Kagomé and square nets. In contrast to [Cu(L2)] and the isomers of [Cu(L3)], [Cu(L1)] exhibits permanent porosity. Thus, the gas adsorption properties of [Cu(L1)] were investigated with N2, CO2 and H2, and the material exhibits an isosteric heat of adsorption competitive with leading MOF sorbents for CO2. [Cu(L1)] displays high H2 adsorption, with the density in the pores approaching that of liquid H2. This article is part of the themed issue 'Coordination polymers and metal-organic frameworks: materials by design'.

  8. Molecular simulations for energy, environmental and pharmaceutical applications of nanoporous materials: from zeolites, metal-organic frameworks to protein crystals.

    PubMed

    Jiang, Jianwen; Babarao, Ravichandar; Hu, Zhongqiao

    2011-07-01

    Nanoporous materials have widespread applications in chemical industry, but the pathway from laboratory synthesis and testing to practical utilization of nanoporous materials is substantially challenging and requires fundamental understanding from the bottom up. With ever-growing computational resources, molecular simulations have become an indispensable tool for material characterization, screening and design. This tutorial review summarizes the recent simulation studies in zeolites, metal-organic frameworks and protein crystals, and provides a molecular overview for energy, environmental and pharmaceutical applications of nanoporous materials with increasing degree of complexity in building blocks. It is demonstrated that molecular-level studies can bridge the gap between physical and engineering sciences, unravel microscopic insights that are otherwise experimentally inaccessible, and assist in the rational design of new materials. The review is concluded with major challenges in future simulation exploration of novel nanoporous materials for emerging applications.

  9. Nanoscale metal-organic materials.

    PubMed

    Carné, Arnau; Carbonell, Carlos; Imaz, Inhar; Maspoch, Daniel

    2011-01-01

    Metal-organic materials are found to be a fascinating novel class of functional nanomaterials. The limitless combinations between inorganic and organic building blocks enable researchers to synthesize 0- and 1-D metal-organic discrete nanostructures with varied compositions, morphologies and sizes, fabricate 2-D metal-organic thin films and membranes, and even structure them on surfaces at the nanometre length scale. In this tutorial review, the synthetic methodologies for preparing these miniaturized materials as well as their potential properties and future applications are discussed. This review wants to offer a panoramic view of this embryonic class of nanoscale materials that will be of interest to a cross-section of researchers working in chemistry, physics, medicine, nanotechnology, materials chemistry, etc., in the next years.

  10. Multiaxis sensing using metal organic frameworks

    DOEpatents

    Talin, Albert Alec; Allendorf, Mark D.; Leonard, Francois; Stavila, Vitalie

    2017-01-17

    A sensor device including a sensor substrate; and a thin film comprising a porous metal organic framework (MOF) on the substrate that presents more than one transduction mechanism when exposed to an analyte. A method including exposing a porous metal organic framework (MOF) on a substrate to an analyte; and identifying more than one transduction mechanism in response to the exposure to the analyte.

  11. Hydrogen storage studies on palladium-doped carbon materials (AC, CB, CNMs) @ metal-organic framework-5.

    PubMed

    Viditha, V; Srilatha, K; Himabindu, V

    2016-05-01

    Metal organic frameworks (MOFs) are a rapidly growing class of porous materials and are considered as best adsorbents for their high surface area and extraordinary porosity. The MOFs are synthesized by using various chemicals like triethylamine, terepthalic acid, zinc acetate dihydrate, chloroform, and dimethylformamide (DMF). Synthesized MOFs are intercalated with palladium/activated carbon, carbon black, and carbon nanomaterials by chemical reduction method for the purpose of enhancing the hydrogen adsorption capacities. We have observed that the palladium doped activated carbon on MOF-5 showed high hydrogen storage capacity. This may be due to the affinity of the palladium toward hydrogen molecule. The samples are characterized by X-ray diffraction, scanning electron microscopy (SEM), and Brunauer-Emmett-Teller (BET) surface area analysis. We have observed a clear decrease in the BET surface area and pore volume. The obtained results show a better performance for the synthesized sample. To our best knowledge, no one has reported the work on palladium-doped carbon materials (activated carbon, carbon black, carbon nanomaterials) impregnated to the metal-organic framework-5. We have attempted to synthesize carbon nanomaterials using indigenously fabricated chemical vapor deposition (CVD) unit as a support. We have observed an increase in the hydrogen storage capacities.

  12. Gas adsorption on metal-organic frameworks

    DOEpatents

    Willis, Richard R [Cary, IL; Low, John J. , Faheem, Syed A.; Benin, Annabelle I [Oak Forest, IL; Snurr, Randall Q [Evanston, IL; Yazaydin, Ahmet Ozgur [Evanston, IL

    2012-07-24

    The present invention involves the use of certain metal organic frameworks that have been treated with water or another metal titrant in the storage of carbon dioxide. The capacity of these frameworks is significantly increased through this treatment.

  13. Metal-organic frameworks in chromatography.

    PubMed

    Yusuf, Kareem; Aqel, Ahmad; ALOthman, Zeid

    2014-06-27

    Metal-organic frameworks (MOFs) emerged approximately two decades ago and are the youngest class of porous materials. Despite their short existence, MOFs are finding applications in a variety of fields because of their outstanding chemical and physical properties. This review article focuses on the applications of MOFs in chromatography, including high-performance liquid chromatography (HPLC), gas chromatography (GC), and other chromatographic techniques. The use of MOFs in chromatography has already had a significant impact; however, the utilisation of MOFs in chromatography is still less common than other applications, and the number of MOF materials explored in chromatography applications is limited.

  14. Force-Field Prediction of Materials Properties in Metal-Organic Frameworks

    PubMed Central

    2016-01-01

    In this work, MOF bulk properties are evaluated and compared using several force fields on several well-studied MOFs, including IRMOF-1 (MOF-5), IRMOF-10, HKUST-1, and UiO-66. It is found that, surprisingly, UFF and DREIDING provide good values for the bulk modulus and linear thermal expansion coefficients for these materials, excluding those that they are not parametrized for. Force fields developed specifically for MOFs including UFF4MOF, BTW-FF, and the DWES force field are also found to provide accurate values for these materials’ properties. While we find that each force field offers a moderately good picture of these properties, noticeable deviations can be observed when looking at properties sensitive to framework vibrational modes. This observation is more pronounced upon the introduction of framework charges. PMID:28008758

  15. Post-synthesis modification of a metal-organic framework to form metallosalen-containing MOF materials.

    PubMed

    Shultz, Abraham M; Sarjeant, Amy A; Farha, Omar K; Hupp, Joseph T; Nguyen, SonBinh T

    2011-08-31

    A series of metallosalen-based metal-organic frameworks (MOFs) have been prepared by the post-synthesis modification of Mn(III)SO-MOF, a Mn(3+)(salen)-based MOF. Treatment of Mn(III)SO-MOF with H(2)O(2) effects the removal of the Mn(3+) ions from the salen struts, which can then be remetalated with a variety of metal precursors to form isostructural MSO-MOF materials. The presence of the new metallosalen struts in MSO-MOF was fully confirmed by ICP-OES, MALDI-TOF MS, PXRD, and TGA. Furthermore, the remetalated Mn(II)SO-MOF material displays similar catalytic activity and porosity to the parent MOF.

  16. Hydrogen storage in metal-organic frameworks.

    PubMed

    Hu, Yun Hang; Zhang, Lei

    2010-05-25

    Metal-organic frameworks (MOFs) are highly attractive materials because of their ultra-high surface areas, simple preparation approaches, designable structures, and potential applications. In the past several years, MOFs have attracted worldwide attention in the area of hydrogen energy, particularly for hydrogen storage. In this review, the recent progress of hydrogen storage in MOFs is presented. The relationships between hydrogen capacities and structures of MOFs are evaluated, with emphasis on the roles of surface area and pore size. The interaction mechanism between H(2) and MOFs is discussed. The challenges to obtain a high hydrogen capacity at ambient temperature are explored.

  17. Proton-Conducting Metal-Organic Frameworks

    NASA Astrophysics Data System (ADS)

    Ford, Jamie; Simmons, Jason; Yildirim, Taner

    2010-03-01

    Vehicles powered by polymer electrolyte membrane (PEM) fuel cells are an exciting alternative to current fossil fuel technology. The membranes in these cells serve as both charge transporter, ferrying protons from the anode to the cathode, and gas diffusion barrier, preventing the backflow of oxygen to the anode. Currently, hydrated sulfonated polymers are the preferred material for these membranes. The presence of water, however, limits the operating temperature to 100 C, reducing the electrode kinetics and CO tolerance of the entire system. In an effort to increase the efficiency and operating temperature of these fuel cells, we are investigating the proton conductivity of new host/guest materials based on metal-organic frameworks (MOFs) loaded with imidazole. These thermally stable frameworks provide well-defined pores that accommodate imidazole networks and form proton-conducting pathways. Here, we will present the structure and proton dynamics of these materials as elucidated by elastic and inelastic neutron scattering measurements.

  18. Evaluation of metal-organic framework 5 as a new SPE material for the determination of polycyclic aromatic hydrocarbons in environmental waters.

    PubMed

    Yang, Shaolei; Chen, Chunyan; Yan, Zhihong; Cai, Qingyun; Yao, Shouzhuo

    2013-04-01

    Metal-organic frameworks, a new class of materials with high surface area and great porosity, have been widely applied in gas sorption. It is generally known that metal-organic framework 5 cannot be applied in aqueous phase since it is water sensitive. However, this work reveals that the derived material of metal-organic framework 5 is a good SPE sorbent that can be applied to aqueous phases. Metal-organic framework 5 was prepared and used as a SPE sorbent for the determination of polycyclic aromatic hydrocarbons in environmental matrices coupling with HPLC. The water treatment induced changes in the properties were investigated in detail. Even though metal-organic framework 5 is conversed to a second phase after water treatment, it still shows high extraction ability. Under the optimized experimental conditions, good sensitivity levels were achieved with low LODs ranging from 0.4 to 4.0 ng L(-1) and a linearity of 0.004-20 μg L(-1) (R(2) > 0.996) for the investigated polycyclic aromatic hydrocarbons. The method has been validated in the analysis of real water samples with recoveries in the range of 80.2-120.2% and RSDs in the range of 0.5-11.7%.

  19. Stimulus-responsive metal-organic frameworks.

    PubMed

    Nagarkar, Sanjog S; Desai, Aamod V; Ghosh, Sujit K

    2014-09-01

    Materials that can recognize the changes in their local environment and respond by altering their inherent physical and/or chemical properties are strong candidates for future "smart" technology materials. Metal-organic frameworks (MOFs) have attracted a great deal of attention in recent years owing to their designable architecture, host-guest chemistry, and softness as porous materials. Despite this fact, studies on the tuning of the properties of MOFs by external stimuli are still rare. This review highlights the recent developments in the field of stimulus-responsive MOFs or so-called smart MOFs. In particular, the various stimuli used and the utility of stimulus-responsive smart MOFs for various applications such as gas storage and separation, sensing, clean energy, catalysis, molecular motors, and biomedical applications are highlighted by using representative examples. Future directions in the developments of stimulus-responsive smart MOFs and their applications are proposed from a personal perspective.

  20. Metal-organic framework nanocrystals as sacrificial templates for hollow and exceptionally porous titania and composite materials.

    PubMed

    Yang, Hui; Kruger, Paul E; Telfer, Shane G

    2015-10-05

    We report a strategy that employs metal-organic framework (MOF) crystals in two roles for the fabrication of hollow nanomaterials. In the first role the MOF crystals provide a template on which a shell of material can be deposited. Etching of the MOF produces a hollow structure with a predetermined size and morphology. In combination with this strategy, the MOF crystals, including guest molecules in their pores, can provide the components of a secondary material that is deposited inside the initially formed shell. We used this approach to develop a straightforward and reproducible method for constructing well-defined, nonspherical hollow and exceptionally porous titania and titania-based composite nanomaterials. Uniform hollow nanostructures of amorphous titania, which assume the cubic or polyhedral shape of the original template, are delivered using nano- and microsized ZIF-8 and ZIF-67 crystal templates. These materials exhibit outstanding textural properties including hierarchical pore structures and BET surface areas of up to 800 m(2)/g. As a proof of principle, we further demonstrate that metal nanoparticles such as Pt nanoparticles, can be encapsulated into the TiO2 shell during the digestion process and used for subsequent heterogeneous catalysis. In addition, we show that the core components of the ZIF nanocrystals, along with their adsorbed guests, can be used as precursors for the formation of secondary materials, following their thermal decomposition, to produce hollow and porous metal sulfide/titania or metal oxide/titania composite nanostructures.

  1. Hydrogen Storage in Metal-Organic Frameworks

    SciTech Connect

    Long, Jeffrey R.

    2016-04-28

    The design and characterization of new materials for hydrogen storage is an important area of research, as the ability to store hydrogen at lower pressures and higher temperatures than currently feasible would lower operating costs for small hydrogen fuel cell vehicles. In particular, metal-organic frameworks (MOFs) represent promising materials for use in storing hydrogen in this capacity. MOFs are highly porous, three-dimensional crystalline solids that are formed via linkages between metal ions (e.g., iron, nickel, and zinc) and organic molecules. MOFs can store hydrogen via strong adsorptive interactions between the gas molecules and the pores of the framework, providing a high surface area for gas adsorption and thus the opportunity to store hydrogen at significantly lower pressures than with current technologies. By lowering the energy required for hydrogen storage, these materials hold promise in rendering hydrogen a more viable fuel for motor vehicles, which is a highly desirable outcome given the clean nature of hydrogen fuel cells (water is the only byproduct of combustion) and the current state of global climate change resulting from the combustion of fossil fuels. The work presented in this report is the result of collaborative efforts between researchers at Lawrence Berkeley National Lab (LBNL), the National Institute of Standards and Technology (NIST), and General Motors Corporation (GM) to discover novel MOFs promising for H2 storage and characterize their properties. Described herein are several new framework systems with improved gravimetric and volumetric capacity to strongly bind H2 at temperatures relevant for vehicle storage. These materials were rigorously characterized using neutron diffraction, to determine the precise binding locations of hydrogen within the frameworks, and high-pressure H2 adsorption measurements, to provide a comprehensive picture of H2 adsorption at all relevant pressures. A

  2. Cascade reactions catalyzed by metal organic frameworks.

    PubMed

    Dhakshinamoorthy, Amarajothi; Garcia, Hermenegildo

    2014-09-01

    Cascade or tandem reactions where two or more individual reactions are carried out in one pot constitute a clear example of process intensification, targeting the maximization of spatial and temporal productivity with mobilization of minimum resources. In the case of catalytic reactions, cascade processes require bi-/multifunctional catalysts that contain different classes of active sites. Herein, we show that the features and properties of metal-organic frameworks (MOFs) make these solids very appropriate materials for the development of catalysts for cascade reactions. Due to composition and structure, MOFs can incorporate different types of sites at the metal nodes, organic linkers, or at the empty internal pores, allowing the flexible design and synthesis of multifunctional catalysts. After some introductory sections on the relevance of cascade reactions from the point of view of competitiveness, sustainability, and environmental friendliness, the main part of the text provides a comprehensive review of the literature reporting the use of MOFs as heterogeneous catalysts for cascade reactions including those that combine in different ways acid/base, oxidation/reduction, and metal-organic centers. The final section summarizes the current state of the art, indicating that the development of a first commercial synthesis of a high-added-value fine chemical will be a crucial milestone in this area.

  3. Nanostructured Electrode Materials Derived from Metal-Organic Framework Xerogels for High-Energy-Density Asymmetric Supercapacitor.

    PubMed

    Mahmood, Asif; Zou, Ruqiang; Wang, Qingfei; Xia, Wei; Tabassum, Hassina; Qiu, Bin; Zhao, Ruo

    2016-01-27

    This work successfully demonstrates metal-organic framework (MOF) derived strategy to prepare nanoporous carbon (NPC) with or without Fe3O4/Fe nanoparticles by the optimization of calcination temperature as highly active electrode materials for asymmetric supercapacitors (ASC). The nanostructured Fe3O4/Fe/C hybrid shows high specific capacitance of 600 F/g at a current density of 1 A/g and excellent capacitance retention up to 500 F/g at 8 A/g. Furthermore, hierarchically NPC with high surface area also obtained from MOF gels displays excellent electrochemical performance of 272 F/g at 2 mV/s. Considering practical applications, aqueous ASC (aASC) was also assembled, which shows high energy density of 17.496 Wh/kg at the power density of 388.8 W/kg. The high energy density and excellent capacity retention of the developed materials show great promise for the practical utilization of these energy storage devices.

  4. An Electrically Switchable Metal-Organic Framework

    NASA Astrophysics Data System (ADS)

    Fernandez, Carlos A.; Martin, Paul C.; Schaef, Todd; Bowden, Mark E.; Thallapally, Praveen K.; Dang, Liem; Xu, Wu; Chen, Xilin; McGrail, B. Peter

    2014-08-01

    Crystalline metal organic framework (MOF) materials containing interconnected porosity can be chemically modified to promote stimulus-driven (light, magnetic or electric fields) structural transformations that can be used in a number of devices. Innovative research strategies are now focused on understanding the role of chemical bond manipulation to reversibly alter the free volume in such structures of critical importance for electro-catalysis, molecular electronics, energy storage technologies, sensor devices and smart membranes. In this letter, we study the mechanism for which an electrically switchable MOF composed of Cu(TCNQ) (TCNQ = 7,7,8,8-tetracyanoquinodimethane) transitions from a high-resistance state to a conducting state in a reversible fashion by an applied potential. The actual mechanism for this reversible electrical switching is still not understood even though a number of reports are available describing the application of electric-field-induced switching of Cu(TCNQ) in device fabrication.

  5. Multifunctional Metal-Organic Frameworks for Photocatalysis.

    PubMed

    Wang, Sibo; Wang, Xinchen

    2015-07-01

    Metal-organic frameworks (MOFs) have attracted significant research attention in diverse areas due to their unique physical and chemical characteristics that allow their innovative application in various research fields. Recently, the application of MOFs in heterogeneous photocatalysis for water splitting, CO2 reduction, and organic transformation have emerged, aiming at providing alternative solutions to address the world-wide energy and environmental problems by taking advantage of the unique porous structure together with ample physicochemical properties of the metal centers and organic ligands in MOFs. In this review, the latest progress in MOF-involved solar-to-chemical energy conversion reactions are summarized according to their different roles in the photoredox chemical systems, e.g., photocatalysts, co-catalysts, and hosts. The achieved progress and existing problems are evaluated and proposed, and the opportunities and challenges of MOFs and their related materials for their advanced development in photocatalysis are discussed and anticipated.

  6. An Electrically Switchable Metal-Organic Framework

    SciTech Connect

    Fernandez, Carlos A.; Martin, Paul F.; Schaef, Herbert T.; Bowden, Mark E.; Thallapally, Praveen K.; Dang, Liem X.; Xu, Wu; Chen, Xilin; McGrail, B. Peter

    2014-08-19

    Crystalline metal organic framework (MOF) materials containing interconnected porosity can be chemically modified to promote stimulus-driven (light, magnetic or electric fields) structural transformations that can be used in a number of devices. Innovative research strategies are now focused on understanding the role of chemical bond manipulation to reversibly alter the free volume in such structures of critical importance for electro-catalysis, molecular electronics, energy storage technologies, sensor devices and smart membranes. In this letter, we study the mechanism for which an electrically switchable MOF composed of Cu(TCNQ) (TCNQ 5 7,7,8,8-tetracyanoquinodimethane) transitions from a high-resistance state to a conducting state in a reversible fashion by an applied potential. The actual mechanism for this reversible electrical switching is still not understood even though a number of reports are available describing the application of electric-field-induced switching of Cu(TCNQ) in device fabrication.

  7. An Electrically Switchable Metal-Organic Framework

    SciTech Connect

    Fernandez, CA; Martin, PC; Schaef, T; Bowden, ME; Thallapally, PK; Dang, L; Xu, W; Chen, XL; McGrail, BP

    2014-08-19

    Crystalline metal organic framework (MOF) materials containing interconnected porosity can be chemically modified to promote stimulus-driven (light, magnetic or electric fields) structural transformations that can be used in a number of devices. Innovative research strategies are now focused on understanding the role of chemical bond manipulation to reversibly alter the free volume in such structures of critical importance for electro-catalysis, molecular electronics, energy storage technologies, sensor devices and smart membranes. In this letter, we study the mechanism for which an electrically switchable MOF composed of Cu(TCNQ) (TCNQ = 7,7,8,8-tetracyanoquinodimethane) transitions from a high-resistance state to a conducting state in a reversible fashion by an applied potential. The actual mechanism for this reversible electrical switching is still not understood even though a number of reports are available describing the application of electric-field-induced switching of Cu(TCNQ) in device fabrication.

  8. An Electrically Switchable Metal-Organic Framework

    PubMed Central

    Fernandez, Carlos A.; Martin, Paul C.; Schaef, Todd; Bowden, Mark E.; Thallapally, Praveen K.; Dang, Liem; Xu, Wu; Chen, Xilin; McGrail, B. Peter

    2014-01-01

    Crystalline metal organic framework (MOF) materials containing interconnected porosity can be chemically modified to promote stimulus-driven (light, magnetic or electric fields) structural transformations that can be used in a number of devices. Innovative research strategies are now focused on understanding the role of chemical bond manipulation to reversibly alter the free volume in such structures of critical importance for electro-catalysis, molecular electronics, energy storage technologies, sensor devices and smart membranes. In this letter, we study the mechanism for which an electrically switchable MOF composed of Cu(TCNQ) (TCNQ = 7,7,8,8-tetracyanoquinodimethane) transitions from a high-resistance state to a conducting state in a reversible fashion by an applied potential. The actual mechanism for this reversible electrical switching is still not understood even though a number of reports are available describing the application of electric-field-induced switching of Cu(TCNQ) in device fabrication. PMID:25135307

  9. Thermodynamics of metal-organic frameworks

    SciTech Connect

    Wu, Di; Navrotsky, Alexandra

    2015-03-15

    Although there have been extensive studies over the past decade in the synthesis and application of metal-organic frameworks (MOFs), investigation of their thermodynamic stability and of the energetics of guest–host interactions has been much more limited. This review summarizes recent progress in experimental (calorimetric) determination of the thermodynamics of MOF materials. The enthalpies of MOFs relative to dense phase assemblages suggest only modest metastability, with a general increase of enthalpy with increasing molar volume, which becomes less pronounced at higher porosity. The energy landscape of nanoporous materials (inorganic and hybrid) consists of a pair of parallel patterns within a fairly narrow range of metastability of 5–30 kJ per mole of tetrahedra in zeolites and mesoporous silicas or per mole of metal in MOFs. Thus strong thermodynamic instability does not seem to limit framework formation. There are strong interactions within the chemisorption range for small molecule–MOF interactions with defined chemical binding at the metal centers or other specific locations. Coexistence of surface binding and confinement can lead to much stronger guest–host interactions. - Graphical abstract: Energy landscape of inorganic and hybrid porous materials. - Highlights: • Thermochemical data on various MOF structures were experimentally determined. • MOFs are moderately unstable relative to their dense phase assemblage. • Overall energetic landscape of porous materials was revealed. • Guest–host interactions in MOFs were evaluated directly using calorimetry. • Confinement effect and defined chemical binding lead to strong interactions.

  10. Syntheses, structures, tunable emission and white light emitting Eu3+ and Tb3+ doped lanthanide metal-organic framework materials.

    PubMed

    Ma, Ming-Li; Ji, Can; Zang, Shuang-Quan

    2013-08-07

    A series of novel lanthanide metal-organic frameworks, namely, {[Ln2(L)2]·(H2O)3·(Me2NH2)2}n (Ln = La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Gd (7), Tb (8), Ho (9), Er (10)), have been synthesized with hydro(solvo)thermal conditions based on a flexible multicarboxylic acid (H4L = 5-(3,5-dicarboxybenzyloxy)isophthalic acid). Single crystal X-ray diffraction reveals that all of them are isomorphous and possess a (6,6) topological net with a Schläfli symbol of {4(8)·6(7)}. Considering the blue-emission of compound 1 and the intense emission of the Eu and Tb compounds, we successfully construct isostructural Eu(3+) doped Tb compounds whose color can be tuned easily by adjusting the different concentration of the doped ions, and we also obtained white light emitting materials through the doping of Eu and Tb ions in the La compounds.

  11. Smart Optical Composite Materials: Dispersions of Metal-Organic Framework@Superparamagnetic Microrods for Switchable Isotropic-Anisotropic Optical Properties.

    PubMed

    Mandel, Karl; Granath, Tim; Wehner, Tobias; Rey, Marcel; Stracke, Werner; Vogel, Nicolas; Sextl, Gerhard; Müller-Buschbaum, Klaus

    2017-01-24

    A smart optical composite material with dynamic isotropic and anisotropic optical properties by combination of luminescence and high reflectivity was developed. This combination enables switching between luminescence and angle-dependent reflectivity by changing the applied wavelength of light. The composite is formed as anisotropic core/shell particles by coating superparamagnetic iron oxide-silica microrods with a layer of the luminescent metal-organic framework (MOF) (3)∞[Eu2(BDC)3]·2DMF·2H2O (BDC(2-) = 1,4-benzenedicarboxylate). The composite particles can be rotated by an external magnet. Their anisotropic shape causes changes in the reflectivity and diffraction of light depending on the orientation of the composite particle. These rotation-dependent optical properties are complemented by an isotropic luminescence resulting from the MOF shell. If illuminated by UV light, the particles exhibit isotropic luminescence while the same sample shows anisotropic optical properties when illuminated with visible light. In addition to direct switching, the optical properties can be tailored continuously between isotropic red emission and anisotropic reflection of light if the illuminating light is tuned through fractions of both UV and visible light. The integration and control of light emission modes within a homogeneous particle dispersion marks a smart optical material, addressing fundamental directions for research on switchable multifunctional materials. The material can function as an optic compass or could be used as an optic shutter that can be switched by a magnetic field, e.g., for an intensity control for waveguides in the visible range.

  12. Rational Synthesis and Investigation of Porous Metal-Organic Framework Materials from a Preorganized Heterometallic Carboxylate Building Block.

    PubMed

    Sapianik, Aleksandr A; Zorina-Tikhonova, Ekaterina N; Kiskin, Mikhail A; Samsonenko, Denis G; Kovalenko, Konstantin A; Sidorov, Alexey A; Eremenko, Igor L; Dybtsev, Danil N; Blake, Alexander J; Argent, Stephen P; Schröder, Martin; Fedin, Vladimir P

    2017-02-06

    The tetranuclear heterometallic complex [Li2Zn2(piv)6(py)2] (1, where piv(-) = pivalate and py = pyridine) has been successfully employed as a presynthesized node for the construction of four porous metal-organic frameworks (MOFs) [Li2Zn2(R-bdc)3(bpy)]·solv (2-R, R-bdc(2-); R = H, Br, NH2, NO2) by reaction with 4,4'-bipyridine (bpy) and terephthalate anionic linkers. The [Li2Zn2] node is retained in the products, representing a rare example of the rational step-by-step design of isoreticular MOFs based on complex heterometallic building units. The permanent porosity of the activated frameworks was confirmed by gas adsorption isotherm measurements (N2, CO2, CH4). Three compounds, 2-H, 2-Br, and 2-NH2 (but not 2-NO2), feature extensive hysteresis between the adsorption and desorption curves in the N2 isotherms at low pressures. The substituents R decorate the inner surface and also control the aperture of the channels, the volume of the micropores, and the overall surface area, thus affecting both the gas uptake and adsorption selectivity. The highest CO2 absorption at ambient conditions (105 cm(3)·g(-1) or 21 wt % at 273 K and 1 bar for 2-NO2) is above the average values for microporous MOFs. The photoluminescent properties of the prototypic 2-H as well as the corresponding host-guest compounds with various aromatic molecules (benzene, toluene, anisole, and nitrobenzene) were systematically investigated. We discovered a rather complex pattern in the emission response of this material depending on the wavelength of excitation as well as the nature of the guest molecules. On the basis of the crystal structure of 2-H, a mechanism for these luminescent properties is proposed and discussed.

  13. Porosity in metal-organic framework glasses.

    PubMed

    Thornton, A W; Jelfs, K E; Konstas, K; Doherty, C M; Hill, A J; Cheetham, A K; Bennett, T D

    2016-03-07

    The porosity of a glass formed by melt-quenching a metal-organic framework, has been characterized by positron annihilation lifetime spectroscopy. The results reveal porosity intermediate between the related open and dense crystalline frameworks ZIF-4 and ZIF-zni. A structural model for the glass was constructed using an amorphous polymerization algorithm, providing additional insight into the gas-inaccessible nature of porosity and the possible applications of hybrid glasses.

  14. (Metal-Organic Framework)-Polyaniline sandwich structure composites as novel hybrid electrode materials for high-performance supercapacitor

    NASA Astrophysics Data System (ADS)

    Guo, ShuaiNan; Zhu, Yong; Yan, YunYun; Min, YuLin; Fan, JinChen; Xu, QunJie; Yun, Hong

    2016-06-01

    Carbonized Zn-(Metal-Organic Framework)MOF- polyaniline composites for high performance of supercapacitor have been developed from zinc acetate, 8-Hydroxyquinoline, and aniline via a simple process. The as-synthesized product has been characterized by X-ray powder diffraction (XRD), Scanning electron microscopy(SEM), Fourier transform infrared spectra (FT-IR), Transmission electron microscope (TEM). The electrochemical properties of carbonized Zn-MOF/polyaniline electrode were investigated by current charge-discharge and cyclic voltammetry. The specific capacitance of MOF/PANI has been approach to be as high as 477 F g-1 at a current density of 1 A g-1.

  15. Microporous Metal Organic Materials for Hydrogen Storage

    SciTech Connect

    S. G. Sankar; Jing Li; Karl Johnson

    2008-11-30

    We have examined a number of Metal Organic Framework Materials for their potential in hydrogen storage applications. Results obtained in this study may, in general, be summarized as follows: (1) We have identified a new family of porous metal organic framework materials with the compositions M (bdc) (ted){sub 0.5}, {l_brace}M = Zn or Co, bdc = biphenyl dicarboxylate and ted = triethylene diamine{r_brace} that adsorb large quantities of hydrogen ({approx}4.6 wt%) at 77 K and a hydrogen pressure of 50 atm. The modeling performed on these materials agree reasonably well with the experimental results. (2) In some instances, such as in Y{sub 2}(sdba){sub 3}, even though the modeling predicted the possibility of hydrogen adsorption (although only small quantities, {approx}1.2 wt%, 77 K, 50 atm. hydrogen), our experiments indicate that the sample does not adsorb any hydrogen. This may be related to the fact that the pores are extremely small or may be attributed to the lack of proper activation process. (3) Some samples such as Zn (tbip) (tbip = 5-tert butyl isophthalate) exhibit hysteresis characteristics in hydrogen sorption between adsorption and desorption runs. Modeling studies on this sample show good agreement with the desorption behavior. It is necessary to conduct additional studies to fully understand this behavior. (4) Molecular simulations have demonstrated the need to enhance the solid-fluid potential of interaction in order to achieve much higher adsorption amounts at room temperature. We speculate that this may be accomplished through incorporation of light transition metals, such as titanium and scandium, into the metal organic framework materials.

  16. Stepwise Synthesis of Metal-Organic Frameworks.

    PubMed

    Bosch, Mathieu; Yuan, Shuai; Rutledge, William; Zhou, Hong-Cai

    2017-03-28

    Metal-organic frameworks (MOFs) are a category of porous materials that offer unparalleled control over their surface areas (demonstrated as higher than for any other material), pore characteristics, and functionalization. This allows them to be customized for exceptional performance in a wide variety of applications, most commonly including gas storage and separation, drug delivery, luminescence, or heterogeneous catalysis. In order to optimize biomimicry, controlled separations and storage of small molecules, and detailed testing of structure-property relationships, one major goal of MOF research is "rational design" or "pore engineering", or precise control of the placement of multiple functional groups in pores of chosen sizes and shapes. MOF crystal growth can be controlled through judicious design of stepwise synthetic routes, which can also allow functionalization of MOFs in ways that were previously synthetically inaccessible. Organic chemists have developed a library of powerful techniques over the last century, allowing the total synthesis and detailed customization of complex molecules. Our hypothesis is that total synthesis is also possible for customized porous materials, through the development of similar multistep techniques. This will enable the rational design of MOFs, which is a major goal of many researchers in the field. We have begun developing a library of stepwise synthetic techniques for MOFs, allowing the synthesis of ultrastable MOFs with multiple crystallographically ordered and customizable functional groups at controlled locations within the pores. In order to design MOFs with precise control over pore size and shape, stability, and the placement of multiple different functional groups within the pores at tunable distances from one another, we have concentrated on methods which allow us to circumvent the lack of control inherent to one-pot MOF crystallization. Kinetically tuned dimensional augmentation (KTDA) is an approach using

  17. Thermodynamics of Metal-Organic Frameworks

    NASA Astrophysics Data System (ADS)

    Hughes, James Thomas

    Metal-Organic Frameworks (MOF) are crystalline nanoporous lattices constructed from the combination of cation and multi-dentate organic molecules. MOFs can display both chemical and thermal robustness while having large surface areas and pore volumes. In addition the modular composition of MOFs allows a degree of design and control of MOF structures. These unique physical properties have attracted wide interest and position MOFs to make meaningful contributions towards many applications, such as adsorption, catalysis, separation, and sensing. Despite the extensive investigative work over the last decade on MOF materials, the initial synthesis is still done by trial and error. Of the identified structures some MOFs are robust while others are fragile. It is unclear what role thermodynamics plays in the formation energies of MOFs and guest molecules interactions within the pores. Better understanding of thermochemical properties of MOFs is critical if MOF synthesis is to obtain true predictive design. To address these questions aqueous solution calorimetry was performed on ten different frameworks in both the as-synthesized and activated state. To understand the structural energetics of MOFs, the heat of formation from dense states (metal oxide and protonated organic linkers) to the open MOF framework was measured. Chapter 2 discusses the new aqueous calorimetry methodology developed to measure the enthalpy of solution for hybrid materials. Chapters 3, 4 and 5 detail the enthalpies of formation from their dense states of the frameworks: (MOF-5, ZIF-zni, ZIF-1, ZIF-3, ZIF-4, ZIF-7, ZIF-8, ZIF-9 and Cu-HKUST-1). These chapters also compare the MOF heat of formation energetics to those of zeolites, zeotypes and mesoporous silica materials. Finding that MOFs are metastable with respect to their dense states (metal oxide and protonated organic), following the current destabilization trend of the main group porous materials. The thermochemical effect of solvent on the MOF

  18. Mechanical Alloying of Metal-Organic Frameworks.

    PubMed

    Panda, Tamas; Horike, Satoshi; Hagi, Keisuke; Ogiwara, Naoki; Kadota, Kentaro; Itakura, Tomoya; Tsujimoto, Masahiko; Kitagawa, Susumu

    2017-02-20

    The solvent-free mechanical milling process for two distinct metal-organic framework (MOF) crystals induced the formation of a solid solution, which is not feasible by conventional solution-based syntheses. X-ray and STEM-EDX studies revealed that performing mechanical milling under an Ar atmosphere promotes the high diffusivity of each metal ion in an amorphous solid matrix; the amorphous state turns into the porous crystalline structure by vapor exposure treatment to form a new phase of a MOF solid solution.

  19. Immobilization of Bacillus subtilis lipase on a Cu-BTC based hierarchically porous metal-organic framework material: a biocatalyst for esterification.

    PubMed

    Cao, Yu; Wu, Zhuofu; Wang, Tao; Xiao, Yu; Huo, Qisheng; Liu, Yunling

    2016-04-28

    Bacillus subtilis lipase (BSL2) has been successfully immobilized into a Cu-BTC based hierarchically porous metal-organic framework material for the first time. The Cu-BTC hierarchically porous MOF material with large mesopore apertures is prepared conveniently by using a template-free strategy under mild conditions. The immobilized BSL2 presents high enzymatic activity and perfect reusability during the esterification reaction. After 10 cycles, the immobilized BSL2 still exhibits 90.7% of its initial enzymatic activity and 99.6% of its initial conversion.

  20. Hydrogen Storage in Metal-Organic Frameworks

    SciTech Connect

    Omar M. Yaghi

    2012-04-26

    Conventional storage of large amounts of hydrogen in its molecular form is difficult and expensive because it requires employing either extremely high pressure gas or very low temperature liquid. Because of the importance of hydrogen as a fuel, the DOE has set system targets for hydrogen storage of gravimetric (5.5 wt%) and volumetric (40 g L-1) densities to be achieved by 2015. Given that these are system goals, a practical material will need to have higher capacity when the weight of the tank and associated cooling or regeneration system is considered. The size and weight of these components will vary substantially depending on whether the material operates by a chemisorption or physisorption mechanism. In the latter case, metal-organic frameworks (MOFs) have recently been identified as promising adsorbents for hydrogen storage, although little data is available for their sorption behavior. This grant was focused on the study of MOFs with these specific objectives. (1) To examine the effects of functionalization, catenation, and variation of the metal oxide and organic linkers on the low-pressure hydrogen adsorption properties of MOFs. (2) To develop a strategy for producing MOFs with high surface area and porosity to reduce the dead space and increase the hydrogen storage capacity per unit volume. (3) To functionalize MOFs by post synthetic functionalization with metals to improve the adsorption enthalpy of hydrogen for the room temperature hydrogen storage. This effort demonstrated the importance of open metal sites to improve the adsorption enthalpy by the systematic study, and this is also the origin of the new strategy, which termed isoreticular functionalization and metalation. However, a large pore volume is still a prerequisite feature. Based on our principle to design highly porous MOFs, guest-free MOFs with ultrahigh porosity have been experimentally synthesized. MOF-210, whose BET surface area is 6240 m2 g-1 (the highest among porous solids), takes up

  1. Dynamic interplay between spin-crossover and host-guest function in a nanoporous metal-organic framework material.

    SciTech Connect

    Southon, P. D.; Liu, L.; Fellows, E. A.; Price, D. J.; Halder, G. J.; Chapman, K. W.; Moubaraki, B.; Murray, K. S.; Letard, J.F.; Kepert, C. J.; Univ. Sydney; Monash Univ.; Universite Bordeaux

    2009-01-01

    The nanoporous metal-organic framework [Fe(pz)Ni(CN){sub 4}], 1 (where pz is pyrazine), exhibits hysteretic spin-crossover at ambient conditions and is robust to the adsorption and desorption of a wide range of small molecular guests, both gases (N{sub 2}, O{sub 2}, CO{sub 2}) and vapors (methanol, ethanol, acetone, acetonitrile, and toluene). Through the comprehensive analysis of structure, host-guest properties, and spin-crossover behaviors, it is found that this pillared Hofmann system uniquely displays both guest-exchange-induced changes to spin-crossover and spin-crossover-induced changes to host-guest properties, with direct dynamic interplay between these two phenomena. Guest desorption and adsorption cause pronounced changes to the spin-crossover behavior according to a systematic trend in which larger guests stabilize the high-spin state and therefore depress the spin-crossover temperature of the host lattice. When stabilizing the alternate spin state of the host at any given temperature, these processes directly stimulate the spin-crossover process, providing a chemisensing function. Exploitation of the bistability of the host allows the modification of adsorption properties at a fixed temperature through control of the host spin state, with each state shown to display differing chemical affinities to guest sorption. Guest desorption then adsorption, and vice versa, can be used to switch between spin states in the bistable temperature region, adding a guest-dependent memory effect to this system.

  2. Thermal conversion of an Fe3O4@metal-organic framework: a new method for an efficient Fe-Co/nanoporous carbon microwave absorbing material

    NASA Astrophysics Data System (ADS)

    Zhang, Xingmiao; Ji, Guangbin; Liu, Wei; Quan, Bin; Liang, Xiaohui; Shang, Chaomei; Cheng, Yan; Du, Youwei

    2015-07-01

    A novel FeCo nanoparticle embedded nanoporous carbon composite (Fe-Co/NPC) was synthesized via in situ carbonization of dehydro-ascorbic acid (DHAA) coated Fe3O4 nanoparticles encapsulated in a metal-organic framework (zeolitic imidazolate framework-67, ZIF-67). The molar ratio of Fe/Co significantly depends on the encapsulated content of Fe3O4 in ZIF-67. The composites filled with 50 wt% of the Fe-Co/NPC-2.0 samples in paraffin show a maximum reflection loss (RL) of -21.7 dB at a thickness of 1.2 mm; in addition, a broad absorption bandwidth for RL < -10 dB which covers from 12.2 to 18 GHz can be obtained, and its minimum reflection loss and bandwidth (RL values exceeding -10 dB) are far greater than those of commercial carbonyl iron powder under a very low thickness (1-1.5 mm). This study not only provides a good reference for future preparation of carbon-based lightweight microwave absorbing materials but also broadens the application of such kinds of metal-organic frameworks.A novel FeCo nanoparticle embedded nanoporous carbon composite (Fe-Co/NPC) was synthesized via in situ carbonization of dehydro-ascorbic acid (DHAA) coated Fe3O4 nanoparticles encapsulated in a metal-organic framework (zeolitic imidazolate framework-67, ZIF-67). The molar ratio of Fe/Co significantly depends on the encapsulated content of Fe3O4 in ZIF-67. The composites filled with 50 wt% of the Fe-Co/NPC-2.0 samples in paraffin show a maximum reflection loss (RL) of -21.7 dB at a thickness of 1.2 mm; in addition, a broad absorption bandwidth for RL < -10 dB which covers from 12.2 to 18 GHz can be obtained, and its minimum reflection loss and bandwidth (RL values exceeding -10 dB) are far greater than those of commercial carbonyl iron powder under a very low thickness (1-1.5 mm). This study not only provides a good reference for future preparation of carbon-based lightweight microwave absorbing materials but also broadens the application of such kinds of metal-organic frameworks. Electronic

  3. A two-fold interpenetrating 3D metal-organic framework material constructed from helical chains linked via 4,4'-H{sub 2}bpz fragments

    SciTech Connect

    Xie Yiming; Zhao Zhenguo; Wu Xiaoyuan; Zhang Qisheng; Chen Lijuan; Wang Fei; Chen Shanci; Lu Canzhong

    2008-12-15

    A 3-connected dia-f-type metal-organic framework compound {l_brace}[Ag(L){sub 3/2}H{sub 2}PO{sub 4}]{r_brace}{sub n} (1) has been synthesized by self-assembly of 4,4'-H{sub 2}bpz (L=4,4'-H{sub 2}bpz=3,3',5,5'-tetramethyl-4,4'-bipyrazole) and Ag{sub 4}P{sub 2}O{sub 7} under hydrothermal conditions. It crystallizes in the tetragonal space group I4{sub 1}/acd with a=21.406(4) A, b=21.406(4) A, c=36.298(8) A, Z=32. X-ray single-crystal diffraction reveals that 1 has a three-dimensional framework with an unprecedented alternate left- and right-handed helices structure, featuring a non-uniform two-fold interpenetrated (4.14{sup 2}) net. Photoluminescent investigation reveals that the title compound displays interesting emissions in a wide region, which shows that the title compound may be a good potential candidate as a photoelectric material. - Graphical abstract: A 3-connected dia-f-type metal-organic framework compound [Ag(4,4'-bpz){sub 3/2}H{sub 2}PO{sub 4}] shows unprecedented alternating left- and right-handed helices structure, featuring a non-uniform two-fold interpenetrated (4.14{sup 2}) net.

  4. Evaluating metal-organic frameworks for natural gas storage

    SciTech Connect

    Mason, JA; Veenstra, M; Long, JR

    2014-01-01

    Metal-organic frameworks have received significant attention as a new class of adsorbents for natural gas storage; however, inconsistencies in reporting high-pressure adsorption data and a lack of comparative studies have made it challenging to evaluate both new and existing materials. Here, we briefly discuss high-pressure adsorption measurements and review efforts to develop metal-organic frameworks with high methane storage capacities. To illustrate the most important properties for evaluating adsorbents for natural gas storage and for designing a next generation of improved materials, six metal-organic frameworks and an activated carbon, with a range of surface areas, pore structures, and surface chemistries representative of the most promising adsorbents for methane storage, are evaluated in detail. High-pressure methane adsorption isotherms are used to compare gravimetric and volumetric capacities, isosteric heats of adsorption, and usable storage capacities. Additionally, the relative importance of increasing volumetric capacity, rather than gravimetric capacity, for extending the driving range of natural gas vehicles is highlighted. Other important systems-level factors, such as thermal management, mechanical properties, and the effects of impurities, are also considered, and potential materials synthesis contributions to improving performance in a complete adsorbed natural gas system are discussed.

  5. Locating Gases in Porous Materials: Cryogenic Loading of Fuel-Related Gases Into a Sc-based Metal-Organic Framework under Extreme Pressures.

    PubMed

    Sotelo, Jorge; Woodall, Christopher H; Allan, Dave R; Gregoryanz, Eugene; Howie, Ross T; Kamenev, Konstantin V; Probert, Michael R; Wright, Paul A; Moggach, Stephen A

    2015-11-02

    An alternative approach to loading metal organic frameworks with gas molecules at high (kbar) pressures is reported. The technique, which uses liquefied gases as pressure transmitting media within a diamond anvil cell along with a single-crystal of a porous metal-organic framework, is demonstrated to have considerable advantages over other gas-loading methods when investigating host-guest interactions. Specifically, loading the metal-organic framework Sc2BDC3 with liquefied CO2 at 2 kbar reveals the presence of three adsorption sites, one previously unreported, and resolves previous inconsistencies between structural data and adsorption isotherms. A further study with supercritical CH4 at 3-25 kbar demonstrates hyperfilling of the Sc2 BDC3 and two high-pressure displacive and reversible phase transitions are induced as the filled MOF adapts to reduce the volume of the system.

  6. Applications of metal-organic frameworks in heterogeneous supramolecular catalysis.

    PubMed

    Liu, Jiewei; Chen, Lianfen; Cui, Hao; Zhang, Jianyong; Zhang, Li; Su, Cheng-Yong

    2014-08-21

    This review summarizes the use of metal-organic frameworks (MOFs) as a versatile supramolecular platform to develop heterogeneous catalysts for a variety of organic reactions, especially for liquid-phase reactions. Following a background introduction about catalytic relevance to various metal-organic materials, crystal engineering of MOFs, characterization and evaluation methods of MOF catalysis, we categorize catalytic MOFs based on the types of active sites, including coordinatively unsaturated metal sites (CUMs), metalloligands, functional organic sites (FOS), as well as metal nanoparticles (MNPs) embedded in the cavities. Throughout the review, we emphasize the incidental or deliberate formation of active sites, the stability, heterogeneity and shape/size selectivity for MOF catalysis. Finally, we briefly introduce their relevance into photo- and biomimetic catalysis, and compare MOFs with other typical porous solids such as zeolites and mesoporous silica with regard to their different attributes, and provide our view on future trends and developments in MOF-based catalysis.

  7. Water-Stable Zirconium-Based Metal-Organic Framework Material with High-Surface Area and Gas-Storage Capacities

    SciTech Connect

    Gutov, OV; Bury, W; Gomez-Gualdron, DA; Krungleviciute, V; Fairen-Jimenez, D; Mondloch, JE; Sarjeant, AA; Al-Juaid, SS; Snurr, RQ; Hupp, JT; Yildirim, T; Farha, OK

    2014-08-14

    We designed, synthesized, and characterized a new Zr-based metal-organic framework material, NU-1100, with a pore volume of 1.53 ccg(-1) and Brunauer-Emmett-Teller (BET) surface area of 4020 m(2)g(-1); to our knowledge, currently the highest published for Zr-based MOFs. CH4/CO2/H-2 adsorption isotherms were obtained over a broad range of pressures and temperatures and are in excellent agreement with the computational predictions. The total hydrogen adsorption at 65 bar and 77 K is 0.092 gg(-1), which corresponds to 43 gL(-1). The volumetric and gravimetric methane-storage capacities at 65 bar and 298 K are approximately 180 v(STP)/v and 0.27 gg(-1), respectively.

  8. Water-stable zirconium-based metal-organic framework material with high-surface area and gas-storage capacities.

    PubMed

    Gutov, Oleksii V; Bury, Wojciech; Gomez-Gualdron, Diego A; Krungleviciute, Vaiva; Fairen-Jimenez, David; Mondloch, Joseph E; Sarjeant, Amy A; Al-Juaid, Salih S; Snurr, Randall Q; Hupp, Joseph T; Yildirim, Taner; Farha, Omar K

    2014-09-22

    We designed, synthesized, and characterized a new Zr-based metal-organic framework material, NU-1100, with a pore volume of 1.53 ccg(-1) and Brunauer-Emmett-Teller (BET) surface area of 4020 m(2) g(-1) ; to our knowledge, currently the highest published for Zr-based MOFs. CH4 /CO2 /H2 adsorption isotherms were obtained over a broad range of pressures and temperatures and are in excellent agreement with the computational predictions. The total hydrogen adsorption at 65 bar and 77 K is 0.092 g g(-1) , which corresponds to 43 g L(-1) . The volumetric and gravimetric methane-storage capacities at 65 bar and 298 K are approximately 180 vSTP /v and 0.27 g g(-1) , respectively.

  9. Layer-by-Layer Assembled Films of Perylene Diimide- and Squaraine-Containing Metal-Organic Framework-like Materials: Solar Energy Capture and Directional Energy Transfer.

    PubMed

    Park, Hea Jung; So, Monica C; Gosztola, David; Wiederrecht, Gary P; Emery, Jonathan D; Martinson, Alex B F; Er, Süleyman; Wilmer, Christopher E; Vermeulen, Nicolaas A; Aspuru-Guzik, Alán; Stoddart, J Fraser; Farha, Omar K; Hupp, Joseph T

    2016-09-28

    We demonstrate that thin films of metal-organic framework (MOF)-like materials, containing two perylenediimides (PDICl4, PDIOPh2) and a squaraine dye (S1), can be fabricated by layer-by-layer assembly (LbL). Interestingly, these LbL films absorb across the visible light region (400-750 nm) and facilitate directional energy transfer. Due to the high spectral overlap and oriented transition dipole moments of the donor (PDICl4 and PDIOPh2) and acceptor (S1) components, directional long-range energy transfer from the bluest to reddest absorber was successfully demonstrated in the multicomponent MOF-like films. These findings have significant implications for the development of solar energy conversion devices based on MOFs.

  10. The surface chemistry of metal-organic frameworks.

    PubMed

    McGuire, Christina V; Forgan, Ross S

    2015-03-28

    Metal-organic frameworks (MOFs) have received particular attention over the last 20 years as a result of their attractive properties offering potential applications in a number of areas. Typically, these characteristics are tuned by functionalisation of the bulk of the MOF material itself. This Feature Article focuses instead on modification of MOF particles at their surfaces only, which can also offer control over the bulk properties of the material. The differing surface modification techniques available to the synthetic chemist will be discussed, with a focus on the effect of surface modification of MOFs on their fundamental properties and application in adsorption, catalysis, drug delivery and other areas.

  11. Evolution of form in metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Lee, Jiyoung; Kwak, Ja Hun; Choe, Wonyoung

    2017-01-01

    Self-assembly has proven to be a widely successful synthetic strategy for functional materials, especially for metal-organic materials (MOMs), an emerging class of porous materials consisting of metal-organic frameworks (MOFs) and metal-organic polyhedra (MOPs). However, there are areas in MOM synthesis in which such self-assembly has not been fully utilized, such as controlling the interior of MOM crystals. Here we demonstrate sequential self-assembly strategy for synthesizing various forms of MOM crystals, including double-shell hollow MOMs, based on single-crystal to single-crystal transformation from MOP to MOF. Moreover, this synthetic strategy also yields other forms, such as solid, core-shell, double and triple matryoshka, and single-shell hollow MOMs, thereby exhibiting form evolution in MOMs. We anticipate that this synthetic approach might open up a new direction for the development of diverse forms in MOMs, with highly advanced areas such as sequential drug delivery/release and heterogeneous cascade catalysis targeted in the foreseeable future.

  12. Metal-adeninate vertices for the construction of an exceptionally porous metal-organic framework.

    PubMed

    An, Jihyun; Farha, Omar K; Hupp, Joseph T; Pohl, Ehmke; Yeh, Joanne I; Rosi, Nathaniel L

    2012-01-03

    Metal-organic frameworks comprising metal-carboxylate cluster vertices and long, branched organic linkers are the most porous materials known, and therefore have attracted tremendous attention for many applications, including gas storage, separations, catalysis and drug delivery. To increase metal-organic framework porosity, the size and complexity of linkers has increased. Here we present a promising alternative strategy for constructing mesoporous metal-organic frameworks that addresses the size of the vertex rather than the length of the organic linker. This approach uses large metal-biomolecule clusters, in particular zinc-adeninate building units, as vertices to construct bio-MOF-100, an exclusively mesoporous metal-organic framework. Bio-MOF-100 exhibits a high surface area (4,300 m(2) g(-1)), one of the lowest crystal densities (0.302 g cm(-3)) and the largest metal-organic framework pore volume reported to date (4.3 cm(3) g(-1)).

  13. Hierarchical porous anatase TiO2 derived from a titanium metal-organic framework as a superior anode material for lithium ion batteries.

    PubMed

    Xiu, Zhiliang; Alfaruqi, Muhammad Hilmy; Gim, Jihyeon; Song, Jinju; Kim, Sungjin; Vu Thi, Trang; Duong, Pham Tung; Baboo, Joseph Paul; Mathew, Vinod; Kim, Jaekook

    2015-08-07

    Hierarchical meso-/macroporous anatase TiO2 was synthesized by the hydrolysis of a titanium metal-organic framework precursor followed by calcination in air. This unique porous feature enables the superior rate capability and excellent cycling stability of anatase TiO2 as an anode for rechargeable lithium-ion batteries.

  14. Metal-organic frameworks with dynamic interlocked components

    NASA Astrophysics Data System (ADS)

    Vukotic, V. Nicholas; Harris, Kristopher J.; Zhu, Kelong; Schurko, Robert W.; Loeb, Stephen J.

    2012-06-01

    The dynamics of mechanically interlocked molecules such as rotaxanes and catenanes have been studied in solution as examples of rudimentary molecular switches and machines, but in this medium, the molecules are randomly dispersed and their motion incoherent. As a strategy for achieving a higher level of molecular organization, we have constructed a metal-organic framework material using a [2]rotaxane as the organic linker and binuclear Cu(II) units as the nodes. Activation of the as-synthesized material creates a void space inside the rigid framework that allows the soft macrocyclic ring of the [2]rotaxane to rotate rapidly, unimpeded by neighbouring molecular components. Variable-temperature 13C and 2H solid-state NMR experiments are used to characterize the nature and rate of the dynamic processes occurring inside this unique material. These results provide a blueprint for the future creation of solid-state molecular switches and molecular machines based on mechanically interlocked molecules.

  15. Metal-organic frameworks for Xe/Kr separation

    DOEpatents

    Ryan, Patrick J.; Farha, Omar K.; Broadbelt, Linda J.; Snurr, Randall Q.; Bae, Youn-Sang

    2013-08-27

    Metal-organic framework (MOF) materials are provided and are selectively adsorbent to xenon (Xe) over another noble gas such as krypton (Kr) and/or argon (Ar) as a result of having framework voids (pores) sized to this end. MOF materials having pores that are capable of accommodating a Xe atom but have a small enough pore size to receive no more than one Xe atom are desired to preferentially adsorb Xe over Kr in a multi-component (Xe--Kr mixture) adsorption method. The MOF material has 20% or more, preferably 40% or more, of the total pore volume in a pore size range of 0.45-0.75 nm which can selectively adsorb Xe over Kr in a multi-component Xe--Kr mixture over a pressure range of 0.01 to 1.0 MPa.

  16. Metal-organic frameworks for Xe/Kr separation

    DOEpatents

    Ryan, Patrick J.; Farha, Omar K.; Broadbelt, Linda J.; Snurr, Randall Q.; Bae, Youn-Sang

    2014-07-22

    Metal-organic framework (MOF) materials are provided and are selectively adsorbent to xenon (Xe) over another noble gas such as krypton (Kr) and/or argon (Ar) as a result of having framework voids (pores) sized to this end. MOF materials having pores that are capable of accommodating a Xe atom but have a small enough pore size to receive no more than one Xe atom are desired to preferentially adsorb Xe over Kr in a multi-component (Xe--Kr mixture) adsorption method. The MOF material has 20% or more, preferably 40% or more, of the total pore volume in a pore size range of 0.45-0.75 nm which can selectively adsorb Xe over Kr in a multi-component Xe--Kr mixture over a pressure range of 0.01 to 1.0 MPa.

  17. Stimuli-Responsive Metal Organic Frameworks: Stimuli-Responsive Metal Organic Frameworks for Energy-Efficient Post Combustion Capture

    SciTech Connect

    2010-07-01

    IMPACCT Project: A team led by three professors at Texas A&M is developing a subset of metal organic frameworks that respond to stimuli such as small changes in temperature to trap CO2 and then release it for storage. These frameworks are a promising class of materials for carbon capture applications because their structure and chemistry can be controlled with great precision. Because the changes in temperature required to trap and release CO2 in Texas A&M’s frameworks are much smaller than in other carbon capture approaches, the amount of energy or stimulus that has to be diverted from coal-fired power plants to accomplish this is greatly reduced. The team is working to alter the materials so they bind only with CO2, and are stable enough to withstand the high temperatures found in the chimneys of coal-fired power plants.

  18. From metal-organic framework to intrinsically fluorescent carbon nanodots.

    PubMed

    Amali, Arlin Jose; Hoshino, Hideto; Wu, Chun; Ando, Masanori; Xu, Qiang

    2014-07-01

    Highly photoluminescent carbon nanodots (CNDs) were synthesized for the first time from metal-organic framework (MOF, ZIF-8) nanoparticles. Coupled with fluorescence and non-toxic characteristics, these carbon nanodots could potentially be used in biosafe color patterning.

  19. Metal-organic framework for the separation of alkane isomers

    DOEpatents

    Long, Jeffrey R.; Herm, Zoey R.; Wiers, Brian M.; Krishna, Rajamani

    2017-01-10

    A metal organic framework Fe.sub.2(bdp).sub.3 (BDP.sup.2-=1,4-benzenedipyrazolate) with triangular channels is particularly suited for C5-C7 separations of alkanes according to the number of branches in the molecule rather than by carbon number. The metal-organic framework can offer pore geometries that is unavailable in zeolites or other porous media, facilitating distinct types of shape-based molecular separations.

  20. Coated/Sandwiched rGO/CoSx Composites Derived from Metal-Organic Frameworks/GO as Advanced Anode Materials for Lithium-Ion Batteries.

    PubMed

    Yin, Dongming; Huang, Gang; Zhang, Feifei; Qin, Yuling; Na, Zhaolin; Wu, Yaoming; Wang, Limin

    2016-01-22

    Rational composite materials made from transition metal sulfides and reduced graphene oxide (rGO) are highly desirable for designing high-performance lithium-ion batteries (LIBs). Here, rGO-coated or sandwiched CoSx composites are fabricated through facile thermal sulfurization of metal-organic framework/GO precursors. By scrupulously changing the proportion of Co(2+) and organic ligands and the solvent of the reaction system, we can tune the forms of GO as either a coating or a supporting layer. Upon testing as anode materials for LIBs, the as-prepared CoSx -rGO-CoSx and rGO@CoSx composites demonstrate brilliant electrochemical performances such as high initial specific capacities of 1248 and 1320 mA h g(-1) , respectively, at a current density of 100 mA g(-1) , and stable cycling abilities of 670 and 613 mA h g(-1) , respectively, after 100 charge/discharge cycles, as well as superior rate capabilities. The excellent electrical conductivity and porous structure of the CoSx /rGO composites can promote Li(+) transfer and mitigate internal stress during the charge/discharge process, thus significantly improving the electrochemical performance of electrode materials.

  1. Rapidly assessing the activation conditions and porosity of metal-organic frameworks using thermogravimetric analysis

    SciTech Connect

    McDonald, TM; Bloch, ED; Long, JR

    2015-01-01

    A methodology utilizing a thermogravimetric analyzer to monitor propane uptake following incremental increases of the temperature is demonstrated as a means of rapidly identifying porous materials and determining the optimum activation conditions of metal-organic frameworks.

  2. Near-infrared emitting ytterbium metal-organic frameworks with tunable excitation properties.

    PubMed

    White, Kiley A; Chengelis, Demetra A; Zeller, Matthias; Geib, Steven J; Szakos, Jessica; Petoud, Stéphane; Rosi, Nathaniel L

    2009-08-14

    The design of metal-organic frameworks (MOFs) incorporating near-infrared emitting ytterbium cations and organic sensitizers allows for the preparation of new materials with tunable and enhanced photophysical properties.

  3. Metal-organic framework derived Fe2O3@NiCo2O4 porous nanocages as anode materials for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Huang, Gang; Zhang, Leilei; Zhang, Feifei; Wang, Limin

    2014-04-01

    Metal-organic frameworks (MOFs) with high surface areas and uniform microporous structures have shown potential application in many fields. Here we report a facial strategy to synthesize Fe2O3@NiCo2O4 porous nanocages by annealing core-shell Co3[Fe(CN)6]2@Ni3[Co(CN)6]2 nanocubes in air. The obtained samples have been systematically characterized by XRD, SEM, TEM and N2 adsorption-desorption analysis. The results show that the Fe2O3@NiCo2O4 porous nanocages have an average diameter of 213 nm and a shell thickness of about 30 nm. As anode materials for Li-ion batteries, the Fe2O3@NiCo2O4 porous nanocages exhibit a high initial discharge capacity of 1311.4 mA h g-1 at a current density of 100 mA g-1 (about 0.1 C). The capacity is retained at 1079.6 mA h g-1 after 100 cycles. The synergistic effect of the different components and the porous hollow structure contributes to the outstanding performance of the composite electrode.Metal-organic frameworks (MOFs) with high surface areas and uniform microporous structures have shown potential application in many fields. Here we report a facial strategy to synthesize Fe2O3@NiCo2O4 porous nanocages by annealing core-shell Co3[Fe(CN)6]2@Ni3[Co(CN)6]2 nanocubes in air. The obtained samples have been systematically characterized by XRD, SEM, TEM and N2 adsorption-desorption analysis. The results show that the Fe2O3@NiCo2O4 porous nanocages have an average diameter of 213 nm and a shell thickness of about 30 nm. As anode materials for Li-ion batteries, the Fe2O3@NiCo2O4 porous nanocages exhibit a high initial discharge capacity of 1311.4 mA h g-1 at a current density of 100 mA g-1 (about 0.1 C). The capacity is retained at 1079.6 mA h g-1 after 100 cycles. The synergistic effect of the different components and the porous hollow structure contributes to the outstanding performance of the composite electrode. Electronic supplementary information (ESI) available: Detailed supplementary figures. See DOI: 10.1039/c3nr06041a

  4. A theoretical study of the hydrogen-storage potential of (H2)4CH4 in metal organic framework materials and carbon nanotubes.

    PubMed

    Li, Q; Thonhauser, T

    2012-10-24

    The hydrogen-methane compound (H(2))(4)CH(4)-or for short H4M-is one of the most promising hydrogen-storage materials. This van der Waals compound is extremely rich in molecular hydrogen: 33.3 mass%, not including the hydrogen bound in CH(4); including it, we reach even 50.2 mass%. Unfortunately, H4M is not stable under ambient pressure and temperature, requiring either low temperature or high pressure. In this paper, we investigate the properties and structure of the molecular and crystalline forms of H4M, using ab initio methods based on van der Waals DFT (vdW-DF). We further investigate the possibility of creating the pressures required to stabilize H4M through external agents such as metal organic framework (MOF) materials and carbon nanotubes, with very encouraging results. In particular, we find that certain MOFs can create considerable pressure for H4M in their cavities, but not enough to stabilize it at room temperature, and moderate cooling is still necessary. On the other hand, we find that all the investigated carbon nanotubes can create the high pressures required for H4M to be stable at room temperature, with direct implications for new and exciting hydrogen-storage applications.

  5. A theoretical study of the hydrogen-storage potential of (H2)4CH4 in metal organic framework materials and carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Li, Q.; Thonhauser, T.

    2012-10-01

    The hydrogen-methane compound (H2)4CH4—or for short H4M—is one of the most promising hydrogen-storage materials. This van der Waals compound is extremely rich in molecular hydrogen: 33.3 mass%, not including the hydrogen bound in CH4; including it, we reach even 50.2 mass%. Unfortunately, H4M is not stable under ambient pressure and temperature, requiring either low temperature or high pressure. In this paper, we investigate the properties and structure of the molecular and crystalline forms of H4M, using ab initio methods based on van der Waals DFT (vdW-DF). We further investigate the possibility of creating the pressures required to stabilize H4M through external agents such as metal organic framework (MOF) materials and carbon nanotubes, with very encouraging results. In particular, we find that certain MOFs can create considerable pressure for H4M in their cavities, but not enough to stabilize it at room temperature, and moderate cooling is still necessary. On the other hand, we find that all the investigated carbon nanotubes can create the high pressures required for H4M to be stable at room temperature, with direct implications for new and exciting hydrogen-storage applications.

  6. Carbon-Coated Fe3O4/VOx Hollow Microboxes Derived from Metal-Organic Frameworks as a High-Performance Anode Material for Lithium-Ion Batteries.

    PubMed

    Zhao, Zhi-Wei; Wen, Tao; Liang, Kuang; Jiang, Yi-Fan; Zhou, Xiao; Shen, Cong-Cong; Xu, An-Wu

    2017-02-01

    As the ever-growing demand for high-performance power sources, lithium-ion batteries with high storage capacities and outstanding rate performance have been widely considered as a promising storage device. In this work, starting with metal-organic frameworks, we have developed a facile approach to the synthesis of hybrid Fe3O4/VOx hollow microboxes via the process of hydrolysis and ion exchange and subsequent calcination. In the constructed architecture, the hollow structure provides an efficient lithium ion diffusion pathway and extra space to accommodate the volume expansion during the insertion and extraction of Li(+). With the assistance of carbon coating, the obtained Fe3O4/VOx@C microboxes exhibit excellent cyclability and enhanced rate performance when employed as an anode material for lithium-ion batteries. As a result, the obtained Fe3O4/VOx@C delivers a high Coulombic efficiency (near 100%) and outstanding reversible specific capacity of 742 mAh g(-1) after 400 cycles at a current density of 0.5 A g(-1). Moreover, a remarkable reversible capacity of 556 mAh g(-1) could be retained even at a current density of 2 A g(-1). This study provides a fundamental understanding for the rational design of other composite oxides as high-performance electrode materials for lithium-ion batteries.

  7. High-Performance Energy Storage and Conversion Materials Derived from a Single Metal-Organic Framework/Graphene Aerogel Composite.

    PubMed

    Xia, Wei; Qu, Chong; Liang, Zibin; Zhao, Bote; Dai, Shuge; Qiu, Bin; Jiao, Yang; Zhang, Qiaobao; Huang, Xinyu; Guo, Wenhan; Dang, Dai; Zou, Ruqiang; Xia, Dingguo; Xu, Qiang; Liu, Meilin

    2017-04-13

    Metal oxides and carbon-based materials are the most promising electrode materials for a wide range of low-cost and highly efficient energy storage and conversion devices. Creating unique nanostructures of metal oxides and carbon materials is imperative to the development of a new generation of electrodes with high energy and power density. Here we report our findings in the development of a novel graphene aerogel assisted method for preparation of metal oxide nanoparticles (NPs) derived from bulk MOFs (Co-based MOF, Co(mIM)2 (mIM = 2-methylimidazole). The presence of cobalt oxide (CoOx) hollow NPs with a uniform size of 35 nm monodispersed in N-doped graphene aerogels (NG-A) was confirmed by microscopic analyses. The evolved structure (denoted as CoOx/NG-A) served as a robust Pt-free electrocatalyst with excellent activity for the oxygen reduction reaction (ORR) in an alkaline electrolyte solution. In addition, when Co was removed, the resulting nitrogen-rich porous carbon-graphene composite electrode (denoted as C/NG-A) displayed exceptional capacitance and rate capability in a supercapacitor. Further, this method is readily applicable to creation of functional metal oxide hollow nanoparticles on the surface of other carbon materials such as graphene and carbon nanotubes, providing a good opportunity to tune their physical or chemical activities.

  8. Biomimicry in metal-organic materials

    SciTech Connect

    Zhang, MW; Gu, ZY; Bosch, M; Perry, Z; Zhou, HC

    2015-06-15

    Nature has evolved a great number of biological molecules which serve as excellent constructional or functional units for metal-organic materials (MOMs). Even though the study of biomimetic MOMs is still at its embryonic stage, considerable progress has been made in the past few years. In this critical review, we will highlight the recent advances in the design, development and application of biomimetic MOMs, and illustrate how the incorporation of biological components into MOMs could further enrich their structural and functional diversity. More importantly, this review will provide a systematic overview of different methods for rational design of MOMs with biomimetic features. Published by Elsevier B.V.

  9. Metal-organic frameworks for membrane-based separations

    NASA Astrophysics Data System (ADS)

    Denny, Michael S.; Moreton, Jessica C.; Benz, Lauren; Cohen, Seth M.

    2016-12-01

    As research into metal-organic frameworks (MOFs) enters its third decade, efforts are naturally shifting from fundamental studies to applications, utilizing the unique features of these materials. Engineered forms of MOFs, such as membranes and films, are being investigated to transform laboratory-synthesized MOF powders to industrially viable products for separations, chemical sensors and catalysts. Following encouraging demonstrations of gas separations using MOF-based membranes, liquid-phase separations are now being explored in an effort to build effective membranes for these settings. In this Review, we highlight MOF applications that are in their nascent stages, specifically liquid-phase separations using MOF-based mixed-matrix membranes. We also highlight the analytical techniques that provide important insights into these materials, particularly at surfaces and interfaces, to better understand MOFs and their interactions with other materials, which will ultimately lead to their use in advanced technologies.

  10. Efficient and Selective Uptake of TcO4(-) by a Cationic Metal-Organic Framework Material with Open Ag(+) Sites.

    PubMed

    Sheng, Daopeng; Zhu, Lin; Xu, Chao; Xiao, Chengliang; Wang, Yanlong; Wang, Yaxing; Chen, Lanhua; Diwu, Juan; Chen, Jing; Chai, Zhifang; Albrecht-Schmitt, Thomas E; Wang, Shuao

    2017-03-21

    (99)Tc is one of the most problematic radioisotopes in used nuclear fuel owing to its combined features of high fission yield, long half-life, and high environmental mobility. There are only a handful of functional materials that can remove TcO4(-) anion from aqueous solution and identifying for new, stable materials with high anion-exchange capacities, fast kinetics, and good selectivity remains a challenge. We report here an 8-fold interpenetrated three-dimensional cationic metal-organic framework material, SCU-100, which is assembled from a tetradentate neutral nitrogen-donor ligand and two-coordinate Ag(+) cations as potential open metal sites. The structure also contains a series of 1D channels filled with unbound nitrate anions. SCU-100 maintains its crystallinity in aqueous solution over a wide pH range from 1 to 13 and exhibits excellent β and γ radiation-resistance. Initial anion exchange studies show that SCU-100 is able to both quantitatively and rapidly remove TcO4(-) from water within 30 min. The exchange capacity for the surrogate ReO4(-) reaches up to 541 mg/g and the distribution coefficient Kd is up to 1.9 × 10(5) mL/g, which are significantly higher than all previously tested inorganic anion sorbent materials. More importantly, SCU-100 can selectively capture TcO4(-) in the presence of large excess of competitive anions (NO3(-), SO4(2-), CO3(2-), and PO4(3-)) and remove as much as 87% of TcO4(-) from the Hanford low-level waste melter off-gas scrubber simulant stream within 2 h. The sorption mechanism is well elucidated by single crystal X-ray diffraction, showing that the sorbed ReO4(-) anion is able to selectively coordinate to the open Ag(+) sites forming Ag-O-Re bonds and a series of hydrogen bonds. This further leads to a single-crystal-to-single-crystal transformation from an 8-fold interpenetrated framework with disordered nitrate anions to a 4-fold interpenetrated framework with fully ordered ReO4(-) anions. This work represents a

  11. Metal-organic framework derived Fe2O3@NiCo2O4 porous nanocages as anode materials for Li-ion batteries.

    PubMed

    Huang, Gang; Zhang, Leilei; Zhang, Feifei; Wang, Limin

    2014-05-21

    Metal-organic frameworks (MOFs) with high surface areas and uniform microporous structures have shown potential application in many fields. Here we report a facial strategy to synthesize Fe2O3@NiCo2O4 porous nanocages by annealing core-shell Co3[Fe(CN)6]2@Ni3[Co(CN)6]2 nanocubes in air. The obtained samples have been systematically characterized by XRD, SEM, TEM and N2 adsorption-desorption analysis. The results show that the Fe2O3@NiCo2O4 porous nanocages have an average diameter of 213 nm and a shell thickness of about 30 nm. As anode materials for Li-ion batteries, the Fe2O3@NiCo2O4 porous nanocages exhibit a high initial discharge capacity of 1311.4 mA h g(-1) at a current density of 100 mA g(-1) (about 0.1 C). The capacity is retained at 1079.6 mA h g(-1) after 100 cycles. The synergistic effect of the different components and the porous hollow structure contributes to the outstanding performance of the composite electrode.

  12. High methane storage capacity in aluminum metal-organic frameworks.

    PubMed

    Gándara, Felipe; Furukawa, Hiroyasu; Lee, Seungkyu; Yaghi, Omar M

    2014-04-09

    The use of porous materials to store natural gas in vehicles requires large amounts of methane per unit of volume. Here we report the synthesis, crystal structure and methane adsorption properties of two new aluminum metal-organic frameworks, MOF-519 and MOF-520. Both materials exhibit permanent porosity and high methane volumetric storage capacity: MOF-519 has a volumetric capacity of 200 and 279 cm(3) cm(-3) at 298 K and 35 and 80 bar, respectively, and MOF-520 has a volumetric capacity of 162 and 231 cm(3) cm(-3) under the same conditions. Furthermore, MOF-519 exhibits an exceptional working capacity, being able to deliver a large amount of methane at pressures between 5 and 35 bar, 151 cm(3) cm(-3), and between 5 and 80 bar, 230 cm(3) cm(-3).

  13. Iodine confinement into metal-organic frameworks (MOFs)-low temperature sintering glasses to form novel glass composite material (GCM) alternative waste forms.

    SciTech Connect

    Nenoff, Tina Maria; Garino, Terry J.; Sava, Dorina Florentina

    2010-11-01

    The safe handling of reprocessed fuel addresses several scientific goals, especially when considering the capture and long-term storage of volatile radionuclides that are necessary during this process. Despite not being a major component of the off-gas, radioiodine (I{sub 2}) is particularly challenging, because it is a highly mobile gas and {sup 129}I is a long-lived radionuclide (1.57 x 10{sup 7} years). Therefore, its capture and sequestration is of great interest on a societal level. Herein, we explore novel routes toward the effective capture and storage of iodine. In particular, we report on the novel use of a new class of porous solid-state functional materials (metal-organic frameworks, MOFs), as high-capacity adsorbents of molecular iodine. We further describe the formation of novel glass-composite material (GCM) waste forms from the mixing and sintering of the I{sub 2}-containing MOFs with Bi-Zn-O low-temperature sintering glasses and silver metal flakes. Our findings indicate that, upon sintering, a uniform monolith is formed, with no evidence of iodine loss; iodine is sequestered during the heating process by the in situ formation of AgI. Detailed materials characterization analysis is presented for the GCMs. This includes powder X-ray diffraction, scanning electron microscopy coupled with energy-dispersive spectroscopy (SEM-EDS), thermal analysis (thermogravimetric analysis (TGA)), and chemical durability tests including aqueous leach studies (product consistency test (PCT)), with X-ray fluorescence (XRF) and inductively coupled plasma-mass spectrometry (ICP-MS) of the PCT leachate.

  14. Increasing the Stability of Metal-Organic Frameworks

    DOE PAGES

    Bosch, Mathieu; Zhang, Muwei; Zhou, Hong-Cai

    2014-01-01

    Metal-organic frameworks (MOFs) are a new category of advanced porous materials undergoing study by many researchers for their vast variety of both novel structures and potentially useful properties arising from them. Their high porosities, tunable structures, and convenient process of introducing both customizable functional groups and unsaturated metal centers have afforded excellent gas sorption and separation ability, catalytic activity, luminescent properties, and more. However, the robustness and reactivity of a given framework are largely dependent on its metal-ligand interactions, where the metal-containing clusters are often vulnerable to ligand substitution by water or other nucleophiles, meaning that the frameworks may collapsemore » upon exposure even to moist air. Other frameworks may collapse upon thermal or vacuum treatment or simply over time. This instability limits the practical uses of many MOFs. In order to further enhance the stability of the framework, many different approaches, such as the utilization of high-valence metal ions or nitrogen-donor ligands, were recently investigated. This review details the efforts of both our research group and others to synthesize MOFs possessing drastically increased chemical and thermal stability, in addition to exemplary performance for catalysis, gas sorption, and separation.« less

  15. "Heterogeneity within order" in metal-organic frameworks.

    PubMed

    Furukawa, Hiroyasu; Müller, Ulrich; Yaghi, Omar M

    2015-03-09

    Metal-organic frameworks (MOFs) are constructed by linking inorganic units with organic linkers to make extended networks. Though more than 20 000 MOF structures have been reported most of these are ordered and largely composed of a limited number of different kinds building units, and very few have multiple different building units (heterogeneous). Although heterogeneity and multiplicity is a fundamental characteristic of biological systems, very few synthetic materials incorporate heterogeneity without losing crystalline order. Thus, the question arises: how do we introduce heterogeneity into MOFs without losing their ordered structure? This Review outlines strategies for varying the building units within both the backbone of the MOF and its pores to produce the heterogeneity that is sought after. The impact this heterogeneity imparts on the properties of a MOF is highlighted. We also provide an update on the MOF industry as part of this themed issue for the 150th anniversary of BASF.

  16. Structure and properties of an amorphous metal-organic framework.

    PubMed

    Bennett, Thomas D; Goodwin, Andrew L; Dove, Martin T; Keen, David A; Tucker, Matthew G; Barney, Emma R; Soper, Alan K; Bithell, Erica G; Tan, Jin-Chong; Cheetham, Anthony K

    2010-03-19

    ZIF-4, a metal-organic framework (MOF) with a zeolitic structure, undergoes a crystal-amorphous transition on heating to 300 degrees C. The amorphous form, which we term a-ZIF, is recoverable to ambient conditions or may be converted to a dense crystalline phase of the same composition by heating to 400 degrees C. Neutron and x-ray total scattering data collected during the amorphization process are used as a basis for reverse Monte Carlo refinement of an atomistic model of the structure of a-ZIF. The structure is best understood in terms of a continuous random network analogous to that of a-SiO2. Optical microscopy, electron diffraction and nanoindentation measurements reveal a-ZIF to be an isotropic glasslike phase capable of plastic flow on its formation. Our results suggest an avenue for designing broad new families of amorphous and glasslike materials that exploit the chemical and structural diversity of MOFs.

  17. Structure and Properties of an Amorphous Metal-Organic Framework

    NASA Astrophysics Data System (ADS)

    Bennett, Thomas D.; Goodwin, Andrew L.; Dove, Martin T.; Keen, David A.; Tucker, Matthew G.; Barney, Emma R.; Soper, Alan K.; Bithell, Erica G.; Tan, Jin-Chong; Cheetham, Anthony K.

    2010-03-01

    ZIF-4, a metal-organic framework (MOF) with a zeolitic structure, undergoes a crystal-amorphous transition on heating to 300°C. The amorphous form, which we term a-ZIF, is recoverable to ambient conditions or may be converted to a dense crystalline phase of the same composition by heating to 400°C. Neutron and x-ray total scattering data collected during the amorphization process are used as a basis for reverse Monte Carlo refinement of an atomistic model of the structure of a-ZIF. The structure is best understood in terms of a continuous random network analogous to that of a-SiO2. Optical microscopy, electron diffraction and nanoindentation measurements reveal a-ZIF to be an isotropic glasslike phase capable of plastic flow on its formation. Our results suggest an avenue for designing broad new families of amorphous and glasslike materials that exploit the chemical and structural diversity of MOFs.

  18. Imparting functionality to biocatalysts via embedding enzymes into nanoporous materials by a de novo approach: size-selective sheltering of catalase in metal-organic framework microcrystals.

    PubMed

    Shieh, Fa-Kuen; Wang, Shao-Chun; Yen, Chia-I; Wu, Chang-Cheng; Dutta, Saikat; Chou, Lien-Yang; Morabito, Joseph V; Hu, Pan; Hsu, Ming-Hua; Wu, Kevin C-W; Tsung, Chia-Kuang

    2015-04-08

    We develop a new concept to impart new functions to biocatalysts by combining enzymes and metal-organic frameworks (MOFs). The proof-of-concept design is demonstrated by embedding catalase molecules into uniformly sized ZIF-90 crystals via a de novo approach. We have carried out electron microscopy, X-ray diffraction, nitrogen sorption, electrophoresis, thermogravimetric analysis, and confocal microscopy to confirm that the ~10 nm catalase molecules are embedded in 2 μm single-crystalline ZIF-90 crystals with ~5 wt % loading. Because catalase is immobilized and sheltered by the ZIF-90 crystals, the composites show activity in hydrogen peroxide degradation even in the presence of protease proteinase K.

  19. Highly mesoporous metal-organic framework assembled in a switchable solvent

    NASA Astrophysics Data System (ADS)

    Peng, Li; Zhang, Jianling; Xue, Zhimin; Han, Buxing; Sang, Xinxin; Liu, Chengcheng; Yang, Guanying

    2014-07-01

    The mesoporous metal-organic frameworks are a family of materials that have pore sizes ranging from 2 to 50 nm, which have shown promising applications in catalysis, adsorption, chemical sensing and so on. The preparation of mesoporous metal-organic frameworks usually needs the supramolecular or cooperative template strategy. Here we report the template-free assembly of mesoporous metal-organic frameworks by using CO2-expanded liquids as switchable solvents. The mesocellular metal-organic frameworks with large mesopores (13-23 nm) are formed, and their porosity properties can be easily adjusted by controlling CO2 pressure. Moreover, the use of CO2 can accelerate the reaction for metal-organic framework formation from metal salt and organic linker due to the viscosity-lowering effect of CO2, and the product can be recovered through CO2 extraction. The as-synthesized mesocellular metal-organic frameworks are highly active in catalysing the aerobic oxidation of benzylic alcohols under mild temperature at atmospheric pressure.

  20. Highly mesoporous metal-organic framework assembled in a switchable solvent.

    PubMed

    Peng, Li; Zhang, Jianling; Xue, Zhimin; Han, Buxing; Sang, Xinxin; Liu, Chengcheng; Yang, Guanying

    2014-07-22

    The mesoporous metal-organic frameworks are a family of materials that have pore sizes ranging from 2 to 50 nm, which have shown promising applications in catalysis, adsorption, chemical sensing and so on. The preparation of mesoporous metal-organic frameworks usually needs the supramolecular or cooperative template strategy. Here we report the template-free assembly of mesoporous metal-organic frameworks by using CO2-expanded liquids as switchable solvents. The mesocellular metal-organic frameworks with large mesopores (13-23 nm) are formed, and their porosity properties can be easily adjusted by controlling CO2 pressure. Moreover, the use of CO2 can accelerate the reaction for metal-organic framework formation from metal salt and organic linker due to the viscosity-lowering effect of CO2, and the product can be recovered through CO2 extraction. The as-synthesized mesocellular metal-organic frameworks are highly active in catalysing the aerobic oxidation of benzylic alcohols under mild temperature at atmospheric pressure.

  1. Metal-organic frameworks: Shuttling in the solid state

    NASA Astrophysics Data System (ADS)

    Olson, Mark A.

    2015-06-01

    Incorporating mechanically interlocked molecular shuttles within a metal-organic framework that has enough free space in the crystal lattice to permit volume-conserving translational motion sets the stage for defect-free molecular-electronic device fabrication and more.

  2. Omar Yaghi on Chemistry and Metal Organic Frameworks

    SciTech Connect

    Omar Yaghi

    2012-07-23

    In this edited version of the hour long talk, Omar Yaghi, director of the Molecular Foundry, sat down in conversation with Jeff Miller, head of Public Affairs, on July 11th, 2012 to discuss his fascination with the hidden world of chemistry and his work on Metal Organic Frameworks.

  3. Omar Yaghi on Chemistry and Metal Organic Frameworks

    ScienceCinema

    Omar Yaghi

    2016-07-12

    In this edited version of the hour long talk, Omar Yaghi, director of the Molecular Foundry, sat down in conversation with Jeff Miller, head of Public Affairs, on July 11th, 2012 to discuss his fascination with the hidden world of chemistry and his work on Metal Organic Frameworks.

  4. Synthesis and Characterization of Functionalized Metal-organic Frameworks

    PubMed Central

    Karagiaridi, Olga; Bury, Wojciech; Sarjeant, Amy A.; Hupp, Joseph T.; Farha, Omar K.

    2014-01-01

    Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and technological applications. Their signature property is their ultrahigh porosity, which however imparts a series of challenges when it comes to both constructing them and working with them. Securing desired MOF chemical and physical functionality by linker/node assembly into a highly porous framework of choice can pose difficulties, as less porous and more thermodynamically stable congeners (e.g., other crystalline polymorphs, catenated analogues) are often preferentially obtained by conventional synthesis methods. Once the desired product is obtained, its characterization often requires specialized techniques that address complications potentially arising from, for example, guest-molecule loss or preferential orientation of microcrystallites. Finally, accessing the large voids inside the MOFs for use in applications that involve gases can be problematic, as frameworks may be subject to collapse during removal of solvent molecules (remnants of solvothermal synthesis). In this paper, we describe synthesis and characterization methods routinely utilized in our lab either to solve or circumvent these issues. The methods include solvent-assisted linker exchange, powder X-ray diffraction in capillaries, and materials activation (cavity evacuation) by supercritical CO2 drying. Finally, we provide a protocol for determining a suitable pressure region for applying the Brunauer-Emmett-Teller analysis to nitrogen isotherms, so as to estimate surface area of MOFs with good accuracy. PMID:25225784

  5. Synthesis and characterization of functionalized metal-organic frameworks.

    PubMed

    Karagiaridi, Olga; Bury, Wojciech; Sarjeant, Amy A; Hupp, Joseph T; Farha, Omar K

    2014-09-05

    Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and technological applications. Their signature property is their ultrahigh porosity, which however imparts a series of challenges when it comes to both constructing them and working with them. Securing desired MOF chemical and physical functionality by linker/node assembly into a highly porous framework of choice can pose difficulties, as less porous and more thermodynamically stable congeners (e.g., other crystalline polymorphs, catenated analogues) are often preferentially obtained by conventional synthesis methods. Once the desired product is obtained, its characterization often requires specialized techniques that address complications potentially arising from, for example, guest-molecule loss or preferential orientation of microcrystallites. Finally, accessing the large voids inside the MOFs for use in applications that involve gases can be problematic, as frameworks may be subject to collapse during removal of solvent molecules (remnants of solvothermal synthesis). In this paper, we describe synthesis and characterization methods routinely utilized in our lab either to solve or circumvent these issues. The methods include solvent-assisted linker exchange, powder X-ray diffraction in capillaries, and materials activation (cavity evacuation) by supercritical CO2 drying. Finally, we provide a protocol for determining a suitable pressure region for applying the Brunauer-Emmett-Teller analysis to nitrogen isotherms, so as to estimate surface area of MOFs with good accuracy.

  6. Metal-organic frameworks for lithium ion batteries and supercapacitors

    SciTech Connect

    Ke, Fu-Sheng; Wu, Yu-Shan; Deng, Hexiang

    2015-03-15

    Porous materials have been widely used in batteries and supercapacitors attribute to their large internal surface area (usually 100–1000 m{sup 2} g{sup −1}) and porosity that can favor the electrochemical reaction, interfacial charge transport, and provide short diffusion paths for ions. As a new type of porous crystalline materials, metal-organic frameworks (MOFs) have received huge attention in the past decade due to their unique properties, i.e. huge surface area (up to 7000 m{sup 2} g{sup −1}), high porosity, low density, controllable structure and tunable pore size. A wide range of applications including gas separation, storage, catalysis, and drug delivery benefit from the recent fast development of MOFs. However, their potential in electrochemical energy storage has not been fully revealed. Herein, the present mini review appraises recent and significant development of MOFs and MOF-derived materials for rechargeable lithium ion batteries and supercapacitors, to give a glimpse into these potential applications of MOFs. - Graphical abstract: MOFs with large surface area and high porosity can offer more reaction sites and charge carriers diffusion path. Thus MOFs are used as cathode, anode, electrolyte, matrix and precursor materials for lithium ion battery, and also as electrode and precursor materials for supercapacitors. - Highlights: • MOFs have potential in electrochemical area due to their high porosity and diversity. • We summarized and compared works on MOFs for lithium ion battery and supercapacitor. • We pointed out critical challenges and provided possible solutions for future study.

  7. Toxic Industrial Chemical Removal by Isostructural Metal-Organic Frameworks

    DTIC Science & Technology

    2011-01-01

    ISOSTRUCTURAL METAL-ORGANIC FRAMEWORKS Gregory W. Peterson RESEARCH AND TECHNOLOGY DIRECTORATE T. Grant Glover Bryan J. Schindler SCIENCE...APPLICATIONS INTERNATIONAL CORPORATION Gunpowder, MD 21010-0068 David Britt Omar Yaghi UNIVERSITY OF CALIFORNIA Los Angeles, CA 90095-1569 January 2011...Frameworks 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) Peterson, Gregory W. (ECBC); Glover, T. Grant; Schindler

  8. Hydrogen storage by physisorption on Metal Organic Frameworks

    NASA Astrophysics Data System (ADS)

    Dailly, Anne

    2008-03-01

    Cryo-adsorption systems based on materials with high specific surface areas have the main advantage that they can store and release hydrogen with fast kinetics and high reversibility over multiples cycles. Recently Metal Organic Frameworks (MOFs) have been proposed as promising adsorbents for hydrogen. These crystallographically well organized hybrid solids resulting from the three dimensional connection of inorganic clusters using organic linkers show the largest specific surface areas of all known crystalline solids. The determination of the relationships between physical properties (chemistry, structure, surface area ) of the MOFs and their hydrogen storage behavior is a key step in the characterization of these materials, if they are to be designed for hydrogen storage applications. Excess hydrogen sorption measurements for different MOFs will be presented. We show that maximum hydrogen uptake at high pressure and 77K does not always scale with the specific surface area. A linear correlation trend only apply within a class of specific materials and breaks down when the surface area measurement does not represent the surface sites that are available to H2. The influence of pore size and shape will also be discussed by comparing several MOFs with different structure types. The hydrogen adsorption and binding energy at low pressure are strongly dependent on the metal ions and the pore size.

  9. Destruction of chemical warfare agents using metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Mondloch, Joseph E.; Katz, Michael J.; Isley, William C., III; Ghosh, Pritha; Liao, Peilin; Bury, Wojciech; Wagner, George W.; Hall, Morgan G.; Decoste, Jared B.; Peterson, Gregory W.; Snurr, Randall Q.; Cramer, Christopher J.; Hupp, Joseph T.; Farha, Omar K.

    2015-05-01

    Chemical warfare agents containing phosphonate ester bonds are among the most toxic chemicals known to mankind. Recent global military events, such as the conflict and disarmament in Syria, have brought into focus the need to find effective strategies for the rapid destruction of these banned chemicals. Solutions are needed for immediate personal protection (for example, the filtration and catalytic destruction of airborne versions of agents), bulk destruction of chemical weapon stockpiles, protection (via coating) of clothing, equipment and buildings, and containment of agent spills. Solid heterogeneous materials such as modified activated carbon or metal oxides exhibit many desirable characteristics for the destruction of chemical warfare agents. However, low sorptive capacities, low effective active site loadings, deactivation of the active site, slow degradation kinetics, and/or a lack of tailorability offer significant room for improvement in these materials. Here, we report a carefully chosen metal-organic framework (MOF) material featuring high porosity and exceptional chemical stability that is extraordinarily effective for the degradation of nerve agents and their simulants. Experimental and computational evidence points to Lewis-acidic ZrIV ions as the active sites and to their superb accessibility as a defining element of their efficacy.

  10. Destruction of chemical warfare agents using metal-organic frameworks.

    PubMed

    Mondloch, Joseph E; Katz, Michael J; Isley, William C; Ghosh, Pritha; Liao, Peilin; Bury, Wojciech; Wagner, George W; Hall, Morgan G; DeCoste, Jared B; Peterson, Gregory W; Snurr, Randall Q; Cramer, Christopher J; Hupp, Joseph T; Farha, Omar K

    2015-05-01

    Chemical warfare agents containing phosphonate ester bonds are among the most toxic chemicals known to mankind. Recent global military events, such as the conflict and disarmament in Syria, have brought into focus the need to find effective strategies for the rapid destruction of these banned chemicals. Solutions are needed for immediate personal protection (for example, the filtration and catalytic destruction of airborne versions of agents), bulk destruction of chemical weapon stockpiles, protection (via coating) of clothing, equipment and buildings, and containment of agent spills. Solid heterogeneous materials such as modified activated carbon or metal oxides exhibit many desirable characteristics for the destruction of chemical warfare agents. However, low sorptive capacities, low effective active site loadings, deactivation of the active site, slow degradation kinetics, and/or a lack of tailorability offer significant room for improvement in these materials. Here, we report a carefully chosen metal-organic framework (MOF) material featuring high porosity and exceptional chemical stability that is extraordinarily effective for the degradation of nerve agents and their simulants. Experimental and computational evidence points to Lewis-acidic Zr(IV) ions as the active sites and to their superb accessibility as a defining element of their efficacy.

  11. On the performance of Cu-BTC metal organic framework for carbon tetrachloride gas removal.

    PubMed

    Calero, Sofía; Martín-Calvo, Ana; Hamad, Said; García-Pérez, Elena

    2011-01-07

    The performance of Cu-BTC metal organic framework for carbon tetrachloride removal from air has been studied using molecular simulations. According to our results, this material shows extremely high adsorption selectivity in favour of carbon tetrachloride. We demonstrate that this selectivity can be further enhanced by selective blockage of the framework.

  12. Smart Metal-Organic Framework Coatings: Triggered Antibiofilm Compound Release.

    PubMed

    Claes, Birgit; Boudewijns, Tom; Muchez, Laurens; Hooyberghs, Geert; Van der Eycken, Erik V; Vanderleyden, Jozef; Steenackers, Hans P; De Vos, Dirk E

    2017-02-08

    Metal-organic frameworks (MOFs) have a large potential for delivery of active molecules. Here, a MOF coating is investigated as a smart host matrix for triggered release of antibiofilm compounds. In addition to a coating consisting of the regular Fe-terephthalate MIL-88B(Fe), a new hydrophobic MIL-88B(Fe) coating is synthesized in hydrothermal conditions using palmitic acid as a lattice terminating group. These porous materials are used as a host matrix for the antibiofilm compound 5-(4-chlorophenyl)-N-(2-isobutyl)-2-aminoimidazole, which has a specific biofilm-inhibiting effect at concentrations at which no activity against planktonic cells is detected. The stability of MIL-88B(Fe) in distilled water and tryptic soy broth medium is investigated, together with the ability of iron(III) chelators to serve as a trigger for controlled decomposition of MIL-88B(Fe) by metal complexation. Organic iron chelators are used to mimic the iron chelating function of siderophores, which are specific molecules excreted by biofilm-forming bacteria. Trisodium citrate is able to chelate metal ions from the junctions of the framework. By sequestration of these metal ions, the host matrix is partially degraded, resulting in an antibiofilm compound release. Finally, the antibiofilm properties against Salmonella Typhimurium are validated by monitoring biofilm growth on MOF layers either loaded or not with aminoimidazole. A strong proof-of-concept is shown for efficient inhibition of biofilm growth through triggered antibiofilm compound release.

  13. A metal-organic framework-derived bifunctional oxygen electrocatalyst

    NASA Astrophysics Data System (ADS)

    Xia, Bao Yu; Yan, Ya; Li, Nan; Wu, Hao Bin; Lou, Xiong Wen (David); Wang, Xin

    2016-01-01

    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.

  14. Single crystalline hollow metal-organic frameworks: a metal-organic polyhedron single crystal as a sacrificial template.

    PubMed

    Kim, Hyehyun; Oh, Minhak; Kim, Dongwook; Park, Jeongin; Seong, Junmo; Kwak, Sang Kyu; Lah, Myoung Soo

    2015-02-28

    Single crystalline hollow metal-organic frameworks (MOFs) with cavity dimensions on the order of several micrometers and hundreds of micrometers were prepared using a metal-organic polyhedron single crystal as a sacrificial hard template. The hollow nature of the MOF crystal was confirmed by scanning electron microscopy of the crystal sliced using a focused ion beam.

  15. In situ synthesized 3D heterometallic metal-organic framework (MOF) as a high-energy-density material shows high heat of detonation, good thermostability and insensitivity.

    PubMed

    Feng, Yaya; Liu, Xiangyu; Duan, Linqiang; Yang, Qi; Wei, Qing; Xie, Gang; Chen, Sanping; Yang, Xuwu; Gao, Shengli

    2015-02-07

    A reticular 3D heterometallic metal-organic framework (MOF), [Cu4Na(Mtta)5(CH3CN)]n () (N% = 40.08%), has been synthesized, using a 5-methyl tetrazole (Mtta) ligand formed from acetonitrile and azide, through in situ synthesis and structurally characterized by X-ray single crystal diffraction. The fluorescence spectra demonstrate that undergoes an interesting structural transformation in aqueous solution, yielding the compound [Cu4Na(Mtta)5H2O]n () as confirmed by (1)H NMR, IR and PXRD. Thermoanalysis showed that possesses excellent thermostability up to 335 °C. The calculated detonation properties and the sensitivity test illustrate that compound could be used as a potential explosive. In addition, the non-isothermal kinetics for were studied using the Kissinger and Ozawa-Doyle methods. The enthalpy of formation was obtained from the determination of the constant-volume combustion energy.

  16. Controlling Thermal Expansion: A Metal-Organic Frameworks Route.

    PubMed

    Balestra, Salvador R G; Bueno-Perez, Rocio; Hamad, Said; Dubbeldam, David; Ruiz-Salvador, A Rabdel; Calero, Sofia

    2016-11-22

    Controlling thermal expansion is an important, not yet resolved, and challenging problem in materials research. A conceptual design is introduced here, for the first time, for the use of metal-organic frameworks (MOFs) as platforms for controlling thermal expansion devices that can operate in the negative, zero, and positive expansion regimes. A detailed computer simulation study, based on molecular dynamics, is presented to support the targeted application. MOF-5 has been selected as model material, along with three molecules of similar size and known differences in terms of the nature of host-guest interactions. It has been shown that adsorbate molecules can control, in a colligative way, the thermal expansion of the solid, so that changing the adsorbate molecules induces the solid to display positive, zero, or negative thermal expansion. We analyze in depth the distortion mechanisms, beyond the ligand metal junction, to cover the ligand distortions, and the energetic and entropic effect on the thermo-structural behavior. We provide an unprecedented atomistic insight on the effect of adsorbates on the thermal expansion of MOFs as a basic tool toward controlling the thermal expansion.

  17. Metal-organic framework composites: from fundamentals to applications

    NASA Astrophysics Data System (ADS)

    Li, Shaozhou; Huo, Fengwei

    2015-04-01

    Metal-organic frameworks (MOFs) are a class of crystallized porous polymeric materials consisting of metal ions or clusters linked together by organic bridging ligands. Due to their permanent porosity, rich surface chemistry and tuneable pore sizes, MOFs have emerged as one type of important porous solid and have attracted intensive interests in catalysis, gas adsorption, separation and storage over the past two decades. When compared with pure MOFs, the combination of MOFs with functional species or matrix materials not only shows enhanced properties, but also broadens the applications of MOFs in new fields, such as bio-imaging, drug delivery and electrical catalysis, owing to the interactions of the functional species/matrix with the MOF structures. Although the synthesis, chemical modification and potential applications of MOFs have been reviewed previously, there is an increasing awareness on the synthesis and applications of their composites, which have rarely been reviewed. This review aims to fill this gap and discuss the fabrication, properties, and applications of MOF composites. The remaining challenges and future opportunities in this field, in terms of processing techniques, maximizing composite properties, and prospects for applications, have also been indicated.

  18. Biomimetic mineralization of metal-organic frameworks as protective coatings for biomacromolecules

    PubMed Central

    Liang, Kang; Ricco, Raffaele; Doherty, Cara M.; Styles, Mark J.; Bell, Stephen; Kirby, Nigel; Mudie, Stephen; Haylock, David; Hill, Anita J.; Doonan, Christian J.; Falcaro, Paolo

    2015-01-01

    Enhancing the robustness of functional biomacromolecules is a critical challenge in biotechnology, which if addressed would enhance their use in pharmaceuticals, chemical processing and biostorage. Here we report a novel method, inspired by natural biomineralization processes, which provides unprecedented protection of biomacromolecules by encapsulating them within a class of porous materials termed metal-organic frameworks. We show that proteins, enzymes and DNA rapidly induce the formation of protective metal-organic framework coatings under physiological conditions by concentrating the framework building blocks and facilitating crystallization around the biomacromolecules. The resulting biocomposite is stable under conditions that would normally decompose many biological macromolecules. For example, urease and horseradish peroxidase protected within a metal-organic framework shell are found to retain bioactivity after being treated at 80 °C and boiled in dimethylformamide (153 °C), respectively. This rapid, low-cost biomimetic mineralization process gives rise to new possibilities for the exploitation of biomacromolecules. PMID:26041070

  19. Metallacarboranes: Towards promising hydrogen storage metal organic framework

    NASA Astrophysics Data System (ADS)

    Singh, Abhishek; Sadrzadeh, Arta; Yakobson, Boris

    2011-03-01

    Using first principles calculations we show the high hydrogen storage capacity of metallacarboranes, where the transition metal (TM) atoms bind hydrogen via Kubas interaction. The average binding energy of ~ 0.3 eV/H favorably lies within the reversible adsorption range The Sc and Ti are found to be the optimum metal atoms maximizing the number of stored H2 molecules. Depending upon the structure, metallacarboranes can adsorb up to 8 wt% of hydrogen, which exceeds DOE goal for 2015. Being integral part of the cage, TMs do not suffer from the aggregation problem. Furthermore, the presence of carbon atom in the cages permits linking the metallacarboranes to form metal organic frameworks (MOF), thus able to adsorb hydrogen via Kubas interaction, in addition to van der Waals physisorption. A. K. Singh, A. Sadrzadeh, and B. I. Yakobson, Metallacarboranes: Toward Promising Hydrogen Storage Metal Organic Frameworks, JACS 132,14126 (2010).

  20. Surface interactions and quantum kinetic molecular sieving for H2 and D2 adsorption on a mixed metal-organic framework material.

    PubMed

    Chen, Banglin; Zhao, Xuebo; Putkham, Apipong; Hong, Kunlun; Lobkovsky, Emil B; Hurtado, Eric J; Fletcher, Ashleigh J; Thomas, K Mark

    2008-05-21

    A rational strategy has been used to immobilize open metal sites in ultramicroporosity for stronger binding of multiple H 2 molecules per unsaturated metal site for H 2 storage applications. The synthesis and structure of a mixed zinc/copper metal-organic framework material Zn 3(BDC) 3[Cu(Pyen)] .(DMF) 5(H 2O) 5 (H 2BDC = 1,4 benzenedicarboxylic acid and PyenH 2 = 5-methyl-4-oxo-1,4-dihydro-pyridine-3-carbaldehyde) is reported. Desolvation provides a bimodal porous structure Zn 3(BDC) 3[Cu(Pyen)] (M'MOF 1) with narrow porosity (<0.56 nm) and an array of pores in the bc crystallographic plane where the adsorbate-adsorbent interactions are maximized by both the presence of open copper centers and overlap of the potential energy fields from pore walls. The H 2 and D 2 adsorption isotherms for M'MOF 1 at 77.3 and 87.3 K were reversible with virtually no hysteresis. Methods for determination of the isosteric enthalpies of H 2 and D 2 adsorption were compared. A virial model gave the best agreement (average deviation <1 standard deviation) with the isotherm data. This was used in conjunction with the van't Hoff isochore giving isosteric enthalpies at zero surface coverage of 12.29 +/- 0.53 and 12.44 +/- 0.50 kJ mol (-1) for H 2 and D 2 adsorption, respectively. This is the highest value so far observed for hydrogen adsorption on a porous material. The enthalpy of adsorption, decreases with increasing amount adsorbed to 9.5 kJ mol (-1) at approximately 1.9 mmol g (-1) (2 H 2 or D 2 molecules per Cu corresponding to adsorption on both sides of planar Cu open centers) and is virtually unchanged in the range 1.9-3.6 mmol g (-1). Virial analysis of isotherms at 87.3 K is also consistent with two H 2 or D 2 molecules being bound to each open Cu center. The adsorption kinetics follow a double exponential model, corresponding to diffusion along two types of pores, a slow component with high activation energy (13.35 +/- 0.59 kJ mol (-1)) for the narrow pores and a faster

  1. Metal-Organic Frameworks for Thin-Layer Chromatographic Applications.

    PubMed

    Schenk, Claudia; Kutzscher, Christel; Drache, Franziska; Helten, Stella; Senkovska, Irena; Kaskel, Stefan

    2017-01-25

    Preparation of thin-layer chromatographic (TLC) plates based on metal-organic frameworks (MOFs) as porous stationary phases is described. DUT-67 (DUT = Dresden University of Technology), a zirconium based MOF, was used in combination with a fluorescent indicator as stationary phase for analyzing a small selection of a wide spectrum of relevant analytes. The successful separation of benzaldehyde from trans-cinnamaldehyde and 4-aminophenol from 2-aminotoluene is reported as a model system using optimized eluent mixtures containing acetic acid.

  2. Mechanochemical synthesis of an yttrium based metal-organic framework.

    PubMed

    Singh, Niraj K; Hardi, Meenakshi; Balema, Viktor P

    2013-02-01

    For the first time a metal hydride has been used for the preparation of a metal-organic framework. MIL-78 has been synthesized by the solid-state mechanochemical reaction between yttrium hydride and trimesic acid. The process does not involve solvents and does not generate liquid by-products, thus proving the viability of the solid-state approach to the synthesis of MOFs.

  3. Investigating the potential of metal-organic framework material as an adsorbent for matrix solid-phase dispersion extraction of pesticides during analysis of dehydrated Hyptis pectinata medicinal plant by GC/MS.

    PubMed

    Aquino, Adriano; Ferreira, Jordana Alves; Navickiene, Sandro; Wanderley, Kaline A; de Sá, Gilberto F; Júnior, Severino A

    2012-01-01

    Metal-organic frameworks aluminum terephthalate MIL-53 and Cu-benzene-1,3,5-tricarboxylate (BTC) were tested for extraction of pyrimethanil, ametryn, dichlofluanid, tetraconazole, flumetralin, kresoximmethyl, and tebuconazole from the medicinal plant Hyptis pectinata, with analysis using GC/MS in the selected ion monitoring mode. Experiments carried out at different fortification levels (0.1, 0.5, and 1.0 microg/g) resulted in recoveries in the range 61 to 107% with RSD values between 3 and 12% for the metal-organic framework materials. Detection and quantification limits ranged from 0.02 to 0.07 and 0.05 to 0.1 microg/g, respectively, for the different pesticides studied. The method developed was linear over the range tested (0.04-20.0 microg/g), with correlation coefficients ranging from 0.9987 to 0.9998. Comparison of MIL-53 and Cu-BTC with C18-bonded silica showed good performance of the MIL-53 metal-organic framework as a sorbent for the pesticides tested.

  4. Energy Storage during Compression of Metal-Organic Frameworks.

    PubMed

    Miao, Yu-Run; Su, Zhi; Suslick, Kenneth S

    2017-04-05

    Practical applications of metal-organic framework (MOF) materials require an in-depth understanding of their mechanical properties. We have investigated the mechanical properties and energy absorption behavior of single crystals of four isostructural UiO-type MOFs under uniaxial compression. In situ nanocompression experiments were used to measure the mechanical behavior of individual MOF nanocrystals under compression within a transmission electron microscope. The plasticity and endothermicity during deformation of MOFs shows a surprising potential for absorption and dissipation of mechanical shock. At compressive stress below 2 GPa, relatively small amounts of energy (<0.3 kJ/g) are absorbed by the compression of these MOFs. As the stress was increased, however, the energy absorption was significantly enhanced. Above 2 GPa, the energy absorption typically reaches 3-4 kJ/g; for comparison, the energy release in the explosion of TNT is ∼4 kJ/g. Gram for gram, MOFs can absorb as much energy as a high explosive can release.

  5. Multiphoton absorption in graphene and metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Weiqiang, Chen

    Materials possessing large multiphoton absorption are of direct relevance to both photonics applications and materials physics. In this dissertation, we present our investigations into two novel materials: namely, (1) graphene and (2) metal-organic frameworks (MOFs). The dissertation divides into two parts. The first part of the dissertation reports our systematical Z-scan measurements onto two-photon absorption (2PA) in graphene in the spectral range of 435-1100 nm with femtosecond laser pulses. We report that the measured 2PA coefficients of graphene in the near-infrared (NIR) range of 800-1100 nm can be explained by a theoretical model based on the optical transitions near the Dirac point (K point). We also determine the 2PA coefficients of graphene in the visible spectrum (435-700 nm) and observe an enhancement induced by the excitonic Fano resonance at the saddle point (M point). By applying the second-order, time-dependent perturbation theory on interband transitions among three states near the saddle point, we develop a semi-empirical model to take excitons in graphene into consideration. And the model is in agreement with the photon-energy dependence of the observed 2PA spectrum with a scaling factor of B = (1 5) x 102 cm/MW/eV5. Our results verify, for the first time, that the excitonic Fano resonance plays an important role for the 2PA of graphene in the visible spectrum. Besides, we also detail our measurements on the spectral dependence of one-photon absorption (1PA) saturation in graphene over the visible-NIR range. A quadratic photon energy dependence of the measured saturation intensity/fluence is observed over the investigated spectral range. The underlying photo-dynamics is discussed. In the second part of the dissertation, we investigate multiphoton excited photoluminescence (MEPL) from three solid-state crystals of metal-organic frameworks (MOFs): (1) [Zn2(trans,trans-4,4 stilbenedicarboxylic acid (SDC))2(trans, trans-9, 10-bis (4-pyridylethenyl

  6. Integration of metal-organic frameworks into an electrochemical dielectric thin film for electronic applications

    PubMed Central

    Li, Wei-Jin; Liu, Juan; Sun, Zhi-Hua; Liu, Tian-Fu; Lü, Jian; Gao, Shui-Ying; He, Chao; Cao, Rong; Luo, Jun-Hua

    2016-01-01

    The integration of porous metal-organic frameworks onto the surface of materials, for use as functional devices, is currently emerging as a promising approach for gas sensing and flexible displays. However, research focused on potential applications in electronic devices is in its infancy. Here we present a facile strategy by which interpenetrated, crystalline metal-organic framework films are deposited onto conductive metal-plate anodes via in situ temperature-controlled electrochemical assembly. The nanostructure of the surface as well as the thickness and uniformity of the film are well controlled. More importantly, the resulting films exhibit enhanced dielectric properties compared to traditional inorganic or organic gate dielectrics. This study demonstrates the successful implementation of the rational design of metal-organic framework thin films on conductive supports with high-performance dielectric properties. PMID:27282348

  7. Integration of metal-organic frameworks into an electrochemical dielectric thin film for electronic applications

    NASA Astrophysics Data System (ADS)

    Li, Wei-Jin; Liu, Juan; Sun, Zhi-Hua; Liu, Tian-Fu; Lü, Jian; Gao, Shui-Ying; He, Chao; Cao, Rong; Luo, Jun-Hua

    2016-06-01

    The integration of porous metal-organic frameworks onto the surface of materials, for use as functional devices, is currently emerging as a promising approach for gas sensing and flexible displays. However, research focused on potential applications in electronic devices is in its infancy. Here we present a facile strategy by which interpenetrated, crystalline metal-organic framework films are deposited onto conductive metal-plate anodes via in situ temperature-controlled electrochemical assembly. The nanostructure of the surface as well as the thickness and uniformity of the film are well controlled. More importantly, the resulting films exhibit enhanced dielectric properties compared to traditional inorganic or organic gate dielectrics. This study demonstrates the successful implementation of the rational design of metal-organic framework thin films on conductive supports with high-performance dielectric properties.

  8. Homochiral metal-organic framework used as a stationary phase for high-performance liquid chromatography.

    PubMed

    Kong, Jiao; Zhang, Mei; Duan, Ai-Hong; Zhang, Jun-Hui; Yang, Rui; Yuan, Li-Ming

    2015-02-01

    Metal-organic frameworks are promising porous materials. Chiral metal-organic frameworks have attracted considerable attention in controlling enantioselectivity. In this study, a homochiral metal-organic framework [Co(2) (D-cam)(2) (TMDPy)] (D-cam = D-camphorates, TMDPy = 4,4'-trimethylenedipyridine) with a non-interpenetrating primitive cubic net has been used as a chiral stationary phase in high-performance liquid chromatography. It has allowed the successful separation of six positional isomers and six chiral compounds. The good selectivity and baseline separation, or at least 60% valley separation, confirmed its excellent molecular recognition characteristics. The relative standard deviations for the retention time of run-to-run and column-to-column were less than 1.8 and 3.1%, respectively. These results demonstrate that [Co(2) (D-cam)(2) (TMDPy)] may represent a promising chiral stationary phase for use in high-performance liquid chromatography.

  9. Pore Space Partition in Metal-Organic Frameworks.

    PubMed

    Zhai, Quan-Guo; Bu, Xianhui; Zhao, Xiang; Li, Dong-Sheng; Feng, Pingyun

    2017-02-21

    Metal-organic framework (MOF) materials have emerged as one of the favorite crystalline porous materials (CPM) because of their compositional and geometric tunability and many possible applications. In efforts to develop better MOFs for gas storage and separation, a number of strategies including creation of open metal sites and implantation of Lewis base sites have been used to tune host-guest interactions. In addition to these chemical factors, the geometric features such as pore size and shape, surface area, and pore volume also play important roles in sorption energetics and uptake capacity. For efficient capture of small gas molecules such as carbon dioxide under ambient conditions, large surface area or high pore volume are often not needed. Instead, maximizing host-guest interactions or the density of binding sites by encaging gas molecules in snug pockets of pore space can be a fruitful approach. To put this concept into practice, the pore space partition (PSP) concept has been proposed and has achieved a great experimental success. In this account, we will highlight many efforts to implement PSP in MOFs and impact of PSP on gas uptake performance. In the synthetic design of PSP, it is helpful to distinguish between factors that contribute to the framework formation and factors that serve the purpose of PSP. Because of the need for complementary structural roles, the synthesis of MOFs with PSP often involves multicomponent systems including mixed ligands, mixed inorganic nodes, or both. It is possible to accomplish both framework formation and PSP with a single type of polyfunctional ligands that use some functional groups (called framework-forming group) for framework formation and the remaining functional groups (called pore-partition group) for PSP. Alternatively, framework formation and PSP can be shouldered by different chemical species. For example, in a mixed-ligand system, one ligand (called framework-forming agent) can play the role of the

  10. Transition metal complexes supported on metal-organic frameworks for heterogeneous catalysts

    DOEpatents

    Farha, Omar K.; Hupp, Joseph T.; Delferro, Massimiliano; Klet, Rachel C.

    2017-02-07

    A robust mesoporous metal-organic framework comprising a hafnium-based metal-organic framework and a single-site zirconium-benzyl species is provided. The hafnium, zirconium-benzyl metal-organic framework is useful as a catalyst for the polymerization of an alkene.

  11. Metal-organic framework derived ZnO/ZnFe2O4/C nanocages as stable cathode material for reversible lithium-oxygen batteries.

    PubMed

    Yin, Wei; Shen, Yue; Zou, Feng; Hu, Xianluo; Chi, Bo; Huang, Yunhui

    2015-03-04

    Tremendous efforts have been devoted to exploring various Li-O2 cathode catalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). However, most of the high-activity ORR/OER catalysts can also accelerate side-reactions, such as electrolyte degradation on cycling. To address this issue, we change our strategy from pursuing highly active catalysts to developing stable cathodes that are compatible with the electrolyte. In this work, hierarchical mesoporous ZnO/ZnFe2O4/C (ZZFC) nanocages are synthesized from the templates of metal-organic framework (MOF) nanocages. Such ZZFC nanocages have lower ORR/OER catalytic activity as compared with the widely used catalysts for fuel cells, but they do not catalyze the degradation of organic electrolyte during operation. Furthermore, the optimized porosity and conductivity can fit well the needs of the Li-O2 cathode. When employed in a Li-O2 battery, the ZZFC cathode delivers a primary discharge/charge capacity exceeding 11 000 mAh g(-1) at a current density of 300 mA g(-1) and an improved cyclability with capacity of 5000 mAh g(-1) for 15 cycles. The superior electrochemical performance is ascribed to the hierarchical porosity and little degradation of the organic electrolyte.

  12. Investigation of metal hydride nanoparticles templated in metal organic frameworks.

    SciTech Connect

    Jacobs, Benjamin W.; Herberg, Julie L.; Highley, Aaron M.; Grossman, Jeffrey; Wagner, Lucas; Bhakta, Raghu; Peaslee, D.; Allendorf, Mark D.; Liu, X.; Behrens, Richard, Jr.; Majzoub, Eric H.

    2010-11-01

    Hydrogen is proposed as an ideal carrier for storage, transport, and conversion of energy. However, its storage is a key problem in the development of hydrogen economy. Metal hydrides hold promise in effectively storing hydrogen. For this reason, metal hydrides have been the focus of intensive research. The chemical bonds in light metal hydrides are predominantly covalent, polar covalent or ionic. These bonds are often strong, resulting in high thermodynamic stability and low equilibrium hydrogen pressures. In addition, the directionality of the covalent/ionic bonds in these systems leads to large activation barriers for atomic motion, resulting in slow hydrogen sorption kinetics and limited reversibility. One method for enhancing reaction kinetics is to reduce the size of the metal hydrides to nano scale. This method exploits the short diffusion distances and constrained environment that exist in nanoscale hydride materials. In order to reduce the particle size of metal hydrides, mechanical ball milling is widely used. However, microscopic mechanisms responsible for the changes in kinetics resulting from ball milling are still being investigated. The objective of this work is to use metal organic frameworks (MOFs) as templates for the synthesis of nano-scale NaAlH4 particles, to measure the H2 desorption kinetics and thermodynamics, and to determine quantitative differences from corresponding bulk properties. Metal-organic frameworks (MOFs) offer an attractive alternative to traditional scaffolds because their ordered crystalline lattice provides a highly controlled and understandable environment. The present work demonstrates that MOFs are stable hosts for metal hydrides and their reactive precursors and that they can be used as templates to form metal hydride nanoclusters on the scale of their pores (1-2 nm). We find that using the MOF HKUST-1 as template, NaAlH4 nanoclusters as small as 8 formula units can be synthesized inside the pores. A detailed picture of

  13. Metal-organic frameworks as selectivity regulators for hydrogenation reactions

    NASA Astrophysics Data System (ADS)

    Zhao, Meiting; Yuan, Kuo; Wang, Yun; Li, Guodong; Guo, Jun; Gu, Lin; Hu, Wenping; Zhao, Huijun; Tang, Zhiyong

    2016-11-01

    Owing to the limited availability of natural sources, the widespread demand of the flavouring, perfume and pharmaceutical industries for unsaturated alcohols is met by producing them from α,β-unsaturated aldehydes, through the selective hydrogenation of the carbon-oxygen group (in preference to the carbon-carbon group). However, developing effective catalysts for this transformation is challenging, because hydrogenation of the carbon-carbon group is thermodynamically favoured. This difficulty is particularly relevant for one major category of heterogeneous catalyst: metal nanoparticles supported on metal oxides. These systems are generally incapable of significantly enhancing the selectivity towards thermodynamically unfavoured reactions, because only the edges of nanoparticles that are in direct contact with the metal-oxide support possess selective catalytic properties; most of the exposed nanoparticle surfaces do not. This has inspired the use of metal-organic frameworks (MOFs) to encapsulate metal nanoparticles within their layers or inside their channels, to influence the activity of the entire nanoparticle surface while maintaining efficient reactant and product transport owing to the porous nature of the material. Here we show that MOFs can also serve as effective selectivity regulators for the hydrogenation of α,β-unsaturated aldehydes. Sandwiching platinum nanoparticles between an inner core and an outer shell composed of an MOF with metal nodes of Fe3+, Cr3+ or both (known as MIL-101; refs 19, 20, 21) results in stable catalysts that convert a range of α,β-unsaturated aldehydes with high efficiency and with significantly enhanced selectivity towards unsaturated alcohols. Calculations reveal that preferential interaction of MOF metal sites with the carbon-oxygen rather than the carbon-carbon group renders hydrogenation of the former by the embedded platinum nanoparticles a thermodynamically favoured reaction. We anticipate that our basic design

  14. Metal-Organic Frameworks for Highly Selective Separations

    SciTech Connect

    Omar M. Yaghi

    2009-09-28

    This grant was focused on the study of metal-organic frameworks with these specific objectives. (1) To examine the use of MOFs with well-defined open metal sites for binding of gases and small organics. (2) To develop a strategy for producing MOFs that combine large pore size with high surface area for their use in gas adsorption and separation of polycyclic organic compounds. (3) To functionalize MOFs for the storage of inert gases such as methane. A brief outline of our progress towards these objectives is presented here as it forms part of the basis for the ideas to be developed under the present proposal.

  15. Surface functionalization of metal organic frameworks for mixed matrix membranes

    DOEpatents

    Albenze, Erik; Lartey, Michael; Li, Tao; Luebke, David R.; Nulwala, Hunaid B.; Rosi, Nathaniel L.; Venna, Surendar R.

    2017-03-21

    Mixed Matrix Membrane (MMM) are composite membranes for gas separation and comprising a quantity of inorganic filler particles, in particular metal organic framework (MOF), dispersed throughout a polymer matrix comprising one or more polymers. This disclosure is directed to MOF functionalized through addition of a pendant functional group to the MOF, in order to improve interaction with a surrounding polymer matrix in a MMM. The improved interaction aids in avoiding defects in the MMM due to incompatible interfaces between the polymer matrix and the MOF particle, in turn increasing the mechanical and gas separation properties of the MMM. The disclosure is also directed to a MMM incorporating the surface functionalized MOF.

  16. Carbon Dioxide Separation with Novel Microporous Metal Organic Frameworks

    SciTech Connect

    Richard Willis; Annabelle Benin; John Low; Ganesh Venimadhavan; Syed Faheem; David Lesch; Adam Matzger; Randy Snurr

    2008-02-04

    The goal of this program was to develop a low cost novel sorbent to remove carbon dioxide from flue gas and gasification streams in electric utilities. Porous materials named metal-organic frameworks (MOFs) were found to have good capacity and selectivity for the capture of carbon dioxide. Several materials from the initial set of reference MOFs showed extremely high CO{sub 2} adsorption capacities and very desirable linear isotherm shapes. Sample preparation occurred at a high level, with a new family of materials suitable for intellectual property protection prepared and characterized. Raman spectroscopy was shown to be useful for the facile characterization of MOF materials during adsorption and especially, desorption. Further, the development of a Raman spectroscopic-based method of determining binary adsorption isotherms was initiated. It was discovered that a stronger base functionality will need to be added to MOF linkers in order to enhance CO{sub 2} selectivity over other gases via a chemisorption mechanism. A concentrated effort was expended on being able to accurately predict CO{sub 2} selectivities and on the calculation of predicted MOF surface area values from first principles. A method of modeling hydrolysis on MOF materials that correlates with experimental data was developed and refined. Complimentary experimental data were recorded via utilization of a combinatorial chemistry heat treatment unit and high-throughput X-ray diffractometer. The three main Deliverables for the project, namely (a) a MOF for pre-combustion (e.g., IGCC) CO{sub 2} capture, (b) a MOF for post-combustion (flue gas) CO{sub 2} capture, and (c) an assessment of commercial potential for a MOF in the IGCC application, were completed. The key properties for MOFs to work in this application - high CO{sub 2} capacity, good adsorption/desorption rates, high adsorption selectivity for CO{sub 2} over other gases such as methane and nitrogen, high stability to contaminants, namely

  17. Porous molybdenum carbide nano-octahedrons synthesized via confined carburization in metal-organic frameworks for efficient hydrogen production

    PubMed Central

    Wu, Hao Bin; Xia, Bao Yu; Yu, Le; Yu, Xin-Yao; Lou, Xiong Wen (David)

    2015-01-01

    Electrochemical water splitting has been considered as a promising approach to produce clean and sustainable hydrogen fuel. However, the lack of high-performance and low-cost electrocatalysts for hydrogen evolution reaction hinders the large-scale application. As a new class of porous materials with tunable structure and composition, metal-organic frameworks have been considered as promising candidates to synthesize various functional materials. Here we demonstrate a metal-organic frameworks-assisted strategy for synthesizing nanostructured transition metal carbides based on the confined carburization in metal-organic frameworks matrix. Starting from a compound consisting of copper-based metal-organic frameworks host and molybdenum-based polyoxometalates guest, mesoporous molybdenum carbide nano-octahedrons composed of ultrafine nanocrystallites are successfully prepared as a proof of concept, which exhibit remarkable electrocatalytic performance for hydrogen production from both acidic and basic solutions. The present study provides some guidelines for the design and synthesis of nanostructured electrocatalysts. PMID:25758159

  18. Interplay between defects, disorder and flexibility in metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Bennett, Thomas D.; Cheetham, Anthony K.; Fuchs, Alain H.; Coudert, François-Xavier

    2017-01-01

    Metal-organic frameworks are a novel family of chemically diverse materials, which are of interest across engineering, physics, chemistry, biology and medicine-based disciplines. Since the development of the field in its current form more than two decades ago, priority has been placed on the synthesis of new structures. However, more recently, a clear trend has emerged in shifting the emphasis from material design to exploring the chemical and physical properties of structures already known. In particular, although such nanoporous materials were traditionally seen as rigid crystalline structures, there is growing evidence that large-scale flexibility, the presence of defects and long-range disorder are not the exception in metal-organic frameworks, but the rule. Here we offer some perspective into how these concepts are perhaps inescapably intertwined, highlight recent advances in our understanding and discuss how a consideration of the interfaces between them may lead to enhancements of the materials' functionalities.

  19. Microporous metal-organic frameworks for storage and separation of small hydrocarbons.

    PubMed

    He, Yabing; Zhou, Wei; Krishna, Rajamani; Chen, Banglin

    2012-12-18

    Hydrocarbons are very important energy resources and raw materials for some industrially important products and fine chemicals. There is a need for the discovery of better materials that offer enhanced capacities for safe storage of hydrocarbons. Furthermore, the development of improved separation technologies will lead to significant reduction in energy requirements and costs. In this feature article, we provide an overview of the current status of the emerging microporous metal-organic frameworks for the storage and separation of small hydrocarbons.

  20. Postsynthetic Tuning of Metal-Organic Frameworks for Targeted Applications.

    PubMed

    Islamoglu, Timur; Goswami, Subhadip; Li, Zhanyong; Howarth, Ashlee J; Farha, Omar K; Hupp, Joseph T

    2017-02-08

    Metal-organic frameworks (MOFs) are periodic, hybrid, atomically well-defined porous materials that typically form by self-assembly and consist of inorganic nodes (metal ions or clusters) and multitopic organic linkers. MOFs as a whole offer many intriguing properties, including ultrahigh porosity, tunable chemical functionality, and low density. These properties point to numerous potential applications, including gas storage, chemical separations, catalysis, light harvesting, and chemical sensing, to name a few. Reticular chemistry, or the linking of molecular building blocks into predetermined network structures, has been employed to synthesize thousands of MOFs. Given the vast library of candidate nodes and linkers, the number of potentially synthetically accessible MOFs is enormous. Nevertheless, a powerful complementary approach to obtain specific structures with desired chemical functionality is to modify known MOFs after synthesis. This approach is particularly useful when incorporation of particular chemical functionalities via direct synthesis is challenging or impossible. The challenges may stem from limited stability or solubility of precursors, unwanted secondary reactivity of precursors, or incompatibility of functional groups with the conditions needed for direct synthesis. MOFs can be postsynthetically modified by replacing the metal nodes and/or organic linkers or via functionalization of the metal nodes and/or organic linkers. Here we describe some of our efforts toward the development and application of postsynthetic strategies for imparting desired chemical functionalities in MOFs of known topology. The techniques include methods for functionalizing MOF nodes, i.e., solvent-assisted ligand incorporation (SALI) and atomic layer deposition in MOFs (AIM) as well as a method to replace structural linkers, termed solvent-assisted linker exchange (SALE), also known as postsynthethic exchange (PSE). For each functionalization strategy, we first describe

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

    PubMed

    Xiang, Shengchang; He, Yabing; Zhang, Zhangjing; Wu, Hui; Zhou, Wei; Krishna, Rajamani; Chen, Banglin

    2012-07-17

    Carbon dioxide capture and separation are important industrial processes that allow the use of carbon dioxide for the production of a range of chemical products and materials, and to minimize the effects of carbon dioxide emission. Porous metal-organic frameworks are promising materials to achieve such separations and to replace current technologies, which use aqueous solvents to chemically absorb carbon dioxide. Here we show that a metal-organic frameworks (UTSA-16) displays high uptake (160 cm(3) cm(-3)) of CO(2) at ambient conditions, making it a potentially useful adsorbent material for post-combustion carbon dioxide capture and biogas stream purification. This has been further confirmed by simulated breakthrough experiments. The high storage capacities and selectivities of UTSA-16 for carbon dioxide capture are attributed to the optimal pore cages and the strong binding sites to carbon dioxide, which have been demonstrated by neutron diffraction studies.

  2. Metal-Organic Frameworks as Catalysts for Oxidation Reactions.

    PubMed

    Dhakshinamoorthy, Amarajothi; Asiri, Abdullah M; Garcia, Hermenegildo

    2016-06-06

    This Concept is aimed at describing the current state of the art in metal-organic frameworks (MOFs) as heterogeneous catalysts for liquid-phase oxidations, focusing on three important substrates, namely, alkenes, alkanes and alcohols. Emphases are on the nature of active sites that have been incorporated within MOFs and on future targets to be set in this area. Thus, selective alkene epoxidation with peroxides or oxygen catalyzed by constitutional metal nodes of MOFs as active sites are still to be developed. Moreover, no noble metal-free MOF has been reported to date that can act as a general catalyst for the aerobic oxidation of primary and secondary aliphatic alcohols. In contrast, in the case of alkanes, a target should be to tune the polarity of MOF internal pores to control the outcome of the autooxidation process, resulting in the selective formation of alcohol/ketone mixtures at high conversion.

  3. Transformation of metal-organic frameworks for molecular sieving membranes

    NASA Astrophysics Data System (ADS)

    Li, Wanbin; Zhang, Yufan; Zhang, Congyang; Meng, Qin; Xu, Zehai; Su, Pengcheng; Li, Qingbiao; Shen, Chong; Fan, Zheng; Qin, Lei; Zhang, Guoliang

    2016-04-01

    The development of simple, versatile strategies for the synthesis of metal-organic framework (MOF)-derived membranes are of increasing scientific interest, but challenges exist in understanding suitable fabrication mechanisms. Here we report a route for the complete transformation of a series of MOF membranes and particles, based on multivalent cation substitution. Through our approach, the effective pore size can be reduced through the immobilization of metal salt residues in the cavities, and appropriate MOF crystal facets can be exposed, to achieve competitive molecular sieving capabilities. The method can also be used more generally for the synthesis of a variety of MOF membranes and particles. Importantly, we design and synthesize promising MOF membranes candidates that are hard to achieve through conventional methods. For example, our CuBTC/MIL-100 membrane exhibits 89, 171, 241 and 336 times higher H2 permeance than that of CO2, O2, N2 and CH4, respectively.

  4. Transformation of metal-organic frameworks for molecular sieving membranes

    PubMed Central

    Li, Wanbin; Zhang, Yufan; Zhang, Congyang; Meng, Qin; Xu, Zehai; Su, Pengcheng; Li, Qingbiao; Shen, Chong; Fan, Zheng; Qin, Lei; Zhang, Guoliang

    2016-01-01

    The development of simple, versatile strategies for the synthesis of metal-organic framework (MOF)-derived membranes are of increasing scientific interest, but challenges exist in understanding suitable fabrication mechanisms. Here we report a route for the complete transformation of a series of MOF membranes and particles, based on multivalent cation substitution. Through our approach, the effective pore size can be reduced through the immobilization of metal salt residues in the cavities, and appropriate MOF crystal facets can be exposed, to achieve competitive molecular sieving capabilities. The method can also be used more generally for the synthesis of a variety of MOF membranes and particles. Importantly, we design and synthesize promising MOF membranes candidates that are hard to achieve through conventional methods. For example, our CuBTC/MIL-100 membrane exhibits 89, 171, 241 and 336 times higher H2 permeance than that of CO2, O2, N2 and CH4, respectively. PMID:27090597

  5. Recent progress in the synthesis of metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Sun, Yujia; Zhou, Hong-Cai

    2015-10-01

    Metal-organic frameworks (MOFs) have attracted considerable attention for various applications due to their tunable structure, porosity and functionality. In general, MOFs have been synthesized from isolated metal ions and organic linkers under hydrothermal or solvothermal conditions via one-spot reactions. The emerging precursor approach and kinetically tuned dimensional augmentation strategy add more diversity to this field. In addition, to speed up the crystallization process and create uniform crystals with reduced size, many alternative synthesis routes have been explored. Recent advances in microwave-assisted synthesis and electrochemical synthesis are presented in this review. In recent years, post-synthetic approaches have been shown to be powerful tools to synthesize MOFs with modified functionality, which cannot be attained via de novo synthesis. In this review, some current accomplishments of post-synthetic modification (PSM) based on covalent transformations and coordinative interactions as well as post-synthetic exchange (PSE) in robust MOFs are provided.

  6. Coordinative alignment of molecules in chiral metal-organic frameworks.

    PubMed

    Lee, Seungkyu; Kapustin, Eugene A; Yaghi, Omar M

    2016-08-19

    A chiral metal-organic framework, MOF-520, was used to coordinatively bind and align molecules of varying size, complexity, and functionality. The reduced motional degrees of freedom obtained with this coordinative alignment method allowed the structures of molecules to be determined by single-crystal x-ray diffraction techniques. The chirality of the MOF backbone also served as a reference in the structure solution for an unambiguous assignment of the absolute configuration of bound molecules. Sixteen molecules representing four common functional groups (primary alcohol, phenol, vicinal diol, and carboxylic acid), ranging in complexity from methanol to plant hormones (gibberellins, containing eight stereocenters), were crystallized and had their precise structure determined. We distinguished single and double bonds in gibberellins, and we enantioselectively crystallized racemic jasmonic acid, whose absolute configuration had only been inferred from derivatives.

  7. Superexchange Charge Transport in Loaded Metal Organic Frameworks.

    PubMed

    Neumann, Tobias; Liu, Jianxi; Wächter, Tobias; Friederich, Pascal; Symalla, Franz; Welle, Alexander; Mugnaini, Veronica; Meded, Velimir; Zharnikov, Michael; Wöll, Christof; Wenzel, Wolfgang

    2016-07-26

    In the past, nanoporous metal-organic frameworks (MOFs) have been mostly studied for their huge potential with regard to gas storage and separation. More recently, the discovery that the electrical conductivity of a widely studied, highly insulating MOF, HKUST-1, improves dramatically when loaded with guest molecules has triggered a huge interest in the charge carrier transport properties of MOFs. The observed high conductivity, however, is difficult to reconcile with conventional transport mechanisms: neither simple hopping nor band transport models are consistent with the available experimental data. Here, we combine theoretical results and new experimental data to demonstrate that the observed conductivity can be explained by an extended hopping transport model including virtual hops through localized MOF states or molecular superexchange. Predictions of this model agree well with precise conductivity measurements, where experimental artifacts and the influence of defects are largely avoided by using well-defined samples and the Hg-drop junction approach.

  8. Recent progress in the synthesis of metal-organic frameworks.

    PubMed

    Sun, Yujia; Zhou, Hong-Cai

    2015-10-01

    Metal-organic frameworks (MOFs) have attracted considerable attention for various applications due to their tunable structure, porosity and functionality. In general, MOFs have been synthesized from isolated metal ions and organic linkers under hydrothermal or solvothermal conditions via one-spot reactions. The emerging precursor approach and kinetically tuned dimensional augmentation strategy add more diversity to this field. In addition, to speed up the crystallization process and create uniform crystals with reduced size, many alternative synthesis routes have been explored. Recent advances in microwave-assisted synthesis and electrochemical synthesis are presented in this review. In recent years, post-synthetic approaches have been shown to be powerful tools to synthesize MOFs with modified functionality, which cannot be attained via de novo synthesis. In this review, some current accomplishments of post-synthetic modification (PSM) based on covalent transformations and coordinative interactions as well as post-synthetic exchange (PSE) in robust MOFs are provided.

  9. Metal-Organic Frameworks for CO2 Chemical Transformations.

    PubMed

    He, Hongming; Perman, Jason A; Zhu, Guangshan; Ma, Shengqian

    2016-12-01

    Carbon dioxide (CO2 ), as the primary greenhouse gas in the atmosphere, triggers a series of environmental and energy related problems in the world. Therefore, there is an urgent need to develop multiple methods to capture and convert CO2 into useful chemical products, which can significantly improve the environment and promote sustainable development. Over the past several decades, metal-organic frameworks (MOFs) have shown outstanding heterogeneous catalytic activity due in part to their high internal surface area and chemical functionalities. These properties and the ability to synthesize MOF platforms allow experiments to test structure-function relationships for transforming CO2 into useful chemicals. Herein, recent developments are highlighted for MOFs participating as catalysts for the chemical fixation and photochemical reduction of CO2 . Finally, opportunities and challenges facing MOF catalysts are discussed in this ongoing research area.

  10. Selective sulfur dioxide adsorption on crystal defect sites on an isoreticular metal organic framework series.

    PubMed

    Rodríguez-Albelo, L Marleny; López-Maya, Elena; Hamad, Said; Ruiz-Salvador, A Rabdel; Calero, Sofia; Navarro, Jorge A R

    2017-02-15

    The widespread emissions of toxic gases from fossil fuel combustion represent major welfare risks. Here we report the improvement of the selective sulfur dioxide capture from flue gas emissions of isoreticular nickel pyrazolate metal organic frameworks through the sequential introduction of missing-linker defects and extra-framework barium cations. The results and feasibility of the defect pore engineering carried out are quantified through a combination of dynamic adsorption experiments, X-ray diffraction, electron microscopy and density functional theory calculations. The increased sulfur dioxide adsorption capacities and energies as well as the sulfur dioxide/carbon dioxide partition coefficients values of defective materials compared to original non-defective ones are related to the missing linkers enhanced pore accessibility and to the specificity of sulfur dioxide interactions with crystal defect sites. The selective sulfur dioxide adsorption on defects indicates the potential of fine-tuning the functional properties of metal organic frameworks through the deliberate creation of defects.

  11. Selective sulfur dioxide adsorption on crystal defect sites on an isoreticular metal organic framework series

    NASA Astrophysics Data System (ADS)

    Rodríguez-Albelo, L. Marleny; López-Maya, Elena; Hamad, Said; Ruiz-Salvador, A. Rabdel; Calero, Sofia; Navarro, Jorge A. R.

    2017-02-01

    The widespread emissions of toxic gases from fossil fuel combustion represent major welfare risks. Here we report the improvement of the selective sulfur dioxide capture from flue gas emissions of isoreticular nickel pyrazolate metal organic frameworks through the sequential introduction of missing-linker defects and extra-framework barium cations. The results and feasibility of the defect pore engineering carried out are quantified through a combination of dynamic adsorption experiments, X-ray diffraction, electron microscopy and density functional theory calculations. The increased sulfur dioxide adsorption capacities and energies as well as the sulfur dioxide/carbon dioxide partition coefficients values of defective materials compared to original non-defective ones are related to the missing linkers enhanced pore accessibility and to the specificity of sulfur dioxide interactions with crystal defect sites. The selective sulfur dioxide adsorption on defects indicates the potential of fine-tuning the functional properties of metal organic frameworks through the deliberate creation of defects.

  12. Selective sulfur dioxide adsorption on crystal defect sites on an isoreticular metal organic framework series

    PubMed Central

    Rodríguez-Albelo, L. Marleny; López-Maya, Elena; Hamad, Said; Ruiz-Salvador, A. Rabdel; Calero, Sofia; Navarro, Jorge A.R.

    2017-01-01

    The widespread emissions of toxic gases from fossil fuel combustion represent major welfare risks. Here we report the improvement of the selective sulfur dioxide capture from flue gas emissions of isoreticular nickel pyrazolate metal organic frameworks through the sequential introduction of missing-linker defects and extra-framework barium cations. The results and feasibility of the defect pore engineering carried out are quantified through a combination of dynamic adsorption experiments, X-ray diffraction, electron microscopy and density functional theory calculations. The increased sulfur dioxide adsorption capacities and energies as well as the sulfur dioxide/carbon dioxide partition coefficients values of defective materials compared to original non-defective ones are related to the missing linkers enhanced pore accessibility and to the specificity of sulfur dioxide interactions with crystal defect sites. The selective sulfur dioxide adsorption on defects indicates the potential of fine-tuning the functional properties of metal organic frameworks through the deliberate creation of defects. PMID:28198376

  13. Metal-Organic Framework-Based Nanomedicine Platforms for Drug Delivery and Molecular Imaging.

    PubMed

    Cai, Wen; Chu, Cheng-Chao; Liu, Gang; Wáng, Yì-Xiáng J

    2015-10-07

    Metal-organic frameworks (MOFs), which are a unique class of hybrid porous materials built from metal ions and organic linkers, have attracted significant research interest in recent years. Compared with conventional porous materials, MOFs exhibit a variety of advantages, including a large surface area, a tunable pore size and shape, an adjustable composition and structure, biodegradability, and versatile functionalities, which enable MOFs to perform as promising platforms for drug delivery, molecular imaging, and theranostic applications. In this article, the recent research progress related to nanoscale metal-organic frameworks (NMOFs) is summarized with a focus on synthesis strategies and drug delivery, molecular imaging, and theranostic applications. The future challenges and opportunities of NMOFs are also discussed in the context of translational medical research. More effort is warranted to develop clinically translatable NMOFs for various applications in nanomedicine.

  14. Metal-organic framework templated inorganic sorbents for rapid and efficient extraction of heavy metals.

    PubMed

    Abney, C W; Gilhula, J C; Lu, K; Lin, W

    2014-12-17

    An innovative wet-treatment with Na2 S transforms two indium metal-organic frameworks (MOFs) into a series of porous inorganic sorbents. These MOF-templated materials display remarkable affinity for heavy metals with saturation occurring in less than 1 h. The saturation capacity for Hg(II) exceeds 2 g g(-1) , more than doubling the best thiol-functionalized sorbents in the literature.

  15. One-pot synthesis of protein-embedded metal-organic frameworks with enhanced biological activities.

    PubMed

    Lyu, Fengjiao; Zhang, Yifei; Zare, Richard N; Ge, Jun; Liu, Zheng

    2014-10-08

    Protein molecules were directly embedded in metal-organic frameworks (MOFs) by a coprecipitation method. The protein molecules majorly embedded on the surface region of MOFs display high biological activities. As a demonstration of the power of such materials, the resulting Cyt c embedded in ZIF-8 showed a 10-fold increase in peroxidase activity compared to free Cyt c in solution and thus gave convenient, fast, and highly sensitive detection of trace amounts of explosive organic peroxides in solution.

  16. Application of metal-organic frameworks for purification of vegetable oils.

    PubMed

    Vlasova, E A; Yakimov, S A; Naidenko, E V; Kudrik, E V; Makarov, S V

    2016-01-01

    Reported here is the synthesis of aluminum-, zinc- and titanium-containing metal-organic frameworks based on terephthalic acid and an investigation on the possibility of using these compounds as adsorbents for the purification of unrefined vegetable oils. It is found that aluminum-, zinc- and titanium-containing metal-organic frameworks improve the physicochemical properties of unrefined vegetable oils (more pleasant taste and odor) due to the binding of free fatty acids and peroxide compounds. It is established that the synthesized materials are more effective in these respects as compared with traditional adsorbents. An adsorption mechanism of free fatty acids and peroxides is proposed. Last but not least, the used MOF can be easily recycled at least five times, via solvent washing.

  17. Metal-organic frameworks: structure, properties, methods of synthesis and characterization

    NASA Astrophysics Data System (ADS)

    Butova, V. V.; Soldatov, M. A.; Guda, A. A.; Lomachenko, K. A.; Lamberti, C.

    2016-03-01

    This review deals with key methods of synthesis and characterization of metal-organic frameworks (MOFs). The modular structure affords a wide variety of MOFs with different active metal sites and organic linkers. These compounds represent a new stage of development of porous materials in which the pore size and the active site structure can be modified within wide limits. The set of experimental methods considered in this review is sufficient for studying the short-range and long-range order of the MOF crystal structure, determining the morphology of samples and elucidating the processes that occur at the active metal site in the course of chemical reactions. The interest in metal-organic frameworks results, first of all, from their numerous possible applications, ranging from gas separation and storage to chemical reactions within the pores. The bibliography includes 362 references.

  18. Evaluation of Metal-Organic Frameworks and Porous Polymer Networks for CO2 -Capture Applications.

    PubMed

    Verdegaal, Wolfgang M; Wang, Kecheng; Sculley, Julian P; Wriedt, Mario; Zhou, Hong-Cai

    2016-03-21

    This manuscript presents experimental data for 20 adsorption materials (metal-organic frameworks, porous polymer networks, and Zeolite-5A), including CO2 and N2 isotherms and heat capacities. With input from only experimental data, working capacities per energy for each material were calculated. Furthermore, by running seven different carbon-capture scenarios in which the initial flue-gas composition and process temperature was systematically changed, we present a range of performances for each material and quantify how sensitive each is to these varying parameters. The presented calculations provide researchers with a tool to investigate promising carbon-capture materials more easily and completely.

  19. Anisotropic thermal expansion in a metal-organic framework.

    PubMed

    Madsen, Solveig Røgild; Lock, Nina; Overgaard, Jacob; Iversen, Bo Brummerstedt

    2014-06-01

    Ionothermal reaction between Mn(II)(acetate)2·4H2O and 1,3,5-benzenetricarboxylic acid (H3BTC) in either of the two ionic liquids 1-ethyl-3-methylimidazolium bromide (EMIMBr) and 1-ethyl-3-methylimidazolium tosylate (EMIMOTs) resulted in the formation of the new metal-organic framework (MOF) EMIM[Mn(II)BTC] (BTC = 1,3,5-benzenetricarboxylate). The compound crystallizes in the orthorhombic space group Pbca with unit-cell parameters of a = 14.66658 (12), b = 12.39497 (9), c = 16.63509 (14) Å at 100 K. Multi-temperature single-crystal (15-340 K) and powder X-ray diffraction studies (100-400 K) reveal strongly anisotropic thermal expansion properties. The linear thermal expansion coefficients, αL(l), attain maximum values at 400 K along the a- and b-axis, with αL(a) = 115 × 10(-6) K(-1) and αL(b) = 75 × 10(-6) K(-1). At 400 K a negative thermal expansion coefficient of -40 × 10(-6) K(-1) is observed along the c-axis. The thermal expansion is coupled to a continuous deformation of the framework, which causes the structure to expand in two directions. Due to the rigidity of the linker, the expansion in the ab plane causes the network to contract along the c-axis. Hirshfeld surface analysis has been used to describe the interaction between the framework structure and the EMIM cation that resides within the channel. This reveals a number of rather weak interactions and one governing hydrogen-bonding interactions.

  20. Nanosizing a Metal-Organic Framework Enzyme Carrier for Accelerating Nerve Agent Hydrolysis

    DTIC Science & Technology

    2016-10-05

    Chem. Soc. 2016, 138 (26), 8052− 8055. (12) Furukawa, H.; Cordova, K. E.; O’Keeffe, M.; Yaghi, O. M. The Chemistry and Applications of Metal- Organic ...Y.; Xie, L.-H.; Rutledge, W.; Li, J.-R.; Zhou, H.-C. Zr-Based Metal- Organic Frameworks: Design, Synthesis, Structure, and Applications . Chem. Soc... Application of Consistency Criteria to Calculate Bet Areas of Micro- and Mesoporous Metal- Organic Frameworks. J. Am. Chem. Soc. 2016, 138 (1), 215−224. (64

  1. Spectroscopic Evidence for Room Temperature Interaction of Molecular Oxygen with Cobalt Porphyrin Linker Sites within a Metal-Organic Framework.

    PubMed

    Lahanas, Nicole; Kucheryavy, Pavel; Lockard, Jenny V

    2016-10-17

    Metalloporphyrin-based metal-organic frameworks offer a promising platform for developing solid-state porous materials with accessible, coordinatively unsaturated metal sites. Probing small-molecule interactions at the metalloporphyrin sites within these materials on a molecular level under ambient conditions is crucial for both understanding and ultimately harnessing this functionality for potential catalytic purposes. Co-PCN-222, a metal-organic framework based on cobalt(II) porphyrin linkers. is investigated using in situ UV-vis diffuse-reflectance and X-ray absorption spectroscopy. Spectroscopic evidence for the axial interaction of diatomic oxygen with the framework's open metalloporphyrin sites at room temperature is presented and discussed.

  2. Recent Advances in Carbon Capture with Metal-Organic Frameworks.

    PubMed

    Stylianou, Kyriakos C; Queen, Wendy L

    2015-01-01

    The escalating level of CO(2) in the atmosphere is one of the most critical environmental issues of our age. The carbon capture and storage from pilot test plants represents an option for reducing CO(2) emissions, however, the energy cost associated with post-combustion carbon capture process alone is ∼30% of the total energy generated by the power plant. Thus, the generation of carbon capture adsorbents with high uptake capacities, great separation performance and low cost is of paramount importance. Metal-organic frameworks are infinite networks of metal-containing nodes bridged by organic ligands through coordination bonds into porous extended structures and several reports have revealed that they are ideal candidates for the selective capture of CO(2). In this review we summarize recent advances related to the synthesis of porous MOFs and the latest strategies to enhance the CO(2) adsorption enthalpies and capacities at low-pressures, increase hydrolytic and mechanical stabilities, and improve the ease of regeneration. Although they show great promise for post-combustion carbon capture, there are still major challenges that must be overcome before they can be used for such a large-scale application.

  3. CO2-Selective Nanoporous Metal-Organic Framework Microcantilevers

    PubMed Central

    Yim, Changyong; Lee, Moonchan; Yun, Minhyuk; Kim, Gook-Hee; Kim, Kyong Tae; Jeon, Sangmin

    2015-01-01

    Nanoporous anodic aluminum oxide (AAO) microcantilevers are fabricated and MIL-53 (Al) metal-organic framework (MOF) layers are directly synthesized on each cantilever surface by using the aluminum oxide as the metal ion source. Exposure of the MIL53-AAO cantilevers to various concentrations of CO2, N2, CO, and Ar induces changes in their deflections and resonance frequencies. The results of the resonance frequency measurements for the different adsorbed gas molecules are almost identical when the frequency changes are normalized by the molecular weights of the gases. In contrast, the deflection measurements show that only CO2 adsorption induces substantial bending of the MIL53-AAO cantilevers. This selective deflection of the cantilevers is attributed to the strong interactions between CO2 and the hydroxyl groups in MIL-53, which induce structural changes in the MIL-53 layers. Simultaneous measurements of the resonance frequency and the deflection are performed to show that the diffusion of CO2 into the nanoporous MIL-53 layers occurs very rapidly, whereas the binding of CO2 to hydroxyl groups occurs relatively slowly, which indicates that the adsorption of CO2 onto the MIL-53 layers and the desorption of CO2 from the MIL-53 layers are reaction limited. PMID:26035805

  4. Doping of Metal-Organic Frameworks with Functional Guest Molecules and Nanoparticles

    NASA Astrophysics Data System (ADS)

    Schröder, Felicitas; Fischer, Roland A.

    Nanoparticle synthesis within metal-organic frameworks (MOFs) is performed by the adsorption of suitable precursor molecules for the metal component and subsequent decomposition to the composite materials nanoparticles@MOF. This chapter will review different approaches of loading MOFs with more complex organic molecules and metal-organic precursor molecules. The related reactions inside MOFs are discussed with a focus on stabilizing reactive intermediates in the corresponding cavities. The syntheses of metal and metal oxide nanoparticles inside MOFs are reviewed, and different synthetic routes compared. Emphasis is placed on the micro structural characterization of the materials nanoparticles@MOF with a particular focus on the location of embedded nanoparticles using TEM methods. Some first examples of applications of the doped MOFs in heterogeneous catalysis and hydrogen storage are described.

  5. Metal-organic organopolymeric hybrid framework by reversible [2+2] cycloaddition reaction.

    PubMed

    Park, In-Hyeok; Chanthapally, Anjana; Zhang, Zhenjie; Lee, Shim Sung; Zaworotko, Michael J; Vittal, Jagadese J

    2014-01-07

    Organic polymers are usually amorphous or possess very low crystallinity. The metal complexes of organic polymeric ligands are also difficult to crystallize by traditional methods because of their poor solubilities and their 3D structures can not be determined by single-crystal X-ray crystallography owing to a lack of single crystals. Herein, we report the crystal structure of a 1D Zn(II) coordination polymer fused with an organic polymer ligand made in situ by a [2+2] cycloaddition reaction of a six-fold interpenetrated metal-organic framework. It is also shown that this organic polymer ligand can be depolymerized in a single-crystal-to-single-crystal (SCSC) fashion by heating. This strategy could potentially be extended to make a range of monocrystalline metal organopolymeric complexes and metal-organic organopolymeric hybrid materials. Such monocrystalline metal complexes of organic polymers have hitherto been inaccessible for materials researchers.

  6. An ordered bcc CuPd nanoalloy synthesised via the thermal decomposition of Pd nanoparticles covered with a metal-organic framework under hydrogen gas.

    PubMed

    Li, Guangqin; Kobayashi, Hirokazu; Kusada, Kohei; Taylor, Jared M; Kubota, Yoshiki; Kato, Kenichi; Takata, Masaki; Yamamoto, Tomokazu; Matsumura, Syo; Kitagawa, Hiroshi

    2014-11-18

    Presented here is the synthesis of an ordered bcc copper-palladium nanoalloy, via the decomposition of a Pd nanoparticle@metal-organic framework composite material. In situ XRD measurements were performed in order to understand the mechanism of the decomposition process. This result gives a further perspective into the synthesis of new nanomaterials via metal-organic framework decomposition.

  7. Computational studies of adsorption in metal organic frameworks and interaction of nanoparticles in condensed phases

    SciTech Connect

    Annapureddy, Harsha V.; Motkuri, Radha K.; Nguyen, Phuong T.; Truong, T. B.; Thallapally, Praveen K.; McGrail, B. Peter; Dang, Liem X.

    2014-01-08

    In this review, we describe recent efforts in which computer simulations were used to systematically study nano-structured metal organic frameworks, with particular emphasis on their application in heating and cooling processes. These materials also are known as metal organic heat carriers. We used both molecular dynamics and Grand Canonical Monte Carlo simulation techniques to gain a molecular-level understanding of the adsorption mechanism of gases in these porous materials. We investigated the uptake of various gases such as refrigerants R12 and R143a and also the elemental gases Xe and Rn by the metal organic framework (i.e., Ni2(dhtp)). We also evaluated the effects of temperature and pressure on the uptake mechanism. Our computed results compared reasonably well with available experimental measurements, thus validating our potential models and approaches. In addition, we also investigated the structural, diffusive, and adsorption properties of different hydrocarbons in Ni2(dhtp). To elucidate the mechanism of nanoparticle dispersion in condensed phases, we also studied the interactions among nanoparticles in various liquids, such as n-hexane, water and methanol. This work was performed at Pacific Northwest National Laboratory (PNNL) and was supported by the Division of Chemical Sciences, Geosciences and Biosciences, Office of Basic Energy Sciences, U.S. Department of Energy (DOE). PNNL is operated by Battelle for the DOE. The authors also gratefully acknowledge support received from the National Energy Technology Laboratory of DOE's Office of Fossil Energy.

  8. The Importance of Polymorphism in Metal-Organic Framework Studies.

    PubMed

    Aulakh, Darpandeep; Varghese, Juby R; Wriedt, Mario

    2015-09-08

    Polymorphic phase transitions remain frequently undetected in routine metal-organic framework (MOF) studies; however, their discovery is of major importance in interpreting structure-property relationships. We herein report a reversible enantiotropic single-crystal to single-crystal polymorphic phase transition of a new microporous MOF [Eu(BDC)(NO3)(DMF)2]n (H2BDC = 1,4-benzenedicarboxylic acid; DMF = dimethylformamide). While modification 1LT at 170 K crystallizes in the monoclinic space group P21/c with unit cell dimensions of a = 17.673(2) Å, b = 20.023(2) Å, c = 10.555(9) Å, β = 90.129(4)°, modification 1HT at 290 K crystallizes in higher symmetry space group C2/c with unit cell dimensions of a = 17.200(7) Å, b = 10.737(4) Å, c = 10.684(4) Å, β = 90.136(2)°. This temperature-induced phase transition is accompanied by a small change in the solvent-accessible voids from 46.8 in 1LT to 49.8% in 1HT, which triggers a significant change in the adsorption properties as compared to a reported isostructural compound. Detailed investigations on the phase transition were studied with variable-temperature single-crystal X-ray diffraction (SCXRD), powder X-ray diffraction, and differential scanning calorimetry measurements. The herein-presented investigations emphasize the importance of polymorphic phase transitions in routine MOF studies originating from low-temperature SCXRD data and high-temperature physical property characterizations in avoiding the use of a wrong structure in interpreting structure-property relationships.

  9. Template-Directed Approach Towards the Realization of Ordered Heterogeneity in Bimetallic Metal-Organic Frameworks.

    PubMed

    Kim, Daeok; Coskun, Ali

    2017-03-29

    Controlling the arrangement of different metal ions to achieve ordered heterogeneity in metal-organic frameworks (MOFs) has been a great challenge. Herein, we introduce a template-directed approach, in which a 1D metal-organic polymer incorporating well-defined binding pockets for the secondary metal ions used as a structural template and starting material for the preparation of well-ordered bimetallic MOF-74s under heterogeneous-phase hydrothermal reaction conditions in the presence of secondary metal ions such as Ni(2+) and Mg(2+) in 3 h. The resulting bimetallic MOF-74s were found to possess a nearly 1:1 metal ratio regardless of their initial stoichiometry in the reaction mixture, thus demonstrating the possibility of controlling the arrangement of metal ions within the secondary building blocks in MOFs to tune their intrinsic properties such as gas affinity.

  10. Computational studies of adsorption in metal organic frameworks and interaction of nanoparticles in condensed phases

    SciTech Connect

    Annapureddy, HVR; Motkuri, RK; Nguyen, PTM; Truong, TB; Thallapally, PK; McGrail, BP; Dang, LX

    2014-02-05

    In this review, we describe recent efforts to systematically study nano-structured metal organic frameworks (MOFs), also known as metal organic heat carriers, with particular emphasis on their application in heating and cooling processes. We used both molecular dynamics and grand canonical Monte Carlo simulation techniques to gain a molecular-level understanding of the adsorption mechanism of gases in these porous materials. We investigated the uptake of various gases such as refrigerants R12 and R143a. We also evaluated the effects of temperature and pressure on the uptake mechanism. Our computed results compared reasonably well with available measurements from experiments, thus validating our potential models and approaches. In addition, we investigated the structural, diffusive and adsorption properties of different hydrocarbons in Ni-2(dhtp). Finally, to elucidate the mechanism of nanoparticle dispersion in condensed phases, we studied the interactions among nanoparticles in various liquids, such as n-hexane, water and methanol.

  11. High-internal-phase emulsions stabilized by metal-organic frameworks and derivation of ultralight metal-organic aerogels

    PubMed Central

    Zhang, Bingxing; Zhang, Jianling; Liu, Chengcheng; Peng, Li; Sang, Xinxin; Han, Buxing; Ma, Xue; Luo, Tian; Tan, Xiuniang; Yang, Guanying

    2016-01-01

    To design high-internal-phase emulsion (HIPE) systems is of great interest from the viewpoints of both fundamental researches and practical applications. Here we demonstrate for the first time the utilization of metal-organic framework (MOF) for HIPE formation. By stirring the mixture of water, oil and MOF at room temperature, the HIPE stabilized by the assembly of MOF nanocrystals at oil-water interface could be formed. The MOF-stabilized HIPE provides a novel route to produce highly porous metal-organic aerogel (MOA) monolith. After removing the liquids from the MOF-stabilized HIPE, the ultralight MOA with density as low as 0.01 g·cm−3 was obtained. The HIPE approach for MOA formation has unique advantages and is versatile in producing different kinds of ultralight MOAs with tunable porosities and structures. PMID:26892258

  12. Electrodeposition of WO3 nanoparticles into surface mounted metal-organic framework HKUST-1 thin films.

    PubMed

    Yoo, Hyeonseok; Welle, Alexander; Guo, Wei; Choi, Jinsub; Redel, Engelbert

    2017-03-17

    We describe a novel procedure to fabricate WO3@surface-mounted metal-organic framework (SURMOF) hybrid materials by electrodeposition of WO3 nanoparticles into HKUST-1, also termed Cu3(BTC)2 SURMOFs. These materials have been characterized using x-ray diffraction, time-of-flight secondary ion mass spectrometry, scanning electron microscopy, x-ray photoelectron spectroscopy as well as linear sweep voltammetry. The WO3 semiconductor/SURMOF heterostructures were further tested as hybrid electrodes in their performance for hydrogen evolution reaction from water.

  13. Efficient photocatalytic degradation of rhodamine 6G with a quantum dot-metal organic framework nanocomposite.

    PubMed

    Kaur, Rajnish; Vellingiri, Kowsalya; Kim, Ki-Hyun; Paul, A K; Deep, Akash

    2016-07-01

    The hybrid structures of metal organic frameworks (MOFs) and nanoparticles may offer the realization of effective photocatalytic materials due to combined benefits of the porous and molecular sieving properties of MOF matrix and the functional characteristics of encapsulated nanoparticles. In this study, cadmium telluride (CdTe) quantum dots (QD) are conjugated with a europium-MOF for the synthesis of a novel nanocomposite material with photocatalytic properties. Successful synthesis of a QD/Eu-MOF nanocomposite was characterized with various spectroscopic and microscopic techniques. This QD/Eu-MOF is found to be an effective catalyst to complete the degradation of Rhodamine 6G dye within 50 min.

  14. Continuous-Flow Microwave Synthesis of Metal-Organic Frameworks: A Highly Efficient Method for Large-Scale Production.

    PubMed

    Taddei, Marco; Steitz, Daniel Antti; van Bokhoven, Jeroen Anton; Ranocchiari, Marco

    2016-03-01

    Metal-organic frameworks are having a tremendous impact on novel strategic applications, with prospective employment in industrially relevant processes. The development of such processes is strictly dependent on the ability to generate materials with high yield efficiency and production rate. We report a versatile and highly efficient method for synthesis of metal-organic frameworks in large quantities using continuous flow processing under microwave irradiation. Benchmark materials such as UiO-66, MIL-53(Al), and HKUST-1 were obtained with remarkable mass, space-time yields, and often using stoichiometric amounts of reactants. In the case of UiO-66 and MIL-53(Al), we attained unprecedented space-time yields far greater than those reported previously. All of the syntheses were successfully extended to multi-gram high quality products in a matter of minutes, proving the effectiveness of continuous flow microwave technology for the large scale production of metal-organic frameworks.

  15. Preparation, Characterization, and Postsynthetic Modification of Metal-Organic Frameworks: Synthetic Experiments for an Undergraduate Laboratory Course in Inorganic Chemistry

    ERIC Educational Resources Information Center

    Sumida, Kenji; Arnold, John

    2011-01-01

    Metal-organic frameworks (MOFs) are crystalline materials that are composed of an infinite array of metal nodes (single ions or clusters) linked to one another by polyfunctional organic compounds. Because of their extraordinary surface areas and high degree of control over the physical and chemical properties, these materials have received much…

  16. Reaction Engineering with Metal-Organic Framework Catalysts

    NASA Astrophysics Data System (ADS)

    Melkonian, Arek Viken

    To date, there has been no comprehensive attempt to perform and/or describe catalytic reactions in the gas phase that utilize metal-organic frameworks (MOFs) as catalysts. In addition, there has been no attempt to reaction engineer these MOF catalysts in order to determine their regimes of optimal catalytic activity and possible limitations to their use. A zinc-based MOF that has been post-synthetically modified with a homogeneous palladium catalyst, Pd(CH 3CN)2Cl2, is used to catalyze the hydrogenation of propylene. The catalyst is assembled in a packed-bed reactor under a continuous flow of reactants. The reaction is optimized with respect to isoreticular metalation, reactant flow rate, and reactor temperature. Maximum catalytic conversion is found at intermediate metalations of 40% and 60%, high hydrogen flow of 50 ccm, and intermediate reactor temperatures of 100 °C and 150 °C. The MOF-60 catalyst is exposed to a traditional catalyst poison, carbon monoxide (CO). It is found that the MOF is reversibly poisoned upon introduction of CO. Upon poisoning, catalytic conversions rates of 90%-100% are dramatically reduced to less than 10%-30%, depending on the CO flow rate and the reactor temperature. The CO poisoning is shown to be reversible, a similar effect as found with palladium on carbon (Pd/C). The time scale of poisoning and recovery is very fast for both the MOF catalyst and Pd/C (approximately 10-30 seconds). Other effects of temperature on the MOF-40 are also investigated. At fixed reactant flow, the temperature grid is partitioned into finer steps of 10 °C to determine the temperature that yields the highest catalytic conversion. It is found that conversion is nearly uniform in the range between the highest conversions, i.e., conversion plateaus between the optimum temperatures. The catalyst also exhibits a weak thermal hysteresis. There is no significant improvement in conversion with thermal cycling after alternating the reactor temperature between

  17. Metal-organic frameworks based on uranyl and phosphonate ligands.

    PubMed

    Monteiro, Bernardo; Fernandes, José A; Pereira, Cláudia C L; Vilela, Sérgio M F; Tomé, João P C; Marçalo, Joaquim; Almeida Paz, Filipe A

    2014-02-01

    Three new crystalline metal-organic frameworks have been prepared from the reaction of uranyl nitrate with nitrilotris(methylphosphonic acid) [H6nmp, N(CH2PO3H2)3], 1,4-phenylenebis(methylene)diphosphonic acid [H4pmd, C6H4(PO3H2)2], and (benzene-1,3,5-triyltris(methylene))triphosphonic acid [H6bmt, C6H3(PO3H2)3]. Compound [(UO2)2F(H3nmp)(H2O)]·4H2O (I) crystallizes in space group C2/c, showing two crystallographically independent uranyl centres with pentagonal bipyramidal coordination geometries. While one metal centre is composed of a {(UO2)O3(μ-F)}2 dimer, the other comprises an isolated {(UO2)O5} polyhedron. Compound [(UO2)(H2pmd)] (II) crystallizes in space group P21/c, showing a centrosymmetric uranyl centre with an octahedral {(UO2)O4} coordination geometry. Compound [(UO2)3(H3bmt)2(H2O)2]·14H2O (III) crystallizes in space group P\\bar 1, showing two crystallographically independent uranyl centres. One uranyl centre is a {(UO2)O5} pentagonal bipyramid similar to that in (I), while the other is a {(UO2)O4} centrosymmetric octahedron similar to that in (II). Compounds (I) and (III) contain solvent-accessible volumes accounting for ca 23.6 and 26.9% of their unit-cell volume, respectively. In (I) the cavity has a columnar shape and is occupied by disordered water molecules, while in (III) the cavity is a two-dimensional layer with more ordered water molecules. All compounds have been studied in the solid state using FT-IR spectroscopy. Topological studies show that compounds (I) and (III) are trinodal, with 3,6,6- and 4,4,6-connected networks, respectively. Compound (II) is instead a 4-connected uninodal network of the type cds.

  18. Heterogeneity of functional groups in a metal-organic framework displays magic number ratios.

    PubMed

    Sue, Andrew C-H; Mannige, Ranjan V; Deng, Hexiang; Cao, Dennis; Wang, Cheng; Gándara, Felipe; Stoddart, J Fraser; Whitelam, Stephen; Yaghi, Omar M

    2015-05-05

    Multiple organic functionalities can now be apportioned into nanoscale domains within a metal-coordinated framework, posing the following question: how do we control the resulting combination of "heterogeneity and order"? Here, we report the creation of a metal-organic framework, MOF-2000, whose two component types are incorporated in a 2:1 ratio, even when the ratio of component types in the starting solution is varied by an order of magnitude. Statistical mechanical modeling suggests that this robust 2:1 ratio has a nonequilibrium origin, resulting from kinetic trapping of component types during framework growth. Our simulations show how other "magic number" ratios of components can be obtained by modulating the topology of a framework and the noncovalent interactions between component types, a finding that may aid the rational design of functional multicomponent materials.

  19. Review of Molecular Simulations of Methane Storage in Metal-Organic Frameworks.

    PubMed

    Lee, Seung-Joon; Bae, Youn-Sang

    2016-05-01

    Methane storage in porous materials is one of the hot issues because it can replace dangerous high-pressure compressed natural gas (CNG) tanks in natural gas vehicles. Among the diverse adsorbents, metal-organic frameworks (MOFs) are considered to be promising due to their extremely high surface areas and low crystal densities. Molecular simulation has been considered as an important tool for finding an appropriate MOF for methane storage. We review several important roles of molecular modeling for the studies of methane adsorption in MOFs.

  20. Photochromic metal-organic frameworks: reversible control of singlet oxygen generation.

    PubMed

    Park, Jihye; Feng, Dawei; Yuan, Shuai; Zhou, Hong-Cai

    2015-01-07

    The controlled generation of singlet oxygen is of great interest owing to its potential applications including industrial wastewater treatment, photochemistry, and photodynamic therapy. Two photochromic metal-organic frameworks, PC-PCN and SO-PCN, have been developed. A photochromic reaction has been successfully realized in PC-PCN while maintaining its single crystallinity. In particular, as a solid-state material which inherently integrates the photochromic switch and photosensitizer, SO-PCN has demonstrated reversible control of (1)O2 generation. Additionally, SO-PCN shows catalytic activity towards photooxidation of 1,5-dihydroxynaphthalene.

  1. Unprecedented selectivity in molecular recognition of carbohydrates by a metal-organic framework.

    PubMed

    Yabushita, Mizuho; Li, Peng; Bernales, Varinia; Kobayashi, Hirokazu; Fukuoka, Atsushi; Gagliardi, Laura; Farha, Omar K; Katz, Alexander

    2016-06-04

    Metal-organic framework (MOF) material NU-1000 adsorbs dimers cellobiose and lactose from aqueous solution, in amounts exceeding 1250 mg gNU-1000(-1) while completely excluding the adsorption of the monomer glucose, even in a competitive mode with cellobiose. The MOF also discriminates between dimers consisting of α and β linkages, showing no adsorption of maltose. Electronic structure calculations demonstrate that key to this selective molecular recognition is the number of favorable CH-π interactions made by the sugar with pyrene units of the MOF.

  2. Experimental comparison of chiral metal-organic framework used as stationary phase in chromatography.

    PubMed

    Xie, Sheng-Ming; Zhang, Mei; Fei, Zhi-Xin; Yuan, Li-Ming

    2014-10-10

    Chiral metal-organic frameworks (MOFs) are a new class of multifunctional material, which possess diverse structures and unusual properties such as high surface area, uniform and permanent cavities, as well as good chemical and thermal stability. Their chiral functionality makes them attractive as novel enantioselective adsorbents and stationary phases in separation science. In this paper, the experimental comparison of a chiral MOF [In₃O(obb)₃(HCO₂)(H₂O)] solvent used as a stationary phase was investigated in gas chromatography (GC), high-performance liquid chromatography (HPLC) and capillary electrochromatography (CEC). The potential relationship between the structure and components of chiral MOFs with their chiral recognition ability and selectivity are presented.

  3. [Synthesis and applications of chiral metal-organic framework in the selective separation of enantiomers].

    PubMed

    Qi, Xiaoyue; Li, Xianjiang; Bai, Yu; Liu, Huwei

    2016-01-01

    Chirality is a universal phenomenon in nature. Chiral separation is vitally important in drug development, agricultural chemistry, pharmacology, environmental science, biology and many other fields. Chiral metal-organic frameworks (MOFs) are a new group of porous materials with special topology and designable pore structures, as well as their high specific surface area, porosity, excellent thermal stability, solvent resistance, etc. Thus, chiral MOFs are promising with various applications in the field of analytical chemistry. This review summarizes the synthesis strategies of chiral MOFs and their applications in the selective separation of enantiomers, as well as related mechanism.

  4. Assembly of a metal-organic framework by sextuple intercatenation of discrete adamantane-like cages.

    PubMed

    Kuang, Xiaofei; Wu, Xiaoyuan; Yu, Rongmin; Donahue, James P; Huang, Jinshun; Lu, Can-Zhong

    2010-06-01

    Metal-organic frameworks form a unique class of multifunctional hybrid materials and have myriad applications, including gas storage and catalysis. Their structure is usually achieved through the infinite coordination of metal ions and multidentate organic ligands by means of strong covalent bonds. Threaded molecules such as catenanes and rotaxanes have largely been restricted to comprising components of two-dimensional interlocking rings or polygons. There are very few examples of the catenation of polyhedral cages. Although it has been postulated that the infinite extended architecture can be obtained from the polycatenation of a discrete cage based on such threading, this has not been documented to date. Here we describe an infinite three-dimensional metal-organic framework composed of catenated polyhedral cages, in which the framework is achieved by mechanical interlocking of all of the vertices of the cages. The three-dimensional polycatenated framework shows twofold self-interpenetration in its crystal packing. The penetration of polycatenanes creates nanosized voids into which the Keggin polyoxometalate anions are perfectly accommodated as counteranions.

  5. Evaluating metal-organic frameworks for post-combustion carbon dioxide capture via temperature swing adsorption

    SciTech Connect

    Mason, JA; Sumida, K; Herm, ZR; Krishna, R; Long, JR

    2011-08-01

    Two representative metal-organic frameworks, Zn4O(BTB)(2)(BTB3- = 1,3,5-benzenetribenzoate; MOF-177) and Mg-2(dobdc) (dobdc(4-) = 1,4-dioxido-2,5-benzenedicarboxylate; Mg-MOF-74, CPO-27-Mg), are evaluated in detail for their potential use in post-combustion CO2 capture via temperature swing adsorption (TSA). Low-pressure single-component CO2 and N-2 adsorption isotherms were measured every 10 degrees C from 20 to 200 degrees C, allowing the performance of each material to be analyzed precisely. In order to gain a more complete understanding of the separation phenomena and the thermodynamics of CO2 adsorption, the isotherms were analyzed using a variety of methods. With regard to the isosteric heat of CO2 adsorption, Mg-2(dobdc) exhibits an abrupt drop at loadings approaching the saturation of the Mg2+ sites, which has significant implications for regeneration in different industrial applications. The CO2/N-2 selectivities were calculated using ideal adsorbed solution theory (IAST) for MOF-177, Mg-2(dobdc), and zeolite NaX, and working capacities were estimated using a simplified TSA model. Significantly, MOF-177 fails to exhibit a positive working capacity even at regeneration temperatures as high as 200 degrees C, while Mg-2(dobdc) reaches a working capacity of 17.6 wt% at this temperature. Breakthrough simulations were also performed for the three materials, demonstrating the superior performance of Mg-2(dobdc) over MOF-177 and zeolite NaX. These results show that the presence of strong CO2 adsorption sites is essential for a metal-organic framework to be of utility in post-combustion CO2 capture via a TSA process, and present a methodology for the evaluation of new metal-organic frameworks via analysis of single-component gas adsorption isotherms.

  6. Facile electrosynthesis of nano flower like metal-organic framework and its nanocomposite with conjugated polymer as a novel and hybrid electrode material for highly capacitive pseudocapacitors.

    PubMed

    Naseri, Maryam; Fotouhi, Lida; Ehsani, Ali; Dehghanpour, Saeed

    2016-12-15

    The [Cu(btec)0.5DMF] (H4btec=1,2,4,5-benzenetetracarboxylate acid) was electrosynthesized on the graphite working electrode by applying catholic potential. The [Cu(btec)0.5DMF] grows on a graphite surface which results from the coordination of 1,2,4,5-benzenetetracarboxylate anions with Cu(2+) cations. The electrosynthesized [Cu(btec)0.5DMF] was characterized by X-ray diffraction, scanning electron microscopy. Furthermore, POAP/Cu(btec)0.5DMF nanocomposite film electrosynthesized on the surface of the carbon paste electrode by cyclic voltammetry. Different electrochemical methods including galvanostatic charge-discharge experiments, cyclic voltammetry and electrochemical impedance spectroscopy are carried out in order to investigate the performance of the system. This work introduces new nanocomposite materials for electrochemical redox capacitors with advantages including ease synthesis, high active surface area and stability in an aqueous electrolyte.

  7. Carbonization and oxidation of metal-organic frameworks based on 1,4-naphthalene dicarboxylates.

    PubMed

    Chen, Jiun-Jen; Chen, Ya-Ting; Senthil Raja, Duraisamy; Kang, Yu-Hao; Tseng, Pen-Chang; Lin, Chia-Her

    2015-10-01

    Three new isostructural metal-organic frameworks (MOFs), [V(OH)(NDC)] (1), [Cr(OH)(NDC)] (2), and [Ga(OH)(NDC)] (3) have been synthesized hydrothermally using 1,4-naphthalene dicarboxylate (NDC) as the linker. These MOFs (1, 2 and 3) have been used as a template for the synthesis of metal-oxide-inserted nanoporous carbon materials. The newly synthesized MOFs and the resulting porous carbon hybrid functional materials have been characterized using powder x-ray diffraction, scanning electron microscopy, transmission electron microscopy, and energy dispersive x-ray spectroscopic analysis. Results show that compounds 2 and 3 form their respective metal oxide nanoparticles on the surface of the carbon materials during carbonization at 800 °C. The gas sorption properties of the new MOFs and their corresponding carbon frameworks have been reported.

  8. Rapid syntheses of a metal-organic framework material Cu3(BTC)2(H2O)3 under microwave: a quantitative analysis of accelerated syntheses.

    PubMed

    Khan, Nazmul Abedin; Haque, Enamul; Jhung, Sung Hwa

    2010-03-20

    A typical MOF material, Cu-BTC has been synthesized with microwave and conventional electric heating in various conditions to elucidate, for the first time, the quantitative acceleration in the synthesis of a MOF by microwaves. The acceleration by microwaves is mainly due to rapid nucleation rather than rapid crystal growth, even though both stages are accelerated. The acceleration in the nucleation stage by microwaves is due to the very large pre-exponential factor (about 1.4 x 10(10) times that of conventional synthesis) in the Arrhenius plot. However, the activation energy for the nucleation in the case of microwave synthesis is higher than the activation energy of conventional synthesis. The large acceleration in the nucleation, compared with that in the crystal growth, is observed once again by the syntheses in two-steps (changing heating methods from microwave into conventional heating or from conventional heating into microwave heating just after the nucleation is completed). The crystal size of Cu-BTC obtained by microwave-nucleation is generally smaller than the Cu-BTC made by conventional-nucleation, probably due to rapid nucleation and the small size of nuclei with microwave-nucleation.

  9. A Highly Energetic N-Rich Zeolite-Like Metal-Organic Framework with Excellent Air Stability and Insensitivity.

    PubMed

    Qin, Jun-Sheng; Zhang, Ji-Chuan; Zhang, Min; Du, Dong-Ying; Li, Jing; Su, Zhong-Min; Wang, Yuan-Yuan; Pang, Si-Ping; Li, Sheng-Hua; Lan, Ya-Qian

    2015-12-01

    A stable N-rich aromatic ligand is employed to prepare energetic zeolite-like metal-organic frameworks. IFMC-1 shows excellent air stability, and the lowest sensitivity toward impact, friction, and electrostatic discharge and the highest predicted heat of detonation among the reported coordination polymers, and even commercial materials (such as trinitrotoluene (TNT)).

  10. A facilely synthesized amino-functionalized metal-organic framework for highly specific and efficient enrichment of glycopeptides.

    PubMed

    Zhang, Yi-Wei; Li, Ze; Zhao, Qiang; Zhou, Ying-Lin; Liu, Hu-Wei; Zhang, Xin-Xiang

    2014-10-09

    A facilely synthesized amino-functionalized metal-organic framework (MOF) MIL-101(Cr)-NH2 was first applied for highly specific glycopeptide enrichment based on the hydrophilic interactions. With the special characteristics of the MOF, the material performed well in selectivity and sensitivity for both standard glycoprotein samples and complex biological samples.

  11. Kinetically tuned dimensional augmentation as a versatile synthetic route towards robust metal-organic frameworks.

    PubMed

    Feng, Dawei; Wang, Kecheng; Wei, Zhangwen; Chen, Ying-Pin; Simon, Cory M; Arvapally, Ravi K; Martin, Richard L; Bosch, Mathieu; Liu, Tian-Fu; Fordham, Stephen; Yuan, Daqiang; Omary, Mohammad A; Haranczyk, Maciej; Smit, Berend; Zhou, Hong-Cai

    2014-12-04

    Metal-organic frameworks with high stability have been pursued for many years due to the sustainability requirement for practical applications. However, researchers have had great difficulty synthesizing chemically ultra-stable, highly porous metal-organic frameworks in the form of crystalline solids, especially as single crystals. Here we present a kinetically tuned dimensional augmentation synthetic route for the preparation of highly crystalline and extremely robust metal-organic frameworks with a preserved metal cluster core. Through this versatile synthetic route, we obtain large single crystals of 34 different iron-containing metal-organic frameworks. Among them, PCN-250(Fe2Co) exhibits high volumetric uptake of hydrogen and methane, and is also stable in water and aqueous solutions with a wide range of pH values.

  12. An amine-functionalized metal-organic framework as a sensing platform for DNA detection.

    PubMed

    Zhang, Hao-Tian; Zhang, Jian-Wei; Huang, Gang; Du, Zi-Yi; Jiang, Hai-Long

    2014-10-18

    An amine-functionalized metal-organic framework (MOF) has been employed as an effective fluorescent sensing platform for DNA detection and is capable of distinguishing complementary and mismatched target sequences with high sensitivity and selectivity.

  13. Role of hydrocarbons in pore expansion and contraction of a flexible metal-organic framework

    SciTech Connect

    Motkuri, Radha K.; Thallapally, Praveen K.; Nune, Satish K.; Fernandez, Carlos A.; McGrail, B. Peter; Atwood, Jerry L.

    2011-05-06

    A flexible metal organic framework obtained from a flexible organic linker shows a breathing phenomenon upon adsorption of polar protic and non-polar solvents. Sorption profiles indicate favorable interactions with non-polar solvents over polar solvents.

  14. Magnetic Metal-Organic Frameworks for Efficient Carbon Dioxide Capture and Remote Trigger Release.

    PubMed

    Li, Haiqing; Sadiq, Muhammad Munir; Suzuki, Kiyonori; Ricco, Raffaele; Doblin, Christian; Hill, Anita J; Lim, Seng; Falcaro, Paolo; Hill, Matthew R

    2016-03-02

    Magnetic metal-organic framework (MOF) composites show highly efficient CO2 desorption capacities upon their exposure to an alternating magnetic field, demonstrating a magnetic induction swing strategy for potentially low-energy regeneration of MOF adsorbents.

  15. Homochiral helical metal-organic frameworks of group 1 metals.

    PubMed

    Reger, Daniel L; Leitner, Andrew; Smith, Mark D; Tran, T Thao; Halasyamani, P Shiv

    2013-09-03

    The reactions of (S)-2-(1,8-naphthalimido)propanoic acid (HL(ala)) and (S)-2-(1,8-naphthalimido)-3-hydroxypropanoic acid (HL(ser)), protonated forms of ligands that contain a carboxylate donor group, an enantiopure chiral center, and a 1,8-naphthalimide π···π stacking supramolecular tecton and in the case of HL(ser) an alcohol functional group, with the appropriate alkali metal hydroxide followed by a variety of crystallization methods leads to the formation of crystalline K(L(ala))(MeOH) (1), K(L(ala))(H2O) (2), Na(L(ala))(H2O) (3), KL(ser) (4), CsL(ser) (5), and CsL(ala) (6). Each of these new complexes has a solid state structure based on six-coordinate metals linked into homochiral helical rod secondary building unit (SBU) central cores. In addition to the bonding of the carboxylate and solvent (in the case of L(ser) the ligand alcohol) to the metals, both oxygens on the 1,8-naphthalimide act as donor groups. One naphthalimide oxygen bonds to the same helical rod SBU as the carboxylate group of that ligand forming a chelate ring. The other naphthalimide oxygen bonds to adjacent SBUs. In complexes 1-3, this inter-rod link has a square arrangement bonding four other rods forming a three-dimensional enantiopure metal-organic framework (MOF) structure, whereas in 4-6 this link has a linear arrangement bonding two other rods forming a two-dimensional, sheet structure. In the latter case, the third dimension is supported exclusively by interdigitated π···π stacking interactions of the naphthalimide supramolecular tecton, forming enantiopure supramolecular MOF solids. Compounds 1-3 lose the coordinated solvent when heating above 100 °C. For 1, the polycrystalline powder reverts to 1 only by recrystallization from methanol, whereas compounds 2 and 3 undergo gas/solid, single-crystal to single-crystal transformations to form dehydrated compounds 2* and 3*, and rehydration occurs when crystals of these new complexes are left out in air. The reversible single

  16. Metal organic frameworks for enzyme immobilization in biofuel cells

    NASA Astrophysics Data System (ADS)

    Bodell, JaDee

    Interest in biofuel cells has been rapidly expanding as an ever-growing segment of the population gains access to electronic devices. The largest areas of growth for new populations using electronic devices are often in communities without electrical infrastructure. This lack of infrastructure in remote environments is one of the key driving factors behind the development of biofuel cells. Biofuel cells employ biological catalysts such as enzymes to catalyze oxidation and reduction reactions of select fuels to generate power. There are several benefits to using enzymes to catalyze reactions as compared to traditional fuel cells which use metal catalysts. First, enzymes are able to catalyze reactions at or near room temperature, whereas traditional metal catalysts are only efficient at very high temperatures. Second, biofuel cells can operate under mild pH conditions which is important for the eventual design of safe, commercially viable devices. Also, biofuel cells allow for implantable and flexible technologies. Finally, enzymes exhibit high selectivity and can be combined to fully oxidize or reduce the fuel which can generate several electrons from a single molecule of fuel, increasing the overall device efficiency. One of the main challenges which persist in biofuel cells is the instability of enzymes over time which tend to denature after hours or days. For a viable commercial biofuel cell to be produced, the stability of enzymes must be extended to months or years. Enzymes have been shown to have improved stability after being immobilized. The focus of this research was to find a metal organic framework (MOF) structure which could successfully immobilize enzymes while still allowing for electron transport to occur between the catalytic center of the enzyme and the electrode surface within a biofuel cell for power generation. Four MOF structures were successfully synthesized and were subsequently tested to determine the MOF's ability to immobilize the following

  17. Engineering chiral porous metal-organic frameworks for enantioselective adsorption and separation

    NASA Astrophysics Data System (ADS)

    Peng, Yongwu; Gong, Tengfei; Zhang, Kang; Lin, Xiaochao; Liu, Yan; Jiang, Jianwen; Cui, Yong

    2014-07-01

    The separation of racemic molecules is of substantial significance not only for basic science but also for technical applications, such as fine chemicals and drug development. Here we report two isostructural chiral metal-organic frameworks decorated with chiral dihydroxy or -methoxy auxiliares from enantiopure tetracarboxylate-bridging ligands of 1,1‧-biphenol and a manganese carboxylate chain. The framework bearing dihydroxy groups functions as a solid-state host capable of adsorbing and separating mixtures of a range of chiral aromatic and aliphatic amines, with high enantioselectivity. The host material can be readily recycled and reused without any apparent loss of performance. The utility of the present adsorption separation is demonstrated in the large-scale resolution of racemic 1-phenylethylamine. Control experiments and molecular simulations suggest that the chiral recognition and separation are attributed to the different orientations and specific binding energies of the enantiomers in the microenvironment of the framework.

  18. Textile/metal-organic-framework composites as self-detoxifying filters for chemical-warfare agents.

    PubMed

    López-Maya, Elena; Montoro, Carmen; Rodríguez-Albelo, L Marleny; Aznar Cervantes, Salvador D; Lozano-Pérez, A Abel; Cenís, José Luis; Barea, Elisa; Navarro, Jorge A R

    2015-06-01

    The current technology of air-filtration materials for protection against highly toxic chemicals, that is, chemical-warfare agents, is mainly based on the broad and effective adsorptive properties of hydrophobic activated carbons. However, adsorption does not prevent these materials from behaving as secondary emitters once they are contaminated. Thus, the development of efficient self-cleaning filters is of high interest. Herein, we report how we can take advantage of the improved phosphotriesterase catalytic activity of lithium alkoxide doped zirconium(IV) metal-organic framework (MOF) materials to develop advanced self-detoxifying adsorbents of chemical-warfare agents containing hydrolysable P-F, P-O, and C-Cl bonds. Moreover, we also show that it is possible to integrate these materials onto textiles, thereby combining air-permeation properties of the textiles with the self-detoxifying properties of the MOF material.

  19. Metal-organic frameworks post-synthetically modified with ferrocenyl groups: framework effects on redox processes and surface conduction.

    PubMed

    Halls, Jonathan E; Hernán-Gómez, Alberto; Burrows, Andrew D; Marken, Frank

    2012-02-07

    Metal-organic framework (MOF) materials based on zinc(II) and aluminium(III) dicarboxylate frameworks with covalently attached ferrocene functional redox groups were synthesised by post-synthetic modification and investigated by voltammetry in aqueous and non-aqueous media. In the voltammetry experiments, ferrocene oxidation occurs in all cases, but chemically reversible and stable ferrocene oxidation without decay of the voltammetric response requires a "mild" dichloroethane solvent environment. The voltammetric response in this case is identified as "surface-confined" with fast surface-hopping of electrons and without affecting the bulk of MOF microcrystals. In aqueous media a more complex pH-dependent multi-stage redox process is observed associated with chemically irreversible bulk oxidation and disintegration of the MOF framework. A characteristic 30 mV per pH unit dependence of redox potentials is observed attributed to a "framework effect": the hydroxide-driven MOF framework dissolution.

  20. A novel metal-organic framework for high storage and separation of acetylene at room temperature

    SciTech Connect

    Duan, Xing; Wang, Huizhen; Ji, Zhenguo; Cui, Yuanjing; Yang, Yu; Qian, Guodong

    2016-09-15

    A novel 3D microporous metal-organic framework with NbO topology, [Cu{sub 2}(L)(H{sub 2}O){sub 2}]∙(DMF){sub 6}·(H{sub 2}O){sub 2} (ZJU-10, ZJU = Zhejiang University; H{sub 4}L =2′-hydroxy-[1,1′:4′,1″-terphenyl]-3,3″,5,5″-tetracarboxylic acid; DMF =N,N-dimethylformamide), has been synthesized and structurally characterized. With suitable pore sizes and open Cu{sup 2+} sites, ZJU-10a exhibits high BET surface area of 2392 m{sup 2}/g, as well as moderately high C{sub 2}H{sub 2} volumetric uptake capacity of 132 cm{sup 3}/cm{sup 3}. Meanwhile, ZJU-10a is a promising porous material for separation of acetylene from methane and carbon dioxide gas mixtures at room temperature. - Graphical abstract: A new NbO-type microporous metal-organic framework ZJU-10 with suitable pore size and open Cu{sup 2+} sites was synthesized to realize the strong interaction with acetylene molecules, which can separate the acetylene from methane and carbon dioxane gas mixtures at room temperature. Display Omitted - Highlights: • A novel 3D NbO-type microporous metal-organic framework ZJU-10 was solvothermally synthesized and structurally characterized. • ZJU-10a exhibits high BET surface area of 2392 m{sup 2}/g. • ZJU-10a shows a moderately high C{sub 2}H{sub 2} gravimetric (volumetric) uptake capacity of 174 (132) cm{sup 3}/g at 298 K and 1 bar. • ZJU-10a can separate acetylene from methane and carbon dioxide gas mixtures at room temperature.

  1. Enhanced ethylene separation and plasticization resistance in polymer membranes incorporating metal-organic framework nanocrystals

    NASA Astrophysics Data System (ADS)

    Bachman, Jonathan E.; Smith, Zachary P.; Li, Tao; Xu, Ting; Long, Jeffrey R.

    2016-08-01

    The implementation of membrane-based separations in the petrochemical industry has the potential to reduce energy consumption significantly relative to conventional separation processes. Achieving this goal, however, requires the development of new membrane materials with greater selectivity, permeability and stability than available at present. Here, we report composite materials consisting of nanocrystals of metal-organic frameworks dispersed within a high-performance polyimide, which can exhibit enhanced selectivity for ethylene over ethane, greater ethylene permeability and improved membrane stability. Our results suggest that framework-polymer interactions reduce chain mobility of the polymer while simultaneously boosting membrane separation performance. The increased stability, or plasticization resistance, is expected to improve membrane utility under real process conditions for petrochemical separations and natural gas purification. Furthermore, this approach can be broadly applied to numerous polymers that encounter aggressive environments, potentially making gas separations possible that were previously inaccessible to membranes.

  2. Enhanced ethylene separation and plasticization resistance in polymer membranes incorporating metal-organic framework nanocrystals.

    PubMed

    Bachman, Jonathan E; Smith, Zachary P; Li, Tao; Xu, Ting; Long, Jeffrey R

    2016-08-01

    The implementation of membrane-based separations in the petrochemical industry has the potential to reduce energy consumption significantly relative to conventional separation processes. Achieving this goal, however, requires the development of new membrane materials with greater selectivity, permeability and stability than available at present. Here, we report composite materials consisting of nanocrystals of metal-organic frameworks dispersed within a high-performance polyimide, which can exhibit enhanced selectivity for ethylene over ethane, greater ethylene permeability and improved membrane stability. Our results suggest that framework-polymer interactions reduce chain mobility of the polymer while simultaneously boosting membrane separation performance. The increased stability, or plasticization resistance, is expected to improve membrane utility under real process conditions for petrochemical separations and natural gas purification. Furthermore, this approach can be broadly applied to numerous polymers that encounter aggressive environments, potentially making gas separations possible that were previously inaccessible to membranes.

  3. Metal-organic framework with optimally selective xenon adsorption and separation

    NASA Astrophysics Data System (ADS)

    Banerjee, Debasis; Simon, Cory M.; Plonka, Anna M.; Motkuri, Radha K.; Liu, Jian; Chen, Xianyin; Smit, Berend; Parise, John B.; Haranczyk, Maciej; Thallapally, Praveen K.

    2016-06-01

    Nuclear energy is among the most viable alternatives to our current fossil fuel-based energy economy. The mass deployment of nuclear energy as a low-emissions source requires the reprocessing of used nuclear fuel to recover fissile materials and mitigate radioactive waste. A major concern with reprocessing used nuclear fuel is the release of volatile radionuclides such as xenon and krypton that evolve into reprocessing facility off-gas in parts per million concentrations. The existing technology to remove these radioactive noble gases is a costly cryogenic distillation; alternatively, porous materials such as metal-organic frameworks have demonstrated the ability to selectively adsorb xenon and krypton at ambient conditions. Here we carry out a high-throughput computational screening of large databases of metal-organic frameworks and identify SBMOF-1 as the most selective for xenon. We affirm this prediction and report that SBMOF-1 exhibits by far the highest reported xenon adsorption capacity and a remarkable Xe/Kr selectivity under conditions pertinent to nuclear fuel reprocessing.

  4. Trapping gases in metal-organic frameworks with a selective surface molecular barrier layer

    NASA Astrophysics Data System (ADS)

    Tan, Kui; Zuluaga, Sebastian; Fuentes, Erika; Mattson, Eric C.; Veyan, Jean-François; Wang, Hao; Li, Jing; Thonhauser, Timo; Chabal, Yves J.

    2016-12-01

    The main challenge for gas storage and separation in nanoporous materials is that many molecules of interest adsorb too weakly to be effectively retained. Instead of synthetically modifying the internal surface structure of the entire bulk--as is typically done to enhance adsorption--here we show that post exposure of a prototypical porous metal-organic framework to ethylenediamine can effectively retain a variety of weakly adsorbing molecules (for example, CO, CO2, SO2, C2H4, NO) inside the materials by forming a monolayer-thick cap at the external surface of microcrystals. Furthermore, this capping mechanism, based on hydrogen bonding as explained by ab initio modelling, opens the door for potential selectivity. For example, water molecules are shown to disrupt the hydrogen-bonded amine network and diffuse through the cap without hindrance and fully displace/release the retained small molecules out of the metal-organic framework at room temperature. These findings may provide alternative strategies for gas storage, delivery and separation.

  5. Trapping gases in metal-organic frameworks with a selective surface molecular barrier layer

    PubMed Central

    Tan, Kui; Zuluaga, Sebastian; Fuentes, Erika; Mattson, Eric C.; Veyan, Jean-François; Wang, Hao; Li, Jing; Thonhauser, Timo; Chabal, Yves J.

    2016-01-01

    The main challenge for gas storage and separation in nanoporous materials is that many molecules of interest adsorb too weakly to be effectively retained. Instead of synthetically modifying the internal surface structure of the entire bulk—as is typically done to enhance adsorption—here we show that post exposure of a prototypical porous metal-organic framework to ethylenediamine can effectively retain a variety of weakly adsorbing molecules (for example, CO, CO2, SO2, C2H4, NO) inside the materials by forming a monolayer-thick cap at the external surface of microcrystals. Furthermore, this capping mechanism, based on hydrogen bonding as explained by ab initio modelling, opens the door for potential selectivity. For example, water molecules are shown to disrupt the hydrogen-bonded amine network and diffuse through the cap without hindrance and fully displace/release the retained small molecules out of the metal-organic framework at room temperature. These findings may provide alternative strategies for gas storage, delivery and separation. PMID:27958274

  6. Metal-organic framework with optimally selective xenon adsorption and separation.

    PubMed

    Banerjee, Debasis; Simon, Cory M; Plonka, Anna M; Motkuri, Radha K; Liu, Jian; Chen, Xianyin; Smit, Berend; Parise, John B; Haranczyk, Maciej; Thallapally, Praveen K

    2016-06-13

    Nuclear energy is among the most viable alternatives to our current fossil fuel-based energy economy. The mass deployment of nuclear energy as a low-emissions source requires the reprocessing of used nuclear fuel to recover fissile materials and mitigate radioactive waste. A major concern with reprocessing used nuclear fuel is the release of volatile radionuclides such as xenon and krypton that evolve into reprocessing facility off-gas in parts per million concentrations. The existing technology to remove these radioactive noble gases is a costly cryogenic distillation; alternatively, porous materials such as metal-organic frameworks have demonstrated the ability to selectively adsorb xenon and krypton at ambient conditions. Here we carry out a high-throughput computational screening of large databases of metal-organic frameworks and identify SBMOF-1 as the most selective for xenon. We affirm this prediction and report that SBMOF-1 exhibits by far the highest reported xenon adsorption capacity and a remarkable Xe/Kr selectivity under conditions pertinent to nuclear fuel reprocessing.

  7. In Silico Discovery of High Deliverable Capacity Metal-Organic Frameworks

    NASA Astrophysics Data System (ADS)

    Bao, Yi; Martin, Richard; Simon, Cory; Haranczyk, Maciej; Smit, Berend; Deem, Michael; Michael W. Deem Team; Maciej Haranczyk Team; Berend Smit Team

    2015-03-01

    Metal organic frameworks (MOFs) are actively being explored as potential adsorbed natural gas storage materials for small vehicles. Experimental exploration of potential materials is limited by the throughput of synthetic chemistry. We here describe a computational methodology to complement and guide these experimental efforts. The method uses known chemical transformations in silico to identify MOFs with high methane deliverable capacity. The procedure explicitly considers synthesizability with geometric requirements on organic linkers. We efficiently search the composition and conformation space of organic linkers for nine MOF networks, finding 48 materials with higher predicted deliverable capacity (at 65 bar storage, 5.8 bar depletion, and 298 K) than MOF-5 in four of the nine networks. The best material has a predicted deliverable capacity 8% higher than that of MOF-5. US Department of Energy.

  8. Bimetallic Metal-Organic Frameworks for Controlled Catalytic Graphitization of Nanoporous Carbons

    PubMed Central

    Tang, Jing; Salunkhe, Rahul R.; Zhang, Huabin; Malgras, Victor; Ahamad, Tansir; Alshehri, Saad M.; Kobayashi, Naoya; Tominaka, Satoshi; Ide, Yusuke; Kim, Jung Ho; Yamauchi, Yusuke

    2016-01-01

    Single metal-organic frameworks (MOFs), constructed from the coordination between one-fold metal ions and organic linkers, show limited functionalities when used as precursors for nanoporous carbon materials. Herein, we propose to merge the advantages of zinc and cobalt metals ions into one single MOF crystal (i.e., bimetallic MOFs). The organic linkers that coordinate with cobalt ions tend to yield graphitic carbons after carbonization, unlike those bridging with zinc ions, due to the controlled catalytic graphitization by the cobalt nanoparticles. In this work, we demonstrate a feasible method to achieve nanoporous carbon materials with tailored properties, including specific surface area, pore size distribution, degree of graphitization, and content of heteroatoms. The bimetallic-MOF-derived nanoporous carbon are systematically characterized, highlighting the importance of precisely controlling the properties of the carbon materials. This can be done by finely tuning the components in the bimetallic MOF precursors, and thus designing optimal carbon materials for specific applications. PMID:27471193

  9. Bimetallic Metal-Organic Frameworks for Controlled Catalytic Graphitization of Nanoporous Carbons

    NASA Astrophysics Data System (ADS)

    Tang, Jing; Salunkhe, Rahul R.; Zhang, Huabin; Malgras, Victor; Ahamad, Tansir; Alshehri, Saad M.; Kobayashi, Naoya; Tominaka, Satoshi; Ide, Yusuke; Kim, Jung Ho; Yamauchi, Yusuke

    2016-07-01

    Single metal-organic frameworks (MOFs), constructed from the coordination between one-fold metal ions and organic linkers, show limited functionalities when used as precursors for nanoporous carbon materials. Herein, we propose to merge the advantages of zinc and cobalt metals ions into one single MOF crystal (i.e., bimetallic MOFs). The organic linkers that coordinate with cobalt ions tend to yield graphitic carbons after carbonization, unlike those bridging with zinc ions, due to the controlled catalytic graphitization by the cobalt nanoparticles. In this work, we demonstrate a feasible method to achieve nanoporous carbon materials with tailored properties, including specific surface area, pore size distribution, degree of graphitization, and content of heteroatoms. The bimetallic-MOF-derived nanoporous carbon are systematically characterized, highlighting the importance of precisely controlling the properties of the carbon materials. This can be done by finely tuning the components in the bimetallic MOF precursors, and thus designing optimal carbon materials for specific applications.

  10. Homochiral metal-organic frameworks and their application in chromatography enantioseparations.

    PubMed

    Peluso, Paola; Mamane, Victor; Cossu, Sergio

    2014-10-10

    The last frontier in the chiral stationary phases (CSPs) field for chromatography enantioseparations is represented by homochiral metal-organic frameworks (MOFs), a class of organic-inorganic hybrid materials built from metal-connecting nodes and organic-bridging ligands. The modular nature of these materials allows to design focused structures by combining properly metal, organic ligands and rigid polytopic spacers. Intriguingly, chiral ligands introduce molecular chirality in the MOF-network as well as homochirality in the secondary structure of materials (such as homohelicity) producing homochiral nets in a manner mimicking biopolymers (proteins, polysaccharides) which are characterized by a definite helical sense associated with the chirality of their building blocks (amino acids or sugars). Nowadays, robust and flexible materials characterized by high porosity and surface area became available by using preparative procedures typical of the so-called reticular synthesis. This review focuses on recent developments in the synthesis and applications of homochiral MOFs as supports for chromatography enantioseparations. Indeed, despite this field is in its infancy, interesting results have been produced and a critical overview of the 12 reported applications for gas chromatography (GC) and high-performance liquid chromatography (HPLC) can orient the reader approaching the field. Mechanistic aspects are shortly discussed and a view regarding future trends in this field is provided.

  11. Switching Thin Films of Azobenzene-Containing Metal-Organic Frameworks with Visible Light.

    PubMed

    Müller, Kai; Knebel, Alexander; Zhao, Fangli; Bléger, David; Caro, Jürgen; Heinke, Lars

    2017-04-03

    Stimuli-responsive molecules change their properties when exposed to external signals, such as light, and enable the preparation of smart materials. UV light, which often destroys organic materials, is typically required for activating the desired response of photoswitchable compounds, significantly limiting the potential applications of light-operated smart materials. Herein, we present the first metal-organic framework (MOF), which enables reversible modulation of key properties upon irradiation with visible light only. The fluorinated azobenzene side groups in the MOF structure can be reversibly switched between the trans and cis state by green and violet light, avoiding UV light. It was demonstrated that the uptake of guest molecules by these MOF films can be switched in a fully remote-controlled way. The membrane separation of hydrogen/hydrocarbon mixtures was investigated. The light-induced changes of the MOF pore size result in the switching of the permeation and of the selection factor.

  12. Metal-Organic Framework Thin Films as Stationary Phases in Microfabricated Gas-Chromatography Columns.

    SciTech Connect

    Read, Douglas; Sillerud, Colin Halliday

    2016-01-01

    The overarching goal of this project is to integrate Sandia's microfabricated gas-chromatography ( GC) columns with a stationary phase material that is capable of retaining high-volatility chemicals and permanent gases. The successful integration of such a material with GCs would dramatically expand the repertoire of detectable compounds for Sandia's various microanalysis systems. One such promising class of candidate materials is metal-organic frameworks (MOFs). In this report we detail our methods for controlled deposition of HKUST-1 MOF stationary phases within GC columns. We demonstrate: the chromatographic separation of natural gas; a method for determining MOF film thickness from chromatography alone; and the first-reported GC x GC separation of natural gas -- in general -- let alone for two disparate MOF stationary phases. In addition we determine the fundamental thermodynamic constant for mass sorption, the partition coefficient, for HKUST-1 and several light hydrocarbons and select toxic industrial chemicals.

  13. Tailoring porosity and rotational dynamics in a series of octacarboxylate metal-organic frameworks.

    PubMed

    Moreau, Florian; Kolokolov, Daniil I; Stepanov, Alexander G; Easun, Timothy L; Dailly, Anne; Lewis, William; Blake, Alexander J; Nowell, Harriott; Lennox, Matthew J; Besley, Elena; Yang, Sihai; Schröder, Martin

    2017-03-21

    Modulation and precise control of porosity of metal-organic frameworks (MOFs) is of critical importance to their materials function. Here we report modulation of porosity for a series of isoreticular octacarboxylate MOFs, denoted MFM-180 to MFM-185, via a strategy of selective elongation of metal-organic cages. Owing to the high ligand connectivity, these MOFs do not show interpenetration, and are robust structures that have permanent porosity. Interestingly, activated MFM-185a shows a high Brunauer-Emmett-Teller (BET) surface area of 4,734 m(2) g(-1) for an octacarboxylate MOF. These MOFs show remarkable CH4 and CO2 adsorption properties, notably with simultaneously high gravimetric and volumetric deliverable CH4 capacities of 0.24 g g(-1) and 163 vol/vol (298 K, 5-65 bar) recorded for MFM-185a due to selective elongation of tubular cages. The dynamics of molecular rotors in deuterated MFM-180a-d16 and MFM-181a-d16 were investigated by variable-temperature (2)H solid-state NMR spectroscopy to reveal the reorientation mechanisms within these materials. Analysis of the flipping modes of the mobile phenyl groups, their rotational rates, and transition temperatures paves the way to controlling and understanding the role of molecular rotors through design of organic linkers within porous MOF materials.

  14. Shock resistance of metal-organic framework Cu-1,3,5-benzenetricarboxylate with and without ferrocene inclusion

    NASA Astrophysics Data System (ADS)

    Wei, Q.; Xu, H. W.; Yu, X. H.; Shimada, T.; Rearick, M. S.; Hickmott, D. D.; Zhao, Y. S.; Luo, S. N.

    2011-09-01

    A first-of-its-kind study on the shock response of a metal-organic framework (MOF) material to planar impact is reported. MOF Cu-1,3,5-benzenetricarboxylate (Cu-BTC) without and with ferrocene inclusion show anisotropic structural collapse under shock loading. The shock resistance of the Cu-BTC framework is enhanced drastically (by a factor of six) via molecular-level inclusion of ferrocene into the pore structures.

  15. Shock Resistance of Metal-Organic Framework Cu-1,3,5-Benzenetricarboxylate with and without Ferrocene Inclusion

    NASA Astrophysics Data System (ADS)

    Wei, Q.; Xu, H. W.; Luo, S. N.

    2011-06-01

    A first-of-the-kind study on the dynamic response of a metal-organic framework (MOF) material to impulsive shock wave loading is reported. MOF Cu-1,3,5-benzenetricarboxylate (Cu-BTC) without and with ferrocene inclusion show anisotropic structural collapse under shock loading, likely due to the elastic anisotropy of the network structure. The shock resistance of Cu-BTC framework is enhanced drastically (by a factor of six) via including ferrocene into the pore structures.

  16. Communication: Enthalpy relaxation in a metal-organic zeolite imidazole framework (ZIF-4) glass-former.

    PubMed

    Xu, Di; Liu, Yingdan; Tian, Yongjun; Wang, Li-Min

    2017-03-28

    Amorphization in metal-organic framework materials initiated by the collapsed crystal offers new access to glasses; however, the understanding of such glasses remains to be clarified. Here, we studied the glass transition thermodynamics and kinetics in a zeolitic imidazolate framework ZIF-4 utilizing enthalpy relaxation measurements. The calorimetric glass transition profile and relaxation behaviors in ZIF-4 are found to reproduce the basic features and correlations manifested by conventional melt-quenched glasses. A comparison with various melt-quenched glasses suggests that the low fragility of ZIF-4 is ascribed to the low thermal-pressure coefficient due to the directional tetrahedral bond, partly leading to the low vibrational entropy in the melt-crystal entropy difference.

  17. Porous Metal-Organic Frameworks for Gas Storage and Separation: What, How, and Why?

    PubMed

    Li, Bin; Wen, Hui-Min; Zhou, Wei; Chen, Banglin

    2014-10-16

    Metal-organic frameworks (MOFs) have been emerging as promising multifunctional materials and have shown particularly useful applications for gas storage and separation. We have briefly outlined the early development of this very active research field to provide us a clear picture on what are MOFs and how the research endeavor has been initiated and explored. Following that, we have demonstrated why MOFs are so unique for gas storage and separation: high porosities, tunable framework structures, and immobilized functional sites to fully make use of pore space for gas storage, to optimize their sieving effects, and to differentiate their interactions with gas molecules. Finally, we have provided a perspective on further development of porous MOFs for gas storage and separation.

  18. Made-to-order metal-organic frameworks for trace carbon dioxide removal and air capture.

    PubMed

    Shekhah, Osama; Belmabkhout, Youssef; Chen, Zhijie; Guillerm, Vincent; Cairns, Amy; Adil, Karim; Eddaoudi, Mohamed

    2014-06-25

    Direct air capture is regarded as a plausible alternate approach that, if economically practical, can mitigate the increasing carbon dioxide emissions associated with two of the main carbon polluting sources, namely stationary power plants and transportation. Here we show that metal-organic framework crystal chemistry permits the construction of an isostructural metal-organic framework (SIFSIX-3-Cu) based on pyrazine/copper(II) two-dimensional periodic 4(4) square grids pillared by silicon hexafluoride anions and thus allows further contraction of the pore system to 3.5 versus 3.84 Å for the parent zinc(II) derivative. This enhances the adsorption energetics and subsequently displays carbon dioxide uptake and selectivity at very low partial pressures relevant to air capture and trace carbon dioxide removal. The resultant SIFSIX-3-Cu exhibits uniformly distributed adsorption energetics and offers enhanced carbon dioxide physical adsorption properties, uptake and selectivity in highly diluted gas streams, a performance, to the best of our knowledge, unachievable with other classes of porous materials.

  19. The modulator driven polymorphism of Zr(IV) based metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Drache, Franziska; Bon, Volodymyr; Senkovska, Irena; Getzschmann, Jürgen; Kaskel, Stefan

    2017-01-01

    The reaction of ZrCl4 and 2,5-thiophenedicarboxylic acid (H2tdc) in the presence of trifluoroacetic acid (Htfa) as modulator results in the formation of the new metal-organic framework (MOF) named DUT-126 (DUT = Dresden University of Technology). The nature and concentration of modulators are found to be decisive synthetic parameters affecting the topology of the formed product. DUT-126 (hbr) extends the series of polymorphs differing in topology, namely DUT-67 (reo), DUT-68 (bon) and DUT-69 (bct) to four, where DUT-67 and DUT-68 show the same eight-connected secondary building units as in DUT-126. In DUT-126, linker molecules have a peculiar orientation, resulting in hbr topology, which is described for the first time in this work for MOFs. DUT-126 contains three pore types, including two micropores surrounding mesoporous channels. DUT-126 is stable against hydrolysis and features permanent porosity with a specific surface area of 1297 m2 g-1 and a total pore volume of 0.48 cm3 g-1, calculated from the nitrogen physisorption isotherm measured at 77 K. This article is part of the themed issue 'Coordination polymers and metal-organic frameworks: materials by design'.

  20. Made-to-order metal-organic frameworks for trace carbon dioxide removal and air capture

    PubMed Central

    Shekhah, Osama; Belmabkhout, Youssef; Chen, Zhijie; Guillerm, Vincent; Cairns, Amy; Adil, Karim; Eddaoudi, Mohamed

    2014-01-01

    Direct air capture is regarded as a plausible alternate approach that, if economically practical, can mitigate the increasing carbon dioxide emissions associated with two of the main carbon polluting sources, namely stationary power plants and transportation. Here we show that metal-organic framework crystal chemistry permits the construction of an isostructural metal-organic framework (SIFSIX-3-Cu) based on pyrazine/copper(II) two-dimensional periodic 44 square grids pillared by silicon hexafluoride anions and thus allows further contraction of the pore system to 3.5 versus 3.84 Å for the parent zinc(II) derivative. This enhances the adsorption energetics and subsequently displays carbon dioxide uptake and selectivity at very low partial pressures relevant to air capture and trace carbon dioxide removal. The resultant SIFSIX-3-Cu exhibits uniformly distributed adsorption energetics and offers enhanced carbon dioxide physical adsorption properties, uptake and selectivity in highly diluted gas streams, a performance, to the best of our knowledge, unachievable with other classes of porous materials. PMID:24964404

  1. Efficient methods for screening of metal organic framework membranes for gas separations using atomically detailed models.

    PubMed

    Keskin, Seda; Sholl, David S

    2009-10-06

    Metal organic frameworks (MOFs) define a diverse class of nanoporous materials having potential applications in adsorption-based and membrane-based gas separations. We have previously used atomically detailed models to predict the performance of MOFs for membrane-based separations of gases, but these calculations require considerable computational resources and time. Here, we introduce an efficient approximate method for screening MOFs based on atomistic models that will accelerate the modeling of membrane applications. The validity of this approximate method is examined by comparison with detailed calculations for CH4/H2, CO2/CH4, and CO2/H2 mixtures at room temperature permeating through IRMOF-1 and CuBTC membranes. These results allow us to hypothesize a connection between two computationally efficient correlations predicting mixture adsorption and mixture self-diffusion properties and the validity of our approximate screening method. We then apply our model to six additional MOFs, IRMOF-8, -9, -10, and -14, Zn(bdc)(ted)0.5, and COF-102, to examine the effect of chemical diversity and interpenetration on the performance of metal organic framework membranes for light gas separations.

  2. The modulator driven polymorphism of Zr(IV) based metal-organic frameworks.

    PubMed

    Drache, Franziska; Bon, Volodymyr; Senkovska, Irena; Getzschmann, Jürgen; Kaskel, Stefan

    2017-01-13

    The reaction of ZrCl4 and 2,5-thiophenedicarboxylic acid (H2tdc) in the presence of trifluoroacetic acid (Htfa) as modulator results in the formation of the new metal-organic framework (MOF) named DUT-126 (DUT = Dresden University of Technology). The nature and concentration of modulators are found to be decisive synthetic parameters affecting the topology of the formed product. DUT-126 ( HBR: ) extends the series of polymorphs differing in topology, namely DUT-67 ( REO: ), DUT-68 ( BON: ) and DUT-69 ( BCT: ) to four, where DUT-67 and DUT-68 show the same eight-connected secondary building units as in DUT-126. In DUT-126, linker molecules have a peculiar orientation, resulting in HBR: topology, which is described for the first time in this work for MOFs. DUT-126 contains three pore types, including two micropores surrounding mesoporous channels. DUT-126 is stable against hydrolysis and features permanent porosity with a specific surface area of 1297 m(2) g(-1) and a total pore volume of 0.48 cm(3) g(-1), calculated from the nitrogen physisorption isotherm measured at 77 K.This article is part of the themed issue 'Coordination polymers and metal-organic frameworks: materials by design'.

  3. Transformation of metal-organic framework to polymer gel by cross-linking the organic ligands preorganized in metal-organic framework.

    PubMed

    Ishiwata, Takumi; Furukawa, Yuki; Sugikawa, Kouta; Kokado, Kenta; Sada, Kazuki

    2013-04-10

    Until now, seamless fusion of metal-organic frameworks (MOFs) and covalently cross-linked polymer gels (PG) at molecular level has been extremely rare, since these two matters have been regarded as opposite, that is, hard versus soft. In this report, we demonstrate transformation of cubic MOF crystals to PG via inner cross-linking of the organic linkers in the void space of MOF, followed by decomposition of the metal coordination. The obtained PG behaved as a polyelectrolyte gel, indicating the high content of ionic groups inside. Metal ions were well adsorbed in the PG due to its densely packed carboxylate groups. A chimera-type hybrid material consisting of MOF and PG was obtained by partial hydrolysis of resulting cross-linked MOF. The shape of resulting PG network well reflected the crystal structure of MOF employed as a template. Our results will connect the two different network materials that have been ever studied in the two different fields to provide new soft and hard hybrid materials, and the unique copolymerization in the large void space of the MOF will open a new horizon toward "ideal network polymers" never prepared before now.

  4. Metal-organic frameworks for thermoelectric energy-conversion applications

    SciTech Connect

    Talin, Albert Alec; Jones, Reese E.; Hopkins, Patrick E.

    2016-11-07

    Motivated by low cost, low toxicity, mechanical flexibility, and conformability over complex shapes, organic semiconductors are currently being actively investigated as thermoelectric (TE) materials to replace the costly, brittle, and non-eco-friendly inorganic TEs for near-ambient-temperature applications. Metal–organic frameworks (MOFs) share many of the attractive features of organic polymers, including solution processability and low thermal conductivity. A potential advantage of MOFs and MOFs with guest molecules (Guest@MOFs) is their synthetic and structural versatility, which allows both the electronic and geometric structure to be tuned through the choice of metal, ligand, and guest molecules. This could solve the long-standing challenge of finding stable, high-TE-performance n-type organic semiconductors, as well as promote high charge mobility via the long-range crystalline order inherent in these materials. In this paper, we review recent advances in the synthesis of MOF and Guest@MOF TEs and discuss how the Seebeck coefficient, electrical conductivity, and thermal conductivity could be tuned to further optimize TE performance.

  5. High Methane Storage Capacity in Aluminum Metal-Organic Frameworks

    SciTech Connect

    Gándara, Felipe; Furukawa, Hiroyasu; Lee, Seungkyu; Yaghi, Omar M.

    2014-08-14

    The use of porous materials to store natural gas in vehicles requires large amounts of methane per unit of volume. Here we report the synthesis, crystal structure and methane adsorption properties of two new aluminum metal–organic frameworks, MOF-519 and MOF-520. Both materials exhibit permanent porosity and high methane volumetric storage capacity: MOF-519 has a volumetric capacity of 200 and 279 cm3 cm–3 at 298 K and 35 and 80 bar, respectively, and MOF-520 has a volumetric capacity of 162 and 231 cm3 cm–3 under the same conditions. Furthermore, MOF-519 exhibits an exceptional working capacity, being able to deliver a large amount of methane at pressures between 5 and 35 bar, 151 cm3 cm–3, and between 5 and 80 bar, 230 cm3 cm–3.

  6. Metal-organic frameworks for thermoelectric energy-conversion applications

    DOE PAGES

    Talin, Albert Alec; Jones, Reese E.; Hopkins, Patrick E.

    2016-11-07

    Motivated by low cost, low toxicity, mechanical flexibility, and conformability over complex shapes, organic semiconductors are currently being actively investigated as thermoelectric (TE) materials to replace the costly, brittle, and non-eco-friendly inorganic TEs for near-ambient-temperature applications. Metal–organic frameworks (MOFs) share many of the attractive features of organic polymers, including solution processability and low thermal conductivity. A potential advantage of MOFs and MOFs with guest molecules (Guest@MOFs) is their synthetic and structural versatility, which allows both the electronic and geometric structure to be tuned through the choice of metal, ligand, and guest molecules. This could solve the long-standing challenge of findingmore » stable, high-TE-performance n-type organic semiconductors, as well as promote high charge mobility via the long-range crystalline order inherent in these materials. In this paper, we review recent advances in the synthesis of MOF and Guest@MOF TEs and discuss how the Seebeck coefficient, electrical conductivity, and thermal conductivity could be tuned to further optimize TE performance.« less

  7. Interpenetration as a mechanism for negative thermal expansion in the metal-organic framework Cu3(btb)2 (MOF-14).

    PubMed

    Wu, Yue; Peterson, Vanessa K; Luks, Emily; Darwish, Tamim A; Kepert, Cameron J

    2014-05-12

    Metal-organic framework materials (MOFs) have recently been shown in some cases to exhibit strong negative thermal expansion (NTE) behavior, while framework interpenetration has been found to reduce NTE in many materials. Using powder and single-crystal diffraction methods we investigate the thermal expansion behavior of interpenetrated Cu3(btb)2 (MOF-14) and find that it exhibits an anomalously large NTE effect. Temperature-dependent structural analysis shows that, contrary to other interpenetrated materials, in MOF-14 the large positive thermal expansion of weak interactions that hold the interpenetrating networks together results in a low-energy contractive distortion of the overall framework structure, demonstrating a new mechanism for NTE.

  8. Fluorous Metal Organic Frameworks as Superhydrophobic Adsorbents for Oil Spill Cleanup and Hydrocarbons Storage

    SciTech Connect

    Yang, Chi; Mather, Qian; Wang, Xiaoping; Kaipa, Ushasree; Nesterov, Vladimir; Venero, Augustin; Omary, Mohammad A

    2011-01-01

    We demonstrate that fluorous metal-organic frameworks (FMOFs) are highly hydrophobic porous materials with a high capacity and affinity to C{sub 6}-C{sub 8} hydrocarbons of oil components. FMOF-1 exhibits reversible adsorption with a high capacity for n-hexane, cyclohexane, benzene, toluene, and p-xylene, with no detectable water adsorption even at near 100% relative humidity, drastically outperforming activated carbon and zeolite porous materials. FMOF-2, obtained from annealing FMOF-1, shows enlarged cages and channels with double toluene adsorption vs FMOF-1 based on crystal structures. The results suggest great promise for FMOFs in applications such as removal of organic pollutants from oil spills or ambient humid air, hydrocarbon storage and transportation, water purification, etc. under practical working conditions.

  9. Adsorption of silver nanoparticles from aqueous solution on copper-based metal organic frameworks (HKUST-1).

    PubMed

    Conde-González, J E; Peña-Méndez, E M; Rybáková, S; Pasán, J; Ruiz-Pérez, C; Havel, J

    2016-05-01

    Silver nanoparticles (AgNP) are emerging pollutants. The use of novel materials such as Cu-(benzene 1,3,5-tricarboxylate, BTC) Metal-Organic Framework (MOFs), for AgNP adsorption and their removal from aqueous solutions has been studied. The effect of different parameters was followed and isotherm model was suggested. MOFs adsorbed fast and efficiently AgNP in the range C0 < 10 mg L(-1), being Freundlich isotherm (R = 0.993) these data fitted to. Among studied parameters a remarkable effect of chloride on sorption was found, thus their possible interactions were considered. The high adsorption efficiency of AgNP was achieved and it was found to be very fast. The feasibility of adsorption on Cu-(BTC) was proved in spiked waters. The results showed the potential interest of new material as adsorbent for removing AgNP from environment.

  10. A scalable synthesis of a mesoporous metal-organic framework called NU-1000.

    SciTech Connect

    Wang, Timothy C.; Vermeulen, Nicolaas A.; Kim, In Soo; Martinson, Alex B. F.; Stoddart, J. Fraser; Hupp, Joseph T.; Farha, Omar K.

    2016-01-01

    The synthesis of NU-1000, a mesoporous metal-organic framework (MOF), can be conducted efficiently on a multigram scale from inexpensive starting materials. NU-1000 has been reported as an excellent candidate for gas separation and catalysis. In particular, it is ideal for the catalytic deactivation of nerve agents and shows great promise as a new generic platform for a wide range of applications. Multiple post-synthetic modification protocols have been developed using NU-1000 as the parent material, making it a potentially useful scaffold for several catalytic applications. The procedure for the preparation of NU-1000 can be scaled up reliably and is suitable for the production of 50 grams of the requisite organic linker and ?? grams of NU-1000. The entire synthesis is performed without purification by column chromatography and can be completed within 10 days.

  11. Transferable Force Field for Metal-Organic Frameworks from First-Principles: BTW-FF.

    PubMed

    Bristow, Jessica K; Tiana, Davide; Walsh, Aron

    2014-10-14

    We present an ab-initio derived force field to describe the structural and mechanical properties of metal-organic frameworks (or coordination polymers). The aim is a transferable interatomic potential that can be applied to MOFs regardless of metal or ligand identity. The initial parametrization set includes MOF-5, IRMOF-10, IRMOF-14, UiO-66, UiO-67, and HKUST-1. The force field describes the periodic crystal and considers effective atomic charges based on topological analysis of the Bloch states of the extended materials. Transferable potentials were developed for the four organic ligands comprising the test set and for the associated Cu, Zn, and Zr metal nodes. The predicted materials properties, including bulk moduli and vibrational frequencies, are in agreement with explicit density functional theory calculations. The modal heat capacity and lattice thermal expansion are also predicted.

  12. Surface chemistry of metal-organic frameworks at the liquid-solid interface.

    PubMed

    Zacher, Denise; Schmid, Rochus; Wöll, Christof; Fischer, Roland A

    2011-01-03

    Metal-organic frameworks (MOFs) are a fascinating class of novel inorganic-organic hybrid materials. They are essentially based on classic coordination chemistry and hold much promise for unique applications ranging from gas storage and separation to chemical sensing, catalysis, and drug release. The evolution of the full innovative potential of MOFs, in particular for nanotechnology and device integration, however requires a fundamental understanding of the formation process of MOFs. Also necessary is the ability to control the growth of thin MOF films and the positioning of size- and shape-selected crystals as well as MOF heterostructures on a given surface in a well-defined and oriented fashion. MOFs are solid-state materials typically formed by solvothermal reactions and their crystallization from the liquid phase involves the surface chemistry of their building blocks. This Review brings together various key aspects of the surface chemistry of MOFs.

  13. The role of metal-organic frameworks in a carbon-neutral energy cycle

    NASA Astrophysics Data System (ADS)

    Schoedel, Alexander; Ji, Zhe; Yaghi, Omar M.

    2016-04-01

    Reducing society's reliance on fossil fuels presents one of the most pressing energy and environmental challenges facing our planet. Hydrogen, methane and carbon dioxide, which are some of the smallest and simplest molecules known, may lie at the centre of solving this problem through realization of a carbon-neutral energy cycle. Potentially, this could be achieved through the deployment of hydrogen as the fuel of the long term, methane as a transitional fuel, and carbon dioxide capture and sequestration as the urgent response to ongoing climate change. Here we detail strategies and technologies developed to overcome the difficulties encountered in the capture, storage, delivery and conversion of these gas molecules. In particular, we focus on metal-organic frameworks in which metal oxide ‘hubs’ are linked with organic ‘struts’ to make materials of ultrahigh porosity, which provide a basis for addressing this challenge through materials design on the molecular level.

  14. System and method for generating and/or screening potential metal-organic frameworks

    DOEpatents

    Wilmer, Christopher E; Leaf, Michael; Snurr, Randall Q; Farha, Omar K; Hupp, Joseph T

    2014-12-02

    A system and method for systematically generating potential metal-organic framework (MOFs) structures given an input library of building blocks is provided herein. One or more material properties of the potential MOFs are evaluated using computational simulations. A range of material properties (surface area, pore volume, pore size distribution, powder x-ray diffraction pattern, methane adsorption capability, and the like) can be estimated, and in doing so, illuminate unidentified structure-property relationships that may only have been recognized by taking a global view of MOF structures. In addition to identifying structure-property relationships, this systematic approach to identify the MOFs of interest is used to identify one or more MOFs that may be useful for high pressure methane storage.

  15. System and method for generating and/or screening potential metal-organic frameworks

    DOEpatents

    Wilmer, Christopher E; Leaf, Michael; Snurr, Randall Q; Farha, Omar K; Hupp, Joseph T

    2015-04-21

    A system and method for systematically generating potential metal-organic framework (MOFs) structures given an input library of building blocks is provided herein. One or more material properties of the potential MOFs are evaluated using computational simulations. A range of material properties (surface area, pore volume, pore size distribution, powder x-ray diffraction pattern, methane adsorption capability, and the like) can be estimated, and in doing so, illuminate unidentified structure-property relationships that may only have been recognized by taking a global view of MOF structures. In addition to identifying structure-property relationships, this systematic approach to identify the MOFs of interest is used to identify one or more MOFs that may be useful for high pressure methane storage.

  16. Predictive framework for shape-selective separations in three-dimensional zeolites and metal-organic frameworks.

    PubMed

    First, Eric L; Gounaris, Chrysanthos E; Floudas, Christodoulos A

    2013-05-07

    With the growing number of zeolites and metal-organic frameworks (MOFs) available, computational methods are needed to screen databases of structures to identify those most suitable for applications of interest. We have developed novel methods based on mathematical optimization to predict the shape selectivity of zeolites and MOFs in three dimensions by considering the energy costs of transport through possible pathways. Our approach is applied to databases of over 1800 microporous materials including zeolites, MOFs, zeolitic imidazolate frameworks, and hypothetical MOFs. New materials are identified for applications in gas separations (CO2/N2, CO2/CH4, and CO2/H2), air separation (O2/N2), and chemicals (propane/propylene, ethane/ethylene, styrene/ethylbenzene, and xylenes).

  17. Research Update: Mechanical properties of metal-organic frameworks - Influence of structure and chemical bonding

    NASA Astrophysics Data System (ADS)

    Li, Wei; Henke, Sebastian; Cheetham, Anthony K.

    2014-12-01

    Metal-organic frameworks (MOFs), a young family of functional materials, have been attracting considerable attention from the chemistry, materials science, and physics communities. In the light of their potential applications in industry and technology, the fundamental mechanical properties of MOFs, which are of critical importance for manufacturing, processing, and performance, need to be addressed and understood. It has been widely accepted that the framework topology, which describes the overall connectivity pattern of the MOF building units, is of vital importance for the mechanical properties. However, recent advances in the area of MOF mechanics reveal that chemistry plays a major role as well. From the viewpoint of materials science, a deep understanding of the influence of chemical effects on MOF mechanics is not only highly desirable for the development of novel functional materials with targeted mechanical response, but also for a better understanding of important properties such as structural flexibility and framework breathing. The present work discusses the intrinsic connection between chemical effects and the mechanical behavior of MOFs through a number of prototypical examples.

  18. Luminescent metal-organic framework films as highly sensitive and fast-response oxygen sensors.

    PubMed

    Dou, Zhongshang; Yu, Jiancan; Cui, Yuanjing; Yang, Yu; Wang, Zhiyu; Yang, Deren; Qian, Guodong

    2014-04-16

    Luminescent metal-organic framework films, CPM-5⊃Tb(3+) and MIL-100(In)⊃Tb(3+), have been constructed by postfunctionalization of two porous indium-organic frameworks with different structures, respectively. The MIL-100(In)⊃Tb(3+) film shows high oxygen sensitivity (KSV = 7.59) and short response/recovery time (6 s/53 s).

  19. Postsynthetic Modification of an Alkyne-Tagged Zirconium Metal-Organic Framework via a "Click" Reaction.

    PubMed

    Li, Bijian; Gui, Bo; Hu, Guiping; Yuan, Daqiang; Wang, Cheng

    2015-06-01

    Herein, we report the synthesis and postsynthetic modification of a novel alkyne-tagged zirconium metal-organic framework, UiO-68-alkyne. The alkynyl groups in the pore surface were subjected to a "click" reaction, achieving quantitative conversion and maintaining the crystallinity of the framework.

  20. Foldable interpenetrated metal-organic frameworks/carbon nanotubes thin film for lithium–sulfur batteries

    PubMed Central

    Mao, Yiyin; Li, Gaoran; Guo, Yi; Li, Zhoupeng; Liang, Chengdu; Peng, Xinsheng; Lin, Zhan

    2017-01-01

    Lithium–sulfur batteries are promising technologies for powering flexible devices due to their high energy density, low cost and environmental friendliness, when the insulating nature, shuttle effect and volume expansion of sulfur electrodes are well addressed. Here, we report a strategy of using foldable interpenetrated metal-organic frameworks/carbon nanotubes thin film for binder-free advanced lithium–sulfur batteries through a facile confinement conversion. The carbon nanotubes interpenetrate through the metal-organic frameworks crystal and interweave the electrode into a stratified structure to provide both conductivity and structural integrity, while the highly porous metal-organic frameworks endow the electrode with strong sulfur confinement to achieve good cyclability. These hierarchical porous interpenetrated three-dimensional conductive networks with well confined S8 lead to high sulfur loading and utilization, as well as high volumetric energy density. PMID:28262801

  1. Effect of organic substituents on the adsorption of carbon dioxide on a metal-organic framework

    NASA Astrophysics Data System (ADS)

    Thu Ha, Nguyen Thi; Lefedova, O. V.; Ha, Nguyen Ngoc

    2017-01-01

    The adsorption of carbon dioxide on the MOF-5 metal-organic framework and modifications of it obtained by replacing the hydrogen atoms in the organic ligands with electron donor (-CH3,-OCH3) or electron acceptor groups (-CN,-NO2) is investigated using the grand canonical Monte Carlo (GCMC) method and density functional theory (DFT). It is shown that the adsorption of carbon dioxide molecules on the structures of metal-organic frameworks is most likely on Zn4O clusters, and that the adsorption of carbon dioxide is of a physical nature. The presence of substituents-CH3,-OCH3,-CN in metal-organic frameworks increases their capacity to adsorb carbon dioxide, while that of nitro groups (-NO2) has the opposite effect.

  2. Foldable interpenetrated metal-organic frameworks/carbon nanotubes thin film for lithium-sulfur batteries

    NASA Astrophysics Data System (ADS)

    Mao, Yiyin; Li, Gaoran; Guo, Yi; Li, Zhoupeng; Liang, Chengdu; Peng, Xinsheng; Lin, Zhan

    2017-03-01

    Lithium-sulfur batteries are promising technologies for powering flexible devices due to their high energy density, low cost and environmental friendliness, when the insulating nature, shuttle effect and volume expansion of sulfur electrodes are well addressed. Here, we report a strategy of using foldable interpenetrated metal-organic frameworks/carbon nanotubes thin film for binder-free advanced lithium-sulfur batteries through a facile confinement conversion. The carbon nanotubes interpenetrate through the metal-organic frameworks crystal and interweave the electrode into a stratified structure to provide both conductivity and structural integrity, while the highly porous metal-organic frameworks endow the electrode with strong sulfur confinement to achieve good cyclability. These hierarchical porous interpenetrated three-dimensional conductive networks with well confined S8 lead to high sulfur loading and utilization, as well as high volumetric energy density.

  3. Structural Effects in Visible-Light-Responsive Metal-Organic Frameworks Incorporating ortho-Fluoroazobenzenes.

    PubMed

    Castellanos, Sonia; Goulet-Hanssens, Alexis; Zhao, Fangli; Dikhtiarenko, Alla; Pustovarenko, Alexey; Hecht, Stefan; Gascon, Jorge; Kapteijn, Freek; Bléger, David

    2016-01-11

    The ability to control the interplay of materials with low-energy photons is important as visible light offers several appealing features compared to ultraviolet radiation (less damaging, more selective, predominant in the solar spectrum, possibility to increase the penetration depth). Two different metal-organic frameworks (MOFs) were synthesized from the same linker bearing all-visible ortho-fluoroazobenzene photoswitches as pendant groups. The MOFs exhibit different architectures that strongly influence the ability of the azobenzenes to isomerize inside the voids. The framework built with Al-based nodes has congested 1D channels that preclude efficient isomerization. As a result, local light-heat conversion can be used to alter the CO2 adsorption capacity of the material on exposure to green light. The second framework, built with Zr nodes, provides enough room for the photoswitches to isomerize, which leads to a unique bistable photochromic MOF that readily responds to blue and green light. The superiority of green over UV irradiation was additionally demonstrated by reflectance spectroscopy and analysis of digested samples. This material offers promising perspectives for liquid-phase applications such as light-controlled catalysis and adsorptive separation.

  4. Positronium emission spectra from self-assembled metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Crivelli, P.; Cooke, D.; Barbiellini, B.; Brown, B. L.; Feldblyum, J. I.; Guo, P.; Gidley, D. W.; Gerchow, L.; Matzger, A. J.

    2014-06-01

    Results of positronium (Ps) emission into vacuum from self-assembled metal-organic frameworks (MOFs) are presented and discussed in detail. Four different MOF crystals are considered, namely, MOF-5, IRMOF-8, ZnO4(FMA)3, and IRMOF-20. The measurements reveal that a fraction of the Ps is emitted into vacuum with a distinctly smaller energy than what one would expect for Ps localized in the MOFs' cells. Only calculations considering the Ps delocalized in a Bloch state can reproduce the measured Ps emission energy providing a robust demonstration of wave function delocalization in quantum mechanics. We show how the Bloch state population can be controlled by tuning the initial positron beam energy. Therefore, Ps in MOFs can be used both to simulate the dynamics of delocalized excitations in materials and to probe the MOFs for their advanced characterization.

  5. A novel metal-organic framework for high storage and separation of acetylene at room temperature

    NASA Astrophysics Data System (ADS)

    Duan, Xing; Wang, Huizhen; Ji, Zhenguo; Cui, Yuanjing; Yang, Yu; Qian, Guodong

    2016-09-01

    A novel 3D microporous metal-organic framework with NbO topology, [Cu2(L)(H2O)2]•(DMF)6·(H2O)2 (ZJU-10, ZJU = Zhejiang University; H4L =2‧-hydroxy-[1,1‧:4‧,1″-terphenyl]-3,3″,5,5″-tetracarboxylic acid; DMF =N,N-dimethylformamide), has been synthesized and structurally characterized. With suitable pore sizes and open Cu2+ sites, ZJU-10a exhibits high BET surface area of 2392 m2/g, as well as moderately high C2H2 volumetric uptake capacity of 132 cm3/cm3. Meanwhile, ZJU-10a is a promising porous material for separation of acetylene from methane and carbon dioxide gas mixtures at room temperature.

  6. Cu₃(hexaiminotriphenylene)₂: an electrically conductive 2D metal-organic framework for chemiresistive sensing.

    PubMed

    Campbell, Michael G; Sheberla, Dennis; Liu, Sophie F; Swager, Timothy M; Dincă, Mircea

    2015-03-27

    The utility of metal-organic frameworks (MOFs) as functional materials in electronic devices has been limited to date by a lack of MOFs that display high electrical conductivity. Here, we report the synthesis of a new electrically conductive 2D MOF, Cu3(HITP)2 (HITP=2,3,6,7,10,11-hexaiminotriphenylene), which displays a bulk conductivity of 0.2 S cm(-1) (pellet, two-point-probe). Devices synthesized by simple drop casting of Cu3(HITP)2 dispersions function as reversible chemiresistive sensors, capable of detecting sub-ppm levels of ammonia vapor. Comparison with the isostructural 2D MOF Ni3(HITP)2 shows that the copper sites are critical for ammonia sensing, indicating that rational design/synthesis can be used to tune the functional properties of conductive MOFs.

  7. Condensation of Methane in the Metal-Organic Framework IRMOF-1: Evidence for Two Critical Points.

    PubMed

    Höft, Nicolas; Horbach, Jürgen

    2015-08-19

    Extensive grand canonical Monte Carlo simulations in combination with successive umbrella sampling are used to investigate the condensation of methane in the nanoporous crystalline material IRMOF-1. Two different types of novel condensation transitions are found, each of them ending in a critical point: (i) a fluid-fluid transition at higher densities (the analog of the liquid-gas transition in the bulk) and (ii) a phase transition at low densities on the surface of the IRMOF-1 structure. The nature of these transitions is different from the usual capillary condensation in thin films and cylindrical pores where the coexisting phases are confined in one or two of the three spatial dimensions. In contrast to that, in IRMOF-1 the different phases can be described as bulk phases that are inhomogeneous due to the presence of the metal-organic framework. As a consequence, the condensation transitions in IRMOF-1 belong to the three-dimensional (3D) Ising universality class.

  8. Cross coupling between electric and magnetic orders in a multiferroic metal-organic framework

    PubMed Central

    Tian, Ying; Stroppa, Alessandro; Chai, Yisheng; Yan, Liqin; Wang, Shouguo; Barone, Paolo; Picozzi, Silvia; Sun, Young

    2014-01-01

    The coexistence of both electric and magnetic orders in some metal-organic frameworks (MOFs) has yielded a new class of multiferroics beyond inorganic materials. However, the coupling between two orders in multiferroic MOFs has not been convincingly verified yet. Here we present clear experimental evidences of cross coupling between electric and magnetic orders in a multiferroic MOF [(CH3)2NH2]Fe(HCOO)3 with a perovskite structure. The dielelectric constant exhibit a hump just at the magnetic ordering temperature TN. Moreover, both the direct (magnetic field control of dielectric properties) and converse (electric field control of magnetization) magnetoelectric effects have been observed in the multiferroic state. This work opens up new insights on the origin of ferroelectricity in MOFs and highlights their promise as magnetoelectric multiferroics. PMID:25317819

  9. Characterization of Adsorption Enthalpy of Novel Water-Stable Zeolites and Metal-Organic Frameworks.

    PubMed

    Kim, Hyunho; Cho, H Jeremy; Narayanan, Shankar; Yang, Sungwoo; Furukawa, Hiroyasu; Schiffres, Scott; Li, Xiansen; Zhang, Yue-Biao; Jiang, Juncong; Yaghi, Omar M; Wang, Evelyn N

    2016-01-22

    Water adsorption is becoming increasingly important for many applications including thermal energy storage, desalination, and water harvesting. To develop such applications, it is essential to understand both adsorbent-adsorbate and adsorbate-adsorbate interactions, and also the energy required for adsorption/desorption processes of porous material-adsorbate systems, such as zeolites and metal-organic frameworks (MOFs). In this study, we present a technique to characterize the enthalpy of adsorption/desorption of zeolites and MOF-801 with water as an adsorbate by conducting desorption experiments with conventional differential scanning calorimetry (DSC) and thermogravimetric analyzer (TGA). With this method, the enthalpies of adsorption of previously uncharacterized adsorbents were estimated as a function of both uptake and temperature. Our characterizations indicate that the adsorption enthalpies of type I zeolites can increase to greater than twice the latent heat whereas adsorption enthalpies of MOF-801 are nearly constant for a wide range of vapor uptakes.

  10. Characterization of Adsorption Enthalpy of Novel Water-Stable Zeolites and Metal-Organic Frameworks

    NASA Astrophysics Data System (ADS)

    Kim, Hyunho; Cho, H. Jeremy; Narayanan, Shankar; Yang, Sungwoo; Furukawa, Hiroyasu; Schiffres, Scott; Li, Xiansen; Zhang, Yue-Biao; Jiang, Juncong; Yaghi, Omar M.; Wang, Evelyn N.

    2016-01-01

    Water adsorption is becoming increasingly important for many applications including thermal energy storage, desalination, and water harvesting. To develop such applications, it is essential to understand both adsorbent-adsorbate and adsorbate-adsorbate interactions, and also the energy required for adsorption/desorption processes of porous material-adsorbate systems, such as zeolites and metal-organic frameworks (MOFs). In this study, we present a technique to characterize the enthalpy of adsorption/desorption of zeolites and MOF-801 with water as an adsorbate by conducting desorption experiments with conventional differential scanning calorimetry (DSC) and thermogravimetric analyzer (TGA). With this method, the enthalpies of adsorption of previously uncharacterized adsorbents were estimated as a function of both uptake and temperature. Our characterizations indicate that the adsorption enthalpies of type I zeolites can increase to greater than twice the latent heat whereas adsorption enthalpies of MOF-801 are nearly constant for a wide range of vapor uptakes.

  11. Gas storage in porous metal-organic frameworks for clean energy applications.

    PubMed

    Ma, Shengqian; Zhou, Hong-Cai

    2010-01-07

    Depletion of fossil oil deposits and the escalating threat of global warming have put clean energy research, which includes the search for clean energy carriers such as hydrogen and methane as well as the reduction of carbon dioxide emissions, on the urgent agenda. A significant technical challenge has been recognized as the development of a viable method to efficiently trap hydrogen, methane and carbon dioxide gas molecules in a confined space for various applications. This issue can be addressed by employing highly porous materials as storage media, and porous metal-organic frameworks (MOFs) which have exceptionally high surface areas as well as chemically-tunable structures are playing an unusual role in this respect. In this feature article we provide an overview of the current status of clean energy applications of porous MOFs, including hydrogen storage, methane storage and carbon dioxide capture.

  12. Nanoporous designer solids with huge lattice constant gradients: multiheteroepitaxy of metal-organic frameworks.

    PubMed

    Wang, Zhengbang; Liu, Jinxuan; Lukose, Binit; Gu, Zhigang; Weidler, Peter G; Gliemann, Hartmut; Heine, Thomas; Wöll, Christof

    2014-03-12

    We demonstrate the realization of hierarchically organized MOF (metal-organic framework) multilayer systems with pronounced differences in the size of the nanoscale pores. Unusually large values for the lattice constant mismatch at the MOF-MOF heterojunctions are made possible by a particular liquid-phase epitaxy process. The multiheteroepitaxy is demonstrated for the isoreticular SURMOF-2 series [ Liu et al. Sci. Rep. 2012 , 2 , 921 ] by fabricating trilayer systems with lattice constants of 1.12, 1.34, and 1.55 nm. Despite these large (20%) lattice mismatches, highly crystalline, oriented multilayers were obtained. A thorough theoretical analysis of the MOF-on-MOF heterojunction structure and energetics allows us to identify the two main reasons for this unexpected tolerance of large lattice mismatch: the healing of vacancies with acetate groups and the low elastic constant of MOF materials.

  13. Synthesis and structure of new carbohydrate metal-organic frameworks and inclusion complexes

    NASA Astrophysics Data System (ADS)

    Sha, Jing-Quan; Wu, Lian-He; Li, Shu-Xian; Yang, Xiao-Ning; Zhang, Yu; Zhang, Qian-Nan; Zhu, Pei-Pei

    2015-12-01

    Two new metal-organic framework compounds based on natural β-cyclodextrin molecules (β-CD) and alkali metals (Na+/K+) were synthesized and characterized by elemental analyses, IR, XPRD and 1HNMR. Single-crystal X-ray diffraction analysis reveals that compounds 1 and 2 possess the bowl-like pore and the "8" type double channels configuration. Due to the [blow + channel] double configuration, 5-Fluorouracil (5-FU) and Quercetin inclusion complexes of compound 1 are studied, and the results show that the two kinds of drug with different structure and size can be included into the compound at the same time, which is expected to become a new type of multi-functional green crystalline solid material.

  14. Computational Design of Metal-Organic Frameworks with High Methane Deliverable Capacity

    NASA Astrophysics Data System (ADS)

    Bao, Yi; Martin, Richard; Simon, Cory; Haranczyk, Maciej; Smit, Berend; Deem, Michael; Deem Team; Haranczyk Team; Smit Team

    Metal-organic frameworks (MOFs) are a rapidly emerging class of nanoporous materials with largely tunable chemistry and diverse applications in gas storage, gas purification, catalysis, etc. Intensive efforts are being made to develop new MOFs with desirable properties both experimentally and computationally in the past decades. To guide experimental synthesis with limited throughput, we develop a computational methodology to explore MOFs with high methane deliverable capacity. This de novo design procedure applies known chemical reactions, considers synthesizability and geometric requirements of organic linkers, and evolves a population of MOFs with desirable property efficiently. We identify about 500 MOFs with higher deliverable capacity than MOF-5 in 10 networks. We also investigate the relationship between deliverable capacity and internal surface area of MOFs. This methodology can be extended to MOFs with multiple types of linkers and multiple SBUs. DE-FG02- 12ER16362.

  15. Modulation by Amino Acids: Toward Superior Control in the Synthesis of Zirconium Metal-Organic Frameworks.

    PubMed

    Gutov, Oleksii V; Molina, Sonia; Escudero-Adán, Eduardo C; Shafir, Alexandr

    2016-09-12

    The synthesis of zirconium metal-organic frameworks (Zr MOFs) modulated by various amino acids, including l-proline, glycine, and l-phenylalanine, is shown to be a straightforward approach toward functional-group incorporation and particle-size control. High yields in Zr-MOF synthesis are achieved by employing 5 equivalents of the modulator at 120 °C. At lower temperatures, the method provides a series of Zr MOFs with increased particle size, including many suitable for single-crystal X-ray diffraction studies. Furthermore, amino acid modulators can be incorporated at defect sites in Zr MOFs with an amino acid/ligand ratio of up to 1:1, depending on the ligand structure and reaction conditions. The MOFs obtained through amino acid modulation exhibit an improved CO2 -capture capacity relative to nonfunctionalized materials.

  16. Characterization of Adsorption Enthalpy of Novel Water-Stable Zeolites and Metal-Organic Frameworks

    PubMed Central

    Kim, Hyunho; Cho, H. Jeremy; Narayanan, Shankar; Yang, Sungwoo; Furukawa, Hiroyasu; Schiffres, Scott; Li, Xiansen; Zhang, Yue-Biao; Jiang, Juncong; Yaghi, Omar M.; Wang, Evelyn N.

    2016-01-01

    Water adsorption is becoming increasingly important for many applications including thermal energy storage, desalination, and water harvesting. To develop such applications, it is essential to understand both adsorbent-adsorbate and adsorbate-adsorbate interactions, and also the energy required for adsorption/desorption processes of porous material-adsorbate systems, such as zeolites and metal-organic frameworks (MOFs). In this study, we present a technique to characterize the enthalpy of adsorption/desorption of zeolites and MOF-801 with water as an adsorbate by conducting desorption experiments with conventional differential scanning calorimetry (DSC) and thermogravimetric analyzer (TGA). With this method, the enthalpies of adsorption of previously uncharacterized adsorbents were estimated as a function of both uptake and temperature. Our characterizations indicate that the adsorption enthalpies of type I zeolites can increase to greater than twice the latent heat whereas adsorption enthalpies of MOF-801 are nearly constant for a wide range of vapor uptakes. PMID:26796523

  17. Composite Membranes for CO2 Capture: High Performance Metal Organic Frameworks/Polymer Composite Membranes for Carbon Dioxide Capture

    SciTech Connect

    2010-07-01

    IMPACCT Project: A team of six faculty members at Georgia Tech are developing an enhanced membrane by fitting metal organic frameworks, compounds that show great promise for improved carbon capture, into hollow fiber membranes. This new material would be highly efficient at removing CO2 from the flue gas produced at coal-fired power plants. The team is analyzing thousands of metal organic frameworks to identify those that are most suitable for carbon capture based both on their ability to allow coal exhaust to pass easily through them and their ability to select CO2 from that exhaust for capture and storage. The most suitable frameworks would be inserted into the walls of the hollow fiber membranes, making the technology readily scalable due to their high surface area. This composite membrane would be highly stable, withstanding the harsh gas environment found in coal exhaust.

  18. Tunable electrical conductivity in metal-organic framework thin film devices

    SciTech Connect

    Talin, Albert Alec; Allendorf, Mark D.; Stavila, Vitalie; Leonard, Francois

    2016-05-24

    A composition including a porous metal organic framework (MOF) including an open metal site and a guest species capable of charge transfer that can coordinate with the open metal site, wherein the composition is electrically conductive. A method including infiltrating a porous metal organic framework (MOF) including an open metal site with a guest species that is capable of charge transfer; and coordinating the guest species to the open metal site to form a composition including an electrical conductivity greater than an electrical conductivity of the MOF.

  19. Multirate delivery of multiple therapeutic agents from metal-organic frameworks

    SciTech Connect

    McKinlay, Alistair C.; Allan, Phoebe K.; Renouf, Catherine L.; Duncan, Morven J.; Wheatley, Paul S.; Warrender, Stewart J.; Dawson, Daniel; Ashbrook, Sharon E.; Gil, Barbara; Marszalek, Bartosz; Düren, Tina; Williams, Jennifer J.; Charrier, Cedric; Mercer, Derry K.; Teat, Simon J.; Morris, Russell E.

    2014-12-01

    The highly porous nature of metal-organic frameworks (MOFs) offers great potential for the delivery of therapeutic agents. Here, we show that highly porous metal-organic frameworks can be used to deliver multiple therapeutic agents—a biologically active gas, an antibiotic drug molecule, and an active metal ion—simultaneously but at different rates. The possibilities offered by delivery of multiple agents with different mechanisms of action and, in particular, variable timescales may allow new therapy approaches. Here, we show that the loaded MOFs are highly active against various strains of bacteria.

  20. Alkylamine-tethered stable metal-organic framework for CO(2) capture from flue gas.

    PubMed

    Hu, Yingli; Verdegaal, Wolfgang M; Yu, Shu-Hong; Jiang, Hai-Long

    2014-03-01

    Different alkylamine molecules were post-synthetically tethered to the unsaturated Cr(III) centers in the metal-organic framework MIL-101. The resultant metal-organic frameworks show almost no N2 adsorption with significantly enhanced CO2 capture under ambient conditions as a result of the interaction between amine groups and CO2 molecules. Given the extraordinary stability, high CO2 uptake, ultrahigh CO2 /N2 selectivity, and mild regeneration energy, MIL-101-diethylenetriamine holds exceptional promise for post-combustion CO2 capture and CO2 /N2 separation.

  1. Tunable electrical conductivity in metal-organic framework thin film devices

    SciTech Connect

    Talin, Albert Alec; Allendorf, Mark D.; Stavila, Vitalie; Leonard, Francois

    2016-08-30

    A composition including a porous metal organic framework (MOF) including an open metal site and a guest species capable of charge transfer that can coordinate with the open metal site, wherein the composition is electrically conductive. A method including infiltrating a porous metal organic framework (MOF) including an open metal site with a guest species that is capable of charge transfer; and coordinating the guest species to the open metal site to form a composition including an electrical conductivity greater than an electrical conductivity of the MOF.

  2. Selective Catalysis in Nanoparticle Metal-Organic Framework Composites

    NASA Astrophysics Data System (ADS)

    Stephenson, Casey Justin

    The design of highly selective catalysts are becoming increasingly important, especially as chemical and pharmaceutical industries seek to improve atom economy and minimize energy intensive separations that are often required to separate side products from the desired product. Enzymes are among the most selective of all catalysts, generally operating through molecular recognition whereby an active site analogous to a lock and the substrate is analogous to a key. The assembly of a porous, crystalline material around a catalytically active metal particle could serve as an artificial enzyme. In this vein, we first synthesized the polyvinylpyrrolidone (PVP) coated nanoparticles of interest and then encapsulated them within zeolitic imidazolate framework 8 or ZIF-8. 2.8 nm Pt-PVP nanoparticles, which were encapsulated within ZIF-8 to form Pt ZIF-8 composite. Pt ZIF-8 was inactive for the hydrogenation of cyclic olefins such as cis-cyclooctene and cis-cyclohexene while the composite proved to be a highly selective catalyst for the hydrogenation of terminal olefins, hydrogenating trans-1,3-hexadiene to 3-hexene in 95% selectivity after 24 hours under 1 bar H2. We extended our encapsulation method to sub-2 nm Au nanoparticles to form Au ZIF-8. Au ZIF-8 served as a highly chemoselective catalyst for the hydrogenation of crotonaldehyde an alpha,beta-unsaturated aldehyde, to crotyl alcohol an alpha,beta-unsaturated alcohol, in 90-95% selectivity. In order to investigate nanoparticle size effects on selectivity, 6-10 nm Au nanoparticles were encapsulated within ZIF-8 to form Au6 ZIF-8. Control catalysts with nanoparticles supported on the surface of ZIF-8 were synthesized as well, Au/ZIF-8 and Au6/ZIF-8. Au6 ZIF-8 hydrogenated crotonaldehyde in 85% selectivity towards the unsaturated alcohol. Catalysts with nanoparticles supported on the exterior of ZIF-8 were far less selective towards the unsaturated alcohol. Post-catalysis transmission electron microscopy analysis of Au ZIF

  3. Functionalization of Metal-Organic Frameworks for Enhanced Stability under Humid Carbon Dioxide Capture Conditions.

    PubMed

    Andirova, Dinara; Lei, Yu; Zhao, Xiaodan; Choi, Sunho

    2015-10-26

    Metal-organic frameworks (MOFs) have been highlighted recently as promising materials for CO2 capture. However, in practical CO2 capture processes, such as capture from flue gas or ambient air, the adsorption properties of MOFs tend to be harmed by the presence of moisture possibly because of the hydrophilic nature of the coordinatively unsaturated sites (CUSs) within their framework. In this work, the CUSs of the MOF framework are functionalized with amine-containing molecules to prevent structural degradation in a humid environment. Specifically, the framework of the magnesium dioxybenzenedicarboxylate (Mg/DOBDC) MOF was functionalized with ethylenediamine (ED) molecules to make the overall structure less hydrophilic. Structural analysis after exposure to high-temperature steam showed that the ED-functionalized Mg/DOBDC (ED-Mg/DOBDC) is more stable under humid conditions, than Mg/DOBDC, which underwent drastic structural changes. ED-Mg/DOBDC recovered its CO2 adsorption capacity and initial adsorption rate quite well as opposed to the original Mg/DOBDC, which revealed a significant reduction in its capture capacity and kinetics. These results suggest that the amine-functionalization of the CUSs is an effective way to enhance the structural stability of MOFs as well as their capture of humid CO2 .

  4. High performance hydrogen storage from Be-BTB metal-organic framework at room temperature.

    PubMed

    Lim, Wei-Xian; Thornton, Aaron W; Hill, Anita J; Cox, Barry J; Hill, James M; Hill, Matthew R

    2013-07-09

    The metal-organic framework beryllium benzene tribenzoate (Be-BTB) has recently been reported to have one of the highest gravimetric hydrogen uptakes at room temperature. Storage at room temperature is one of the key requirements for the practical viability of hydrogen-powered vehicles. Be-BTB has an exceptional 298 K storage capacity of 2.3 wt % hydrogen. This result is surprising given that the low adsorption enthalpy of 5.5 kJ mol(-1). In this work, a combination of atomistic simulation and continuum modeling reveals that the beryllium rings contribute strongly to the hydrogen interaction with the framework. These simulations are extended with a thermodynamic energy optimization (TEO) model to compare the performance of Be-BTB to a compressed H2 tank and benchmark materials MOF-5 and MOF-177 in a MOF-based fuel cell. Our investigation shows that none of the MOF-filled tanks satisfy the United States Department of Energy (DOE) storage targets within the required operating temperatures and pressures. However, the Be-BTB tank delivers the most energy per volume and mass compared to the other material-based storage tanks. The pore size and the framework mass are shown to be contributing factors responsible for the superior room temperature hydrogen adsorption of Be-BTB.

  5. Metal-organic framework templated synthesis of Fe2O3/TiO2 nanocomposite for hydrogen production.

    PubMed

    deKrafft, Kathryn E; Wang, Cheng; Lin, Wenbin

    2012-04-17

    A new metal-organic framework (MOF)-templated method has been developed for the synthesis of a metal oxide nanocomposite with interesting photophysical properties. Fe-containing nanoscale MOFs are coated with amorphous titania, then calcined to produce crystalline Fe(2)O(3)/TiO(2) composite nanoparticles. This material enables photocatalytic hydrogen production from water using visible light, which cannot be achieved by either Fe(2)O(3) or TiO(2) alone or a mixture of the two.

  6. Protecting group and switchable pore-discriminating adsorption properties of a hydrophilic-hydrophobic metal-organic framework.

    PubMed

    Mohideen, M Infas H; Xiao, Bo; Wheatley, Paul S; McKinlay, Alistair C; Li, Yang; Slawin, Alexandra M Z; Aldous, David W; Cessford, Naomi F; Düren, Tina; Zhao, Xuebo; Gill, Rachel; Thomas, K Mark; Griffin, John M; Ashbrook, Sharon E; Morris, Russell E

    2011-04-01

    Formed by linking metals or metal clusters through organic linkers, metal-organic frameworks are a class of solids with structural and chemical properties that mark them out as candidates for many emerging gas storage, separation, catalysis and biomedical applications. Important features of these materials include their high porosity and their flexibility in response to chemical or physical stimuli. Here, a copper-based metal-organic framework has been prepared in which the starting linker (benzene-1,3,5-tricarboxylic acid) undergoes selective monoesterification during synthesis to produce a solid with two different channel systems, lined by hydrophilic and hydrophobic surfaces, respectively. The material reacts differently to gases or vapours of dissimilar chemistry, some stimulating subtle framework flexibility or showing kinetic adsorption effects. Adsorption can be switched between the two channels by judicious choice of the conditions. The monoesterified linker is recoverable in quantitative yield, demonstrating possible uses of metal-organic frameworks in molecular synthetic chemistry as 'protecting groups' to accomplish selective transformations that are difficult using standard chemistry techniques.

  7. Protecting group and switchable pore-discriminating adsorption properties of a hydrophilic-hydrophobic metal-organic framework

    NASA Astrophysics Data System (ADS)

    Mohideen, M. Infas H.; Xiao, Bo; Wheatley, Paul S.; McKinlay, Alistair C.; Li, Yang; Slawin, Alexandra M. Z.; Aldous, David W.; Cessford, Naomi F.; Düren, Tina; Zhao, Xuebo; Gill, Rachel; Thomas, K. Mark; Griffin, John M.; Ashbrook, Sharon E.; Morris, Russell E.

    2011-04-01

    Formed by linking metals or metal clusters through organic linkers, metal-organic frameworks are a class of solids with structural and chemical properties that mark them out as candidates for many emerging gas storage, separation, catalysis and biomedical applications. Important features of these materials include their high porosity and their flexibility in response to chemical or physical stimuli. Here, a copper-based metal-organic framework has been prepared in which the starting linker (benzene-1,3,5-tricarboxylic acid) undergoes selective monoesterification during synthesis to produce a solid with two different channel systems, lined by hydrophilic and hydrophobic surfaces, respectively. The material reacts differently to gases or vapours of dissimilar chemistry, some stimulating subtle framework flexibility or showing kinetic adsorption effects. Adsorption can be switched between the two channels by judicious choice of the conditions. The monoesterified linker is recoverable in quantitative yield, demonstrating possible uses of metal-organic frameworks in molecular synthetic chemistry as ‘protecting groups’ to accomplish selective transformations that are difficult using standard chemistry techniques.

  8. Tuning the Adsorption-Induced Phase Change in the Flexible Metal-Organic Framework Co(bdp).

    PubMed

    Taylor, Mercedes K; Runčevski, Tomče; Oktawiec, Julia; Gonzalez, Miguel I; Siegelman, Rebecca L; Mason, Jarad A; Ye, Jinxing; Brown, Craig M; Long, Jeffrey R

    2016-11-16

    Metal-organic frameworks that flex to undergo structural phase changes upon gas adsorption are promising materials for gas storage and separations, and achieving synthetic control over the pressure at which these changes occur is crucial to the design of such materials for specific applications. To this end, a new family of materials based on the flexible metal-organic framework Co(bdp) (bdp(2-) = 1,4-benzenedipyrazolate) has been prepared via the introduction of fluorine, deuterium, and methyl functional groups on the bdp(2-) ligand, namely, Co(F-bdp), Co(p-F2-bdp), Co(o-F2-bdp), Co(D4-bdp), and Co(p-Me2-bdp). These frameworks are isoreticular to the parent framework and exhibit similar structural flexibility, transitioning from a low-porosity, collapsed phase to high-porosity, expanded phases with increasing gas pressure. Powder X-ray diffraction studies reveal that fluorination of the aryl ring disrupts edge-to-face π-π interactions, which work to stabilize the collapsed phase at low gas pressures, while deuteration preserves these interactions and methylation strengthens them. In agreement with these observations, high-pressure CH4 adsorption isotherms show that the pressure of the CH4-induced framework expansion can be systematically controlled by ligand functionalization, as materials without edge-to-face interactions in the collapsed phase expand at lower CH4 pressures, while frameworks with strengthened edge-to-face interactions expand at higher pressures. Importantly, this work puts forth a general design strategy relevant to many other families of flexible metal-organic frameworks, which will be a powerful tool in optimizing these phase-change materials for industrial applications.

  9. Methane storage in flexible metal-organic frameworks with intrinsic thermal management

    NASA Astrophysics Data System (ADS)

    Mason, Jarad A.; Oktawiec, Julia; Taylor, Mercedes K.; Hudson, Matthew R.; Rodriguez, Julien; Bachman, Jonathan E.; Gonzalez, Miguel I.; Cervellino, Antonio; Guagliardi, Antonietta; Brown, Craig M.; Llewellyn, Philip L.; Masciocchi, Norberto; Long, Jeffrey R.

    2015-11-01

    As a cleaner, cheaper, and more globally evenly distributed fuel, natural gas has considerable environmental, economic, and political advantages over petroleum as a source of energy for the transportation sector. Despite these benefits, its low volumetric energy density at ambient temperature and pressure presents substantial challenges, particularly for light-duty vehicles with little space available for on-board fuel storage. Adsorbed natural gas systems have the potential to store high densities of methane (CH4, the principal component of natural gas) within a porous material at ambient temperature and moderate pressures. Although activated carbons, zeolites, and metal-organic frameworks have been investigated extensively for CH4 storage, there are practical challenges involved in designing systems with high capacities and in managing the thermal fluctuations associated with adsorbing and desorbing gas from the adsorbent. Here, we use a reversible phase transition in a metal-organic framework to maximize the deliverable capacity of CH4 while also providing internal heat management during adsorption and desorption. In particular, the flexible compounds Fe(bdp) and Co(bdp) (bdp2- = 1,4-benzenedipyrazolate) are shown to undergo a structural phase transition in response to specific CH4 pressures, resulting in adsorption and desorption isotherms that feature a sharp ‘step’. Such behaviour enables greater storage capacities than have been achieved for classical adsorbents, while also reducing the amount of heat released during adsorption and the impact of cooling during desorption. The pressure and energy associated with the phase transition can be tuned either chemically or by application of mechanical pressure.

  10. Methane storage in flexible metal-organic frameworks with intrinsic thermal management.

    PubMed

    Mason, Jarad A; Oktawiec, Julia; Taylor, Mercedes K; Hudson, Matthew R; Rodriguez, Julien; Bachman, Jonathan E; Gonzalez, Miguel I; Cervellino, Antonio; Guagliardi, Antonietta; Brown, Craig M; Llewellyn, Philip L; Masciocchi, Norberto; Long, Jeffrey R

    2015-11-19

    As a cleaner, cheaper, and more globally evenly distributed fuel, natural gas has considerable environmental, economic, and political advantages over petroleum as a source of energy for the transportation sector. Despite these benefits, its low volumetric energy density at ambient temperature and pressure presents substantial challenges, particularly for light-duty vehicles with little space available for on-board fuel storage. Adsorbed natural gas systems have the potential to store high densities of methane (CH4, the principal component of natural gas) within a porous material at ambient temperature and moderate pressures. Although activated carbons, zeolites, and metal-organic frameworks have been investigated extensively for CH4 storage, there are practical challenges involved in designing systems with high capacities and in managing the thermal fluctuations associated with adsorbing and desorbing gas from the adsorbent. Here, we use a reversible phase transition in a metal-organic framework to maximize the deliverable capacity of CH4 while also providing internal heat management during adsorption and desorption. In particular, the flexible compounds Fe(bdp) and Co(bdp) (bdp(2-) = 1,4-benzenedipyrazolate) are shown to undergo a structural phase transition in response to specific CH4 pressures, resulting in adsorption and desorption isotherms that feature a sharp 'step'. Such behaviour enables greater storage capacities than have been achieved for classical adsorbents, while also reducing the amount of heat released during adsorption and the impact of cooling during desorption. The pressure and energy associated with the phase transition can be tuned either chemically or by application of mechanical pressure.

  11. Upconversion fluorescence metal-organic frameworks thermo-sensitive imprinted polymer for enrichment and sensing protein.

    PubMed

    Guo, Ting; Deng, Qiliang; Fang, Guozhen; Gu, Dahai; Yang, Yukun; Wang, Shuo

    2016-05-15

    A novel fluorescence material with thermo-sensitive for the enrichment and sensing of protein was successfully prepared by combining molecular imprinting technology with upconversion nanoparticles (UCNPs) and metal-organic frameworks (MOFs). Herein, the UCNPs acted as signal reporter for composite materials because of its excellent fluorescence property and chemical stability. MOFs were introduced to molecularly imprinted polymer (MIP) due to its high specific surface area which increases the rate of mass transfer relative to that of traditional bulk MIP. The thermo-sensitive imprinted material which allows for swelling and shrinking with response to temperature changes was prepared by choosing Bovine hemoglobin (BHB) as the template, N-isopropyl acrylamide (NIPAAM) as the temperature-sensitive functional monomer and N,N-methylenebisacrylamide (MBA) as the cross-linker. The recognition characterizations of imprinted material-coated UCNPs/MOFs (UCNPs/MOFs/MIP) were evaluated, and the results showed that the fluorescence intensity of UCNPs/MOFs/MIP reduced gradually with the increase of BHB concentration. The fluorescence material was response to the temperature. The adsorption capacity was as much as 167.6 mg/g at 28°C and 101.2mg/g at 44°C, which was higher than that of traditional MIP. Therefore, this new fluorescence material for enrichment and sensing protein is very promising for future applications.

  12. Structuring of metal-organic frameworks at the mesoscopic/macroscopic scale.

    PubMed

    Furukawa, Shuhei; Reboul, Julien; Diring, Stéphane; Sumida, Kenji; Kitagawa, Susumu

    2014-08-21

    The assembly of metal ions with organic ligands through the formation of coordination bonds gives crystalline framework materials, known as metal-organic frameworks (MOFs), which recently emerged as a new class of porous materials. Besides the structural designability of MOFs at the molecular length scale, the researchers in this field very recently made important advances in creating more complex architectures at the mesoscopic/macroscopic scale, in which MOF nanocrystals are used as building units to construct higher-order superstructures. The structuring of MOFs in such a hierarchical order certainly opens a new opportunity to improve the material performance via design of the physical form rather than altering the chemical component. This review highlights these superstructures and their applications by categorizing them into four dimensionalities, zero-dimensional (0D), one-dimensional (1D), two-dimensional (2D), and three-dimensional (3D) superstructures. Because the key issue for structuring of MOFs is to spatially control the nucleation process in desired locations, this review conceptually categorizes the available synthetic methodologies from the viewpoint of the reaction system.

  13. Incorporation of Molecular Catalysts in Metal-Organic Frameworks for Highly Efficient Heterogeneous Catalysis.

    PubMed

    Wu, Chuan-De; Zhao, Min

    2017-03-03

    Porous metal-organic frameworks (MOFs) are built from periodically alternate organic moieties and metal ions/clusters. The unique features of the open framework structures, the high surface areas, the permanent porosity, and the appropriate hydrophilic and hydrophobic pore nature mean that MOF materials are a class of ideal host matrices for immobilization of molecular catalysts. The emerging porous materials can not only retain but are also able to enhance the catalytic functions of the single individuals. MOF catalysts have the following super characters: i) uniformly dispersed catalytic sites on the pore surfaces to improve the utility, ii) appropriate hydrophilic and hydrophobic pore nature to facilitate the recognition and transportation of reactant and product molecules, iii) a collaborative microenvironment to realize synergistic catalysis, and iv) simple separation and recovery for long-term usage. Accompanying the development of the synthetic strategies and the technologies for the characterization of MOF materials, MOF catalysis has undergone an upsurge, which has transcended the stage of opportunism. Here, the rational design and synthesis of MOF catalysts are discussed, along with the key factors of active sites, microenvironments, and transmission channels that lead to the distinct catalytic properties of MOF catalysts.

  14. Aqueous phase sensing of cyanide ions using a hydrolytically stable metal-organic framework.

    PubMed

    Karmakar, Avishek; Joarder, Biplab; Mallick, Abhik; Samanta, Partha; Desai, Aamod V; Basu, Sudipta; Ghosh, Sujit K

    2017-01-19

    A pure aqueous phase recognition and corresponding detoxification of highly toxic cyanide ions has been achieved by a fluorescent metal-organic framework (MOF). The cyanide detoxification has been shown to be effective even in in vitro studies and the MOF could be recycled to show the same efficiency of detoxification.

  15. A microporous metal-organic framework with polarized trifluoromethyl groups for high methane storage.

    PubMed

    Chang, Ganggang; Li, Bin; Wang, Hailong; Bao, Zongbi; Yildirim, Taner; Yao, Zizhu; Xiang, Shengchang; Zhou, Wei; Chen, Banglin

    2015-10-11

    A novel NbO-type metal-organic framework UTSA-88a with polarized trifluoromethyl groups exhibits a notably high methane storage capacity of 248 cm(3) (STP) cm(-3) (at room temperature and 65 bar) and a working capacity of 185 cm(3) (STP) cm(-3).

  16. Polydopamine tethered enzyme/metal-organic framework composites with high stability and reusability.

    PubMed

    Wu, Xiaoling; Yang, Cheng; Ge, Jun; Liu, Zheng

    2015-12-07

    An enzyme/metal-organic framework (MOF) composite with both highly stable and easily reusable features was prepared via tethering enzyme/MOF nanocrystals with polydopamine (PDA). The micrometer-sized PDA tethered enzyme/MOF composite can be easily repeatedly used without obvious activity loss, promising for efficient enzymatic catalysis at low cost with long-term operational stability under harsh conditions.

  17. Enantiopure anion templated synthesis of a zeolitic metal-organic framework.

    PubMed

    Xu, Zhong-Xuan; Ma, Yu-Lu; Zhang, Jian

    2016-01-31

    Utilizing (R)-H3CIA as a chiral template, an unprecedented homochiral metal-organic framework (MOF) with zeotype GIS topology is obtained from achiral 1.4-DIB ligands and Zn(II) ions, which opens up a feasible approach to create zeolitic MOFs with homochirality.

  18. Unusual parallel and inclined interlocking modes in polyrotaxane-like metal-organic frameworks.

    PubMed

    Yang, Jin; Ma, Jian-Fang; Batten, Stuart R; Su, Zhong-Min

    2008-05-21

    We describe here two unusual polyrotaxane-like metal-organic frameworks of [Co2(1,3-bix)2(bpea)2] and [Cd4(1,4-bix)4(bpea)4] x 4H2O , where both species contain loops and rods that are interlaced in a highly rare "parallel" fashion in , but, uniquely, in an "inclined" fashion in .

  19. Lipase-supported metal-organic framework bioreactor catalyzes warfarin synthesis.

    PubMed

    Liu, Wan-Ling; Yang, Ni-Shin; Chen, Ya-Ting; Lirio, Stephen; Wu, Cheng-You; Lin, Chia-Her; Huang, Hsi-Ya

    2015-01-02

    A green and sustainable strategy synthesizes clinical medicine warfarin anticoagulant by using lipase-supported metal-organic framework (MOF) bioreactors (see scheme). These findings may be beneficial for future studies in the industrial production of chemical, pharmaceutical, and agrochemical precursors.

  20. CO2 Capture in Dry and Wet Conditions in UTSA-16 Metal-Organic Framework.

    PubMed

    Masala, Alessio; Vitillo, Jenny G; Mondino, Giorgia; Grande, Carlos A; Blom, Richard; Manzoli, Maela; Marshall, Marc; Bordiga, Silvia

    2017-01-11

    Water is the strongest competitor to CO2 in the adsorption on microporous materials, affecting their performances as CO2 scrubbers in processes such as postcombustion carbon capture. The metal-organic framework (MOF) UTSA-16 is considered a promising material for its capacity to efficiently capture CO2 in large quantities, thanks to the presence of open metal sites (OMSs). It is here shown that UTSA-16 is also able to desorb fully water already at room temperature. This property is unique from all the other materials with OMSs reported so far. UTSA-16 retains indeed the 70% of its CO2 separation capacity after admittance of water in a test flow, created to simulate the emissions from a real postcombustion carbon-capture process. This important aspect not yet observed for any other amine-free material, associated with a high material stability-tested for 160 cycles-and a small temperature swing necessary for regeneration, places UTSA-16 in the restrict number of systems with a real technological future for CO2 separation.

  1. Computational screening of large molecule adsorption by metal-organic frameworks.

    SciTech Connect

    Allendorf, Mark D.; Greathouse, Jeffery A.

    2010-04-01

    Grand canonical Monte Carlo simulations were performed to investigate trends in low-pressure adsorption of a broad range of organic molecules by a set of metal-organic frameworks (MOFs). The organic analytes considered here are relevant to applications in chemical detection: small aromatics (o-, m-, and p-xylene), polycyclic aromatic hydrocarbons (naphthalene, anthracene, phenanthrene), explosives (TNT and RDX), and chemical warfare agents (GA and VM). The framework materials included several Zn-MOFs (IRMOFs 1-3, 7, 8), a Cr-MOF (CrMIL-53lp), and a Cu-MOF (HKUST-1). Many of the larger organics were significantly adsorbed by the target MOFs at low pressure, which is consistent with the exceptionally high isosteric heats of adsorption (25 kcal/mol - 60 kcal/mol) for this range of analyte. At a higher loading pressure of 101 kPa, the Zn-MOFs show a much higher volumetric uptake than either CrMIL-53-lp or HKUST-1 for all types of analyte. Within the Zn-MOF series, analyte loading is proportional to free volume, and loading decreases with increasing analyte size due to molecular packing effects. CrMIL-53lp showed the highest adsorption energy for all analytes, suggesting that this material may be suitable for low-level detection of organics.

  2. Metal-Organic Frameworks: Bimetallic Metal-Organic Frameworks: Probing the Lewis Acid Site for CO2 Conversion (Small 17/2016).

    PubMed

    Zou, Ruyi; Li, Pei-Zhou; Zeng, Yong-Fei; Liu, Jia; Zhao, Ruo; Duan, Hui; Luo, Zhong; Wang, Jin-Gui; Zou, Ruqiang; Zhao, Yanli

    2016-05-01

    On page 2334, R. Q. Zou, Y. L. Zhao, and co-workers present a porous metal-organic framework (MOF) that serves as a platform for studying the metal exchange effect on both CO2 adsorption and catalytic fixation. The effect is demonstrated by catalytic CO2 cycloaddition with propylene oxide to produce propylene carbonate. Molecular dynamic simulations are carried out to further confirm the catalytic performance of these MOFs on chemical fixation of CO2 to carbonates. This research sheds light on how metal exchange could influence the intrinsic properties of MOFs.

  3. High Methane Storage Working Capacity in Metal-Organic Frameworks with Acrylate Links.

    PubMed

    Jiang, Juncong; Furukawa, Hiroyasu; Zhang, Yue-Biao; Yaghi, Omar M

    2016-08-17

    High methane storage capacity in porous materials is important for the design and manufacture of vehicles powered by natural gas. Here, we report the synthesis, crystal structures and methane adsorption properties of five new zinc metal-organic frameworks (MOFs), MOF-905, MOF-905-Me2, MOF-905-Naph, MOF-905-NO2, and MOF-950. All these MOFs consist of the Zn4O(-CO2)6 secondary building units (SBUs) and benzene-1,3,5-tri-β-acrylate, BTAC. The permanent porosity of all five materials was confirmed, and their methane adsorption measured up to 80 bar to reveal that MOF-905 is among the best performing methane storage materials with a volumetric working capacity (desorption at 5 bar) of 203 cm(3) cm(-3) at 80 bar and 298 K, a value rivaling that of HKUST-1 (200 cm(3) cm(-3)), the benchmark compound for methane storage in MOFs. This study expands the scope of MOF materials with ultrahigh working capacity to include linkers having the common acrylate connectivity.

  4. A Rigid Nested Metal-Organic Framework Featuring a Thermoresponsive Gating Effect Dominated by Counterions.

    PubMed

    Gao, Qiang; Xu, Jian; Cao, Dapeng; Chang, Ze; Bu, Xian-He

    2016-11-21

    We herein report a rigid nested metal-organic framework (MOF) featuring a unique thermoresponsive gating adsorption behavior, which, in contrast to any known flexibility modes for stimuli-responsive MOFs, depends on the thermal motion of the extra-framework counterions. In addition, this MOF also exhibits adsorption selectivity of CO2 over N2 , H2 , and Ar at 273 K, thus enabling a strategic separation and encapsulation of CO2 .

  5. Peptide assembly-driven metal-organic framework (MOF) motors for micro electric generators.

    PubMed

    Ikezoe, Yasuhiro; Fang, Justin; Wasik, Tomasz L; Uemura, Takashi; Zheng, Yongtai; Kitagawa, Susumu; Matsui, Hiroshi

    2015-01-14

    Peptide-metal-organic framework (Pep-MOF) motors, whose motions are driven by anisotropic surface tension gradients created via peptide self-assembly around frameworks, can rotate microscopic rotors and magnets fast enough to generate an electric power of 0.1 μW. A new rigid Pep-MOF motor can be recycled by refilling the peptide fuel into the nanopores of the MOF.

  6. Selective, Tunable O2 Binding in Cobalt(II)-Triazolate/Pyrazolate Metal-Organic Frameworks.

    PubMed

    Xiao, Dianne J; Gonzalez, Miguel I; Darago, Lucy E; Vogiatzis, Konstantinos D; Haldoupis, Emmanuel; Gagliardi, Laura; Long, Jeffrey R

    2016-06-08

    The air-free reaction of CoCl2 with 1,3,5-tri(1H-1,2,3-triazol-5-yl)benzene (H3BTTri) in N,N-dimethylformamide (DMF) and methanol leads to the formation of Co-BTTri (Co3[(Co4Cl)3(BTTri)8]2·DMF), a sodalite-type metal-organic framework. Desolvation of this material generates coordinatively unsaturated low-spin cobalt(II) centers that exhibit a strong preference for binding O2 over N2, with isosteric heats of adsorption (Qst) of -34(1) and -12(1) kJ/mol, respectively. The low-spin (S = 1/2) electronic configuration of the metal centers in the desolvated framework is supported by structural, magnetic susceptibility, and computational studies. A single-crystal X-ray structure determination reveals that O2 binds end-on to each framework cobalt center in a 1:1 ratio with a Co-O2 bond distance of 1.973(6) Å. Replacement of one of the triazolate linkers with a more electron-donating pyrazolate group leads to the isostructural framework Co-BDTriP (Co3[(Co4Cl)3(BDTriP)8]2·DMF; H3BDTriP = 5,5'-(5-(1H-pyrazol-4-yl)-1,3-phenylene)bis(1H-1,2,3-triazole)), which demonstrates markedly higher yet still fully reversible O2 affinities (Qst = -47(1) kJ/mol at low loadings). Electronic structure calculations suggest that the O2 adducts in Co-BTTri are best described as cobalt(II)-dioxygen species with partial electron transfer, while the stronger binding sites in Co-BDTriP form cobalt(III)-superoxo moieties. The stability, selectivity, and high O2 adsorption capacity of these materials render them promising new adsorbents for air separation processes.

  7. Metal-organic and zeolite imidazolate frameworks (MOFs and ZIFs) for highly selective separations

    SciTech Connect

    Yaghi, Omar M

    2012-09-17

    Metal-organic and zeolite imidazolate frameworks (MOFs and ZIFs) have been investigated for the realization as separation media with high selectivity. These structures are held together with strong bonds, making them architecturally, chemically, and thermally stable. Therefore, employing well designed building units, it is possible to discover promising materials for gas and vapor separation. This grant was focused on the study of MOFs and ZIFs with these specific objectives: (i) to develop a strategy for producing MOFs and ZIFs that combine high surface areas with active sites for their use in gas adsorption and separation of small organic compounds, (ii) to introduce active sites in the framework by a post-synthetic modification and metalation of MOFs and ZIFs, and (iii) to design and synthesize MOFs with extremely high surface areas and large pore volumes to accommodate large amounts of guest molecules. By the systematic study, this effort demonstrated how to introduce active functional groups in the frameworks, and this is also the origin of a new strategy, which is termed isoreticular functionalization and metalation. However, a large pore volume is still a prerequisite feature. One of the solutions to overcome this challenge is an isoreticular expansion of a MOF's structure. With triangular organic linker and square building units, we demonstrated that MOF-399 has a unit cell volume 17 times larger than that of the first reported material isoreticular to it, and it has the highest porosity (94%) and lowest density (0.126 g cm-3) of any MOF reported to date. MOFs are not just low density materials; the guest-free form of MOF-210 demonstrates an ultrahigh porosity, whose BET surface area was estimated to be 6240 m2 g-1 by N2 adsorption measurements.

  8. Functionalization of metal-organic frameworks through the postsynthetic transformation of olefin side groups.

    PubMed

    Hindelang, Konrad; Kronast, Alexander; Vagin, Sergei I; Rieger, Bernhard

    2013-06-17

    For the first time, the adaptability of the C=C double bond as a versatile precursor for the postsynthetic modification (PSM) of microporous materials was extensively investigated and evaluated. Therefore, an olefin-tagged 4,4'-bipyridine linker was synthesized and successfully introduced as pillar linker within a 9,10-triptycenedicarboxylate (TDC) zinc paddle-wheel metal-organic framework (MOF) through microwave-assisted synthesis. Different reactions, predominately used in organic chemistry, were tested, leading to the development of new postsynthetic reactions for the functionalization of solid materials. The postsynthetic oxidation of the olefin side groups applying osmium tetroxide (OsO₄) as a catalyst led to the formation of a microporous material with free vicinal diol functionalities. The epoxidation with dimethyldioxirane (DMDO) enabled the synthesis of epoxy-functionalized MOFs. In addition to that, reaction procedures for a postsynthetic hydroboration with borane dimethyl sulfide as well as a photoinduced thiol-ene click reaction with ethyl mercaptan were developed. For all of these PSMs, yields of more than 90% were obtained, entirely maintaining the crystallinity of the MOFs. Since the direct introduction of the corresponding groups by means of pre-synthetic approaches is hardly possible, these new PSMs are useful tools for the functionalization of porous solids towards applications such as selective adsorption, separation, and catalysis.

  9. Reversible Capture and Release of Elemental Halogens with a Redox-Active Metal-Organic Framework.

    PubMed

    Tulchinsky, Yuri; Hendon, Christopher H; Lomachenko, Kirill A; Borfecchia, Elisa; Melot, Brent C; Hudson, Matthew R; Tarver, Jacob D; Korzynski, Maciej D; Stubbs, Amanda W; Kagan, Jacob J; Lamberti, Carlo; Brown, Craig M; Dinca, Mircea

    2017-03-28

    Extreme toxicity, corrosiveness, and volatility pose serious challenges for the safe storage and transportation of elemental chlorine and bromine, which play critical roles in the chemical industry. Solid materials capable of forming stable non-volatile compounds upon reaction with elemental halogens may partially mitigate these challenges by allowing safe halogen release on demand. Here, we demonstrate that elemental halogens quantitatively oxidize coordinatively unsaturated Co(II) ions in a robust azolate metal-organic framework (MOF) to produce an air-stable and safe-to-handle Co(III) material featuring terminal Co(III)-halogen bonds. Thermal treatment of the oxidized MOF causes homolytic cleavage of the Co(III)-halogen bonds, reduction to Co(II), and concomitant release of elemental halogens. Remarkably, the reversible chemical storage and thermal release of elemental halogens occur with no significant losses of structural integrity, the parent cobaltous MOF retaining crystallinity and porosity even after three oxidation/reduction cycles. These results highlight a material operating via redox mechanism that may find utility in the storage and capture of other noxious and corrosive gases.

  10. Graphene-Templated Synthesis of Magnetic Metal Organic Framework Nanocomposites for Selective Enrichment of Biomolecules.

    PubMed

    Cheng, Gong; Wang, Zhi-Gang; Denagamage, Sachira; Zheng, Si-Yang

    2016-04-27

    Successful control of homogeneous and complete coating of graphene or graphene-based composites with well-defined metal organic framework (MOF) layers is a great challenge. Herein, novel magnetic graphene MOF composites were constructed via a simple strategy for self-assembly of well-distributed, dense, and highly porous MOFs on both sides of graphene nanosheets. Graphene functionalized with magnetic nanoparticles and carboxylic groups on both sides was explored as the backbone and template to direct the controllable self-assembly of MOFs. The prepared composite materials have a relatively high specific surface area (345.4 m(2) g(-1)), and their average pore size is measured to be 3.2 nm. Their relatively high saturation magnetization (23.8 emu g(-1)) indicates their strong magnetism at room temperature. Moreover, the multifunctional composite was demonstrated to be a highly effective affinity material in selective extraction and separation of low-concentration biomolecules from biological samples, in virtue of the size-selection property of the unique porous structure and the excellent affinity of the composite materials. Besides providing a solution for the construction of well-defined functional graphene-based MOFs, this work could also contribute to selective extraction of biomolecules, in virtue of the universal affinity between immobilized metal ions and biomolecules.

  11. Adsorption, separation, and catalytic properties of densified metal-organic frameworks

    SciTech Connect

    Nandasiri, Manjula I.; Jambovane, Sachin R.; McGrail, B. Peter; Schaef, Herbert T.; Nune, Satish. K.

    2016-03-01

    Metal-organic frameworks (MOFs) are one of the widely investigated materials of 21st century due to their unique properties such as structural tailorability, controlled porosity and crystallinity. These exceptional properties make them promising candidates for various applications including gas adsorption and storage, separation, and catalysis. However, commercial applications of MOFs produced by conventional methods including solvothermal or hydrothermal synthesis are rather limited or restricted because they often produce fine powders. The use of MOF powders for industrial applications often results in pressure drop problems similar to the case with Zeolites. To realize these materials for practical applications, densification of MOFs is routinely employed to form pellets, extrudates or beads to improve the overall density, volumetric adsorption, mechanical and thermal properties. However, the improvements come with some drawbacks such as reduction in overall porosity, surface area, and gravimetric adsorption capacity. Thus, optimizing the properties of densified MOF’s by tuning the packing density is very crucial for realizing these materials for industrial applications. In this review, various methods of densification of MOFs, their properties, and applications are discussed.

  12. Mathematical modeling and experimental breakthrough curves of carbon dioxide adsorption on metal organic framework CPM-5.

    PubMed

    Sabouni, Rana; Kazemian, Hossein; Rohani, Sohrab

    2013-08-20

    It is essential to capture carbon dioxide from flue gas because it is considered one of the main causes of global warming. Several materials and different methods have been reported for CO2 capturing including adsorption onto zeolites and porous membranes, as well as absorption in amine solutions. All such methods require high energy input and high cost. A new class of porous materials called Metal Organic Frameworks (MOFs) exhibited excellent performance in extracting carbon dioxide from a gas mixture. In this study, the breakthrough curves for the adsorption of carbon dioxide on CPM-5 (crystalline porous materials) were obtained experimentally and theoretically using a laboratory-scale fixed-bed column at different experimental conditions such as feed flow rate, adsorption temperature, and feed concentration. It was found that the CPM-5 has a dynamic CO2 adsorption capacity of 11.9 wt % (2.7 mmol/g) (corresponding to 8 mL/min, 298 K, and 25% v/v CO2). The tested CPM-5 showed an outstanding adsorption equilibrium capacity (e.g., 2.3 mmol/g (10.2 wt %) at 298 K) compared to other adsorbents, which can be considered as an attractive adsorbent for separation of CO2 from flue gas.

  13. Exceptionally Low Shear Modulus in a Prototypical Imidazole-Based Metal-Organic Framework

    NASA Astrophysics Data System (ADS)

    Tan, Jin-Chong; Civalleri, Bartolomeo; Lin, Chung-Cherng; Valenzano, Loredana; Galvelis, Raimondas; Chen, Po-Fei; Bennett, Thomas D.; Mellot-Draznieks, Caroline; Zicovich-Wilson, Claudio M.; Cheetham, Anthony K.

    2012-03-01

    Using Brillouin scattering, we measured the single-crystal elastic constants (Cij’s) of a prototypical metal-organic framework (MOF): zeolitic imidazolate framework (ZIF)-8 [Zn(2-methylimidazolate)2], which adopts a zeolitic sodalite topology and exhibits large porosity. Its Cij’s under ambient conditions are (in GPa) C11=9.522(7), C12=6.865(14), and C44=0.967(4). Tensorial analysis of the Cij’s reveals the complete picture of the anisotropic elasticity in cubic ZIF-8. We show that ZIF-8 has a remarkably low shear modulus Gmin⁡≲1GPa, which is the lowest yet reported for a single-crystalline extended solid. Using ab initio calculations, we demonstrate that ZIF-8’s Cij’s can be reliably predicted, and its elastic deformation mechanism is linked to the pliant ZnN4 tetrahedra. Our results shed new light on the role of elastic constants in establishing the structural stability of MOF materials and thus their suitability for practical applications.

  14. Liquid chromatographic separation in metal-organic framework MIL-101: a molecular simulation study.

    PubMed

    Hu, Zhongqiao; Chen, Yifei; Jiang, Jianwen

    2013-02-05

    A molecular simulation study is reported to investigate liquid chromatographic separation in metal-organic framework MIL-101. Two mixtures are considered: three amino acids (Arg, Phe, and Trp) in aqueous solution and three xylene isomers (p-, m-, and o-xylene) dissolved in hexane. For the first mixture, the elution order is found to be Arg > Phe > Trp. The hydrophilic Arg has the strongest interaction with the polar mobile phase (water) and the weakest interaction with the stationary phase (MIL-101), and thus transports at the fastest velocity. Furthermore, Arg forms the largest number of hydrogen bonds with water and possesses the largest hydrophilic solvent-accessible surface area. For the second mixture, the elution order is p-xylene > m-xylene > o-xylene, consistent with available experimental observation. With the largest polarity as compared to p- and m-xylenes, o-xylene interacts the most strongly with the stationary phase and exhibits the slowest transport velocity. For both mixtures, the underlying separation mechanism is elucidated from detailed energetic and structural analysis. It is revealed that the separation can be attributed to the cooperative solute-solvent and solute-framework interactions. This simulation study, for the first time, provides molecular insight into liquid chromatographic separation in a MOF and suggests that MIL-101 might be an interesting material for the separation of industrially important liquid mixtures.

  15. Osteogenic activity and antibacterial effect of porous titanium modified with metal-organic framework films.

    PubMed

    Chen, Junyu; Zhang, Xin; Huang, Chao; Cai, He; Hu, Shanshan; Wan, Qianbing; Pei, Xibo; Wang, Jian

    2017-03-01

    As a new class of crystalline nanoporous materials, metal-organic frameworks (MOFs) have recently been used for biomedical applications due to their large surface area, high porosity, and theoretically infinite structures. To improve the biological performance of titanium, MOF films were applied to surface modification of titanium. Zn-based MOF films composed of zeolitic imidazolate framework-8 (ZIF-8) crystals with nanoscale and microscale sizes (nanoZIF-8 and microZIF-8) were prepared on porous titanium surfaces by hydrothermal and solvothermal methods, respectively. The ZIF-8 films were characterized by powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). The nanoZIF-8 film exhibited good biocompatibility, whereas the microZIF-8 film showed obvious cytotoxicity to MG63 cells. Compared to pure titanium and alkali- and heat-treated porous titanium, the nanoZIF-8 film not only enhanced alkaline phosphatase (ALP) activity, extracellular matrix mineralization, and expression of osteogenic genes (ALP, Runx2) in MG63 cells but also inhibited the growth of Streptococcus mutans. These results indicate that MOF films or coatings may be promising candidates for bone tissue engineering. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 834-846, 2017.

  16. A molecular shuttle that operates inside a metal-organic framework

    NASA Astrophysics Data System (ADS)

    Zhu, Kelong; O'Keefe, Christopher A.; Vukotic, V. Nicholas; Schurko, Robert W.; Loeb, Stephen J.

    2015-06-01

    A ‘molecular shuttle’ is an interlocked molecular assembly in which a macrocyclic ring is able to move back and forth between two recognition sites. This large-amplitude translational motion was first characterized in solution in 1991. Since that report, many mechanically interlocked molecules (MIMs) have been designed, synthesized and shown to mimic the complex functions of macroscopic switches and machines. Here, we show that this fundamental concept—the translational motion of a molecular shuttle—can be organized, initiated and made to operate inside a crystalline, solid-state material. A metal-organic framework (MOF) designated UWDM-4 was prepared that contains a rigid linker that is a molecular shuttle. It was demonstrated by variable-temperature 1H-13C cross-polarization/magic-angle spinning (CP/MAS) and 13C 2D exchange correlation spectroscopy (EXSY) solid-state NMR at 21.1 T on a 13C-enriched sample that the macrocyclic ring undergoes rapid shuttling along the rigid axle built between struts of the framework.

  17. Light Hydrocarbon Adsorption Mechanisms in Two Calcium-Based Microporous Metal Organic Frameworks

    SciTech Connect

    Plonka, Anna M.; Chen, Xianyin; Wang, Hao; Krishna, Rajamani; Dong, Xinglong; Banerjee, Debasis; Woerner, William R.; Han, Yu; Li, Jing; Parise, John B.

    2016-01-25

    The adsorption mechanism of ethane, ethylene, and acetylene (C2Hn; n = 2, 4, 6) on two microporous metal organic frameworks (MOFs) is described here that is consistent with observations from single crystal and powder X-ray diffraction, calorimetric measurements, and gas adsorption isotherm measurements. Two calcium-based MOFs, designated as SBMOF-1 and SBMOF-2 (SB: Stony Brook), form three-dimensional frameworks with one-dimensional open channels. As determined from single crystal diffraction experiments, channel geometries of both SBMOF-1 and SBMOF-2 provide multiple adsorption sites for hydrocarbon molecules through C–H···π and C–H···O interactions, similarly to interactions in the molecular and protein crystals. In conclusion, both materials selectively adsorb C2 hydrocarbon gases over methane as determined with IAST and breakthrough calculations as well as experimental breakthrough measurements, with C2H6/CH4 selectivity as high as 74 in SBMOF-1.

  18. Unravelling surface and interfacial structures of a metal-organic framework by transmission electron microscopy.

    PubMed

    Zhu, Yihan; Ciston, Jim; Zheng, Bin; Miao, Xiaohe; Czarnik, Cory; Pan, Yichang; Sougrat, Rachid; Lai, Zhiping; Hsiung, Chia-En; Yao, Kexin; Pinnau, Ingo; Pan, Ming; Han, Yu

    2017-02-20

    Metal-organic frameworks (MOFs) are crystalline porous materials with designable topology, porosity and functionality, having promising applications in gas storage and separation, ion conduction and catalysis. It is challenging to observe MOFs with transmission electron microscopy (TEM) due to the extreme instability of MOFs upon electron beam irradiation. Here, we use a direct-detection electron-counting camera to acquire TEM images of the MOF ZIF-8 with an ultralow dose of 4.1 electrons per square ångström to retain the structural integrity. The obtained image involves structural information transferred up to 2.1 Å, allowing the resolution of individual atomic columns of Zn and organic linkers in the framework. Furthermore, TEM reveals important local structural features of ZIF-8 crystals that cannot be identified by diffraction techniques, including armchair-type surface terminations and coherent interfaces between assembled crystals. These observations allow us to understand how ZIF-8 crystals self-assemble and the subsequent influence of interfacial cavities on mass transport of guest molecules.

  19. A molecular shuttle that operates inside a metal-organic framework.

    PubMed

    Zhu, Kelong; O'Keefe, Christopher A; Vukotic, V Nicholas; Schurko, Robert W; Loeb, Stephen J

    2015-06-01

    A 'molecular shuttle' is an interlocked molecular assembly in which a macrocyclic ring is able to move back and forth between two recognition sites. This large-amplitude translational motion was first characterized in solution in 1991. Since that report, many mechanically interlocked molecules (MIMs) have been designed, synthesized and shown to mimic the complex functions of macroscopic switches and machines. Here, we show that this fundamental concept-the translational motion of a molecular shuttle-can be organized, initiated and made to operate inside a crystalline, solid-state material. A metal-organic framework (MOF) designated UWDM-4 was prepared that contains a rigid linker that is a molecular shuttle. It was demonstrated by variable-temperature (1)H-(13)C cross-polarization/magic-angle spinning (CP/MAS) and (13)C 2D exchange correlation spectroscopy (EXSY) solid-state NMR at 21.1 T on a (13)C-enriched sample that the macrocyclic ring undergoes rapid shuttling along the rigid axle built between struts of the framework.

  20. Ab initio investigation on hydrogen adsorption capability in Zn and Cu-based metal organic frameworks

    NASA Astrophysics Data System (ADS)

    Tanuwijaya, V. V.; Hidayat, N. N.; Agusta, M. K.; Dipojono, H. K.

    2015-09-01

    One of the biggest challenge in material technology for hydrogen storage application is to increase hydrogen uptake in room temperature and pressure. As a class of highly porous material, Metal-Organic Frameworks (MOF) holds great potential with its tunable structure. However, little is known about the effect of metal cluster to its hydrogen storage capability. Investigation on this matter has been carried out carefully on small cluster of Zn and Cu-based MOF using first principles method. The calculation of two distinct building units of MOFs, namely octahedral and paddle-wheel models, have been done with B3LYP density functional method using 6-31G(d,p) and LANL2DZ basis sets. From geometry optimization of Zn-based MOF linked by benzene-dicarboxylate (MOF-5), it is found that hydrogen tends to keep distance from metal cluster group and stays above benzene ring. In the other hand, hydrogen molecule prefers to stay atop of the exposed Cu atom in Cu-based MOF system linked by the same linker group (Cu-bdc). Calculated hydrogen binding enthalpies for Zn and Cu octahedral cages at ZnO3 sites are 1.64kJ/mol and 2.73kJ/mol respectively, while hydrogen binding enthalpies for Zn and Cu paddle-wheel cages calculated on top of metal atoms are found to be at 6.05kJ/mol and 6.10kJ/mol respectively. Major difference between Zn-MOF-5 and Cu-bdc hydrogen uptake performance might be caused by unsaturated metal sites present in Cu-bdc system and the influence of their geometric structures, although a small difference on binding energy in the type of transition metal used is also observed. The comparison between Zn and Cu-based MOF may contribute to a comprehensive understanding of metal clusters and the importance of selecting best transition metal for design and synthesis of metal-organic frameworks.

  1. Hollow silica-copper-carbon anodes using copper metal-organic frameworks as skeletons

    NASA Astrophysics Data System (ADS)

    Sun, Zixu; Xin, Fengxia; Cao, Can; Zhao, Chongchong; Shen, Cai; Han, Wei-Qiang

    2015-12-01

    Hollow silica-copper-carbon (H-SCC) nanocomposites are first synthesized using copper metal-organic frameworks as skeletons to form Cu-MOF@SiO2 and then subjected to heat treatment. In the composites, the hollow structure and the void space from the collapse of the MOF skeleton can accommodate the huge volume change, buffer the mechanical stress caused by lithium ion insertion/extraction and maintain the structural integrity of the electrode and a long cycling stability. The ultrafine copper with a uniform size of around 5 nm and carbon with homogeneous distribution from the decomposition of the MOF skeleton can not only enhance the electrical conductivity of the composite and preserve the structural and interfacial stabilization, but also suppress the aggregation of silica nanoparticles and cushion the volume change. In consequence, the resulting material as an anode for lithium-ion batteries (LIBs) delivers a reversible capacity of 495 mA h g-1 after 400 cycles at a current density of 500 mA g-1. The synthetic method presented in this paper provides a facile and low-cost strategy for the large-scale production of hollow silica/copper/carbon nanocomposites as an anode in LIBs.Hollow silica-copper-carbon (H-SCC) nanocomposites are first synthesized using copper metal-organic frameworks as skeletons to form Cu-MOF@SiO2 and then subjected to heat treatment. In the composites, the hollow structure and the void space from the collapse of the MOF skeleton can accommodate the huge volume change, buffer the mechanical stress caused by lithium ion insertion/extraction and maintain the structural integrity of the electrode and a long cycling stability. The ultrafine copper with a uniform size of around 5 nm and carbon with homogeneous distribution from the decomposition of the MOF skeleton can not only enhance the electrical conductivity of the composite and preserve the structural and interfacial stabilization, but also suppress the aggregation of silica nanoparticles and

  2. Ab initio investigation on hydrogen adsorption capability in Zn and Cu-based metal organic frameworks

    SciTech Connect

    Tanuwijaya, V. V.; Hidayat, N. N. Agusta, M. K. Dipojono, H. K.

    2015-09-30

    One of the biggest challenge in material technology for hydrogen storage application is to increase hydrogen uptake in room temperature and pressure. As a class of highly porous material, Metal-Organic Frameworks (MOF) holds great potential with its tunable structure. However, little is known about the effect of metal cluster to its hydrogen storage capability. Investigation on this matter has been carried out carefully on small cluster of Zn and Cu-based MOF using first principles method. The calculation of two distinct building units of MOFs, namely octahedral and paddle-wheel models, have been done with B3LYP density functional method using 6-31G(d,p) and LANL2DZ basis sets. From geometry optimization of Zn-based MOF linked by benzene-dicarboxylate (MOF-5), it is found that hydrogen tends to keep distance from metal cluster group and stays above benzene ring. In the other hand, hydrogen molecule prefers to stay atop of the exposed Cu atom in Cu-based MOF system linked by the same linker group (Cu-bdc). Calculated hydrogen binding enthalpies for Zn and Cu octahedral cages at ZnO{sub 3} sites are 1.64kJ/mol and 2.73kJ/mol respectively, while hydrogen binding enthalpies for Zn and Cu paddle-wheel cages calculated on top of metal atoms are found to be at 6.05kJ/mol and 6.10kJ/mol respectively. Major difference between Zn-MOF-5 and Cu-bdc hydrogen uptake performance might be caused by unsaturated metal sites present in Cu-bdc system and the influence of their geometric structures, although a small difference on binding energy in the type of transition metal used is also observed. The comparison between Zn and Cu-based MOF may contribute to a comprehensive understanding of metal clusters and the importance of selecting best transition metal for design and synthesis of metal-organic frameworks.

  3. Modulating supramolecular binding of carbon dioxide in a redox-active porous metal-organic framework

    NASA Astrophysics Data System (ADS)

    Lu, Zhenzhong; Godfrey, Harry G. W.; da Silva, Ivan; Cheng, Yongqiang; Savage, Mathew; Tuna, Floriana; McInnes, Eric J. L.; Teat, Simon J.; Gagnon, Kevin J.; Frogley, Mark D.; Manuel, Pascal; Rudić, Svemir; Ramirez-Cuesta, Anibal J.; Easun, Timothy L.; Yang, Sihai; Schröder, Martin

    2017-02-01

    Hydrogen bonds dominate many chemical and biological processes, and chemical modification enables control and modulation of host-guest systems. Here we report a targeted modification of hydrogen bonding and its effect on guest binding in redox-active materials. MFM-300(VIII) {[VIII2(OH)2(L)], LH4=biphenyl-3,3',5,5'-tetracarboxylic acid} can be oxidized to isostructural MFM-300(VIV), [VIV2O2(L)], in which deprotonation of the bridging hydroxyl groups occurs. MFM-300(VIII) shows the second highest CO2 uptake capacity in metal-organic framework materials at 298 K and 1 bar (6.0 mmol g-1) and involves hydrogen bonding between the OH group of the host and the O-donor of CO2, which binds in an end-on manner, =1.863(1) Å. In contrast, CO2-loaded MFM-300(VIV) shows CO2 bound side-on to the oxy group and sandwiched between two phenyl groups involving a unique ...c.g.phenyl interaction [3.069(2), 3.146(3) Å]. The macroscopic packing of CO2 in the pores is directly influenced by these primary binding sites.

  4. Modulating supramolecular binding of carbon dioxide in a redox-active porous metal-organic framework.

    PubMed

    Lu, Zhenzhong; Godfrey, Harry G W; da Silva, Ivan; Cheng, Yongqiang; Savage, Mathew; Tuna, Floriana; McInnes, Eric J L; Teat, Simon J; Gagnon, Kevin J; Frogley, Mark D; Manuel, Pascal; Rudić, Svemir; Ramirez-Cuesta, Anibal J; Easun, Timothy L; Yang, Sihai; Schröder, Martin

    2017-02-13

    Hydrogen bonds dominate many chemical and biological processes, and chemical modification enables control and modulation of host-guest systems. Here we report a targeted modification of hydrogen bonding and its effect on guest binding in redox-active materials. MFM-300(V(III)) {[V(III)2(OH)2(L)], LH4=biphenyl-3,3',5,5'-tetracarboxylic acid} can be oxidized to isostructural MFM-300(V(IV)), [V(IV)2O2(L)], in which deprotonation of the bridging hydroxyl groups occurs. MFM-300(V(III)) shows the second highest CO2 uptake capacity in metal-organic framework materials at 298 K and 1 bar (6.0 mmol g(-1)) and involves hydrogen bonding between the OH group of the host and the O-donor of CO2, which binds in an end-on manner, =1.863(1) Å. In contrast, CO2-loaded MFM-300(V(IV)) shows CO2 bound side-on to the oxy group and sandwiched between two phenyl groups involving a unique ···c.g.phenyl interaction [3.069(2), 3.146(3) Å]. The macroscopic packing of CO2 in the pores is directly influenced by these primary binding sites.

  5. Design and Synthesis of Novel Porous Metal-Organic Frameworks (MOFs) Toward High Hydrogen Storage Capacity

    SciTech Connect

    Mohamed, Eddaoudi; Zaworotko, Michael; Space, Brian; Eckert, Juergen

    2013-05-08

    Statement of Objectives: 1. Synthesize viable porous MOFs for high H2 storage at ambient conditions to be assessed by measuring H2 uptake. 2. Develop a better understanding of the operative interactions of the sorbed H2 with the organic and inorganic constituents of the sorbent MOF by means of inelastic neutron scattering (INS, to characterize the H2-MOF interactions) and computational studies (to interpret the data and predict novel materials suitable for high H2 uptake at moderate temperatures and relatively low pressures). 3. Synergistically combine the outcomes of objectives 1 and 2 to construct a made-to-order inexpensive MOF that is suitable for super H2 storage and meets the DOE targets - 6% H2 per weight (2kWh/kg) by 2010 and 9% H2 per weight (3kWh/kg) by 2015. The ongoing research is a collaborative experimental and computational effort focused on assessing H2 storage and interactions with pre-selected metal-organic frameworks (MOFs) and zeolite-like MOFs (ZMOFs), with the eventual goal of synthesizing made-to-order high H2 storage materials to achieve the DOE targets for mobile applications. We proposed in this funded research to increase the amount of H2 uptake, as well as tune the interactions (i.e. isosteric heats of adsorption), by targeting readily tunable MOFs:

  6. Nanomechanical investigation of thin-film electroceramic/metal-organic framework multilayers

    SciTech Connect

    Best, James P. E-mail: engelbert.redel@kit.edu Michler, Johann; Maeder, Xavier; Liu, Jianxi; Wang, Zhengbang; Tsotsalas, Manuel; Liu, Jinxuan; Gliemann, Hartmut; Weidler, Peter G.; Redel, Engelbert E-mail: engelbert.redel@kit.edu Wöll, Christof E-mail: engelbert.redel@kit.edu; Röse, Silvana; Oberst, Vanessa; Walheim, Stefan

    2015-09-07

    Thin-film multilayer stacks of mechanically hard magnetron sputtered indium tin oxide (ITO) and mechanically soft highly porous surface anchored metal-organic framework (SURMOF) HKUST-1 were studied using nanoindentation. Crystalline, continuous, and monolithic surface anchored MOF thin films were fabricated using a liquid-phase epitaxial growth method. Control over respective fabrication processes allowed for tuning of the thickness of the thin film systems with a high degree of precision. It was found that the mechanical indentation of such thin films is significantly affected by the substrate properties; however, elastic parameters were able to be decoupled for constituent thin-film materials (E{sub ITO} ≈ 96.7 GPa, E{sub HKUST−1} ≈ 22.0 GPa). For indentation of multilayer stacks, it was found that as the layer thicknesses were increased, while holding the relative thickness of ITO and HKUST-1 constant, the resistance to deformation was significantly altered. Such an observation is likely due to small, albeit significant, changes in film texture, interfacial roughness, size effects, and controlling deformation mechanism as a result of increasing material deposition during processing. Such effects may have consequences regarding the rational mechanical design and utilization of MOF-based hybrid thin-film devices.

  7. Modulating supramolecular binding of carbon dioxide in a redox-active porous metal-organic framework

    PubMed Central

    Lu, Zhenzhong; Godfrey, Harry G. W.; da Silva, Ivan; Cheng, Yongqiang; Savage, Mathew; Tuna, Floriana; McInnes, Eric J. L.; Teat, Simon J.; Gagnon, Kevin J.; Frogley, Mark D.; Manuel, Pascal; Rudić, Svemir; Ramirez-Cuesta, Anibal J.; Easun, Timothy L.; Yang, Sihai; Schröder, Martin

    2017-01-01

    Hydrogen bonds dominate many chemical and biological processes, and chemical modification enables control and modulation of host–guest systems. Here we report a targeted modification of hydrogen bonding and its effect on guest binding in redox-active materials. MFM-300(VIII) {[VIII2(OH)2(L)], LH4=biphenyl-3,3′,5,5′-tetracarboxylic acid} can be oxidized to isostructural MFM-300(VIV), [VIV2O2(L)], in which deprotonation of the bridging hydroxyl groups occurs. MFM-300(VIII) shows the second highest CO2 uptake capacity in metal-organic framework materials at 298 K and 1 bar (6.0 mmol g−1) and involves hydrogen bonding between the OH group of the host and the O-donor of CO2, which binds in an end-on manner, =1.863(1) Å. In contrast, CO2-loaded MFM-300(VIV) shows CO2 bound side-on to the oxy group and sandwiched between two phenyl groups involving a unique ···c.g.phenyl interaction [3.069(2), 3.146(3) Å]. The macroscopic packing of CO2 in the pores is directly influenced by these primary binding sites. PMID:28194014

  8. Scalable synthesis and post-modification of a mesoporous metal-organic framework called NU-1000.

    PubMed

    Wang, Timothy C; Vermeulen, Nicolaas A; Kim, In Soo; Martinson, Alex B F; Stoddart, J Fraser; Hupp, Joseph T; Farha, Omar K

    2016-01-01

    The synthesis of NU-1000, a highly robust mesoporous (containing pores >2 nm) metal-organic framework (MOF), can be conducted efficiently on a multigram scale from inexpensive starting materials. Tetrabromopyrene and (4-(ethoxycarbonyl)phenyl)boronic acid can easily be coupled to prepare the requisite organic strut with four metal-binding sites in the form of four carboxylic acids, while zirconyl chloride octahydrate is used as a precursor for the well-defined metal oxide clusters. NU-1000 has been reported as an excellent candidate for the separation of gases, and it is a versatile scaffold for heterogeneous catalysis. In particular, it is ideal for the catalytic deactivation of nerve agents, and it shows great promise as a new generic platform for a wide range of applications. Multiple post-synthetic modification protocols have been developed using NU-1000 as the parent material, making it a potentially useful scaffold for several catalytic applications. The procedure for the preparation of NU-1000 can be scaled up reliably, and it is suitable for the production of 50 g of the tetracarboxylic acid containing organic linker and 200 mg-2.5 g of NU-1000. The entire synthesis is performed without purification by column chromatography and can be completed within 10 d.

  9. A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability.

    PubMed

    Cavka, Jasmina Hafizovic; Jakobsen, Søren; Olsbye, Unni; Guillou, Nathalie; Lamberti, Carlo; Bordiga, Silvia; Lillerud, Karl Petter

    2008-10-22

    Porous crystals are strategic materials with industrial applications within petrochemistry, catalysis, gas storage, and selective separation. Their unique properties are based on the molecular-scale porous character. However, a principal limitation of zeolites and similar oxide-based materials is the relatively small size of the pores, typically in the range of medium-sized molecules, limiting their use in pharmaceutical and fine chemical applications. Metal organic frameworks (MOFs) provided a breakthrough in this respect. New MOFs appear at a high and an increasing pace, but the appearances of new, stable inorganic building bricks are rare. Here we present a new zirconium-based inorganic building brick that allows the synthesis of very high surface area MOFs with unprecedented stability. The high stability is based on the combination of strong Zr-O bonds and the ability of the inner Zr6-cluster to rearrange reversibly upon removal or addition of mu3-OH groups, without any changes in the connecting carboxylates. The weak thermal, chemical, and mechanical stability of most MOFs is probably the most important property that limits their use in large scale industrial applications. The Zr-MOFs presented in this work have the toughness needed for industrial applications; decomposition temperature above 500 degrees C and resistance to most chemicals, and they remain crystalline even after exposure to 10 tons/cm2 of external pressure.

  10. Functionalization of plasmonic metamaterials utilizing metal-organic framework thin films

    NASA Astrophysics Data System (ADS)

    Jakšić, Zoran; Popović, Zora; Djerdj, Igor; Jaćimović, Željko K.; Radulović, Katarina

    2012-05-01

    We considered theoretically and experimentally a strategy to functionalize plasmonic metamaterials utilizing either a metal-organic framework (MOF) or inorganic-organic hybrids for application in adsorption-based gas sensing. MOFs are one-dimensional (1D), 2D or 3D crystalline compounds that simultaneously contain metal ions or ion clusters and organic moieties, forming thus porous networks ensuring an increased effective surface for adsorption. Metamaterials can enhance plasmonic sensor performance through metal-dielectric nanocompositing that simultaneously tailors the electromagnetic response and boosts adsorption of the targeted analyte through the use of nanopores. To perform functionalization, it is necessary to integrate one or several layers of MOF nanocrystals with the metamaterial scaffold. The simplest approach is to use dip or drop coating or the layer-by-layer technique. The scaffolds that we considered included freestanding, ultrathin membranes and sandwich structures with nanoaperture arrays. For this investigation, we used a non-aqueous sol-gel route to synthesize vanadium oxyanthracene carboxylate, a novel material with 1D crystal structure. Our results suggest that preferential concentration of analyte within the MOF pores may ensure improved adsorption and thus sensor sensitivity enhancement. Also, one may increase selectivity by introducing nanoparticle fillers or by utilizing other functionalizing materials such as catalysts or ligands.

  11. Electronic origins of photocatalytic activity in d0 metal organic frameworks

    PubMed Central

    Nasalevich, Maxim A.; Hendon, Christopher H.; Santaclara, Jara G.; Svane, Katrine; van der Linden, Bart; Veber, Sergey L.; Fedin, Matvey V.; Houtepen, Arjan J.; van der Veen, Monique A.; Kapteijn, Freek; Walsh, Aron; Gascon, Jorge

    2016-01-01

    Metal-organic frameworks (MOFs) containing d0 metals such as NH2-MIL-125(Ti), NH2-UiO-66(Zr) and NH2-UiO-66(Hf) are among the most studied MOFs for photocatalytic applications. Despite structural similarities, we demonstrate that the electronic properties of these MOFs are markedly different. As revealed by quantum chemistry, EPR measurements and transient absorption spectroscopy, the highest occupied and lowest unoccupied orbitals of NH2-MIL-125(Ti) promote a long lived ligand-to-metal charge transfer upon photoexcitation, making this material suitable for photocatalytic applications. In contrast, in case of UiO materials, the d-orbitals of Zr and Hf, are too low in binding energy and thus cannot overlap with the π* orbital of the ligand, making both frontier orbitals localized at the organic linker. This electronic reconfiguration results in short exciton lifetimes and diminishes photocatalytic performance. These results highlight the importance of orbital contributions at the band edges and delineate future directions in the development of photo-active hybrid solids. PMID:27020767

  12. Tunable anisotropic thermal expansion of a porous zinc(II) metal-organic framework.

    PubMed

    Grobler, Ilne; Smith, Vincent J; Bhatt, Prashant M; Herbert, Simon A; Barbour, Leonard J

    2013-05-01

    A novel three-dimensional metal-organic framework (MOF) that displays anisotropic thermal expansion has been prepared and characterized by single-crystal X-ray diffraction (SCD) and thermal analysis. The as-prepared MOF has one-dimensional channels containing guest molecules that can be removed and/or exchanged for other guest molecules in a single-crystal to single-crystal fashion. When the original guest molecules are replaced there is a noticeable effect on the host mechanics, altering the thermal expansion properties of the material. This study of the thermal expansion coefficients of different inclusion complexes of the host MOF involved systematic alteration of guest size, i.e., methanol, ethanol, n-propanol, and isopropanol, showing that fine control over the thermal expansion coefficients can be achieved and that the coefficients can be correlated with the size of the guest. As a proof of concept, this study demonstrates the realizable principle that a single-crystal material with an exchangeable guest component (as opposed to a composite) may be used to achieve a tunable thermal expansion coefficient. In addition, this study demonstrates that greater variance in the absolute dimensions of a crystal can be achieved when one has two variables that affect it, i.e., the host-guest interactions and temperature.

  13. Immobilization of Metal-Organic Framework Nanocrystals for Advanced Design of Supported Nanocatalysts.

    PubMed

    Li, Ping; Zeng, Hua Chun

    2016-11-02

    In recent years, metal-organic frameworks (MOFs) have been employed as heterogeneous catalysts or precursors for synthesis of catalytic materials. However, conventional MOFs and their derivatives usually exhibit limited mass transfer and modest catalytic activities owing to a lengthy diffusion path and less exposed active sites. In contrast, it has been generally conceived that nanoscale MOFs are beneficial to materials utilization and mass transport, but their instability poses a serious issue to practical application. To tackle above challenges, herein we develop a novel and facile approach to the design and synthesis of nanocomposites through in situ growth and directed immobilization of nanoscale MOFs onto layered double hydroxides (LDH). The resulting supported nano-MOFs inherit advantages of pristine MOF nanocrystals and meanwhile gain enhanced stability and workability under reactive environments. A series of uniform nanometer-sized MOFs, including monometallic (ZIF-8, ZIF-67, and Cu-BTC) and bimetallic (CoZn-ZIF), can be readily synthesized onto hierarchically structured flowerlike MgAl-LDH supports with high dispersion and precision. Additionally, the resultant MgAl-LDH/MOFs can serve as a generic platform to prepare integrated nanocatalysts via controlled thermolysis. Knoevenagel condensation and reduction of 4-nitrophenol (4-NP) are used as model reactions for demonstrating the technological merits of these nanocatalysts. Therefore, this work elucidates that the synthetic immobilization of nanoscale MOFs onto conventional catalyst supports is a viable route to develop integrated nanocatalysts with high controllability over structural architecture and chemical composition.

  14. Systematic and Dramatic Tuning on Gas Sorption Performance in Heterometallic Metal-Organic Frameworks.

    PubMed

    Zhai, Quan-Guo; Bu, Xianhui; Mao, Chengyu; Zhao, Xiang; Feng, Pingyun

    2016-03-02

    Despite their having much greater potential for compositional and structural diversity, heterometallic metal-organic frameworks (MOFs) reported so far have lagged far behind their homometallic counterparts in terms of CO2 uptake performance. Now the power of heterometallic MOFs is in full display, as shown by a series of new materials (denoted CPM-200s) with superior CO2 uptake capacity (up to 207.6 cm(3)/g at 273 K and 1 bar), close to the all-time record set by MOF-74-Mg. The isosteric heat of adsorption can also be tuned from -16.4 kJ/mol for CPM-200-Sc/Mg to -79.6 kJ/mol for CPM-200-V/Mg. The latter value is the highest reported for MOFs with Lewis acid sites. Some members of the CPM-200s family consist of combinations of metal ions (e.g., Mg/Ga, Mg/Fe, Mg/V, Mg/Sc) that have never been shown to coexist in any known crystalline porous materials. Such previously unseen combinations become reality through a cooperative crystallization process, which leads to the most intimate form of integration between even highly dissimilar metals, such as Mg(2+) and V(3+). The synergistic effects of heterometals bestow CPM-200s with the highest CO2 uptake capacity among known heterometallic MOFs and place them in striking distance of the all-time CO2 uptake record.

  15. Metal-organic framework-based separator for lithium-sulfur batteries

    NASA Astrophysics Data System (ADS)

    Bai, Songyan; Liu, Xizheng; Zhu, Kai; Wu, Shichao; Zhou, Haoshen

    2016-07-01

    Lithium-sulfur batteries are a promising energy-storage technology due to their relatively low cost and high theoretical energy density. However, one of their major technical problems is the shuttling of soluble polysulfides between electrodes, resulting in rapid capacity fading. Here, we present a metal-organic framework (MOF)-based battery separator to mitigate the shuttling problem. We show that the MOF-based separator acts as an ionic sieve in lithium-sulfur batteries, which selectively sieves Li+ ions while efficiently suppressing undesired polysulfides migrating to the anode side. When a sulfur-containing mesoporous carbon material (approximately 70 wt% sulfur content) is used as a cathode composite without elaborate synthesis or surface modification, a lithium-sulfur battery with a MOF-based separator exhibits a low capacity decay rate (0.019% per cycle over 1,500 cycles). Moreover, there is almost no capacity fading after the initial 100 cycles. Our approach demonstrates the potential for MOF-based materials as separators for energy-storage applications.

  16. Lanthanide near infrared imaging in living cells with Yb3+ nano metal organic frameworks.

    PubMed

    Foucault-Collet, Alexandra; Gogick, Kristy A; White, Kiley A; Villette, Sandrine; Pallier, Agnès; Collet, Guillaume; Kieda, Claudine; Li, Tao; Geib, Steven J; Rosi, Nathaniel L; Petoud, Stéphane

    2013-10-22

    We have created unique near-infrared (NIR)-emitting nanoscale metal-organic frameworks (nano-MOFs) incorporating a high density of Yb(3+) lanthanide cations and sensitizers derived from phenylene. We establish here that these nano-MOFs can be incorporated into living cells for NIR imaging. Specifically, we introduce bulk and nano-Yb-phenylenevinylenedicarboxylate-3 (nano-Yb-PVDC-3), a unique MOF based on a PVDC sensitizer-ligand and Yb(3+) NIR-emitting lanthanide cations. This material has been structurally characterized, its stability in various media has been assessed, and its luminescent properties have been studied. We demonstrate that it is stable in certain specific biological media, does not photobleach, and has an IC50 of 100 μg/mL, which is sufficient to allow live cell imaging. Confocal microscopy and inductively coupled plasma measurements reveal that nano-Yb-PVDC-3 can be internalized by cells with a cytoplasmic localization. Despite its relatively low quantum yield, nano-Yb-PVDC-3 emits a sufficient number of photons per unit volume to serve as a NIR-emitting reporter for imaging living HeLa and NIH 3T3 cells. NIR microscopy allows for highly efficient discrimination between the nano-MOF emission signal and the cellular autofluorescence arising from biological material. This work represents a demonstration of the possibility of using NIR lanthanide emission for biological imaging applications in living cells with single-photon excitation.

  17. Lanthanide near infrared imaging in living cells with Yb3+ nano metal organic frameworks

    PubMed Central

    Foucault-Collet, Alexandra; Gogick, Kristy A.; White, Kiley A.; Villette, Sandrine; Pallier, Agnès; Collet, Guillaume; Kieda, Claudine; Li, Tao; Geib, Steven J.; Rosi, Nathaniel L.; Petoud, Stéphane

    2013-01-01

    We have created unique near-infrared (NIR)–emitting nanoscale metal-organic frameworks (nano-MOFs) incorporating a high density of Yb3+ lanthanide cations and sensitizers derived from phenylene. We establish here that these nano-MOFs can be incorporated into living cells for NIR imaging. Specifically, we introduce bulk and nano-Yb-phenylenevinylenedicarboxylate-3 (nano-Yb-PVDC-3), a unique MOF based on a PVDC sensitizer-ligand and Yb3+ NIR-emitting lanthanide cations. This material has been structurally characterized, its stability in various media has been assessed, and its luminescent properties have been studied. We demonstrate that it is stable in certain specific biological media, does not photobleach, and has an IC50 of 100 μg/mL, which is sufficient to allow live cell imaging. Confocal microscopy and inductively coupled plasma measurements reveal that nano-Yb-PVDC-3 can be internalized by cells with a cytoplasmic localization. Despite its relatively low quantum yield, nano-Yb-PVDC-3 emits a sufficient number of photons per unit volume to serve as a NIR-emitting reporter for imaging living HeLa and NIH 3T3 cells. NIR microscopy allows for highly efficient discrimination between the nano-MOF emission signal and the cellular autofluorescence arising from biological material. This work represents a demonstration of the possibility of using NIR lanthanide emission for biological imaging applications in living cells with single-photon excitation. PMID:24108356

  18. Evaluation of heterogeneous metal-organic framework organocatalysts prepared by postsynthetic modification.

    PubMed

    Garibay, Sergio J; Wang, Zhenqiang; Cohen, Seth M

    2010-09-06

    A metal-organic framework (MOF) containing 2-amino-1,4-benzenedicarboxylate (NH(2)-BDC) as a building block is shown to undergo chemical modification with a set of cyclic anhydrides. The modification of the aluminum-based MOF known as MIL-53(Al)-NH(2) (MIL = Material Institut Lavoisier) by these reagents is demonstrated by using a variety of methods, including NMR and electrospray ionization mass spectrometry (ESI-MS), and the structural integrity of the modified MOFs has been confirmed by thermal gravimetric analysis (TGA) and powder X-ray diffraction (PXRD). Reaction with these cyclic anhydrides produces MOFs that display carboxylic acid functional groups within their pores. Furthermore, it is shown that maleic acid functionalized MIL-53(Al)-AMMal can act as a Brønsted acid catalyst and facilitate the methanolysis of several small epoxides. Experiments show that MIL-53(Al)-AMMal acts in a heterogeneous manner and is recyclable with consistent activity over at least three catalytic cycles. The findings presented here demonstrate several important features of covalent postsynthetic modification (PSM) on MOFs, including (1) facile introduction of catalytic functionality using simple organic reagents (e.g., anhydrides); (2) the ability to utilize and recycle organocatalytic MOFs; (3) control of catalytic activity through choice of functional group. The findings clearly illustrate that covalent postsynthetic modification represents a powerful means to access new MOF compounds that serve as organocatalytic materials.

  19. Adsorptive removal and separation of chemicals with metal-organic frameworks: Contribution of π-complexation.

    PubMed

    Khan, Nazmul Abedin; Jhung, Sung Hwa

    2017-03-05

    Efficient removal and separation of chemicals from the environment has become a vital issue from a biological and environmental point of view. Currently, adsorptive removal/separation is one of the most promising approaches for cleaning purposes. Selective adsorption/removal of various sulfur- and nitrogen-containing compounds, olefins, and π-electron-rich gases via π-complex formation between an adsorbent and adsorbate molecules is very competitive. Porous metal-organic framework (MOF) materials are very promising in the adsorption/separation of various liquids and gases owing to their distinct characteristics. This review summarizes the literature on the adsorptive removal/separation of various π-electron-rich compounds mainly from fuel and gases using MOF materials containing metal ions that are active for π-complexation. Details of the π-complexation, including mechanism, pros/cons, applications, and efficient ways to form the complex, are discussed systematically. For in-depth understanding, molecular orbital calculations regarding charge transfer between the π-complexing species are also explained in a separate section. From this review, readers will gain an understanding of π-complexation for adsorption and separation, especially with MOFs, to develop new insight for future research.

  20. Porous metal-organic-framework nanoscale carriers as a potential platform for drug delivery and imaging

    NASA Astrophysics Data System (ADS)

    Horcajada, Patricia; Chalati, Tamim; Serre, Christian; Gillet, Brigitte; Sebrie, Catherine; Baati, Tarek; Eubank, Jarrod F.; Heurtaux, Daniela; Clayette, Pascal; Kreuz, Christine; Chang, Jong-San; Hwang, Young Kyu; Marsaud, Veronique; Bories, Phuong-Nhi; Cynober, Luc; Gil, Sophie; Férey, Gérard; Couvreur, Patrick; Gref, Ruxandra

    2010-02-01

    In the domain of health, one important challenge is the efficient delivery of drugs in the body using non-toxic nanocarriers. Most of the existing carrier materials show poor drug loading (usually less than 5wt% of the transported drug versus the carrier material) and/or rapid release of the proportion of the drug that is simply adsorbed (or anchored) at the external surface of the nanocarrier. In this context, porous hybrid solids, with the ability to tune their structures and porosities for better drug interactions and high loadings, are well suited to serve as nanocarriers for delivery and imaging applications. Here we show that specific non-toxic porous iron(III)-based metal-organic frameworks with engineered cores and surfaces, as well as imaging properties, function as superior nanocarriers for efficient controlled delivery of challenging antitumoural and retroviral drugs (that is, busulfan, azidothymidine triphosphate, doxorubicin or cidofovir) against cancer and AIDS. In addition to their high loadings, they also potentially associate therapeutics and diagnostics, thus opening the way for theranostics, or personalized patient treatments.

  1. Electronic origins of photocatalytic activity in d0 metal organic frameworks

    NASA Astrophysics Data System (ADS)

    Nasalevich, Maxim A.; Hendon, Christopher H.; Santaclara, Jara G.; Svane, Katrine; van der Linden, Bart; Veber, Sergey L.; Fedin, Matvey V.; Houtepen, Arjan J.; van der Veen, Monique A.; Kapteijn, Freek; Walsh, Aron; Gascon, Jorge

    2016-03-01

    Metal-organic frameworks (MOFs) containing d0 metals such as NH2-MIL-125(Ti), NH2-UiO-66(Zr) and NH2-UiO-66(Hf) are among the most studied MOFs for photocatalytic applications. Despite structural similarities, we demonstrate that the electronic properties of these MOFs are markedly different. As revealed by quantum chemistry, EPR measurements and transient absorption spectroscopy, the highest occupied and lowest unoccupied orbitals of NH2-MIL-125(Ti) promote a long lived ligand-to-metal charge transfer upon photoexcitation, making this material suitable for photocatalytic applications. In contrast, in case of UiO materials, the d-orbitals of Zr and Hf, are too low in binding energy and thus cannot overlap with the π* orbital of the ligand, making both frontier orbitals localized at the organic linker. This electronic reconfiguration results in short exciton lifetimes and diminishes photocatalytic performance. These results highlight the importance of orbital contributions at the band edges and delineate future directions in the development of photo-active hybrid solids.

  2. Potential of a metal-organic framework as a new material for solid-phase extraction of pesticides from lettuce (Lactuca sativa), with analysis by gas chromatography-mass spectrometry.

    PubMed

    Barreto, Alysson S; da Silva, Rogério Luiz; Dos Santos Silva, Silvia Caroline G; Rodrigues, Marcelo O; de Simone, Carlos A; de Sá, Gilberto F; Júnior, Severino A; Navickiene, Sandro; de Mesquita, Maria Eliane

    2010-12-01

    The metal-organic framework (∞)[(La(0.9)Eu(0.1))(2)(DPA)(3)(H(2)O)(3)] was tested for extraction of pyrimicarb, procymidone, malathion, methyl parathion and α- and β-endosulfan from lettuce, with analysis using GC/MS in SIM mode. Experiments were carried out in triplicate at two fortification levels (0.1 and 0.5 mg/kg), and resulted in recoveries in the range of 78-107%, with RSD values between 1.6 and 8.0% for (∞)[(La(0.9)Eu(0.1))(2)(DPA)(3)(H(2)O)(3)] sorbent. Detection and quantification limits ranged from 0.02 to 0.05 mg/kg and from 0.05 to 0.10 mg/kg, respectively, for the different pesticides studied. The method developed was linear over the range tested (0.05-10.0 μg/mL), with correlation coefficients ranging from 0.9990 to 0.9997. Comparison between (∞)[(La(0.9)Eu(0.1))(2)(DPA)(3)(H(2)O)(3)] and conventional sorbent (silica gel) showed better performance of the (∞)[(La(0.9)Eu(0.1))(2)(DPA)(3)(H(2)O)(3)] polymeric sorbent for all pesticides tested.

  3. Metal-organic fireworks: MOFs as integrated structural scaffolds for pyrotechnic materials.

    PubMed

    Blair, L H; Colakel, A; Vrcelj, R M; Sinclair, I; Coles, S J

    2015-08-07

    A new approach to formulating pyrotechnic materials is presented whereby constituent ingredients are bound together in a solid-state lattice. This reduces the batch inconsistencies arising from the traditional approach of combining powders by ensuring the key ingredients are 'mixed' in appropriate quantities and are in intimate contact. Further benefits of these types of material are increased safety levels as well as simpler logistics, storage and manufacture. A systematic series of new frameworks comprising fuel and oxidiser agents (group 1 and 2 metal nodes & terephthalic acid derivatives as linkers) has been synthesised and structurally characterised. These new materials have been assessed for pyrotechnic effect by calorimetry and burn tests. Results indicate that these materials exhibit the desired pyrotechnic material properties and the effect can be correlated to the dimensionality of the structure. A new approach to formulating pyrotechnic materials is proposed whereby constituent ingredients are bound together in a solid-state lattice. A series of Metal-organic framework frameworks comprising fuel and oxidiser agents exhibits the desired properties of a pyrotechnic material and this effect is correlated to the dimensionality of the structure.

  4. Automatic In-Syringe Dispersive Microsolid Phase Extraction Using Magnetic Metal-Organic Frameworks.

    PubMed

    Maya, Fernando; Palomino Cabello, Carlos; Estela, Jose Manuel; Cerdà, Víctor; Turnes Palomino, Gemma

    2015-08-04

    A novel automatic strategy for the use of micro- and nanomaterials as sorbents for dispersive microsolid phase extraction (D-μ-SPE) based on the lab-in-syringe concept is reported. Using the developed technique, the implementation of magnetic metal-organic framework (MOF) materials for automatic solid-phase extraction has been achieved for the first time. A hybrid material based on submicrometric MOF crystals containing Fe3O4 nanoparticles was prepared and retained in the surface of a miniature magnetic bar. The magnetic bar was placed inside the syringe of an automatic bidirectional syringe pump, enabling dispersion and subsequent magnetic retrieval of the MOF hybrid material by automatic activation/deactivation of magnetic stirring. Using malachite green (MG) as a model adsorption analyte, a limit of detection of 0.012 mg/L and a linear working range of 0.04-2 mg/L were obtained for a sample volume equal to the syringe volume (5 mL). MG preconcentration was linear up to a volume of 40 mL, obtaining an enrichment factor of 120. The analysis throughput is 18 h(-1), and up to 3000 extractions/g of material can be performed. Recoveries ranging between 95 and 107% were obtained for the analysis of MG in different types of water and trout fish samples. The developed automatic D-μ-SPE technique is a safe alternative for the use of small-sized materials for sample preparation and is readily implementable to other magnetic materials independent of their size and shape and can be easily hyphenated to the majority of detectors and separation techniques.

  5. Large-scale generation and screening of hypothetical metal-organic frameworks for applications in gas storage and separations.

    PubMed

    Wilmer, Christopher E; Snurr, Randall Q

    2014-01-01

    Metal-organic frameworks (MOFs) are porous crystals that are synthesized in a building-block approach that greatly facilitates rational design. MOFs are promising materials for gas storage and separation applications, but they are also intriguing for their potential use as catalysts, electrodes, and drug delivery vehicles. For these reasons, MOFs have spurred a renewed interest in the concept of "crystal engineering," where the crystal structure of a material is designed to meet application-specific criteria. This chapter reviews recent work in the computational design of MOFs, with an emphasis on high-throughput methods that generate and screen many thousands of candidates automatically.

  6. Proton Conduction in a Phosphonate-Based Metal-Organic Framework Mediated by Intrinsic "Free Diffusion inside a Sphere".

    PubMed

    Pili, Simona; Argent, Stephen P; Morris, Christopher G; Rought, Peter; García-Sakai, Victoria; Silverwood, Ian P; Easun, Timothy L; Li, Ming; Warren, Mark R; Murray, Claire A; Tang, Chiu C; Yang, Sihai; Schröder, Martin

    2016-05-25

    Understanding the molecular mechanism of proton conduction is crucial for the design of new materials with improved conductivity. Quasi-elastic neutron scattering (QENS) has been used to probe the mechanism of proton diffusion within a new phosphonate-based metal-organic framework (MOF) material, MFM-500(Ni). QENS suggests that the proton conductivity (4.5 × 10(-4) S/cm at 98% relative humidity and 25 °C) of MFM-500(Ni) is mediated by intrinsic "free diffusion inside a sphere", representing the first example of such a mechanism observed in MOFs.

  7. Fluorous Metal-Organic Frameworks with Enhanced Stability and High H2/CO2 Storage Capacities

    PubMed Central

    Zhang, Da-Shuai; Chang, Ze; Li, Yi-Fan; Jiang, Zhong-Yi; Xuan, Zhi-Hong; Zhang, Ying-Hui; Li, Jian-Rong; Chen, Qiang; Hu, Tong-Liang; Bu, Xian-He

    2013-01-01

    A new class of metal-organic frameworks (MOFs) has been synthesized by ligand-functionalization strategy. Systematic studies of their adsorption properties were performed at low and high pressure. Importantly, when fluorine was introduced into the framework via the functionalization, both the framework stabilities and adsorption capacities towards H2/CO2 were enhanced significantly. This consequence can be well interpreted by theoretical studies of these MOFs structures. In addition, one of these MOFs TKL-107 was used to fabricate mixed matrix membranes, which exhibit great potential for the application of CO2 separation. PMID:24264725

  8. Aromatizing olefin metathesis by ligand isolation inside a metal-organic framework.

    PubMed

    Vermeulen, Nicolaas A; Karagiaridi, Olga; Sarjeant, Amy A; Stern, Charlotte L; Hupp, Joseph T; Farha, Omar K; Stoddart, J Fraser

    2013-10-09

    The aromatizing ring-closing metathesis has been shown to take place inside an extended porous framework. Employing a combination of solvent-assisted linker exchange and postsynthesis modification using olefin metathesis, the noninterpenetrated SALEM-14 was formed and converted catalytically into PAH-MOF-1 with polycyclic aromatic hydrocarbon (PAH) pillars. The metal-organic framework in SALEM-14 prevents "intermolecular" olefin metathesis from occurring between the pillars in the presence of the first generation Hoveyda-Grubbs catalyst, while favoring the production of a PAH, which can be released from the framework under acidic conditions in dimethylsulfoxide.

  9. Polydopamine tethered enzyme/metal-organic framework composites with high stability and reusability

    NASA Astrophysics Data System (ADS)

    Wu, Xiaoling; Yang, Cheng; Ge, Jun; Liu, Zheng

    2015-11-01

    An enzyme/metal-organic framework (MOF) composite with both highly stable and easily reusable features was prepared via tethering enzyme/MOF nanocrystals with polydopamine (PDA). The micrometer-sized PDA tethered enzyme/MOF composite can be easily repeatedly used without obvious activity loss, promising for efficient enzymatic catalysis at low cost with long-term operational stability under harsh conditions.An enzyme/metal-organic framework (MOF) composite with both highly stable and easily reusable features was prepared via tethering enzyme/MOF nanocrystals with polydopamine (PDA). The micrometer-sized PDA tethered enzyme/MOF composite can be easily repeatedly used without obvious activity loss, promising for efficient enzymatic catalysis at low cost with long-term operational stability under harsh conditions. Electronic supplementary information (ESI) available: Synthesis of enzyme-MOF nanocrystals, SEM, TEM, CLSM characterization and measurements of enzymatic performances. See DOI: 10.1039/c5nr05190h

  10. A Metal Organic Framework with Spherical Protein Nodes: Rational Chemical Design of 3D Protein Crystals.

    PubMed

    Sontz, Pamela A; Bailey, Jake B; Ahn, Sunhyung; Tezcan, F Akif

    2015-09-16

    We describe here the construction of a three-dimensional, porous, crystalline framework formed by spherical protein nodes that assemble into a prescribed lattice arrangement through metal-organic linker-directed interactions. The octahedral iron storage enzyme, ferritin, was engineered in its C3 symmetric pores with tripodal Zn coordination sites. Dynamic light scattering and crystallographic studies established that this Zn-ferritin construct could robustly self-assemble into the desired bcc-type crystals upon coordination of a ditopic linker bearing hydroxamic acid functional groups. This system represents the first example of a ternary protein-metal-organic crystalline framework whose formation is fully dependent on each of its three components.

  11. Adsorption of gases and large polycyclic organic molecules in metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Siberio-Perez, Diana Yazmin

    Metal-organic frameworks (MOFs) are a class of porous materials with unique properties, including size tunable pores and cavities that allow for high surface areas and high levels of porosity. These properties make MOFs appealing for a number of traditional processes such as separations and catalysis, and for areas of current interest such as gas storage. The implementation of these frameworks into these areas first requires an understanding of the adsorbene-adsorbent interactions. For this reason, the adsorption behavior of CH4, N2, and CO2 (298 K, 30 bar) in a series of isoreticular MOFs (IRMOFs) was investigated by Raman spectroscopy. The data were marked by different shifts to the normal vibrational modes of the gases, depending on the IRMOF to which they were adsorbed. These shifts arise due to interactions within the framework pores, and not with the outer crystal surface. In all cases, Raman spectra at pressures up to 30 bar showed that saturation of the sorption sites does not occur. The observed shifts of the vibrational modes for each gas indicate different chemical environments within different IRMOFs, pointing to the important role the linkers play in the adsorption of gases. Despite the fact that MOFs possess surface areas that exceed those of other porous materials, no method of determining the upper limit in surface area for a material had yet been determined. Here, a general strategy is presented that has allowed for the realization of a structure that has one of the highest surface areas reported to date. The design and inclusion properties of crystalline Zn4O(1,3,5-benzenetribenzoate)2, a framework with a surface area measured to exceed 4,500 m2/g, is reported. This framework, named MOF-177, combines this exceptional level of surface area with an ordered structure that has extra-large pores capable of binding polycyclic organic guest molecules, that include C60 and several dyes. Size and isomer selectivity may also be achieved with MOF-177, as

  12. Protection and deprotection approach for the introduction of functional groups into metal-organic frameworks.

    PubMed

    Yamada, Teppei; Kitagawa, Hiroshi

    2009-05-13

    A noncoordinating hydroxyl group was introduced into a metal-organic framework (MOF) by a procedure involving a protection, complexation, and deprotection (PCD) reaction sequence, and the crystal structure of a novel MOF, [Zn(dhybdc)(bpy)] x 4 DMF (1), was determined. 1 did not have an interpenetrated structure. The three-dimensional pores had large apertures. Results showed that the PCD method is a novel synthetic method for the introduction of various functional groups into MOFs.

  13. Separation of polar compounds using a flexible metal-organic framework

    SciTech Connect

    Motkuri, Radha K.; Thallapally, Praveen K.; Annapureddy, Harsha V.; Dang, Liem X.; Krishna, Rajamani; Nune, Satish K.; Fernandez, Carlos A.; Liu, Jian; McGrail, B. Peter

    2015-01-01

    A flexible metal-organic framework constructed from a flexible linker is shown to possess the capability of separating mixtures of polar compounds by exploiting the differences in the saturation capacities of the constituents. The separation possibilities with the flexible MOF include mixtures of propanol isomers, and various azeotropes. Transient breakthrough simulations show that these sorption-based separations are in favor of the component with higher saturation capacity.

  14. Biomimetic Replication of Microscopic Metal-Organic Framework Patterns Using Printed Protein Patterns.

    PubMed

    Liang, Kang; Carbonell, Carlos; Styles, Mark J; Ricco, Raffaele; Cui, Jiwei; Richardson, Joseph J; Maspoch, Daniel; Caruso, Frank; Falcaro, Paolo

    2015-12-02

    It is demonstrated that metal-organic frameworks (MOFs) can be replicated in a biomimetic fashion from protein patterns. Bendable, fluorescent MOF patterns are formed with micrometer resolution under ambient conditions. Furthermore, this technique is used to grow MOF patterns from fingerprint residue in 30 s with high fidelity. This technique is not only relevant for crime-scene investigation, but also for biomedical applications.

  15. Controlled Encapsulation of Functional Organic Molecules within Metal-Organic Frameworks: In Situ Crystalline Structure Transformation.

    PubMed

    Guan, Jinju; Hu, Yu; Wang, Yu; Li, Hongfeng; Xu, Zhiling; Zhang, Tao; Wu, Peng; Zhang, Suoying; Xiao, Gengwu; Ji, Wenlan; Li, Linjie; Zhang, Meixuan; Fan, Yun; Li, Lin; Zheng, Bing; Zhang, Weina; Huang, Wei; Huo, Fengwei

    2017-01-23

    Functional organic molecules/metal-organic frameworks composites can be obtained by in situ crystalline structure transformation from ZIF-L to ZIF-8-L under double solvent conditions. Interestingly, the as-prepared molecules/ZIF-8-L composites with the leaf-like morphology exhibit good fluorescence properties and size selectivity in fluorescent quenchers due to the molecular sieving effect of the well-defined microporous ZIF-8-L.

  16. Planar Heterojunction Perovskite Solar Cells Incorporating Metal-Organic Framework Nanocrystals.

    PubMed

    Chang, Ting-Hsiang; Kung, Chung-Wei; Chen, Hsin-Wei; Huang, Tzu-Yen; Kao, Sheng-Yuan; Lu, Hsin-Che; Lee, Min-Han; Boopathi, Karunakara Moorthy; Chu, Chih-Wei; Ho, Kuo-Chuan

    2015-11-25

    Zr-based porphyrin metal-organic framework (MOF-525) nanocrystals with a crystal size of about 140 nm are synthesized and incorporated into perovskite solar cells. The morphology and crystallinity of the perovskite thin film are enhanced since the micropores of MOF-525 allow the crystallization of perovskite to occur inside; this observation results in a higher cell efficiency of the obtained MOF/perovskite solar cell.

  17. Surfactant-thermal method to prepare two new cobalt metal-organic frameworks

    SciTech Connect

    Yu, Xianglin; Toh, Yong Siang; Zhao, Jun; Nie, Lina; Ye, Kaiqi; Wang, Yue; Li, Dongsheng; Zhang, Qichun

    2015-12-15

    Employing surfactants as reaction media, two new metal-organic frameworks (MOFs):(HTEA){sub 3}[Co{sub 3}(BTC){sub 3}] (NTU-Z33) and (HTEA)[Co{sub 3}(HBTC){sub 2}(BTC)] (NTU-Z34) (H{sub 3}BTC=1,3,5-benzenetricarboxylic acid, TEA=trimethylamine, and NTU=Nanyang Technological University), have been successfully synthesized and fully characterized. Note that NTU-Z33 has an unusual trimeric [Co{sub 3}(COO){sub 9}] secondary building unit (SBU). Magnetic characterization suggests that both compounds have weak antiferromagnetic behaviors. Our success in preparing new crystalline Co-BTC based MOFs under different surfactant media could provide a new road to prepare new diverse MOFs through various combinations of surfactants. - Graphical abstract: Employing surfactants as reaction media, two new metal-organic frame-works (MOFs) have been successfully synthesized and magnetic study suggests that both compounds have weak antiferromagnetic behaviors. - Highlights: • Two novel metal-organic frame-works (MOFs). • Synthesis through surfactant-thermal condition. • weak antiferromagnetic behaviors for both compounds.

  18. Smart Nanocomposites of Cu-Hemin Metal-Organic Frameworks for Electrochemical Glucose Biosensing

    PubMed Central

    He, Juan; Yang, Han; Zhang, Yayun; Yu, Jie; Miao, Longfei; Song, Yonghai; Wang, Li

    2016-01-01

    Herein, a smart porous material, Cu-hemin metal-organic-frameworks (Cu-hemin MOFs), was synthesized via assembling of Cu2+ with hemin to load glucose oxidase (GOD) for electrochemical glucose biosensing for the first time. The formation of the Cu-hemin MOFs was verified by scanning electron microscopy, X-ray powder diffraction, Fourier transform infrared spectroscopy, N2 adsorption/desorption isotherms, UV-vis absorption spectroscopy, fluorescence spectroscopy, thermal analysis and electrochemical techniques. The results indicated that the Cu-hemin MOFs showed a ball-flower-like hollow cage structure with a large specific surface area and a large number of mesopores. A large number of GOD molecules could be successfully loaded in the pores of Cu-hemin MOFs to keep their bioactivity just like in a solution. The GOD/Cu-hemin MOFs exhibited both good performance toward oxygen reduction reaction via Cu-hemin MOFs and catalytic oxidation of glucose via GOD, superior to other GOD/MOFs and GOD/nanomaterials. Accordingly, the performance of GOD/Cu-hemin MOFs-based electrochemical glucose sensor was enhanced greatly, showing a wide linear range from 9.10 μM to 36.0 mM and a low detection limit of 2.73 μM. Moreover, the sensor showed satisfactory results in detection of glucose in human serum. This work provides a practical design of new electrochemical sensing platform based on MOFs and biomolecules. PMID:27811998

  19. A Green Strategy to Prepare Metal Oxide Superstructure from Metal-Organic Frameworks

    PubMed Central

    Song, Yonghai; Li, Xia; Wei, Changting; Fu, Jinying; Xu, Fugang; Tan, Hongliang; Tang, Juan; Wang, Li

    2015-01-01

    Metal or metal oxides with diverse superstructures have become one of the most promising functional materials in sensor, catalysis, energy conversion, etc. In this work, a novel metal-organic frameworks (MOFs)-directed method to prepare metal or metal oxide superstructure was proposed. In this strategy, nodes (metal ions) in MOFs as precursors to form ordered building blocks which are spatially separated by organic linkers were transformed into metal oxide micro/nanostructure by a green method. Two kinds of Cu-MOFs which could reciprocally transform by changing solvent were prepared as a model to test the method. Two kinds of novel CuO with three-dimensional (3D) urchin-like and 3D rods-like superstructures composed of nanoparticles, nanowires and nanosheets were both obtained by immersing the corresponding Cu-MOFs into a NaOH solution. Based on the as-formed CuO superstructures, a novel and sensitive nonenzymatic glucose sensor was developed. The small size, hierarchical superstructures and large surface area of the resulted CuO superstructures eventually contribute to good electrocatalytic activity of the prepared sensor towards the oxidation of glucose. The proposed method of hierarchical superstructures preparation is simple, efficient, cheap and easy to mass production, which is obviously superior to pyrolysis. It might open up a new way for hierarchical superstructures preparation. PMID:25669731

  20. High-capacity hydrogen and nitric oxide adsorption and storage in a metal-organic framework.

    PubMed

    Xiao, Bo; Wheatley, Paul S; Zhao, Xuebo; Fletcher, Ashleigh J; Fox, Sarah; Rossi, Adriano G; Megson, Ian L; Bordiga, S; Regli, L; Thomas, K Mark; Morris, Russell E

    2007-02-07

    Gas adsorption experiments have been carried out on a copper benzene tricarboxylate metal-organic framework material, HKUST-1. Hydrogen adsorption at 1 and 10 bar (both 77 K) gives an adsorption capacity of 11.16 mmol H2 per g of HKUST-1 (22.7 mg g(-)1, 2.27 wt %) at 1 bar and 18 mmol per g (36.28 mg g(-)1, 3.6 wt %) at 10 bar. Adsorption of D2 at 1 bar (77 K) is between 1.09 (at 1 bar) and 1.20(at <100 mbar) times the H2 values depending on the pressure, agreeing with the theoretical expectations. Gravimetric adsorption measurements of NO on HKUST-1 at 196 K (1 bar) gives a large adsorption capacity of approximately 9 mmol g(-1), which is significantly greater than any other adsorption capacity reported on a porous solid. At 298 K the adsorption capacity at 1 bar is just over 3 mmol g(-1). Infra red experiments show that the NO binds to the empty copper metal sites in HKUST-1. Chemiluminescence and platelet aggregometry experiments indicate that the amount of NO recovered on exposure of the resulting complex to water is enough to be biologically active, completely inhibiting platelet aggregation in platelet rich plasma.

  1. Sintering-Resistant Single-Site Nickel Catalyst Supported by Metal-Organic Framework.

    PubMed

    Li, Zhanyong; Schweitzer, Neil M; League, Aaron B; Bernales, Varinia; Peters, Aaron W; Getsoian, Andrew Bean; Wang, Timothy C; Miller, Jeffrey T; Vjunov, Aleksei; Fulton, John L; Lercher, Johannes A; Cramer, Christopher J; Gagliardi, Laura; Hupp, Joseph T; Farha, Omar K

    2016-02-17

    Developing supported single-site catalysts is an important goal in heterogeneous catalysis since the well-defined active sites afford opportunities for detailed mechanistic studies, thereby facilitating the design of improved catalysts. We present herein a method for installing Ni ions uniformly and precisely on the node of a Zr-based metal-organic framework (MOF), NU-1000, in high density and large quantity (denoted as Ni-AIM) using atomic layer deposition (ALD) in a MOF (AIM). Ni-AIM is demonstrated to be an efficient gas-phase hydrogenation catalyst upon activation. The structure of the active sites in Ni-AIM is proposed, revealing its single-site nature. More importantly, due to the organic linker used to construct the MOF support, the Ni ions stay isolated throughout the hydrogenation catalysis, in accord with its long-term stability. A quantum chemical characterization of the catalyst and the catalytic process complements the experimental results. With validation of computational modeling protocols, we further targeted ethylene oligomerization catalysis by Ni-AIM guided by theoretical prediction. Given the generality of the AIM methodology, this emerging class of materials should prove ripe for the discovery of new catalysts for the transformation of volatile substrates.

  2. Mechanically Interlocked Linkers inside Metal-Organic Frameworks: Effect of Ring Size on Rotational Dynamics.

    PubMed

    Vukotic, V Nicholas; O'Keefe, Christopher A; Zhu, Kelong; Harris, Kristopher J; To, Christine; Schurko, Robert W; Loeb, Stephen J

    2015-08-05

    A series of metal-organic framework (MOF) materials has been prepared, each containing a mechanically interlocked molecule (MIM) as the linker and a copper(II) paddlewheel as the secondary building unit (SBU). The MIM linkers are [2]rotaxanes with varying sizes of crown ether macrocycles ([22]crown-6, 22C6; [24]crown-6, 24C6; [26]crown-6, 26C6; benzo[24]crown-6, B24C6) and an anilinium-based axle containing four carboxylate donor groups. Herein, the X-ray structures of MOFs UWCM-1 (no crown) and UWDM-1(22) are compared and demonstrate the effect of including a macrocycle around the axle of the linker. The rotaxane linkers are linear and result in nbo-type MOFs with void space that allows for motion of the interlocked macrocycle inside the MOF pores, while the macrocycle-free linker is bent and yields a MOF with a novel 12-connected bcc structure. Variable temperature (2)H solid-state nuclear magnetic resonance showed that the macrocycles in UWDM-1(22), UWDM-1(24), and UWDM-1(B24) undergo different degrees and rates of rotation depending on the size and shape of the macrocycle.

  3. Metal Insertion in a Microporous Metal-Organic Framework Lined with 2,2'-Bipyridine

    SciTech Connect

    Bloch, Eric D.; Britt, David; Lee, Chain; Doonan, Christian J.; Uribe-Romo, Fernando J.; Furukawa, Hiroyasu; Long, Jeffrey R.; Yaghi, Omar M.

    2010-10-20

    Reaction of AlCl3·6H2O with 2,2'-bipyridine-5,5'-dicarboxylic acid (H2bpydc) affords Al(OH)(bpydc) (1, MOF-253), the first metal-organic framework with open 2,2'-bipyridine (bpy) coordination sites. The material displays a BET surface area of 2160 m2/g and readily complexes metals to afford, for example, 1·xPdCl2 (x = 0.08, 0.83) and 1·0.97Cu(BF4)2. EXAFS spectroscopy performed on 1·0.83PdCl2 reveals the expected square planar coordination geometry, matching the structure of the model complex (bpy)PdCl2. Finally, significantly, the selectivity factor for binding CO2 over N2 under typical flue gas conditions is observed to increase from 2.8 in 1 to 12 in 1·0.97Cu(BF4)2.

  4. Computational Discovery of Metal-Organic Frameworks for CO2 Capture and Energy Storage

    NASA Astrophysics Data System (ADS)

    Siegel, Donald

    2015-03-01

    Because of their high surface areas, crystallinity, and tunable properties, metal -organic frameworks (MOFs) have attracted intense interest as materials for gas capture and energy storage. An often-cited benefit of MOFs is their large number of possible structures and compositions. Nevertheless, this design flexibility also has drawbacks, as pinpointing optimal compounds from thousands of candidates can be time consuming and costly using experimental approaches. Consequently, computational approaches are garnering increasing importance as a means to accelerate the discovery of high-performing MOFs. Here we combine several computational techniques to identify promising MOFs for CO2 capture and the storage of gaseous fuels (methane and hydrogen). The techniques include: (i) high-throughput screening based on data-mining and empirical correlations; (ii) Monte Carlo simulations based on quantum-mechanically-informed forcefields; and (iii) first-principles calculations of thermodynamics and electronic structure. For CO2 capture and CH4 storage, these techniques are used to explore metal-substituted variants of M-DOBDC and M-HKUST-1. In the case of H2, we identify trends and promising adsorbents amongst 4,000 compounds mined from the Cambridge Structure Database.

  5. A porous metal-organic framework with ultrahigh acetylene uptake capacity under ambient conditions

    PubMed Central

    Pang, Jiandong; Jiang, Feilong; Wu, Mingyan; Liu, Caiping; Su, Kongzhao; Lu, Weigang; Yuan, Daqiang; Hong, Maochun

    2015-01-01

    Acetylene, an important petrochemical raw material, is very difficult to store safely under compression because of its highly explosive nature. Here we present a porous metal-organic framework named FJI-H8, with both suitable pore space and rich open metal sites, for efficient storage of acetylene under ambient conditions. Compared with existing reports, FJI-H8 shows a record-high gravimetric acetylene uptake of 224 cm3 (STP) g−1 and the second-highest volumetric uptake of 196 cm3 (STP) cm−3 at 295 K and 1 atm. Increasing the storage temperature to 308 K has only a small effect on its acetylene storage capacity (∼200 cm3 (STP) g−1). Furthermore, FJI-H8 exhibits an excellent repeatability with only 3.8% loss of its acetylene storage capacity after five cycles of adsorption–desorption tests. Grand canonical Monte Carlo simulation reveals that not only open metal sites but also the suitable pore space and geometry play key roles in its remarkable acetylene uptake. PMID:26123775

  6. Constructing Free Standing Metal Organic Framework MIL-53 Membrane Based on Anodized Aluminum Oxide Precursor

    NASA Astrophysics Data System (ADS)

    Zhang, Yunlu; Gao, Qiuming; Lin, Zhi; Zhang, Tao; Xu, Jiandong; Tan, Yanli; Tian, Weiqian; Jiang, Lei

    2014-05-01

    Metal organic framework (MOF) materials have attracted great attention due to their well-ordered and controllable pores possessing of prominent potentials for gas molecule sorption and separation performances. Organizing the MOF crystals to a continuous membrane with a certain scale will better exhibit their prominent potentials. Reports in recent years concentrate on well grown MOF membranes on specific substrates. Free standing MOF membranes could have more important applications since they are independent from the substrates. However, the method to prepare such a membrane has been a great challenge because good mechanical properties and stabilities are highly required. Here, we demonstrate a novel and facile technique for preparing the free standing membrane with a size as large as centimeter scale. The substrate we use proved itself not only a good skeleton but also an excellent precursor to fulfill the reaction. This kind of membrane owns a strong mechanical strength, based on the fact that it is much thinner than the composite membranes grown on substrates and it could exhibit good property of gas separation.

  7. Carborane-Based Metal-Organic Framework with High Methane and Hydrogen Storage Capacities

    SciTech Connect

    Kennedy, RD; Krungleviciute, V; Clingerman, DJ; Mondloch, JE; Peng, Y; Wilmer, CE; Sarjeant, AA; Snurr, RQ; Hupp, JT; Yildirim, T; Farha, OK; Mirkin, CA

    2013-09-10

    A Cu-carborane-based metal organic framework (MOF), NU-135, which contains a quasi-spherical para-carborane moiety, has been synthesized and characterized. NU-135 exhibits a pore volume of 1.02 cm(3)/g and a gravimetric BET surface area of ca. 2600 m(2)/g, and thus represents the first highly porous carborane-based MOF. As a consequence of the, unique geometry of the carborane unit, NU-135 has a very high volumetric BET surface area of ca. 1900 m(2)/cm(3). CH4, CO2, and H-2 adsorption isotherms were measured over a broad range of pressures and temperatures and are in good agreement with computational predictions. The methane storage capacity of NU-135 at 35 bar and 298 K is ca. 187 v(STP)/v. At 298 K, the pressure required to achieve a methane storage density comparable to that of a compressed natural gas (CNG) tank pressurized to 212 bar, which is a typical storage pressure, is only 65 bar. The methane working capacity (5-65 bar) is 170 v(STP)/v. The volumetric hydrogen storage capacity at 55 bar and 77 K is 49 g/L. These properties are comparable to those of current record holders in the area of methane and hydrogen storage. This initial example lays the groundwork for carborane-based materials with high surface areas.

  8. Quasi-1D physics in metal-organic frameworks: MIL-47(V) from first principles

    PubMed Central

    Jaeken, Jan W; De Baerdemacker, Stijn; Lejaeghere, Kurt; Van Speybroeck, Veronique

    2014-01-01

    Summary The geometric and electronic structure of the MIL-47(V) metal-organic framework (MOF) is investigated by using ab initio density functional theory (DFT) calculations. Special focus is placed on the relation between the spin configuration and the properties of the MOF. The ground state is found to be antiferromagnetic, with an equilibrium volume of 1554.70 Å3. The transition pressure of the pressure-induced large-pore-to-narrow-pore phase transition is calculated to be 82 MPa and 124 MPa for systems with ferromagnetic and antiferromagnetic chains, respectively. For a mixed system, the transition pressure is found to be a weighted average of the ferromagnetic and antiferromagnetic transition pressures. Mapping DFT energies onto a simple-spin Hamiltonian shows both the intra- and inter-chain coupling to be antiferromagnetic, with the latter coupling constant being two orders of magnitude smaller than the former, suggesting the MIL-47(V) to present quasi-1D behavior. The electronic structure of the different spin configurations is investigated and it shows that the band gap position varies strongly with the spin configuration. The valence and conduction bands show a clear V d-character. In addition, these bands are flat in directions orthogonal to VO6 chains, while showing dispersion along the the direction of the VO6 chains, similar as for other quasi-1D materials. PMID:25383285

  9. Constructing Free Standing Metal Organic Framework MIL-53 Membrane Based on Anodized Aluminum Oxide Precursor

    PubMed Central

    Zhang, Yunlu; Gao, Qiuming; Lin, Zhi; Zhang, Tao; Xu, Jiandong; Tan, Yanli; Tian, Weiqian; Jiang, Lei

    2014-01-01

    Metal organic framework (MOF) materials have attracted great attention due to their well-ordered and controllable pores possessing of prominent potentials for gas molecule sorption and separation performances. Organizing the MOF crystals to a continuous membrane with a certain scale will better exhibit their prominent potentials. Reports in recent years concentrate on well grown MOF membranes on specific substrates. Free standing MOF membranes could have more important applications since they are independent from the substrates. However, the method to prepare such a membrane has been a great challenge because good mechanical properties and stabilities are highly required. Here, we demonstrate a novel and facile technique for preparing the free standing membrane with a size as large as centimeter scale. The substrate we use proved itself not only a good skeleton but also an excellent precursor to fulfill the reaction. This kind of membrane owns a strong mechanical strength, based on the fact that it is much thinner than the composite membranes grown on substrates and it could exhibit good property of gas separation. PMID:24821299

  10. Kinetic and steric differences in adsorption in two porous metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Lask, Kathleen; Krungleviciute, Vaiva; Bulut, Murat; Migone, Aldo; Lee, J.-Y.; Li, Jing

    2008-03-01

    Kinetic and steric differences are two of the three fundamental mechanisms underlying the use of adsorption in applications to gas mixture separations. We present experimental results on kinetics and equilibrium adsorption measurements of tetrafluoromethane and argon on two metal-organic framework (MOF) materials: RPM1-Co or [Co3(bpdc)3bpy].4DMF.H2O] (bpdc = biphenyldicarboxylate, bpy = 4,4'-bipyridine, DMF = N,N- dimethylformamide) and Cu-BTC or Cu3(BTC)2(H2O)3 (BTC = benzene-1,3,5-tricarboxylate). The adsorbates display significant differences in their kinetics on RPM1-Co (i.e., there are sizable differences in the time required for each gas to reach equilibrium after it is allowed access to the substrate). Our equilibrium measurements show that CF4 is sterically precluded from adsorbing in the small tetrahedral-shaped side pockets present in Cu-BTC. We will compare our experimental results with predictions for how adsorption kinetics depends on the size of the adsorbate and on those of the pores present in the substrate.

  11. Efficient purification of ethene by an ethane-trapping metal-organic framework

    NASA Astrophysics Data System (ADS)

    Liao, Pei-Qin; Zhang, Wei-Xiong; Zhang, Jie-Peng; Chen, Xiao-Ming

    2015-10-01

    Separating ethene (C2H4) from ethane (C2H6) is of paramount importance and difficulty. Here we show that C2H4 can be efficiently purified by trapping the inert C2H6 in a judiciously designed metal-organic framework. Under ambient conditions, passing a typical cracked gas mixture (15:1 C2H4/C2H6) through 1 litre of this C2H6 selective adsorbent directly produces 56 litres of C2H4 with 99.95%+ purity (required by the C2H4 polymerization reactor) at the outlet, with a single breakthrough operation, while other C2H6 selective materials can only produce ca. <= litre, and conventional C2H4 selective adsorbents require at least four adsorption-desorption cycles to achieve the same C2H4 purity. Single-crystal X-ray diffraction and computational simulation studies showed that the exceptional C2H6 selectivity arises from the proper positioning of multiple electronegative and electropositive functional groups on the ultramicroporous pore surface, which form multiple C-H...N hydrogen bonds with C2H6 instead of the more polar competitor C2H4.

  12. Efficient purification of ethene by an ethane-trapping metal-organic framework

    PubMed Central

    Liao, Pei-Qin; Zhang, Wei-Xiong; Zhang, Jie-Peng; Chen, Xiao-Ming

    2015-01-01

    Separating ethene (C2H4) from ethane (C2H6) is of paramount importance and difficulty. Here we show that C2H4 can be efficiently purified by trapping the inert C2H6 in a judiciously designed metal-organic framework. Under ambient conditions, passing a typical cracked gas mixture (15:1 C2H4/C2H6) through 1 litre of this C2H6 selective adsorbent directly produces 56 litres of C2H4 with 99.95%+ purity (required by the C2H4 polymerization reactor) at the outlet, with a single breakthrough operation, while other C2H6 selective materials can only produce ca. ⩽ litre, and conventional C2H4 selective adsorbents require at least four adsorption–desorption cycles to achieve the same C2H4 purity. Single-crystal X-ray diffraction and computational simulation studies showed that the exceptional C2H6 selectivity arises from the proper positioning of multiple electronegative and electropositive functional groups on the ultramicroporous pore surface, which form multiple C–H···N hydrogen bonds with C2H6 instead of the more polar competitor C2H4. PMID:26510376

  13. Reusable oxidation catalysis using metal-monocatecholato species in a robust metal-organic framework.

    PubMed

    Fei, Honghan; Shin, JaeWook; Meng, Ying Shirley; Adelhardt, Mario; Sutter, Jörg; Meyer, Karsten; Cohen, Seth M

    2014-04-02

    An isolated metal-monocatecholato moiety has been achieved in a highly robust metal-organic framework (MOF) by two fundamentally different postsynthetic strategies: postsynthetic deprotection (PSD) and postsynthetic exchange (PSE). Compared with PSD, PSE proved to be a more facile and efficient functionalization approach to access MOFs that could not be directly synthesized under solvothermal conditions. Metalation of the catechol functionality residing in the MOFs resulted in unprecedented Fe-monocatecholato and Cr-monocatecholato species, which were characterized by X-ray absorption spectroscopy, X-band electron paramagnetic resonance spectroscopy, and (57)Fe Mössbauer spectroscopy. The resulting materials are among the first examples of Zr(IV)-based UiO MOFs (UiO = University of Oslo) with coordinatively unsaturated active metal centers. Importantly, the Cr-metalated MOFs are active and efficient catalysts for the oxidation of alcohols to ketones using a wide range of substrates. Catalysis could be achieved with very low metal loadings (0.5-1 mol %). Unlike zeolite-supported, Cr-exchange oxidation catalysts, the MOF-based catalysts reported here are completely recyclable and reusable, which may make them attractive catalysts for 'green' chemistry processes.

  14. Structural and Dielectric Properties of Ionic Liquid Doped Metal Organic Framework based Polymer Electrolyte Nanocomposites

    NASA Astrophysics Data System (ADS)

    Dutta, Rituraj; Kumar, Ashok

    2016-10-01

    Metal Organic Frameworks (MOFs) are mesoporous materials that can be treated as potential hosts for trapping guest molecules in their pores. Ion conduction and phase behavior dynamics of Ionic Liquids (ILs) can be controlled by tunable interactions of MOFs with the ILs. MOFs incorporated with ionic liquid can be dispersed in the polymers to synthesize polymer electrolyte nanocomposites with high ionic conductivity, electrochemical and thermal stability for applications in energy storage and conversion devices such as rechargeable Li-ion batteries. In the present work we have synthesized Cu-based MOF [Cu3(l,3,5-benzene tricarboxylate)2(H2O)] incorporated with the ionic liquid 1-Butyl-3-methylimidazolium bromide at different weight ratios of MOF and IL. The synthesized MOF-IL composites are dispersed in Poly (ethylene oxide) (PEO). Frequency dependent behavior of permittivity and dielectric loss of the nanocomposites depict the non-Debye dielectric relaxation mechanism. The room temperature Nyquist plots reveal decreasing bulk resistance upto 189 Ω with optimum ionic conductivity of 1.3×10-3S cm-1at maximum doping concentration of IL in the nanocomposite system.

  15. Light-harvesting and ultrafast energy migration in porphyrin-based metal-organic frameworks.

    PubMed

    Son, Ho-Jin; Jin, Shengye; Patwardhan, Sameer; Wezenberg, Sander J; Jeong, Nak Cheon; So, Monica; Wilmer, Christopher E; Sarjeant, Amy A; Schatz, George C; Snurr, Randall Q; Farha, Omar K; Wiederrecht, Gary P; Hupp, Joseph T

    2013-01-16

    Given that energy (exciton) migration in natural photosynthesis primarily occurs in highly ordered porphyrin-like pigments (chlorophylls), equally highly ordered porphyrin-based metal-organic frameworks (MOFs) might be expected to exhibit similar behavior, thereby facilitating antenna-like light-harvesting and positioning such materials for use in solar energy conversion schemes. Herein, we report the first example of directional, long-distance energy migration within a MOF. Two MOFs, namely F-MOF and DA-MOF that are composed of two Zn(II) porphyrin struts [5,15-dipyridyl-10,20-bis(pentafluorophenyl)porphinato]zinc(II) and [5,15-bis[4-(pyridyl)ethynyl]-10,20-diphenylporphinato]zinc(II), respectively, were investigated. From fluorescence quenching experiments and theoretical calculations, we find that the photogenerated exciton migrates over a net distance of up to ~45 porphyrin struts within its lifetime in DA-MOF (but only ~3 in F-MOF), with a high anisotropy along a specific direction. The remarkably efficient exciton migration in DA-MOF is attributed to enhanced π-conjugation through the addition of two acetylene moieties in the porphyrin molecule, which leads to greater Q-band absorption intensity and much faster exciton-hopping (energy transfer between adjacent porphyrin struts). The long distance and directional energy migration in DA-MOF suggests promising applications of this compound or related compounds in solar energy conversion schemes as an efficient light-harvesting and energy-transport component.

  16. Electrically Driven White Light Emission from Intrinsic Metal-Organic Framework.

    PubMed

    Haider, Golam; Usman, Muhammad; Chen, Tzu-Pei; Perumal, Packiyaraj; Lu, Kuang-Lieh; Chen, Yang-Fang

    2016-09-27

    Light-emitting diodes (LEDs) have drawn tremendous potential as a replacement of traditional lighting due to its low-power consumption and longer lifetime. Nowadays, the practical white LEDs (WLED) are contingent on the photon down-conversion of phosphors containing rare-earth elements, which limits its utility, energy, and cost efficiency. In order to resolve the energy crisis and to address the environmental concerns, designing a direct WLED is highly desirable and remains a challenging issue. To circumvent the existing difficulties, in this report, we have designed and demonstrated a direct WLED consisting of a strontium-based metal-organic framework (MOF), {[Sr(ntca)(H2O)2]·H2O}n (1), graphene, and inorganic semiconductors, which can generate a bright white light emission. In addition to the suitable design of a MOF structure, the demonstration of electrically driven white light emission based on a MOF is made possible by the combination of several factors including the unique properties of graphene and the appropriate band alignment between the MOF and semiconductor layer. Because electroluminescence using a MOF as an active material is very rare and intriguing and a direct WLED is also not commonly seen, our work here therefore represents a major discovery which should be very useful and timely for the development of solid-state lighting.

  17. Porous, rigid metal(III)-carboxylate metal-organic frameworks for the delivery of nitric oxide

    NASA Astrophysics Data System (ADS)

    Eubank, Jarrod F.; Wheatley, Paul S.; Lebars, Gaëlle; McKinlay, Alistair C.; Leclerc, Hervé; Horcajada, Patricia; Daturi, Marco; Vimont, Alexandre; Morris, Russell E.; Serre, Christian

    2014-12-01

    The room temperature sorption properties of the biological gas nitric oxide (NO) have been investigated on the highly porous and rigid iron or chromium carboxylate based metal-organic frameworks Material Institut Lavoisier (MIL)-100(Fe or Cr) and MIL-127(Fe). In all cases, a significant amount of NO is chemisorbed at 298 K with a loading capacity that depends both on the nature of the metal cation, the structure and the presence of additional iron(II) Lewis acid sites. In a second step, the release of NO triggered by wet nitrogen gas has been studied by chemiluminescence and indicates that only a partial release of NO occurs as well as a prolonged delivery at the biological level. Finally, an in situ infrared spectroscopy study confirms not only the coordination of NO over the Lewis acid sites and the stronger binding of NO on the additional iron(II) sites, providing further insights over the partial release of NO only in the presence of water at room temperature.

  18. Capturing snapshots of post-synthetic metallation chemistry in metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Bloch, Witold M.; Burgun, Alexandre; Coghlan, Campbell J.; Lee, Richmond; Coote, Michelle L.; Doonan, Christian J.; Sumby, Christopher J.

    2014-10-01

    Post-synthetic metallation is employed strategically to imbue metal-organic frameworks (MOFs) with enhanced performance characteristics. However, obtaining precise structural information for metal-centred reactions that take place within the pores of these materials has remained an elusive goal, because of issues with high symmetry in certain MOFs, lower initial crystallinity for some chemically robust MOFs, and the reduction in crystallinity that can result from carrying out post-synthetic reactions on parent crystals. Here, we report a new three-dimensional MOF possessing pore cavities that are lined with vacant di-pyrazole groups poised for post-synthetic metallation. These metallations occur quantitatively without appreciable loss of crystallinity, thereby enabling examination of the products by single-crystal X-ray diffraction. To illustrate the potential of this platform to garner fundamental insight into metal-catalysed reactions in porous solids we use single-crystal X-ray diffraction studies to structurally elucidate the reaction products of consecutive oxidative addition and methyl migration steps that occur within the pores of the Rh-metallated MOF, 1·[Rh(CO)2][Rh(CO)2Cl2].

  19. Evaluation of Heterogeneous Metal-Organic Framework Organocatalysts Prepared by Postsynthetic Modification

    PubMed Central

    Garibay, Sergio J.; Wang, Zhenqiang; Cohen, Seth M.

    2010-01-01

    A metal-organic framework (MOF) containing 2-amino-1,4-benzenedicarboxylate (NH2-BDC) as a building block is shown to undergo chemical modification with a set of cyclic anhydrides. The modification of the aluminum-based MOF known as MIL-53(Al)-NH2 (MIL = Matérial Institut Lavoisier) by these reagents is demonstrated by using a variety of methods, including NMR and ESI-MS, and the structural integrity of the modified MOFs has been confirmed by TGA, PXRD, and gas sorption analysis. Reaction with these cyclic anhydrides produces MOFs that display carboxylic acid functional groups within their pores. Furthermore, it is shown that maleic acid functionalized MIL-53(Al)-AMMal can act as a Brønsted acid catalyst and facilitate the methanolysis of several small epoxides. Experiments show that MIL-53(Al)-AMMal acts in a heterogeneous manner and is recyclable with consistent activity over at least three catalytic cycles. The findings presented here demonstrate several important features of covalent postsynthetic modification (PSM) on MOFs, including: 1) facile introduction of catalytic functionality using simple organic reagents (e.g. anhydrides); 2) the ability to utilize and recycle organocatalytic MOFs; 3) control of catalytic activity through choice of functional group. The findings clearly illustrate that covalent postsynthetic modification represents a powerful means to access new MOF compounds that serve as organocatalytic materials. PMID:20698561

  20. Metal-Organic Frameworks As Templates for Nanoscale NaAlH 4

    SciTech Connect

    Bhakta, Raghunandan K.; Herberg, Julie L.; Jacobs, Benjamin; Highley, Aaron; Behrens, Richard; Ockwig, Nathan W.; Greathouse, Jeffery A.; Allendorf, Mark D.

    2009-09-01

    Metal-organic frameworks (MOFs) offer an attractive alternative to traditional hard and soft templates for nanocluster synthesis because their ordered crystalline lattice provides a highly controlled and inherently understandable environment. We demonstrate that MOFs are stable hosts for metal hydrides proposed for hydrogen storage and their reactive precursors, providing platform to test recent theoretical predictions that some of these materials can be destabilized with respect to hydrogen desorption by reducing their critical dimension to the nanoscale. With the MOF HKUST-1 as template, we show that NaAlH4 nanoclusters as small as eight formula units can be synthesized. The confinement of these clusters within the MOF pores dramatically accelerates the desorption kinetics, causing decomposition to occur at ~100 °C lower than bulk NaAlH4. However, using simultaneous thermogravimetric modulated beam mass spectrometry, we also show that the thermal decomposition mechanism of NaAlH4 is complex and may involve processes such as nucleation and growth in addition to the normally assumed two-step chemical decomposition reactions.

  1. Functionalization of Metal-Organic Frameworks with Metalloligands and Postsynthetic Modification

    NASA Astrophysics Data System (ADS)

    Garibay, Sergio J.

    Metal-organic frameworks (MOFs) are a hybrid class of porous materials that are comprised of metal clusters and bridging organic ligands. The modular nature these materials makes them suited for chemical strategies aimed at fine-tuning their structure and function. Significant efforts have been spent on developing MOFs for novel applications through the use of functionalized ligands. However, incorporation of functional groups on the ligands can introduce steric, solubility, and metal-coordinating characteristics that can interfere with MOF formation. By targeting the organic linking component of the a prefabricated MOF one can utilize various organic reactions to transform it into a new MOF with altered functional groups and thus different physical and chemical properties. The work in this thesis explores the development of functionalized MOFs through both prefunctionalization and postsynthetic modification (PSM) approaches on a variety of MOFs. In Chapter 2, the use of chiral tris(dipyrrinato) metalloligands was examined in an attempt to introduce chiral functionality into a set MOFs with distinct topologies realized through the use of a racemic analogue. The results further exemplify the difficulties associated with the functionalized linker strategy and suggest that PSM offers a more viable functionalization route. In Chapter 3, the versatile nature of the PSM approach is demonstrated with the successful incorporation of chiral, amine protected, and free carboxylic acid groups into an amine functionalized framework through the use of anhydrides. In Chapter 4, the scope and limitation of a multi-step PSM approach termed tandem PSM is discussed. A set a diverse multifunctional amide and urea MOFs were realized through tandem PSM. While there have been many studies investigating MOFs as heterogeneous catalysts, most examples utilize unsaturated metal sites. In Chapter 5, the utilization of carboxylic acid functionalized MOFs as a solid state Bronsted acid catalyst

  2. Perturbation of spin crossover behavior by covalent post-synthetic modification of a porous metal-organic framework.

    PubMed

    Clements, John E; Price, Jason R; Neville, Suzanne M; Kepert, Cameron J

    2014-09-15

    Covalent post-synthetic modification is a versatile method for gaining high-level synthetic control over functionality within porous metal-organic frameworks and for generating new materials not accessible through one-step framework syntheses. Here we apply this topotactic synthetic approach to a porous spin crossover framework and show through detailed comparison of the structures and properties of the as-synthesised and covalently modified phases that the modification reaction proceeds quantitatively by a thermally activated single-crystal-to-single-crystal transformation to yield a material with lowered spin-switching temperature, decreased lattice cooperativity, and altered color. Structure-function relationships to emerge from this comparison show that the approach provides a new route for tuning spin crossover through control over both outer-sphere and steric interactions.

  3. Metal-organic frameworks for the storage and delivery of biologically active hydrogen sulfide

    SciTech Connect

    Allan, Phoebe K; Wheatley, Paul S; Aldous, David; Mohideen, M Infas; Tang, Chiu; Hriljac, Joseph A; Megson, Ian L; Chapman, Karena W; De Weireld, Guy; Vaesen, Sebastian; Morris, Russell E

    2012-04-02

    Hydrogen sulfide is an extremely toxic gas that is also of great interest for biological applications when delivered in the correct amount and at the desired rate. Here we show that the highly porous metal-organic frameworks with the CPO-27 structure can bind the hydrogen sulfide relatively strongly, allowing the storage of the gas for at least several months. Delivered gas is biologically active in preliminary vasodilation studies of porcine arteries, and the structure of the hydrogen sulfide molecules inside the framework has been elucidated using a combination of powder X-ray diffraction and pair distribution function analysis.

  4. Microporous sensor: gas sorption, guest exchange and guest-dependant luminescence of metal-organic framework.

    PubMed

    Sapchenko, Sergey A; Samsonenko, Denis G; Dybtsev, Danil N; Melgunov, Maxim S; Fedin, Vladimir P

    2011-03-14

    Zn(II)-containing metal-organic framework (MOF) [Zn(4)(dmf)(ur)(2)(ndc)(4)] (ndc(2-) = 2,6-naphtalenedicarboxylate, ur = urotropin, dmf = N,N'-dimethylformamide) was synthesized and characterized by X-ray crystallography and gas sorption analysis. Host MOF retains its crystallinity after guest removal and exchange. Single-crystal to single-crystal formation of different host-guest systems with benzene and ferrocene was investigated. Interesting guest-depended luminescence properties of the porous host framework were observed.

  5. Nonlinear optical properties of Pb-La metal-organic chelidamic acid frameworks

    NASA Astrophysics Data System (ADS)

    Tan, Min; Chen, Ruiqi; Yang, Sanjun; Liu, Qiming

    2017-04-01

    Chelidamic acid, acting as ligands, reacted with metal cation of lead and lanthanum. Both of them were dissolved in water and resulted in novel MOFs complexes by using solvothermal synthesis method. The complexes were characterized by the X-ray diffraction, UV-vis spectrophotometer and Z-scan measurements to investigate their morphology and optical properties. The Z-scan measurements indicated that the obtained lead metal-organic chelidamic acid frameworks showed 6.09 × 10-12 esu of χ(3). The special structure and properties, especially the empty f-electron orbital of the rare earth elements, were used to enhance optical nonlinearity. Using one-step solvothermal synthesis method, we added lanthanum into the lead-chelidamic acid metal organic complexes. By changing the spatial configuration of the ligand in the self-assembly process, novel structural complex metals of the lead-lanthanum metal-organic chelidamic acid frameworks have been successfully synthetized, and the third-order nonlinear susceptibility of χ(3)was enhanced to be 1.13 × 10-11 esu.

  6. A microporous metal-organic framework of a rare sty topology for high CH4 storage at room temperature.

    PubMed

    Duan, Xing; Yu, Jiancan; Cai, Jianfeng; He, Yabing; Wu, Chuande; Zhou, Wei; Yildirim, Taner; Zhang, Zhangjing; Xiang, Shengchang; O'Keeffe, Michael; Chen, Banglin; Qian, Guodong

    2013-03-11

    A rare sty type microporous metal-organic framework, Cu(2)(FDDI) (; H(4)FDDI = tetramethyl 5,5'-(9H-fluorene-2,7-diyl)diisophthalate acid), was solvothermally synthesized and structurally characterized. With open metal sites and suitable pore space for their interactions with methane molecules, exhibits absolute methane storage of 180 cm(3)(STP) cm(-3) at room temperature and 35 bar, enabling it to be one of the very few porous MOFs whose methane storage capacities have met and/or approached the DOE target of 180 cm(3)(STP) cm(-3) for material-based methane storage.

  7. Alkenyl/thiol-derived metal-organic frameworks (MOFs) by means of postsynthetic modification for effective mercury adsorption.

    PubMed

    Liu, Tao; Che, Jin-Xin; Hu, Yong-Zhou; Dong, Xiao-Wu; Liu, Xin-Yuan; Che, Chi-Ming

    2014-10-20

    The synthesis of new functionally diverse alkenyl-derived Cr-MIL-101s (MIL=material of Institute Lavoisier) was realized by a novel and convenient postsynthetic modification (PSM) protocol by means of the carbon-carbon bond-forming Mizoroki-Heck reaction. The new PSM protocol demonstrates a broad scope of substrates with excellent tolerance of functionality under mild reaction conditions. Moreover, a new metal-organic framework (MOF) that bears both alkenyl and thiol side chains prepared by means of the tandem PSM method has shown excellent adsorbent ability in removing mercury ions from water.

  8. Postsynthetic Inner-Surface Functionalization of the Highly Stable Zirconium-Based Metal-Organic Framework DUT-67.

    PubMed

    Drache, Franziska; Bon, Volodymyr; Senkovska, Irena; Marschelke, Claudia; Synytska, Alla; Kaskel, Stefan

    2016-08-01

    A postsynthetic functionalization approach was used to tailor the hydrophobicity of DUT-67, a metal-organic framework (MOF) consisting of 8-connected Zr6O6(OH)2 clusters and 2,5-thiophenedicarboxylate as the ligand, using postsynthetic exchange of the modulator by fluorinated monocarboxylates. Water adsorption isotherms demonstrated that, by the incorporation of such hydrophobic molecules, the hydrophobicity of the inner surface of the network can be tuned. Furthermore, tolerance of the material toward the removal of adsorbed water can be significantly enhanced compared to the parent DUT-67 MOF.

  9. Highly selective luminescent sensing of picric acid based on a water-stable europium metal-organic framework

    NASA Astrophysics Data System (ADS)

    Xia, Tifeng; Zhu, Fengliang; Cui, Yuanjing; Yang, Yu; Wang, Zhiyu; Qian, Guodong

    2017-01-01

    A water-stable metal-organic framework (MOF) EuNDC has been synthesized for selective detection of the well-known contaminant and toxicant picric acid (PA) in aqueous solution. Due to the photo-induced electron transfer and self-absorption mechanism, EuNDC displayed rapid, selective and sensitive detection of PA with a detection limit of 37.6 ppb. Recyclability experiments revealed that EuNDC retains its initial luminescent intensity and same quenching efficiency in each cycle, suggesting high photostability and reusability for long-term sensing applications. The excellent detection performance of EuNDC makes it a promising PA sensing material for practical applications.

  10. Thermal Stabilization of Metal-Organic Framework-Derived Single-Site Catalytic Clusters through Nanocasting.

    PubMed

    Malonzo, Camille D; Shaker, Sammy M; Ren, Limin; Prinslow, Steven D; Platero-Prats, Ana E; Gallington, Leighanne C; Borycz, Joshua; Thompson, Anthony B; Wang, Timothy C; Farha, Omar K; Hupp, Joseph T; Lu, Connie C; Chapman, Karena W; Myers, Jason C; Penn, R Lee; Gagliardi, Laura; Tsapatsis, Michael; Stein, Andreas

    2016-03-02

    Metal-organic frameworks (MOFs) provide convenient systems for organizing high concentrations of single catalytic sites derived from metallic or oxo-metallic nodes. However, high-temperature processes cause agglomeration of these nodes, so that the single-site character and catalytic activity are lost. In this work, we present a simple nanocasting approach to provide a thermally stable secondary scaffold for MOF-based catalytic single sites, preventing their aggregation even after exposure to air at 600 °C. We describe the nanocasting of NU-1000, a MOF with 3 nm channels and Lewis-acidic oxozirconium clusters, with silica. By condensing tetramethylorthosilicate within the NU-1000 pores via a vapor-phase HCl treatment, a silica layer is created on the inner walls of NU-1000. This silica layer provides anchoring sites for the oxozirconium clusters in NU-1000 after the organic linkers are removed at high temperatures. Differential pair distribution functions obtained from synchrotron X-ray scattering confirmed that isolated oxozirconium clusters are maintained in the heated nanocast materials. Pyridine adsorption experiments and a glucose isomerization reaction demonstrate that the clusters remain accessible to reagents and maintain their acidic character and catalytic activity even after the nanocast materials have been heated to 500-600 °C in air. Density functional theory calculations show a correlation between the Lewis acidity of the oxozirconium clusters and their catalytic activity. The ability to produce MOF-derived materials that retain their catalytic properties after exposure to high temperatures makes nanocasting a useful technique for obtaining single-site catalysts suitable for high-temperature reactions.

  11. Mechanism of electrochemical lithiation of a metal-organic framework without redox-active nodes

    NASA Astrophysics Data System (ADS)

    Tang, Bohejin; Huang, Shuping; Fang, Yuan; Hu, Jinbo; Malonzo, Camille; Truhlar, Donald G.; Stein, Andreas

    2016-05-01

    Metal-organic frameworks (MOFs) have many potential uses for separations, storage, and catalysis, but their use as intercalation hosts for batteries has been scarce. In this article, we examine the mechanism of Li insertion in a MOF to provide guidance to future design efforts in this area. As a model system, we choose UiO-66, a MOF with the formula (Zr6O4(OH)4)4(1,4-benzenedicarboxylate)6, as an electrode material for lithium-ion batteries; this MOF is of special interest because the zirconium is not redox active. We report both quantum mechanical characterization of the mechanism and experimental studies in which the material is synthesized as nanoparticles to reduce diffusion lengths for lithium ions and increase the contact area with a conductive carbon phase. The calculated changes in the IR spectra of UiO-66 and lithiated UiO-66 are consistent with the experimental FTIR results. We found experimentally that this MOF can maintain a specific discharge capacity of at least 118 mAh/g for 30 lithiation and delithiation cycles at a rate of C/5, exhibiting good cyclability. Density functional electronic structure calculations show that the charge transfer during lithiation is mainly from Li to node oxygens and carboxylate oxygens, that is, it involves anions rather than cations or aromatic rings, and they provide a mechanistic understanding of the potential for increased Li capacity because the theoretical capacity of UiO-66 with Li at the oxygens in the metal oxide nodes and the carboxylate linkers is more than 400 mAh/g. The lithiation process greatly decreases the bandgap of UiO-66, which is expected to increase its electronic conductivity. The electrode material was also characterized by X-ray diffraction and scanning electron microscopy, which were consistent in confirming that smaller particle sizes were obtained in lower-temperature syntheses.

  12. Surfactant media to grow new crystalline cobalt 1,3,5-benzenetricarboxylate metal-organic frameworks.

    PubMed

    Lu, Hai-Sheng; Bai, Linlu; Xiong, Wei-Wei; Li, Peizhou; Ding, Junfeng; Zhang, Guodong; Wu, Tom; Zhao, Yanli; Lee, Jong-Min; Yang, Yanhui; Geng, Baoyou; Zhang, Qichun

    2014-08-18

    In this report, three new metal-organic frameworks (MOFs), [Co3(μ3-OH)(HBTC)(BTC)2Co(HBTC)]·(HTEA)3·H2O (NTU-Z30), [Co(BTC)]·HTEA·H2O (NTU-Z31), [Co3(BTC)4]·(HTEA)4 (NTU-Z32), where H3BTC = 1,3,5-benzenetricarboxylic acid, TEA = triethylamine, and NTU = Nanyang Technological University, have been successfully synthesized under surfactant media and have been carefully characterized by single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetric analysis, and IR spectromtry. NTU-Z30 has an unusual trimeric [Co3(μ3-OH)(COO)7] secondary building unit (SBU), which is different from the well-known trimeric [Co3O(COO)6] SBU. The topology studies indicate that NTU-Z30 and NTU-Z32 possess two new topologies, 3,3,6,7-c net and 2,8-c net, respectively, while NTU-Z31 has a known topology rtl type (3,6-c net). Magnetic analyses show that all three materials have weak antiferromagnetic behavior. Furthermore, NTU-Z30 has been selected as the heterogeneous catalyst for the aerobic epoxidation of alkene, and our results show that this material exhibits excellent catalytic activity as well as good stability. Our success in growing new crystalline cobalt 1,3,5-benzenetricarboxylate MOFs under surfactant media could pave a new road to preparing new diverse crystalline inorganic materials through a surfactant-thermal method.

  13. Structure-property relationship of metal-organic frameworks (MOFs) and physisorbed off-gas radionuclides.

    SciTech Connect

    Nenoff, Tina Maria; Chupas, Peter J.; Garino, Terry J.; Rodriguez, Mark Andrew; Chapman, Karena W.; Sava, Dorina Florentina

    2010-11-01

    We report on the host-guest interactions between metal-organic frameworks (MOFs) with various profiles and highly polarizable molecules (iodine), with emphasis on identifying preferential sorption sites in these systems. Radioactive iodine 129I, along with other volatile radionuclides (3H, 14C, Xe and Kr), represents a relevant component in the off-gas resulted during nuclear fuel reprocessing. Due to its very long half-life, 15.7 x 106 years, and potential health risks in humans, its efficient capture and long-term storage is of great importance. The leading iodine capture technology to date is based on trapping iodine in silver-exchanged mordenite. Our interests are directed towards improving existent capturing technologies, along with developing novel materials and alternative waste forms. Herein we report the first study that systematically monitors iodine loading onto MOFs, an emerging new class of porous solid-state materials. In this context, MOFs are of particular interest as: (i) they serve as ideal high capacity storage media, (ii) they hold potential for the selective adsorption from complex streams, due to their high versatility and tunability. This work highlights studies on both newly developed in our lab, and known highly porous MOFs that all possess distinct characteristics (specific surface area, pore volume, pore size, and dimension of the window access to the pore). The materials were loaded to saturation, where elemental iodine was introduced from solution, as well as from vapor phase. Uptakes in the range of {approx}125-150 wt% I2 sorbed were achieved, indicating that these materials outperform all other solid adsorbents to date in terms of overall capacity. Additionally, the loaded materials can be efficiently encapsulated in stable waste forms, including as low temperature sintering glasses. Ongoing studies are focused on gathering qualitative information with respect to localizing the physisorbed iodine molecules within the frameworks: X

  14. Unraveling the multi-functional behavior in a series of Metal Organic Frameworks

    SciTech Connect

    Sanda, Suresh; Biswas, Soumava; Parshamoni, Srinivasulu; Konar, Sanjit

    2015-09-15

    Three new 2D/3D Metal-Organic Frameworks (MOFs), ([Zn(2,6-ndc)(aldrithiol)]·3(H{sub 2}O)){sub n} (1), ([Co(2,6-ndc)(aldrithiol)(H{sub 2}O){sub 2}]·2(H{sub 2}O)){sub n} (2), ([Cd{sub 2}(2,6-ndc){sub 2}(aldrithiol){sub 2}(H{sub 2}O){sub 2}]·(aldrithiol)·(EtOH)·3(H{sub 2}O)){sub n} (3), (2,6-ndc = 2,6-naphthalene dicarboxylic acid; aldrithiol = 4,4'-dipyridyl disulphide) have been synthesized and structurally characterized. Compounds 1 and 2 have 2D layered architectures with similar framework topology whereas 3 is a 2-fold interwoven three dimensional framework. Sorption studies reveal that compounds 1-3 selectively adsorbs CO{sub 2} over other gases and H{sub 2}O over other solvents. Proton conductivity study of compounds 1 and 2 show highest values of 6.73 x 10{sup -7} S.cm{sup -1}, 1.96 x 10{sup -5} S.cm{sup -1} at 318 K and 95% RH and these values are humidity dependent. Photoluminescent properties of compounds 1 and 3 show metal perturbed (π*–π and π*-n) intra ligand charge transfer transitions. Additionally, Compound 3 also displays reversible adsorption of molecular iodine. - Graphical abstarct: Three new 2D/3D interpenetrated MOFs are synthesized and their multifunctional material properties such as adsorption, proton conduction, iodine adsorption as well as luminscence have been explored. - Highlights: • We report multifunctional material properties in a series MOFs (Compounds 1-3) • All the compounds show selective adsorption of CO{sub 2} over other gases and H{sub 2}O over other solvents. • The proton conduction property studies of all the compounds reveal the humidity dependent conductivity. • Compound 2 shows reversible adsorption of molecular iodine in the framework. • Photoluminescent properties of compounds 1 and 2 show metal perturbed intra ligand charge transfer transitions.

  15. Metal-Organic Frameworks as Potential Platforms for Carbon Dioxide Capture and Chemical Transformation

    NASA Astrophysics Data System (ADS)

    Gao, Wenyang

    The anthropogenic carbon dioxide (CO2) emission into the atmosphere, mainly through the combustion of fossil fuels, has resulted in a balance disturbance of the carbon cycle. Overwhelming scientific evidence proves that the escalating level of atmospheric CO2 is deemed as the main culprit for global warming and climate change. It is thus imperative to develop viable CO2 capture and sequestration (CCS) technologies to reduce CO2 emissions, which is also essential to avoid the potential devastating effects in future. The drawbacks of energy-cost, corrosion and inefficiency for amine-based wet-scrubbing systems which are currently used in industry, have prompted the exploration of alternative approaches for CCS. Extensive efforts have been dedicated to the development of functional porous materials, such as activated carbons, zeolites, porous organic polymers, and metal-organic frameworks (MOFs) to capture CO2. However, these adsorbents are limited by either poor selectivity for CO2 separation from gas mixtures or low CO2 adsorption capacity. Therefore, it is still highly demanding to design next-generation adsorbent materials fulfilling the requirements of high CO2 selectivity and enough CO2 capacity, as well as high water/moisture stability under practical conditions. Metal-organic frameworks (MOFs) have been positioned at the forefront of this area as a promising type of candidate amongst various porous materials. This is triggered by the modularity and functionality of pore size, pore walls and inner surface of MOFs by use of crystal engineering approaches. In this work, several effective strategies, such as incorporating 1,2,3-triazole groups as moderate Lewis base centers into MOFs and employing flexible azamacrocycle-based ligands to build MOFs, demonstrate to be promising ways to enhance CO 2 uptake capacity and CO2 separation ability of porous MOFs. It is revealed through in-depth studies on counter-intuitive experimental observations that the local electric

  16. A Sr2+-metal-organic framework with high chemical stability: synthesis, crystal structure and photoluminescence property.

    PubMed

    Jia, Yan-Yuan; Liu, Xiao-Ting; Wang, Wen-He; Zhang, Li-Zhu; Zhang, Ying-Hui; Bu, Xian-He

    2017-01-13

    Metal-organic frameworks (MOFs) are typically built by assembly of metal centres and organic linkers, and have emerged as promising crystalline materials in a variety of fields. However, the stability of MOFs is a key limitation for their practical applications. Herein, we report a novel Sr 2+: -MOF [Sr4(Tdada)2(H2O)3(DMF)2] (denoted as NKU- 105: , NKU = Nankai University; H4Tdada = 5,5'-((thiophene-2,5-dicar bonyl)bis(azanediyl))diisophthalic acid; DMF = N,N-dimethylformamide) featuring an open square channel of about 6 Å along the c-axis. Notably, NKU- 105: exhibits much outstanding chemical stability against common organic solvents, boiling water, acids and bases, relative to most MOF materials. Furthermore, NKU- 105: is an environment-friendly luminescent material with a bright cyan emission.This article is part of the themed issue 'Coordination polymers and metal-organic frameworks: materials by design'.

  17. Design and construction of porous metal-organic frameworks based on flexible BPH pillars

    SciTech Connect

    Hao, Xiang-Rong; Yang, Guang-sheng; Shao, Kui-Zhan; Su, Zhong-Min; Yuan, Gang; Wang, Xin-Long

    2013-02-15

    Three metal-organic frameworks (MOFs), [Co{sub 2}(BPDC){sub 2}(4-BPH){center_dot}3DMF]{sub n} (1), [Cd{sub 2}(BPDC){sub 2}(4-BPH){sub 2}{center_dot}2DMF]{sub n} (2) and [Ni{sub 2}(BDC){sub 2}(3-BPH){sub 2} (H{sub 2}O){center_dot}4DMF]{sub n} (3) (H{sub 2}BPDC=biphenyl-4,4 Prime -dicarboxylic acid, H{sub 2}BDC=terephthalic acid, BPH=bis(pyridinylethylidene)hydrazine and DMF=N,N Prime -dimethylformamide), have been solvothermally synthesized based on the insertion of heterogeneous BPH pillars. Framework 1 has 'single-pillared' MOF-5-like motif with inner cage diameters of up to 18.6 A. Framework 2 has 'double pillared' MOF-5-like motif with cage diameters of 19.2 A while 3 has 'double pillared' 8-connected framework with channel diameters of 11.0 A. Powder X-ray diffraction (PXRD) shows that 3 is a dynamic porous framework. - Graphical abstract: By insertion of flexible BPH pillars based on 'pillaring' strategy, three metal-organic frameworks are obtained showing that the porous frameworks can be constructed in a much greater variety. Highlights: Black-Right-Pointing-Pointer Frameworks 1 and 2 have MOF-5 like motif. Black-Right-Pointing-Pointer The cube-like cages in 1 and 2 are quite large, comparable to the IRMOF-10. Black-Right-Pointing-Pointer Framework 1 is 'single-pillared' mode while 2 is 'double-pillared' mode. Black-Right-Pointing-Pointer PXRD and gas adsorption analysis show that 3 is a dynamic porous framework.

  18. Hybrid metal organic scintillator materials system and particle detector

    DOEpatents

    Bauer, Christina A.; Allendorf, Mark D.; Doty, F. Patrick; Simmons, Blake A.

    2011-07-26

    We describe the preparation and characterization of two zinc hybrid luminescent structures based on the flexible and emissive linker molecule, trans-(4-R,4'-R') stilbene, where R and R' are mono- or poly-coordinating groups, which retain their luminescence within these solid materials. For example, reaction of trans-4,4'-stilbenedicarboxylic acid and zinc nitrate in the solvent dimethylformamide (DMF) yielded a dense 2-D network featuring zinc in both octahedral and tetrahedral coordination environments connected by trans-stilbene links. Similar reaction in diethylformamide (DEF) at higher temperatures resulted in a porous, 3-D framework structure consisting of two interpenetrating cubic lattices, each featuring basic to zinc carboxylate vertices joined by trans-stilbene, analogous to the isoreticular MOF (IRMOF) series. We demonstrate that the optical properties of both embodiments correlate directly with the local ligand environments observed in the crystal structures. We further demonstrate that these materials produce high luminescent response to proton radiation and high radiation tolerance relative to prior scintillators. These features can be used to create sophisticated scintillating detection sensors.

  19. Carbon-coated rutile titanium dioxide derived from titanium-metal organic framework with enhanced sodium storage behavior

    NASA Astrophysics Data System (ADS)

    Zou, Guoqiang; Chen, Jun; Zhang, Yan; Wang, Chao; Huang, Zhaodong; Li, Simin; Liao, Hanxiao; Wang, Jufeng; Ji, Xiaobo

    2016-09-01

    Carbon-coated rutile titanium dioxide (CRT) was fabricated through an in-situ pyrolysis of titanium-based metal organic framework (Ti8O8(OH)4[O2CC6H4CO2]6) crystals. Benefiting from the Tisbnd Osbnd C skeleton structure of titanium-based metal organic framework, the CRT possesses abundant channels and micro/mesopores with the diameters ranging from 1.06 to 4.14 nm, shows larger specific surface area (245 m2 g-1) and better electronic conductivity compared with pure titanium dioxide (12.8 m2 g-1). When applied as anode material for sodium-ion batteries, the CRT electrode exhibits a high cycling performance with a reversible capacity of ∼175 mAh g-1 at 0.5 C-rate after 200 cycles, and obtains an excellent rate capability of ∼70 mAh g-1 after 2000 cycles even at a specific current of 3360 mA g-1(20 C-rate). The outstanding rate capability can be attributed to the carbon-coated structure, which may effectively prevent aggregation of the titanium dioxide nanoparticles, accelerate the mass transfer of Na+ and speed up the charge transfer rate. Considering these advantages of this particular framework structure, the CRT can serve as an alternative anode material for the industrial application of SIBs.

  20. Robust Multifunctional Yttrium-Based Metal-Organic Frameworks with Breathing Effect.

    PubMed

    Firmino, Ana D G; Mendes, Ricardo F; Antunes, Margarida M; Barbosa, Paula C; Vilela, Sérgio M F; Valente, Anabela A; Figueiredo, Filipe M L; Tomé, João P C; Paz, Filipe A Almeida

    2017-02-06

    Phosphonate- and yttrium-based metal-organic frameworks (MOFs), formulated as [Y(H5btp)]·5.5H2O (1), [Y(H5btp)]·2.5H2O (2), (H3O)[Y2(H5btp)(H4btp)]·H2O (3), and [Y(H5btp)]·H2O·0.5(MeOH) (4), were prepared using a "green" microwave-assisted synthesis methodology which promoted the self-assembly of the tetraphosphonic organic linker [1,1'-biphenyl]-3,3',5,5'-tetrayltetrakis(phosphonic acid) (H8btp) with Y(3+) cations. This new family of functional materials, isolated in bulk quantities, exhibits a remarkable breathing effect. Structural flexibility was thoroughly studied by means of X-ray crystallography, thermogravimetry, variable-temperature X-ray diffraction, and dehydration and rehydration processes, ultimately evidencing a remarkable reversible single-crystal to single-crystal (SC-SC) transformation solely through the loss and gain of crystallization solvent molecules. Topologically, frameworks remained unaltered throughout this interconversion mechanism, with all compounds being binodal 6,6-connected network with a Schäfli symbol of {4(13).6(2)}{4(8).6(6).8}. Results show that this is one of the most stable and thermally robust families of tetraphosphonate-based MOFs synthesized reported to date. Porous materials 2 and 3 were further studied to ascertain their performance as heterogeneous catalysts and proton conductors, respectively, with outstanding results being registered for both materials. Compound 2 showed a 94% conversion of benzaldehyde into (dimethoxymethyl)benzene after just 1 h of reaction, among the best results registered to date for MOF materials. On the other hand, the protonic conductivity of compound 3 at 98% of relative humidity (2.58 × 10(-2) S cm(-1)) was among the highest registered among MOFs, with the great advantage of the material to be prepared using a simpler and sustainable synthesis methodology, as well as exhibiting a good stability at ambient conditions (temperature and humidity) over time when compared to others.

  1. Dielectric spectroscopy and simulation of cryptophane and metal-organic framework crystals containing internal molecular rotors

    NASA Astrophysics Data System (ADS)

    Winston, Erick B.

    With recent advances in chemistry and crystal engineering, it is now possible to flexibly synthesize stable crystals with internal molecular electric dipole rotors. This represents a nanoscale design approach to the creation of new materials. Potential applications of such systems include electro-optic materials, new ferroelectrics and dielectrics, and perhaps even information storage. In this thesis, the rotational dynamics of molecular rotors in single crystals is investigated by dielectric spectroscopy. Using X-ray crystallography in combination with molecular mechanics or ab initio calculations, the influence of the local crystal environment on the observed dynamics is ascertained. Additionally, the atomic coordinates from the X-ray structure, and molecular dipole moments determined from ab initio calculations, are used to create an approximate model for a Monte Carlo study of the significance of the dipole-dipole interactions among the rotors. The systems studied here represent two different families of synthetic approaches to creating molecular rotors in crystals. One approach consists of synthesizing inclusion compounds in which molecular crystals have internal cavities capable of hosting small molecular guests. Specifically, we look at the globular cryptophane complexes and find that iodomethane rotates in cryptophane-A with remarkably low barriers near 2 kcal·mol-1 (1000 K), in agreement with the molecular mechanics calculations. The other approach consists of synthesizing covalent crystals where the rotor elements are themselves part of the covalently bonded network. We study metal-organic open frameworks (MOFs), in particular IRMOF-2, and find rotation with a single barrier near 7 kcal·mol-1 (3500 K). The barrier is in approximate agreement with ab initio calculations. Statistical analysis of an MC simulation of IRMOF-2 suggests a dipolar phase change at lower temperatures. The residual dielectric effects of the dipole-dipole interaction above the

  2. Development and Test Evaluations for Ni-DOBDC Metal Organic Framework (MOF) Engineered Forms

    SciTech Connect

    Troy G. Garn; Mitchell Greenhalgh

    2013-07-01

    A joint effort to prepare engineered forms of a Ni-DOBDC metal organic framework (MOF) was completed with contributions from PNNL, SNL and the INL. Two independent methods were used at INL and SNL to prepare engineered form (EF) sorbents from Ni-DOBDC MOF powder developed and prepared at PNNL. Xe and Kr capacity test evaluations were performed at ambient temperature with the cryostat experimental setup at INL. The initial INL EF MOF test results indicated a Xe capacity of 1.6 mmol/kg sorbent and no Kr capacity. A large loss of surface area also occurred during minimal testing rendering the INL EF MOF unusable. Four capacity tests were completed using the SNL EF MOF at ambient temperature and resulted in Xe capacities of 1.4, 4.2, 5.0 and 3.8 mmol/kg sorbent with no Kr capacity observed in any ambient temperature tests. Two additional capacity tests were performed at 240 K to further evaluate SNL EF MOF performance. Xe capacities of 50.7 and 49.3 mmol/kg of sorbent and Kr capacities of 0.77 and 0.69 mmol/kg of sorbent were obtained, respectively. Following the adsorption evaluations, the SNL EF MOF material had lost about 40 % of the initial mass and 40 % of the initial surface area. In general, the Xe capacity results at ambient temperature for the INL and SNL EF Ni-DOBDC MOF’s were lower than 9.8 mmol Xe/kg sorbent test results reported by INL in FY-12 using PNNL’s inital EF supplied material.

  3. Light-harvesting metal-organic frameworks (MOFs): efficient strut-to-strut energy transfer in bodipy and porphyrin-based MOFs.

    PubMed

    Lee, Chang Yeon; Farha, Omar K; Hong, Bong Jin; Sarjeant, Amy A; Nguyen, SonBinh T; Hupp, Joseph T

    2011-10-12

    A pillared-paddlewheel type metal-organic framework material featuring bodipy- and porphyrin-based struts, and capable of harvesting light across the entire visible spectrum, has been synthesized. Efficient-essentially quantitative-strut-to-strut energy transfer (antenna behavior) was observed for the well-organized donor-acceptor assembly consituting the ordered MOF structure.

  4. The influence of the enantiomeric ratio of an organic ligand on the structure and chirality of Metal-Organic Frameworks

    PubMed Central

    Burneo, Iván; Stylianou, Kyriakos C.; Imaz, Inhar; Maspoch, Daniel

    2016-01-01

    We have prepared three distinct polyamino acid-based metal-organic frameworks (MOFs) with different chirality and porosity using the same chemistry, by simply modifying the enantiomeric ratio of the chiral organic ligand used. PMID:25253285

  5. Selective fluorescence sensors for detection of nitroaniline and metal Ions based on ligand-based luminescent metal-organic frameworks

    SciTech Connect

    Yu, Zongchao; Wang, Fengqin; Lin, Xiangyi; Wang, Chengmiao; Fu, Yiyuan; Wang, Xiaojun; Zhao, Yongnan; Li, Guodong

    2015-12-15

    Metal-organic frameworks (MOFs) are porous crystalline materials with high potential for applications in fluorescence sensors. In this work, two solvent-induced Zn(II)–based metal-organic frameworks, Zn{sub 3}L{sub 3}(DMF){sub 2} (1) and Zn{sub 3}L{sub 3}(DMA){sub 2}(H{sub 2}O){sub 3} (2) (L=4,4′-stilbenedicarboxylic acid), were investigated as selective sensing materials for detection of nitroaromatic compounds and metal ions. The sensing experiments show that 1 and 2 both exhibit selective fluorescence quenching toward nitroaniline with a low detection limit. In addition, 1 exhibits high selectivity for detection of Fe{sup 3+} and Al{sup 3+} by significant fluorescence quenching or enhancement effect. While for 2, it only exhibits significant fluorescence quenching effect for Fe{sup 3+}. The results indicate that 1 and 2 are both promising fluorescence sensors for detecting and recognizing nitroaniline and metal ions with high sensitivity and selectivity. - Graphical abstract: Two MOFs have been selected as the fluorescence sensing materials for selectively sensing mitroaromatic compounds and metal ions. The high selectivity makes them promising fluorescence sensors for detecting and recognizing nitroaniline and Fe{sup 3+} or Al{sup 3+}.

  6. Structures and H2 adsorption properties of porous scandium metal-organic frameworks.

    PubMed

    Ibarra, Ilich A; Lin, Xiang; Yang, Sihai; Blake, Alexander J; Walker, Gavin S; Barnett, Sarah A; Allan, David R; Champness, Neil R; Hubberstey, Peter; Schröder, Martin

    2010-12-10

    Two new three-dimensional Sc(III) metal-organic frameworks {[Sc(3)O(L(1))(3)(H(2)O)(3)]·Cl(0.5)(OH)(0.5)(DMF)(4)(H(2)O)(3)}(∞) (1) (H(2)L(1)=1,4-benzene-dicarboxylic acid) and {[Sc(3)O(L(2))(2)(H(2)O)(3)](OH)(H(2)O)(5)(DMF)}(∞) (2) (H(3)L(2)=1,3,5-tris(4-carboxyphenyl)benzene) have been synthesised and characterised. The structures of both 1 and 2 incorporate the trinuclear trigonal planar [Sc(3)(O)(O(2)CR)(6)] building block featuring three Sc(III) centres joined by a central μ(3)-O(2-) donor. Each Sc(III) centre is further bound by four oxygen donors from four different bridging carboxylate anions, and a molecule of water located trans to the μ(3)-O(2-) donor completes the six coordination at the metal centre. Frameworks 1 and 2 show high thermal stability with retention of crystallinity up to 350 °C. The desolvated materials 1a and 2a, in which the solvent has been removed from the pores but with water or hydroxide remaining coordinated to Sc(III), show BET surface areas based upon N(2) uptake of 634 and 1233 m(2) g(-1), respectively, and pore volumes calculated from the maximum N(2) adsorption of 0.25 cm(3) g(-1) and 0.62 cm(3) g(-1), respectively. At 20 bar and 78 K, the H(2) isotherms for desolvated 1a and 2a confirm 2.48 and 1.99 wt% total H(2) uptake, respectively. The isosteric heats of adsorption were estimated to be 5.25 and 2.59 kJ mol(-1) at zero surface coverage for 1a and 2a, respectively. Treatment of 2 with acetone followed by thermal desolvation in vacuo generated free metal coordination sites in a new material 2b. Framework 2b shows an enhanced BET surface area of 1511 m(2) g(-1) and a pore volume of 0.76 cm(3) g(-1), with improved H(2) uptake capacity and a higher heat of H(2) adsorption. At 20 bar, H(2) capacity increases from 1.99 wt% in 2a to 2.64 wt% for 2b, and the H(2) adsorption enthalpy rises markedly from 2.59 to 6.90 kJ mol(-1).

  7. Extreme carbon dioxide sorption hysteresis in open-channel rigid metal-organic frameworks.

    PubMed

    Bezuidenhout, Charl X; Smith, Vincent J; Bhatt, Prashant M; Esterhuysen, Catharine; Barbour, Leonard J

    2015-02-09

    A systematic study is presented of three closely related microporous metal-organic frameworks the pore dimensions of which vary according to the choice of 4,4'-bipyridyl linker. The tunable linker allows exploration of the effect of increasing pore dimensions on the sorption behavior of the frameworks. The MOFs described capture CO2 under supercritical conditions and continue to sequester the gas under ambient conditions. Gas sorption isotherms for CO2 are compared with thermogravimetric data, and the CO2 molecules in the channels of the frameworks could be modeled using single-crystal X-ray diffraction analysis. Crystallographic data were used to construct a theoretical model based on DFT methods to calculate framework electrostatic potential maps with a view to understanding the nature of the sorbate-sorbent interactions.

  8. Thin Film Thermoelectric Metal-Organic Framework with High Seebeck Coefficient and Low Thermal Conductivity. Supporting Information

    DTIC Science & Technology

    2015-04-28

    0188 3. DATES COVERED (From - To) - UU UU UU UU Approved for public release; distribution is unlimited. Thin Film Thermoelectric Metal -Organic...is demonstrated based on an electrically conducting metal –organic framework (MOF) using the guest@MOF concept. This demonstration opens a new...thermoelectric response, metal organic framework REPORT DOCUMENTATION PAGE 11. SPONSOR/MONITOR’S REPORT NUMBER(S) 10. SPONSOR/MONITOR’S ACRONYM(S

  9. Extra adsorption and adsorbate superlattice formation in metal-organic frameworks.

    PubMed

    Sung Cho, Hae; Deng, Hexiang; Miyasaka, Keiichi; Dong, Zhiyue; Cho, Minhyung; Neimark, Alexander V; Ku Kang, Jeung; Yaghi, Omar M; Terasaki, Osamu

    2015-11-26

    Metal-organic frameworks (MOFs) have a high internal surface area and widely tunable composition, which make them useful for applications involving adsorption, such as hydrogen, methane or carbon dioxide storage. The selectivity and uptake capacity of the adsorption process are determined by interactions involving the adsorbates and their porous host materials. But, although the interactions of adsorbate molecules with the internal MOF surface and also amongst themselves within individual pores have been extensively studied, adsorbate-adsorbate interactions across pore walls have not been explored. Here we show that local strain in the MOF, induced by pore filling, can give rise to collective and long-range adsorbate-adsorbate interactions and the formation of adsorbate superlattices that extend beyond an original MOF unit cell. Specifically, we use in situ small-angle X-ray scattering to track and map the distribution and ordering of adsorbate molecules in five members of the mesoporous MOF-74 series along entire adsorption-desorption isotherms. We find in all cases that the capillary condensation that fills the pores gives rise to the formation of 'extra adsorption domains'-that is, domains spanning several neighbouring pores, which have a higher adsorbate density than non-domain pores. In the case of one MOF, IRMOF-74-V-hex, these domains form a superlattice structure that is difficult to reconcile with the prevailing view of pore-filling as a stochastic process. The visualization of the adsorption process provided by our data, with clear evidence for initial adsorbate aggregation in distinct domains and ordering before an even distribution is finally reached, should help to improve our understanding of this process and may thereby improve our ability to exploit it practically.

  10. Extra adsorption and adsorbate superlattice formation in metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Sung Cho, Hae; Deng, Hexiang; Miyasaka, Keiichi; Dong, Zhiyue; Cho, Minhyung; Neimark, Alexander V.; Ku Kang, Jeung; Yaghi, Omar M.; Terasaki, Osamu

    2015-11-01

    Metal-organic frameworks (MOFs) have a high internal surface area and widely tunable composition, which make them useful for applications involving adsorption, such as hydrogen, methane or carbon dioxide storage. The selectivity and uptake capacity of the adsorption process are determined by interactions involving the adsorbates and their porous host materials. But, although the interactions of adsorbate molecules with the internal MOF surface and also amongst themselves within individual pores have been extensively studied, adsorbate-adsorbate interactions across pore walls have not been explored. Here we show that local strain in the MOF, induced by pore filling, can give rise to collective and long-range adsorbate-adsorbate interactions and the formation of adsorbate superlattices that extend beyond an original MOF unit cell. Specifically, we use in situ small-angle X-ray scattering to track and map the distribution and ordering of adsorbate molecules in five members of the mesoporous MOF-74 series along entire adsorption-desorption isotherms. We find in all cases that the capillary condensation that fills the pores gives rise to the formation of ‘extra adsorption domains’—that is, domains spanning several neighbouring pores, which have a higher adsorbate density than non-domain pores. In the case of one MOF, IRMOF-74-V-hex, these domains form a superlattice structure that is difficult to reconcile with the prevailing view of pore-filling as a stochastic process. The visualization of the adsorption process provided by our data, with clear evidence for initial adsorbate aggregation in distinct domains and ordering before an even distribution is finally reached, should help to improve our understanding of this process and may thereby improve our ability to exploit it practically.

  11. Stress-induced chemical detection using flexible metal-organic frameworks.

    SciTech Connect

    Allendorf, Mark D.; Hesketh, Peter J.; Gall, Kenneth A.; Choudhury, A.; Pikarsky, J.; Andruszkiewicz, Leanne; Houk, Ronald J. T.; Talin, Albert Alec

    2009-09-01

    In this work we demonstrate the concept of stress-induced chemical detection using metal-organic frameworks (MOFs) by integrating a thin film of the MOF HKUST-1 with a microcantilever surface. The results show that the energy of molecular adsorption, which causes slight distortions in the MOF crystal structure, can be efficiently converted to mechanical energy to create a highly responsive, reversible, and selective sensor. This sensor responds to water, methanol, and ethanol vapors, but yields no response to either N{sub 2} or O{sub 2}. The magnitude of the signal, which is measured by a built-in piezoresistor, is correlated with the concentration and can be fitted to a Langmuir isotherm. Furthermore, we show that the hydration state of the MOF layer can be used to impart selectivity to CO{sub 2}. We also report the first use of surface-enhanced Raman spectroscopy to characterize the structure of a MOF film. We conclude that the synthetic versatility of these nanoporous materials holds great promise for creating recognition chemistries to enable selective detection of a wide range of analytes. A force field model is described that successfully predicts changes in MOF properties and the uptake of gases. This model is used to predict adsorption isotherms for a number of representative compounds, including explosives, nerve agents, volatile organic compounds, and polyaromatic hydrocarbons. The results show that, as a result of relatively large heats of adsorption (> 20 kcal mol{sup -1}) in most cases, we expect an onset of adsorption by MOF as low as 10{sup -6} kPa, suggesting the potential to detect compounds such as RDX at levels as low as 10 ppb at atmospheric pressure.

  12. Thermodynamics of solvent interaction with the metal-organic framework MOF-5.

    PubMed

    Akimbekov, Zamirbek; Wu, Di; Brozek, Carl K; Dincă, Mircea; Navrotsky, Alexandra

    2016-01-14

    The inclusion of solvent in metal-organic framework (MOF) materials is a highly specific form of guest-host interaction. In this work, the energetics of solvent MOF-5 interactions has been investigated by solution calorimetry in 5 M sodium hydroxide (NaOH) at room temperature. Solution calorimetric measurement of enthalpy of formation (ΔH(f)) of Zn4O(C8H4O4)3·C3H7NO (MOF-5·DMF) and Zn4O(C8H4O4)3·0.60C5H11NO (MOF-5·0.60DEF) from the dense components zinc oxide (ZnO), 1,4-benzenedicarboxylic acid (H2BDC), N,N-dimethylformamide (DMF) and N,N-diethylformamide (DEF) gives values of 16.69 ± 1.21 and 45.90 ± 1.46 kJ (mol Zn4O)(-1), respectively. The enthalpies of interaction (ΔH(int)) for DMF and DEF with MOF-5 are -82.78 ± 4.84 kJ (mol DMF)(-1) and -89.28 ± 3.05 kJ (mol DEF)(-1), respectively. These exothermic interaction energies suggest that, at low guest loading, Lewis base solvents interact more strongly with electron accepting Zn4O clusters in the MOF than at high solvent loading. These data provide a quantitative thermodynamic basis to investigate transmetallation and solvent assisted linker exchange (SALE) methods and to synthesize new MOFs.

  13. Optimized synthesis and crystalline stability of γ-cyclodextrin metal-organic frameworks for drug adsorption.

    PubMed

    Liu, Botao; Li, Haiyan; Xu, Xiaonan; Li, Xue; Lv, Nana; Singh, Vikramjeet; Stoddart, J Fraser; York, Peter; Xu, Xu; Gref, Ruxandra; Zhang, Jiwen

    2016-11-30

    The biocompatible and renewable cyclodextrin metal-organic frameworks (CD-MOFs) have addressed a range of opportunities in molecular storage and separation sciences. The reported protocols for their synthesis, however, were carried out at room temperature over long time periods of time (24h), producing crystals of relatively poor uniformity. In this investigation, micron sized γ-CD-MOFs were synthesized by an optimized vapor diffusion method at elevated temperature (50°C) within 6h, after which the size control, crystalline stability and drug adsorption behavior were investigated in detail. In this manner, uniform cubic γ-CD-MOF crystals were obtained when the reaction temperature was raised to 50°C with pre-addition of the reaction solvent. The size of γ-CD-MOFs was adjusted efficiently by changing the reactant concentrations, temperatures, time, γ-CD ratios to KOH and surfactant concentrations, without influencing the porosity and crystallinity of the material markedly. Varing degrees of reduction in crystallinity and change in morphology were observed when the γ-CD-MOF crystals are treated under conditions of high temperature (100°C), high humidity (92.5%) and polar solvents (e.g., MeOH and DMF). In relation to drug adsorption by γ-CD-MOFs, most of the drug molecules containing carboxyl groups showed relatively high adsorption (>5%), while low adsorption (<5%) was found for drugs with nitrogen-containing heterocyclic rings. In addition, the adsorption kinetics of captopril to standard γ-CD-MOFs matched a pseudo-second-order model rather well, whilst captopril adsorption to the damaged γ-CD-MOFs only partially matched the pseudo-second-order model. In summary, based upon the optimized synthesis and size control of γ-CD-MOFs, the crystalline stability and drug adsorption characteristics of γ-CD-MOF crystals have been evaluated as a fundamental requirement of a potential vehicle for drug delivery.

  14. Optimized synthesis and crystalline stability of γ-cyclodextrin metal-organic frameworks for drug adsorption.

    PubMed

    Liu, Botao; Li, Haiyan; Xu, Xiaonan; Li, Xue; Lv, Nana; Singh, Vikramjeet; Stoddart, J Fraser; York, Peter; Xu, Xu; Gref, Ruxandra; Zhang, Jiwen

    2016-09-26

    The biocompatible and renewable cyclodextrin metal-organic frameworks (CD-MOFs) have addressed a range of opportunities in molecular storage and separation sciences. The reported protocols for their synthesis, however, were carried out at room temperature over long time periods of time (24h), producing crystals of relatively poor uniformity. In this investigation, micron sized γ-CD-MOFs were synthesized by an optimized vapor diffusion method at elevated temperature (50°C) within 6h, after which the size control, crystalline stability and drug adsorption behavior were investigated in detail. In this manner, uniform cubic γ-CD-MOF crystals were obtained when the reaction temperature was raised to 50°C with pre-addition of the reaction solvent. The size of γ-CD-MOFs was adjusted efficiently by changing the reactant concentrations, temperatures, time, γ-CD ratios to KOH and surfactant concentrations, without influencing the porosity and crystallinity of the material markedly. Varing degrees of reduction in crystallinity and change in morphology were observed when the γ-CD-MOF crystals are treated under conditions of high temperature (100°C), high humidity (92.5%) and polar solvents (e.g., MeOH and DMF). In relation to drug adsorption by γ-CD-MOFs, most of the drug molecules containing carboxyl groups showed relatively high adsorption (>5%), while low adsorption (<5%) was found for drugs with nitrogen-containing heterocyclic rings. In addition, the adsorption kinetics of captopril to standard γ-CD-MOFs matched a pseudo-second-order model rather well, whilst captopril adsorption to the damaged γ-CD-MOFs only partially matched the pseudo-second-order model. In summary, based upon the optimized synthesis and size control of γ-CD-MOFs, the crystalline stability and drug adsorption characteristics of γ-CD-MOF crystals have been evaluated as a fundamental requirement of a potential vehicle for drug delivery.

  15. A highly stable zeotype mesoporous zirconium metal-organic framework with ultralarge pores.

    SciTech Connect

    Feng, Dawei; Wang, Kecheng; Su, Jie; Liu, Tian-Fu; Park, Jihye; Wei, Zhangwen; Bosch, Mathieu; Yakovenko, Andrey; Zou, Xiaodong; Zhou, Hong-Cai

    2015-01-02

    Through topological rationalization, a zeotype mesoporous Zr-containing metal-organic framework (MOF), namely PCN-777, has been designed and synthesized. PCN-777 exhibits the largest cage size of 3.8nm and the highest pore volume of 2.8cm(3)g(-1) among reported Zr-MOFs. Moreover, PCN-777 shows excellent stability in aqueous environments, which makes it an ideal candidate as a support to incorporate different functional moieties. Through facile internal surface modification, the interaction between PCN-777 and different guests can be varied to realize efficient immobilization

  16. The direct heat measurement of mechanical energy storage metal-organic frameworks.

    PubMed

    Rodriguez, Julien; Beurroies, Isabelle; Loiseau, Thierry; Denoyel, Renaud; Llewellyn, Philip L

    2015-04-07

    In any process, the heat exchanged is an essential property required in its development. Whilst the work related to structural transitions of some flexible metal-organic frameworks (MOFs) has been quantified and linked with potential applications such as molecular springs or shock absorbers, the heat related to such transitions has never been directly measured. This has now been carried out with MIL-53(Al) using specifically devised calorimetry experiments. We project the importance of these heats in devices such as molecular springs or dampers.

  17. Synthesis and characterization of two dimensional metal organic framework of cerium with tetraaza macrocyclic

    SciTech Connect

    Bt Safiin, Nurul Atikah; Yarmo, Ambar; Yamin, Bohari M.

    2013-11-27

    A two dimensional metal organic framework containing cerium sufate layers and ethylenediaminium between layers was obtained by refluxing the mixture of cerium sulphate and 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-7, 14-diene bromide. The complex was characterized by infrared spectroscopy and microelemental analysis. X-ray study showed that the complex adopts eleven coordination environments about the central atom. Thermogravimetric study showed the removal of water molecules at about 70°C followed by a gradual mass loss until the whole structure collapsed at about 400°C.

  18. A porphyrin-based metal-organic framework as a pH-responsive drug carrier

    NASA Astrophysics Data System (ADS)

    Lin, Wenxin; Hu, Quan; Jiang, Ke; Yang, Yanyu; Yang, Yu; Cui, Yuanjing; Qian, Guodong

    2016-05-01

    A low cytotoxic porphyrin-based metal-organic framework (MOF) PCN-221, which exhibited high PC12 cell viability via 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium (MTT) assay, was selected as an oral drug carrier. Methotrexate (MTX) was chosen as the model drug molecule which was absorbed into inner pores and channels of MOFs by diffusion. PCN-221 showed high drug loading and sustained release behavior under physiological environment without "burst effect". The controlled pH-responsive release of drugs by PCN-221 revealed its promising application in oral drug delivery.

  19. Metal-Organic Frameworks derivatives for improving the catalytic activity of CO oxidation reaction.

    PubMed

    Ji, Wenlan; Xu, Zhiling; Liu, Pengfei; Zhang, Suoying; Zhou, Weiqiang; Li, Hongfeng; Zhang, Tao; Li, Linjie; Lu, Xiaohua; Wu, Jiansheng; Zhang, Weina; Huo, Fengwei

    2017-03-15

    Metal-Organic Frameworks (MOFs) based derivatives have attracted an increasing interest in various research fields. However, most of reported papers mainly focused on the pristine MOFs-based derivatives, and researches on the functional MOFs-based derivatives composites are rare. Here, a simple strategy was reported to design the functional MOFs based derivatives composites by the encapsulation of the metal nanoparticles (MNPs) in MOFs matrixes (MNPs@MOFs) and the high-temperature calcination of MNPs@MOFs composites. The as-prepared MNPs@metal oxide composites with the hierarchical pore structure exhibited excellent catalytic activity and high stability for CO oxidation reaction.

  20. Metal-organic framework biosensor with high stability and selectivity in a bio-mimic environment.

    PubMed

    Wu, Xiao-Qin; Ma, Jian-Gong; Li, Han; Chen, Di-Ming; Gu, Wen; Yang, Guang-Ming; Cheng, Peng

    2015-06-04

    A water-stable copper metal-organic framework (MOF), {[Cu2(HL)2(μ2-OH)2(H2O)5]·H2O}n (1, H2L = 2,5-dicarboxylic acid-3,4-ethylene dioxythiophene), was applied for the electrochemical detection of ascorbic acid (AA) without further post-modification. A glass carbon electrode covered with 1 was used as a biosensor for the simultaneous detection of AA and L-tryptophan (L-Trp) from both a single-component solution and a bio-mimic environment.

  1. Metal-Organic Frameworks for Removal of Xe and Kr from Nuclear Fuel Reprocessing Plants

    SciTech Connect

    Liu, Jian; Thallapally, Praveen K.; Strachan, Denis M.

    2012-08-07

    Removal of Xenon (Xe) and Krypton (Kr) from in parts per million (ppm) levels were demonstrated for the first time using two well known metal-organic frameworks (MOFs), HKUST-1 and Ni/DOBDC. Results of an activated carbon were also included for comparison. Ni/DOBDC has higher Xe/Kr selectivities than those of the activated carbon. Moreover, results show that the Ni/DOBDC and HKUST-1 can selectively adsorb Xe and Kr from air even at 1000 ppm concentration. This shows a promising future for MOFs in a radioactive nuclides separation from spent fuel.

  2. Switching Kr/Xe Selectivity with Temperature in a Metal-Organic Framework

    SciTech Connect

    Fernandez, Carlos A.; Liu, Jian; Thallapally, Praveen K.; Strachan, Denis M.

    2012-05-16

    Krypton (Kr) and xenon (Xe) adsorption on two partially fluorinated metal-organic frameworks (FMOFCu and FMOFZn) with different cavity size and topologies were reported. FMOFCu shows an inversion in sorption selectivity toward Kr at temperatures below 0 C while FMOFZn does not. The 1D microtubes packed along the (101) direction connected through small bottleneck windows in FMOFCu appear to be the reason for this peculiar behavior. The FMOFCu shows an estimated Kr/Xe selectivity of 36 at 0.1 bar.

  3. Photoactive chiral metal-organic frameworks for light-driven asymmetric α-alkylation of aldehydes.

    PubMed

    Wu, Pengyan; He, Cheng; Wang, Jian; Peng, Xiaojun; Li, Xuezhao; An, Yonglin; Duan, Chunying

    2012-09-12

    Chiral metal-organic frameworks (MOFs) with porous and tunable nature show promise as heterogeneous asymmetric catalysts. Through incorporating the stereoselective organocatalyst L- or D-pyrrolidin-2-ylimidazole (PYI) and a triphenylamine photoredox group into a single framework, we have developed two enantiomeric MOFs, Zn-PYI1 and Zn-PYI2, to prompt the asymmetric α-alkylation of aliphatic aldehydes in a heterogeneous manner. The strong reductive excited state of the triphenylamaine moiety within these MOFs initiated a photoinduced electron transfer, rendering an active intermediate for the α-alkylation. The chiral PYI moieties acted as cooperative organocatalytic active sites to drive the asymmetric catalysis with significant stereoselectivity. Control experiments using the lanthanide-based metal-organic frameworks Ho-TCA and MOF-150, assembled from 4,4',4"-nitrilotribenzoic acid, as catalysts suggested that both the photosensitizer triphenylamine moiety and the chiral organocatalyst D-/L-PYI moiety were necessary for the light-driven α-alkylation reactions. Further investigations demonstrated that the integration of both photocatalyst and asymmetric organocatalyst into a single MOF makes the enantioselection superior to that of simply mixing the corresponding MOFs with the chiral adduct. The easy availability, excellent stereoselectivity, great separability, and individual components fixed with their well-defined porous and repeating structures make the MOF a versatile platform for a new type of tandem catalyst and cooperative catalyst.

  4. Water-Stable Metal-Organic Framework/Polymer Composites Compatible with Human Hepatocytes.

    PubMed

    Neufeld, Megan J; Ware, Brenton R; Lutzke, Alec; Khetani, Salman R; Reynolds, Melissa M

    2016-08-03

    Metal-organic frameworks (MOFs) have demonstrated promise in biomedical applications as vehicles for drug delivery, as well as for the ability of copper-based MOFs to generate nitric oxide (NO) from endogenous S-nitrosothiols (RSNOs). Because NO is a participant in biological processes where it exhibits anti-inflammatory, antibacterial, and antiplatelet activation properties, it has received significant attention for therapeutic purposes. Previous work has shown that the water-stable MOF H3[(Cu4Cl)3-(BTTri)8] (H3BTTri = 1,3,5-tris(1H-1,2,3-triazol-5-yl)benzene), or CuBTTri, produces NO from RSNOs and can be included within a polymeric matrix to form NO-generating materials. While such materials demonstrate potential, the possibility of MOF degradation leading to copper-related toxicity is a concern that must be addressed prior to adapting these materials for biomedical applications. Herein, we present the first cytotoxicity evaluation of an NO-generating CuBTTri/polymer composite material using 3T3-J2 murine embryonic fibroblasts and primary human hepatocytes (PHHs). CuBTTri/polymer films were prepared from plasticized poly(vinyl chloride) (PVC) and characterized via PXRD, ATR-FTIR, and SEM-EDX. Additionally, the ability of the CuBTTri/polymer films to enhance NO generation from S-nitroso-N-acetylpenicillamine (SNAP) was evaluated. Enhanced NO generation in the presence of the CuBTTri/polymer films was observed, with an average NO flux (0.90 ± 0.13 nmol cm(-2) min(-1)) within the range associated with antithrombogenic surfaces. The CuBTTri/polymer films were analyzed for stability in phosphate buffered saline (PBS) and cell culture media under physiological conditions for a 4 week duration. Cumulative copper release in both cell media (0.84 ± 0.21%) and PBS (0.18 ± 0.01%) accounted for less than 1% of theoretical copper present in the films. In vitro cell studies performed with 3T3-J2 fibroblasts and PHHs did not indicate significant toxicity, providing further

  5. Synthesis Optimization, Shaping, and Heat Reallocation Evaluation of the Hydrophilic Metal-Organic Framework MIL-160(Al).

    PubMed

    Permyakova, Anastasia; Skrylnyk, Oleksandr; Courbon, Emilie; Affram, Maame; Wang, Sujing; Lee, U-Hwang; Valekar, Anil H; Nouar, Farid; Mouchaham, Georges; Devic, Thomas; De Weireld, Guy; Chang, Jong-San; Steunou, Nathalie; Frère, Marc; Serre, Christian

    2017-04-10

    The energy-storage capacities of a series of water-stable porous metal-organic frameworks, based on high-valence metal cations (Al(3+) , Fe(3+) , Cr(3+) , Ti(4+) , Zr(4+) ) and polycarboxylate linkers, were evaluated under the typical conditions of seasonal energy-storage devices. The results showed that the microporous hydrophilic Al-dicarboxylate MIL-160(Al) exhibited one of the best performances. To assess the properties of this material for space-heating applications on a laboratory pilot scale with an open reactor, a new synthetic route involving safer, greener conditions was developed. This led to the production of MIL-160(Al) on a 400 g scale, before the material was shaped into pellets through a wet-granulation method. The material exhibited a very high energy-storage capacity for a physical-sorption material (343 Wh kg(-1) ), which is in full agreement with the predicted value.

  6. Vapor-Phase Deposition and Modification of Metal-Organic Frameworks: State-of-the-Art and Future Directions.

    PubMed

    Stassen, Ivo; De Vos, Dirk; Ameloot, Rob

    2016-10-04

    Materials processing, and thin-film deposition in particular, is decisive in the implementation of functional materials in industry and real-world applications. Vapor processing of materials plays a central role in manufacturing, especially in electronics. Metal-organic frameworks (MOFs) are a class of nanoporous crystalline materials on the brink of breakthrough in many application areas. Vapor deposition of MOF thin films will facilitate their implementation in micro- and nanofabrication research and industries. In addition, vapor-solid modification can be used for postsynthetic tailoring of MOF properties. In this context, we review the recent progress in vapor processing of MOFs, summarize the underpinning chemistry and principles, and highlight promising directions for future research.

  7. Pore surface engineering in a zirconium metal-organic framework via thiol-ene reaction

    NASA Astrophysics Data System (ADS)

    Gui, Bo; Hu, Guiping; Zhou, Tailin; Wang, Cheng

    2015-03-01

    A porous olefin-functionalized Zr(IV)-based metal-organic framework, denoted as UiO-68-allyl, has been constructed. Our results clearly demonstrated that the surface of UiO-68-allyl could be decorated with organic molecule (ethanethiol) via thiol-ene reaction. More importantly, the crystallinity of the framework were maintained during the post-synthetic modification process. However, the microporosity of the framework is retained but the surface area decreased, due to the grafting of ethylthio groups into the pores. From our studies, we can conclude that the strategy of post-synthetic modification of UiO-68-allyl via thiol-ene reaction may be general. Furthermore, we may anchor other desired functional group onto the pore walls in Zr-MOFs via thiol-ene reaction, enabling more potential applications.

  8. Synthesis and Characterization of Metal-Organic Frameworks (MOFs) That Are Difficult to Access De Novo

    NASA Astrophysics Data System (ADS)

    Karagiaridi, Olga

    Metal-organic frameworks (MOFs) are a class of intriguing hybrid materials, comprised of metal-based nodes joined by organic linkers into a crystalline, porous, three-dimensional lattice. Their signature properties (well-defined surfaces, tailorability and ultra-high porosity) render them promising candidates for many applications, including, but not limited to, gas storage, gas separation, catalysis and sensing. One of the greatest challenges associated with MOF synthesis lies in the fact that obtaining a desired MOF structure that is tailored to perform a specific application is often not trivial. Traditional synthetic pathways termed "de novo synthesis" (typically one-pot reactions between the MOF structural building blocks under solvothermal conditions) often give rise to side products that do not possess the desired structure. To circumvent this problem, we have studied in depth two powerful MOF synthetic techniques -- solvent-assisted linker exchange (SALE) and transmetalation. These are heterogeneous reactions of parent MOF crystals with concentrated solutions of organic linkers and inorganic metal salts, respectively, that lead to the replacement of the linkers or metal nodes within the parent MOFs by the desired components, while the overall framework topology is preserved. The projects described in this dissertation have aimed to apply these techniques to transform simple (unfunctionalized) and easy to synthesize representative materials from various MOF systems to structurally and functionally interesting daughter products. Examples include synthesis of MOFs that are energetically "unfavorable", extension of MOF cages by longer linker incorporation, functionalization of MOF pores and endowment of MOFs with permanent and persistent porosity. Through these projects, we have been able to formulate a set of rules that can be applied to predict the successful outcome of SALE. Since the allure of MOFs lies in their applications, expanding the range of

  9. Post Modification of Metal-Organic Framework and Their Application In Cancer Theranostics

    NASA Astrophysics Data System (ADS)

    Lakkakula, Hima bindu

    The research proposal aims to demonstrate that Metal-Organic Frameworks (MOFs) are mainly used for cancer theranostics which is the combination of both diagnostic and therapeutic functions. The research will emphasis on synthesis of Fe- MOFs by solvothermal nucleation, crystallization, characterization by microscopy and spectroscopy and evaluation with different lattice parameters and its morphology. Nowadays MOFs are used for the novel drug delivery purposes. The current published Fe- MOFs research focus is on the cancer theranostics by Indian medicines which will be impregnated into the MOFs and which will evaluate bioavailability and the chemotherapeutic activity of the drug. Nanotechnology provides the target specificity without affecting the healthy tissues. Other research problems to be addressed are the relationship between metal connectivity and ligand-based luminescence, MOF stability in an aqueous environment and activating it at increased temperature serves as a crucial role. The merits of this research are to increase the surface area and pore size of the drug so that the therapeutic efficacy can be improved. Moreover, the stabilization of metal-organic frameworks can also be enhanced with high surface area.

  10. Bi2O3 nanoparticles encapsulated in surface mounted metal-organic framework thin films

    NASA Astrophysics Data System (ADS)

    Guo, Wei; Chen, Zhi; Yang, Chengwu; Neumann, Tobias; Kübel, Christian; Wenzel, Wolfgang; Welle, Alexander; Pfleging, Wilhelm; Shekhah, Osama; Wöll, Christof; Redel, Engelbert

    2016-03-01

    We describe a novel procedure to fabricate a recyclable hybrid-photocatalyst based on Bi2O3@HKUST-1 MOF porous thin films. Bi2O3 nanoparticles (NPs) were synthesized within HKUST-1 (or Cu3(BTC)2) surface-mounted metal-organic frame-works (SURMOFs) and characterized using X-ray diffraction (XRD), a quartz crystal microbalance (QCM) and transmission electron microscopy (TEM). The Bi2O3 semiconductor NPs (diameter 1-3 nm)/SURMOF heterostructures exhibit superior photo-efficiencies compared to NPs synthesized using conventional routes, as demonstrated via the photodegradation of the nuclear fast red (NFR) dye.We describe a novel procedure to fabricate a recyclable hybrid-photocatalyst based on Bi2O3@HKUST-1 MOF porous thin films. Bi2O3 nanoparticles (NPs) were synthesized within HKUST-1 (or Cu3(BTC)2) surface-mounted metal-organic frame-works (SURMOFs) and characterized using X-ray diffraction (XRD), a quartz crystal microbalance (QCM) and transmission electron microscopy (TEM). The Bi2O3 semiconductor NPs (diameter 1-3 nm)/SURMOF heterostructures exhibit superior photo-efficiencies compared to NPs synthesized using conventional routes, as demonstrated via the photodegradation of the nuclear fast red (NFR) dye. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr00532b

  11. Monolithic column incorporated with lanthanide metal-organic framework for capillary electrochromatography.

    PubMed

    Zhang, Li-Shun; Du, Pei-Yao; Gu, Wen; Zhao, Qing-Li; Huang, Yan-Ping; Liu, Zhao-Sheng

    2016-08-26

    A new lanthanide metal-organic frameworks NKU-1 have successfully incorporated into poly (BMA-co-EDMA) monolith and evaluated by capillary electrochromatography (CEC). Lanthanide metal-organic frameworks [Eu2(ABTC)1.5(H2O)3(DMA)] (NKU-1) were synthesized by self-assembly of Eu(III) ions and 3,3',5,5'-azo benzene tetracarboxylic acid ligands have been fabricated into poly(BMA-co-EDMA) monoliths. 1-Butyl-3-methylimidazolium tetrafluoroborate and N,N-dimethylformamide were developed as binary porogen obtaining homogeneous dispersibility for NKU-1 and high permeability for monolithic column. The successful incorporation of NKU-1 into poly(BMA-co-EDMA) was confirmed and characterized by FT-IR spectra, scanning electron microscopy, X-ray diffraction, energy dispersive spectrometer area scanning, and transmission electron microscopy. Separation ability of the NKU-1-poly (BMA-co-EDMA) monoliths was demonstrated by separating four groups of analytes in CEC, including alkylbenzenes, polycyclic aromatic hydrocarbon, aniline series and naphthyl substitutes. Compared with bare monolithic (column efficiency of 100,000plates/m), the NKU-1-poly (BMA-co-EDMA) monoliths have displayed greater column efficiency (maximum 210,000plates/m) and higher permeability, as well as less peak tailing. The results showed that the NKU-1-poly (BMA-co-EDMA) monoliths are promising stationary phases for CEC separations.

  12. Rationally tuned micropores within enantiopure metal-organic frameworks for highly selective separation of acetylene and ethylene.

    PubMed

    Xiang, Sheng-Chang; Zhang, Zhangjing; Zhao, Cong-Gui; Hong, Kunlun; Zhao, Xuebo; Ding, De-Rong; Xie, Ming-Hua; Wu, Chuan-De; Das, Madhab C; Gill, Rachel; Thomas, K Mark; Chen, Banglin

    2011-02-22

    Separation of acetylene and ethylene is an important industrial process because both compounds are essential reagents for a range of chemical products and materials. Current separation approaches include the partial hydrogenation of acetylene into ethylene over a supported Pd catalyst, and the extraction of cracked olefins using an organic solvent; both routes are costly and energy consuming. Adsorption technologies may allow separation, but microporous materials exhibiting highly selective adsorption of C(2)H(2)/C(2)H(4) have not been realized to date. Here, we report the development of tunable microporous enantiopure mixed-metal-organic framework (M'MOF) materials for highly selective separation of C(2)H(2) and C(2)H(4). The high selectivities achieved suggest the potential application of microporous M'MOFs for practical adsorption-based separation of C(2)H(2)/C(2)H(4).

  13. Thermal conversion of core-shell metal-organic frameworks: a new method for selectively functionalized nanoporous hybrid carbon.

    PubMed

    Tang, Jing; Salunkhe, Rahul R; Liu, Jian; Torad, Nagy L; Imura, Masataka; Furukawa, Shuhei; Yamauchi, Yusuke

    2015-02-04

    Core-shell structured ZIF-8@ZIF-67 crystals are well-designed and prepared through a seed-mediated growth method. After thermal treatment of ZIF-8@ZIF-67 crystals, we obtain selectively functionalized nanoporous hybrid carbon materials consisting of nitrogen-doped carbon (NC) as the cores and highly graphitic carbon (GC) as the shells. This is the first example of the integration of NC and GC in one particle at the nanometer level. Electrochemical data strongly demonstrate that this nanoporous hybrid carbon material integrates the advantageous properties of the individual NC and GC, exhibiting a distinguished specific capacitance (270 F·g(-1)) calculated from the galvanostatic charge-discharge curves at a current density of 2 A·g(-1). Our study not only bridges diverse carbon-based materials with infinite metal-organic frameworks but also opens a new avenue for artificially designed nanoarchitectures with target functionalities.

  14. Flexibility and sorption selectivity in rigid metal-organic frameworks: the impact of ether-functionalised linkers.

    PubMed

    Henke, Sebastian; Schmid, Rochus; Grunwaldt, Jan-Dierk; Fischer, Roland A

    2010-12-27

    The functionalisation of well-known rigid metal-organic frameworks (namely, [Zn(4)O(bdc)(3)](n), MOF-5, IRMOF-1 and [Zn(2)(bdc)(2)(dabco)](n); bdc = 1,4-benzene dicarboxylate, dabco = diazabicyclo[2.2.2]octane) with additional alkyl ether groups of the type -O-(CH(2))(n)-O-CH(3) (n = 2-4) initiates unexpected structural flexibility, as well as high sorption selectivity towards CO(2) over N(2) and CH(4) in the porous materials. These novel materials respond to the presence/absence of guest molecules with structural transformations. We found that the chain length of the alkyl ether groups and the substitution pattern of the bdc-type linker have a major impact on structural flexibility and sorption selectivity. Remarkably, our results show that a high crystalline order of the activated material is not a prerequisite to achieve significant porosity and high sorption selectivity.

  15. Hydrogen storage in metal-organic frameworks: An investigation of structure-property relationships

    NASA Astrophysics Data System (ADS)

    Rowsell, Jesse

    Metal-organic frameworks (MOFs) have been identified as candidate hydrogen storage materials due to their ability to physisorb large quantities of small molecules. Thirteen compounds (IRMOF-1, -2, -3, -6, -8, -9, -11, -13, -18, -20, MOF-74, MOF-177 and HKUST-1) have been prepared and fully characterized for the evaluation of their dihydrogen (H2) adsorption properties. All compounds display approximately type I isotherms with no hysteresis at 77 K up to 1 atm. The amount adsorbed ranges from 0.89 to 2.54 wt%; however, saturation is not achieved under these conditions. The influences of link functionalization, catenation and topology are examined for the eleven MOFs composed of Zn4O(O2C-)6 clusters. Enhanced H2 uptake by catenated compounds is rationalized by increased overlap of the surface potentials within their narrower pores. This is corroborated by the larger isosteric heat of adsorption of IRMOF-11 compared to IRMOF-1. Inelastic neutron scattering spectroscopic analysis of four Zn4O-based materials (IRMOF-1, -8, -11, and MOF-74) under a range of H2 loading suggests the presence of multiple localized adsorption sites on both the inorganic and organic moieties. To determine the structural details of the adsorption sites, variable temperature single crystal X-ray diffraction was used to analyze adsorbed argon and dinitrogen molecules in IRMOF-1. The principle binding site was found to be the same for both adsorbates and is located on faces of the octahedral Zn4O(O2C-)6 clusters with close contacts to three carboxylate groups. A total of eight symmetry-independent adsorption sites were identified for argon at 30 K. Similar sites were observed for dinitrogen, suggesting that they are good model adsorbates for the behaviour of dihydrogen. Two additional materials composed of inorganic clusters with coordinatively unsaturated metal sites (MOF-74, HKUST-1) were examined and their increased capacities and isosteric heats of adsorption provide further evidence that the

  16. A malonitrile-functionalized metal-organic framework for hydrogen sulfide detection and selective amino acid molecular recognition

    PubMed Central

    Li, Haiwei; Feng, Xiao; Guo, Yuexin; Chen, Didi; Li, Rui; Ren, Xiaoqian; Jiang, Xin; Dong, Yuping; Wang, Bo

    2014-01-01

    A novel porous polymeric fluorescence probe, MN-ZIF-90, has been designed and synthesized for quantitative hydrogen sulfide (H2S) fluorescent detection and highly selective amino acid recognition. This distinct crystalline structure, derived from rational design and malonitrile functionalization, can trigger significant enhancement of its fluorescent intensity when exposed to H2S or cysteine molecules. Indeed this new metal-organic framework (MOF) structure shows high selectivity of biothiols over other amino acids and exhibits favorable stability. Moreover, in vitro viability assays on HeLa cells show low cytotoxicity of MN-ZIF-90 and its imaging contrast efficiency is further demonstrated by fluorescence microscopy studies. This facile yet powerful strategy also offers great potential of using open-framework materials (i.e. MOFs) as the novel platform for sensing and other biological applications. PMID:24621614

  17. Low-Energy CO2 Release from Metal-Organic Frameworks Triggered by External Stimuli.

    PubMed

    Li, Haiqing; Hill, Matthew R

    2017-03-08

    Groundbreaking research over the past 15 years has established metal-organic frameworks (MOFs) as adsorbents capable of unprecedented gas adsorption capacity. This has encouraged the contemplation of their use in applications such as increasing the storage capacity in natural gas fuel tanks, or the capture of carbon dioxide from coal-fired flue gas streams. However, while the gas adsorption capacity of MOFs is large, not all stored gas can be readily released to realize the efficient regeneration of MOF adsorbents. This leads to an increase in energy requirements, or working capacities significantly lower than the amount of gas adsorbed. This requirement for low energy means to efficiently release more stored gas has motivated the research in our group toward the triggered release of the stored gas from MOFs. Using CO2 as a typical gas adsorbate, we have developed three new methods of releasing stored gas with external stimuli that include light induction swing adsorption, magnetic induction swing adsorption, and their combination, denoted as LISA, MISA and MaLISA, respectively. LISA: Light, being naturally abundant, is particularly interesting for reducing the parasitic energy load on coal-fired power stations for regenerating the CO2 adsorbent. We showed that, by incorporating light-responsive organic linkers, exposure of light to a gas-loaded MOF promoted localized movement in the linkers, expelling around 80% of the adsorbed gas, just from the use of concentrated sunlight. Variation of the light-responsive components such as silver nanoparticles in MOFs allowed the response to be moved from UV to visible wavelengths, improving safety and light penetration depth. MISA: In order to expand this discovery to larger scales, more penetrating forms of radiation were sought. MOFs incorporated with magnetic nanoparticles (Magnetic Framework Composites, MFCs) were developed, and absorb the alternating magnetic fields exceptionally efficiently. The rapid heating of

  18. X-ray crystallographic insights into post-synthetic metalation products in a metal-organic framework.

    PubMed

    Huxley, Michael T; Coghlan, Campbell J; Bloch, Witold M; Burgun, Alexandre; Doonan, Christian J; Sumby, Christopher J

    2017-01-13

    Post-synthetic modification of metal-organic frameworks (MOFs) facilitates a strategic transformation of potentially inert frameworks into functionalized materials, tailoring them for specific applications. In particular, the post-synthetic incorporation of transition-metal complexes within MOFs, a process known as 'metalation', is a particularly promising avenue towards functionalizing MOFs. Herein, we describe the post-synthetic metalation of a microporous MOF with various transition-metal nitrates. The parent framework, 1: , contains free-nitrogen donor chelation sites, which readily coordinate metal complexes in a single-crystal to single-crystal transformation which, remarkably, can be readily monitored by X-ray crystallography. The presence of an open void surrounding the chelation site in 1: prompted us to investigate the effect of the MOF pore environment on included metal complexes, particularly examining whether void space would induce changes in the coordination sphere of chelated complexes reminiscent of those found in the solution state. To test this hypothesis, we systematically metalated 1: with first-row transition-metal nitrates and elucidated the coordination environment of the respective transition-metal complexes using X-ray crystallography. Comparison of the coordination sphere parameters of coordinated transition-metal complexes in 1: against equivalent solid- and solution-state species suggests that the void space in 1: does not markedly influence the coordination sphere of chelated species but we show notably different post-synthetic metalation outcomes when different solvents are used.This article is part of the themed issue 'Coordination polymers and metal-organic frameworks: materials by design'.

  19. Synthesis, structures, and properties of two three-dimensional metal-organic frameworks, based on concurrent ligand extension.

    PubMed

    Shi, Dabin; Ren, Yanwei; Jiang, Huanfeng; Cai, Bowei; Lu, Jiaxian

    2012-06-18

    A tritopic carboxylate ligand, tris(4'-carboxybiphenyl)amine (L-H(3)), has been synthesized and applied in the construction of microporous metal-organic frameworks (MOFs). Two novel metal-organic frameworks (MOFs), {[Zn(2)(L)(OH)]·2DMF·H(2)O}(∞) (1) and {[Cu(L-H)(DMA)]·DMA·2H(2)O}(∞) (2), have been constructed out of L-H(3), Zn(2+), and Cu(2+), respectively. 1 has a 2-fold interpenetrating three-dimensional framework formed by L connectors and the [Zn(2)(CO(2))(3)] secondary building units (SBUs). As for 1, it is worth pointing out that one μ(2)-OH group links two Zn atoms between two neighboring SBUs to produce interesting Zn-O-Zn zigzag chains in the structure. 2 has a two-dimensional grid sheet formed by L-H connectors and the typical paddle-wheel [Cu(2)(CO(2))(4)] SBUs. Two-dimensional (2D) sheets nest with each other, which finally forms a three-dimensional (3D) nested framework. Two MOFs are characterized by infrared (IR) spectroscopy, thermogravimetry, single-crystal and elemental analyses, and powder X-ray diffraction methods. Framework 1' exhibits high permanent porosity (Langmuir surface area = 848 m(2)/g), high thermal stability (up to 450 °C), highly active properties for Friedel-Crafts alkylation reaction, as well as the potential application for the CO(2) gas storage and luminescent material. The catalytic results reveal that 2' is indeed an efficient heterogeneous catalyst for olefin epoxidation reactions.

  20. Lithium inclusion in indium metal-organic frameworks showing increased surface area and hydrogen adsorption

    SciTech Connect

    Bosch, Mathieu; Zhang, Muwei; Feng, Dawei; Yuan, Shuai; Wang, Xuan; Chen, Ying-Pin; Zhou, Hong-Cai

    2014-12-01

    Investigation of counterion exchange in two anionic In-Metal-Organic Frameworks (In-MOFs) showed that partial replacement of disordered ammonium cations was achieved through the pre-synthetic addition of LiOH to the reaction mixture. This resulted in a surface area increase of over 1600% in (Li [In(1,3 − BDC){sub 2}]){sub n} and enhancement of the H{sub 2} uptake of approximately 275% at 80 000 Pa at 77 K. This method resulted in frameworks with permanent lithium content after repeated solvent exchange as confirmed by inductively coupled plasma mass spectrometry. Lithium counterion replacement appears to increase porosity after activation through replacement of bulkier, softer counterions and demonstrates tuning of pore size and properties in MOFs.

  1. Flexible, Luminescent Metal-Organic Frameworks Showing Synergistic Solid-Solution Effects on Porosity and Sensitivity.

    PubMed

    Liu, Si-Yang; Zhou, Dong-Dong; He, Chun-Ting; Liao, Pei-Qin; Cheng, Xiao-Ning; Xu, Yan-Tong; Ye, Jia-Wen; Zhang, Jie-Peng; Chen, Xiao-Ming

    2016-12-23

    Mixing molecular building blocks in the solid solution manner is a valuable strategy to obtain structures and properties in between the isostructural parent metal-organic frameworks (MOFs). We report nonlinear/synergistic solid-solution effects using highly related yet non-isostructural, phosphorescent Cu(I) triazolate frameworks as parent phases. Near the phase boundaries associated with conformational diversity and ligand heterogeneity, the porosity (+150 %) and optical O2 sensitivity (410 times, limit of detection 0.07 ppm) can be drastically improved from the best-performing parent MOFs and even exceeds the records hold by precious-metal complexes (3 ppm) and C70 (0.2 ppm).

  2. Urea Metal-Organic Frameworks for Nitro-Substituted Compounds Sensing.

    PubMed

    Azhdari Tehrani, Alireza; Esrafili, Leili; Abedi, Sedigheh; Morsali, Ali; Carlucci, Lucia; Proserpio, Davide M; Wang, Jun; Junk, Peter C; Liu, Tianfu

    2017-02-06

    Urea groups are known to form strong hydrogen bonds with molecules containing atom(s) that can act as hydrogen bond acceptor(s). Thus, urea is a particularly interesting building block for designing receptors for neutral or charged guests. In the quest for new sensors with enhanced performance for the detection of nitro-substituted compounds, two pillared metal-organic frameworks containing urea functional groups were synthesized and structurally characterized. The sensing properties of these frameworks toward nitro-analytes were investigated and compared to each other. The study clearly reveals the importance of urea groups orientation inside the pore cavity of MOFs, as well as the supramolecular interactions between the interpenetrated networks. This work is interesting as it represents the first example of urea-functionalized MOFs for nitro-analytes recognition.

  3. Peptide Metal-Organic Frameworks for Enantioselective Separation of Chiral Drugs.

    PubMed

    Navarro-Sánchez, José; Argente-García, Ana I; Moliner-Martínez, Yolanda; Roca-Sanjuán, Daniel; Antypov, Dmytro; Campíns-Falcó, Pilar; Rosseinsky, Matthew J; Martí-Gastaldo, Carlos

    2017-03-29

    We report the use of a chiral Cu(II) 3D metal-organic framework (MOF) based on the tripeptide Gly-l-His-Gly (GHG) for the enantioselective separation of metamphetamine and ephedrine. Monte Carlo simulations suggest that chiral recognition is linked to preferential binding of one of the enantiomers as a result of either stronger or additional H-bonds with the framework that lead to energetically more stable diastereomeric adducts. Solid-phase extraction of a racemic mixture by using Cu(GHG) as the extractive phase permits isolating >50% of the (+)-ephedrine enantiomer as target compound in only 4 min. To our knowledge, this represents the first example of a MOF capable of separating chiral polar drugs.

  4. Surface anchored metal-organic frameworks as stimulus responsive antifouling coatings.

    PubMed

    Sancet, Maria Pilar Arpa; Hanke, Maximilian; Wang, Zhengbang; Bauer, Stella; Azucena, Carlos; Arslan, Hasan K; Heinle, Marita; Gliemann, Hartmut; Wöll, Christof; Rosenhahn, Axel

    2013-12-01

    Surface-anchored, crystalline and oriented metal organic frameworks (SURMOFs) have huge potential for biological applications due to their well-defined and highly-porous structure. In this work we describe a MOF-based, fully autonomous system, which combines sensing, a specific response, and the release of an antimicrobial agent. The Cu-containing SURMOF, Cu-SURMOF 2, is stable in artificial seawater and shows stimulus-responsive anti-fouling properties against marine bacteria. When Cobetia marina adheres on the SURMOF, the framework's response is lethal to the adhering microorganism. A thorough analysis reveals that this response is induced by agents secreted from the microbes after adhesion to the substrate, and includes a release of Cu ions resulting from a degradation of the SURMOF. The stimulus-responsive antifouling effect of Cu-SURMOF 2 demonstrates the first application of Cu-SURMOF 2 as autonomous system with great potential for further microbiological and cell culture applications.

  5. Tunable electrical conductivity in metal-organic framework thin-film devices.

    PubMed

    Talin, A Alec; Centrone, Andrea; Ford, Alexandra C; Foster, Michael E; Stavila, Vitalie; Haney, Paul; Kinney, R Adam; Szalai, Veronika; El Gabaly, Farid; Yoon, Heayoung P; Léonard, François; Allendorf, Mark D

    2014-01-03

    We report a strategy for realizing tunable electrical conductivity in metal-organic frameworks (MOFs) in which the nanopores are infiltrated with redox-active, conjugated guest molecules. This approach is demonstrated using thin-film devices of the MOF Cu3(BTC)2 (also known as HKUST-1; BTC, benzene-1,3,5-tricarboxylic acid) infiltrated with the molecule 7,7,8,8-tetracyanoquinododimethane (TCNQ). Tunable, air-stable electrical conductivity over six orders of magnitude is achieved, with values as high as 7 siemens per meter. Spectroscopic data and first-principles modeling suggest that the conductivity arises from TCNQ guest molecules bridging the binuclear copper paddlewheels in the framework, leading to strong electronic coupling between the dimeric Cu subunits. These ohmically conducting porous MOFs could have applications in conformal electronic devices, reconfigurable electronics, and sensors.

  6. In situ solvothermal growth of metal-organic framework-ionic liquid functionalized graphene nanocomposite for highly efficient enrichment of chloramphenicol and thiamphenicol.

    PubMed

    Wu, Mian; Ai, Youhong; Zeng, Baizhao; Zhao, Faqiong

    2016-01-04

    Here we report a facile in situ solvothermal growth method for immobilization of metal-organic framework-ionic liquid functionalized graphene (MOF-5/ILG) composite on etched stainless steel wire. The X-ray diffraction spectra, scanning electron microscopy and transmission electron microscopy images showed that the metal organic framework possessed good crystal shape and its structure was not disturbed by the introduction of ILG. Moreover, the covalent bond established between the amino group of ILG and the carboxylic group of the metal organic framework improved the mechanical stability and structure uniformity of the microcrystals. The obtained material combined the favorable attributes of both metal-organic framework and ILG, having high surface area (820 m(2)/g) and good adsorption capability. Its adsorption properties were explored by preconcentrating chloramphenicol and thiamphenicol from aqueous solutions prior to gas chromatography-flame ionization detection. The MOF-5/ILG exhibited high enrichment capacity for the analytes as they could interact through π-π and H-bonding interaction. Under the optimum conditions, good linearity (correlation coefficients higher than 0.9981), low limits of detection (14.8-19.5 ng/L), and good precision (relative standard deviations less than 6.0% (n=5)) were achieved. The MOF-5/ILG composite displayed durable property. The method was applied to the determination of two antibiotics in milk, honey, urine and serum samples with acceptable relative recoveries of 82.3-103.2%.

  7. An Ultrahydrophobic Fluorous Metal-Organic Framework Derived Recyclable Composite as a Promising Platform to Tackle Marine Oil Spills.

    PubMed

    Mukherjee, Soumya; Kansara, Ankit M; Saha, Debasis; Gonnade, Rajesh; Mullangi, Dinesh; Manna, Biplab; Desai, Aamod V; Thorat, Shridhar H; Singh, Puyam S; Mukherjee, Arnab; Ghosh, Sujit K

    2016-07-25

    Derived from a strategically chosen hexafluorinated dicarboxylate linker aimed at the designed synthesis of a superhydrophobic metal-organic framework (MOF), the fluorine-rich nanospace of a water-stable MOF (UHMOF-100) exhibits excellent water-repellent features. It registered the highest water contact angle (≈176°) in the MOF domain, marking the first example of an ultrahydrophobic MOF. Various experimental and theoretical studies reinforce its distinctive water-repellent characteristics, and the conjugation of superoleophilicity and unparalleled hydrophobicity of a MOF material has been coherently exploited to achieve real-time oil/water separation in recyclable membrane form, with significant absorption capacity performance. This is also the first report of an oil/water separating fluorinated ultrahydrophobic MOF-based membrane material, with potential promise for tackling marine oil spillages.

  8. In situ X-ray diffraction monitoring of a mechanochemical reaction reveals a unique topology metal-organic framework

    NASA Astrophysics Data System (ADS)

    Katsenis, Athanassios D.; Puškarić, Andreas; Štrukil, Vjekoslav; Mottillo, Cristina; Julien, Patrick A.; Užarević, Krunoslav; Pham, Minh-Hao; Do, Trong-On; Kimber, Simon A. J.; Lazić, Predrag; Magdysyuk, Oxana; Dinnebier, Robert E.; Halasz, Ivan; Friščić, Tomislav

    2015-03-01

    Chemical and physical transformations by milling are attracting enormous interest for their ability to access new materials and clean reactivity, and are central to a number of core industries, from mineral processing to pharmaceutical manufacturing. While continuous mechanical stress during milling is thought to create an environment supporting nonconventional reactivity and exotic intermediates, such speculations have remained without proof. Here we use in situ, real-time powder X-ray diffraction monitoring to discover and capture a metastable, novel-topology intermediate of a mechanochemical transformation. Monitoring the mechanochemical synthesis of an archetypal metal-organic framework ZIF-8 by in situ powder X-ray diffraction reveals unexpected amorphization, and on further milling recrystallization into a non-porous material via a metastable intermediate based on a previously unreported topology, herein named katsenite (kat). The discovery of this phase and topology provides direct evidence that milling transformations can involve short-lived, structurally unusual phases not yet accessed by conventional chemistry.

  9. Self-assembly of metal-organic frameworks and graphene oxide as precursors for lithium-ion battery applications

    NASA Astrophysics Data System (ADS)

    Yang, Xia; Liu, Linlin; Yuan, Ruo; Lee, Chun-Sing

    2016-10-01

    We fabricated composites of Fe2O3/reduced graphene oxide as lithium-ion batteries anode material with controlled structures by employing self-assembly of metal-organic frameworks (MOFs) and polymer-functionalized graphene oxide as precursors. By electrostatic interaction, the negatively charged MOFs, Prussian Blue (PB), are assembled on poly(diallyldimethylammonium chloride) (PDDA)-functionalized graphene oxide (positive charge). Then the PB cubes become FeOOH nanosheets when treated with sodium hydroxide. Upon further annealing, the FeOOH nanosheets transform to Fe2O3 nanoparticles while the graphene oxide become reduced graphene oxide simultaneously. It was found that the composites have good performance as anode of lithium-ion battery. This work shows a new way for self-assembling MOFs and 2D materials.

  10. In silico discovery of metal-organic frameworks for precombustion CO2 capture using a genetic algorithm

    PubMed Central

    Chung, Yongchul G.; Gómez-Gualdrón, Diego A.; Li, Peng; Leperi, Karson T.; Deria, Pravas; Zhang, Hongda; Vermeulen, Nicolaas A.; Stoddart, J. Fraser; You, Fengqi; Hupp, Joseph T.; Farha, Omar K.; Snurr, Randall Q.

    2016-01-01

    Discovery of new adsorbent materials with a high CO2 working capacity could help reduce CO2 emissions from newly commissioned power plants using precombustion carbon capture. High-throughput computational screening efforts can accelerate the discovery of new adsorbents but sometimes require significant computational resources to explore the large space of possible materials. We report the in silico discovery of high-performing adsorbents for precombustion CO2 capture by applying a genetic algorithm to efficiently search a large database of metal-organic frameworks (MOFs) for top candidates. High-performing MOFs identified from the in silico search were synthesized and activated and show a high CO2 working capacity and a high CO2/H2 selectivity. One of the synthesized MOFs shows a higher CO2 working capacity than any MOF reported in the literature under the operating conditions investigated here. PMID:27757420

  11. Amides Do Not Always Work: Observation of Guest Binding in an Amide-Functionalized Porous Metal-Organic Framework.

    PubMed

    Benson, Oguarabau; da Silva, Ivan; Argent, Stephen P; Cabot, Rafel; Savage, Mathew; Godfrey, Harry G W; Yan, Yong; Parker, Stewart F; Manuel, Pascal; Lennox, Matthew J; Mitra, Tamoghna; Easun, Timothy L; Lewis, William; Blake, Alexander J; Besley, Elena; Yang, Sihai; Schröder, Martin

    2016-11-16

    An amide-functionalized metal organic framework (MOF) material, MFM-136, shows a high CO2 uptake of 12.6 mmol g(-1) at 20 bar and 298 K. MFM-136 is the first example of an acylamide pyrimidyl isophthalate MOF without open metal sites and, thus, provides a unique platform to study guest binding, particularly the role of free amides. Neutron diffraction reveals that, surprisingly, there is no direct binding between the adsorbed CO2/CH4 molecules and the pendant amide group in the pore. This observation has been confirmed unambiguously by inelastic neutron spectroscopy. This suggests that introduction of functional groups solely may not necessarily induce specific guest-host binding in porous materials, but it is a combination of pore size, geometry, and functional group that leads to enhanced gas adsorption properties.

  12. In silico discovery of metal-organic frameworks for precombustion CO2 capture using a genetic algorithm.

    PubMed

    Chung, Yongchul G; Gómez-Gualdrón, Diego A; Li, Peng; Leperi, Karson T; Deria, Pravas; Zhang, Hongda; Vermeulen, Nicolaas A; Stoddart, J Fraser; You, Fengqi; Hupp, Joseph T; Farha, Omar K; Snurr, Randall Q

    2016-10-01

    Discovery of new adsorbent materials with a high CO2 working capacity could help reduce CO2 emissions from newly commissioned power plants using precombustion carbon capture. High-throughput computational screening efforts can accelerate the discovery of new adsorbents but sometimes require significant computational resources to explore the large space of possible materials. We report the in silico discovery of high-performing adsorbents for precombustion CO2 capture by applying a genetic algorithm to efficiently search a large database of metal-organic frameworks (MOFs) for top candidates. High-performing MOFs identified from the in silico search were synthesized and activated and show a high CO2 working capacity and a high CO2/H2 selectivity. One of the synthesized MOFs shows a higher CO2 working capacity than any MOF reported in the literature under the operating conditions investigated here.

  13. Selective interfacial synthesis of metal-organic frameworks on a polybenzimidazole hollow fiber membrane for gas separation

    NASA Astrophysics Data System (ADS)

    Biswal, Bishnu P.; Bhaskar, Anand; Banerjee, Rahul; Kharul, Ulhas K.

    2015-04-01

    Metal-organic frameworks (MOFs) have gained immense attention as new age materials due to their tuneable properties and diverse applicability. However, efforts on developing promising materials for membrane based gas separation, and control over the crystal growth positions on polymeric hollow fiber membranes still remain key challenges. In this investigation, a new, convenient and scalable room temperature interfacial method for growing MOFs (ZIF-8 and CuBTC) on either the outer or inner side of a polybenzimidazole based hollow fiber (PBI-BuI-HF) membrane surface has been achieved in a controlled manner. This was made possible by the appropriate selection of an immiscible solvent pair and the synthetic conditions. The growth of MOFs on the PBI-BuI-HF membrane by the interfacial method was continuous and showed an appreciable gas separation performance, conveying promise for their applicability.Metal-organic frameworks (MOFs) have gained immense attention as new age materials due to their tuneable properties and diverse applicability. However, efforts on developing promising materials for membrane based gas separation, and control over the crystal growth positions on polymeric hollow fiber membranes still remain key challenges. In this investigation, a new, convenient and scalable room temperature interfacial method for growing MOFs (ZIF-8 and CuBTC) on either the outer or inner side of a polybenzimidazole based hollow fiber (PBI-BuI-HF) membrane surface has been achieved in a controlled manner. This was made possible by the appropriate selection of an immiscible solvent pair and the synthetic conditions. The growth of MOFs on the PBI-BuI-HF membrane by the interfacial method was continuous and showed an appreciable gas separation performance, conveying promise for their applicability. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr00299k

  14. Chiral Cu(salen)-Based Metal-Organic Framework for Heterogeneously Catalyzed Aziridination and Amination of Olefins.

    PubMed

    Liu, Yan; Li, Zijian; Yuan, Guozan; Xia, Qingchun; Yuan, Chen; Cui, Yong

    2016-12-19

    A homochiral 3D porous metal-organic framework was assembled from a chiral dicarboxylic acid-functionalized Cu(salen)-based catalyst and could serve as an efficient heterogeneous catalyst for aziridination and allylic amination of olefins. Besides easy separation and reuse of the catalyst, the chiral framework confinement could impart substrate size selectivity, enhance catalyst activity, and induce product enantioselectivity.

  15. Facile synthesis of multiple enzyme-containing metal-organic frameworks in a biomolecule-friendly environment.

    PubMed

    Wu, Xiaoling; Ge, Jun; Yang, Cheng; Hou, Miao; Liu, Zheng

    2015-09-07

    The one-step and facile synthesis of multi-enzyme-containing metal-organic framework (MOF) nanocrystals in aqueous solution at 25 °C was reported in this study. The GOx&HRP/ZIF-8 nanocomposite displayed high catalytic efficiency, high selectivity and enhanced stability due to the protecting effect of the framework.

  16. An in situ self-assembly template strategy for the preparation of hierarchical-pore metal-organic frameworks

    PubMed Central

    Huang, Hongliang; Li, Jian-Rong; Wang, Keke; Han, Tongtong; Tong, Minman; Li, Liangsha; Xie, Yabo; Yang, Qingyuan; Liu, Dahuan; Zhong, Chongli

    2015-01-01

    Metal-organic frameworks (MOFs) have recently emerged as a new type of nanoporous materials with tailorable structures and functions. Usually, MOFs have uniform pores smaller than 2 nm in size, limiting their practical applications in some cases. Although a few approaches have been adopted to prepare MOFs with larger pores, it is still challenging to synthesize hierarchical-pore MOFs (H-MOFs) with high structural controllability and good stability. Here we demonstrate a facile and versatile method, an in situ self-assembly template strategy for fabricating stable H-MOFs, in which multi-scale soluble and/or acid-sensitive metal-organic assembly (MOA) fragments form during the reactions between metal ions and organic ligands (to construct MOFs), and act as removable dynamic chemical templates. This general strategy was successfully used to prepare various H-MOFs that show rich porous properties and potential applications, such as in large molecule adsorption. Notably, the mesopore sizes of the H-MOFs can be tuned by varying the amount of templates. PMID:26548441

  17. Privileged phosphine-based metal-organic frameworks for broad-scope asymmetric catalysis.

    PubMed

    Falkowski, Joseph M; Sawano, Takahiro; Zhang, Teng; Tsun, Galen; Chen, Yuan; Lockard, Jenny V; Lin, Wenbin

    2014-04-09

    A robust and porous Zr metal-organic framework (MOF) based on a BINAP-derived dicarboxylate linker, BINAP-MOF, was synthesized and post-synthetically metalated with Ru and Rh complexes to afford highly enantioselective catalysts for important organic transformations. The Rh-functionalized MOF is not only highly enantioselective (up to >99% ee) but also 3 times as active as the homogeneous control. XAFS studies revealed that the Ru-functionalized MOF contains Ru-BINAP precatalysts with the same coordination environment as the homogeneous Ru complex. The post-synthetically metalated BINAP-MOFs provide a versatile family of single-site solid catalysts for catalyzing a broad scope of asymmetric organic transformations, including addition of aryl and alkyl groups to α,β-unsaturated ketones and hydrogenation of substituted alkene and carbonyl compounds.

  18. Chemoselective single-site Earth-abundant metal catalysts at metal-organic framework nodes

    NASA Astrophysics Data System (ADS)

    Manna, Kuntal; Ji, Pengfei; Lin, Zekai; Greene, Francis X.; Urban, Ania; Thacker, Nathan C.; Lin, Wenbin

    2016-08-01

    Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal-organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C-H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals.

  19. Hydrogen storage in Pd nanocrystals covered with a metal-organic framework.

    PubMed

    Li, Guangqin; Kobayashi, Hirokazu; Taylor, Jared M; Ikeda, Ryuichi; Kubota, Yoshiki; Kato, Kenichi; Takata, Masaki; Yamamoto, Tomokazu; Toh, Shoichi; Matsumura, Syo; Kitagawa, Hiroshi

    2014-08-01

    Hydrogen is an essential component in many industrial processes. As a result of the recent increase in the development of shale gas, steam reforming of shale gas has received considerable attention as a major source of H2, and the more efficient use of hydrogen is strongly demanded. Palladium is well known as a hydrogen-storage metal and an effective catalyst for reactions related to hydrogen in a variety of industrial processes. Here, we present remarkably enhanced capacity and speed of hydrogen storage in Pd nanocrystals covered with the metal-organic framework (MOF) HKUST-1 (copper(II) 1,3,5-benzenetricarboxylate). The Pd nanocrystals covered with the MOF have twice the storage capacity of the bare Pd nanocrystals. The significantly enhanced hydrogen storage capacity was confirmed by hydrogen pressure-composition isotherms and solid-state deuterium nuclear magnetic resonance measurements. The speed of hydrogen absorption in the Pd nanocrystals is also enhanced by the MOF coating.

  20. Metal-organic framework based highly selective fluorescence turn-on probe for hydrogen sulphide

    NASA Astrophysics Data System (ADS)

    Nagarkar, Sanjog S.; Saha, Tanmoy; Desai, Aamod V.; Talukdar, Pinaki; Ghosh, Sujit K.

    2014-11-01

    Hydrogen sulphide (H2S) is known to play a vital role in human physiology and pathology which stimulated interest in understanding complex behaviour of H2S. Discerning the pathways of H2S production and its mode of action is still a challenge owing to its volatile and reactive nature. Herein we report azide functionalized metal-organic framework (MOF) as a selective turn-on fluorescent probe for H2S detection. The MOF shows highly selective and fast response towards H2S even in presence of other relevant biomolecules. Low cytotoxicity and H2S detection in live cells, demonstrate the potential of MOF towards monitoring H2S chemistry in biological system. To the best of our knowledge this is the first example of MOF that exhibit fast and highly selective fluorescence turn-on response towards H2S under physiological conditions.

  1. A Molecular Artisans Guide to Supramolecular Coordination Complexes and Metal Organic Frameworks

    NASA Astrophysics Data System (ADS)

    Wu, Xialu; Young, David J.; Hor, T. S. Andy

    2015-10-01

    As molecular synthesis advances, we are beginning to learn control of not only the chemical reactivity (and function) of molecules, but also of their interactions with other molecules. It is this basic idea that has led to the current explosion of supramolecular science and engineering. Parallel to this development, chemists have been actively pursuing the design of very large molecules using basic molecular building blocks. Herein, we review the general development of supramolecular chemistry and particularly of two new branches: supramolecular coordination complexes (SCCs) and metal organic frameworks (MOFs). These two fields are discussed in detail with typical examples to illustrate what is now possible and what challenges lie ahead for tomorrow's molecular artisans.

  2. A novel hybrid metal-organic framework-polymeric monolith for solid-phase microextraction.

    PubMed

    Lin, Chen-Lan; Lirio, Stephen; Chen, Ya-Ting; Lin, Chia-Her; Huang, Hsi-Ya

    2014-03-17

    This study describes the fabrication of a novel hybrid metal-organic framework- organic polymer (MOF-polymer) for use as a stationary phase in fritless solid-phase microextraction (SPME) for validating analytical methods. The MOF-polymer was prepared by using ethylene dimethacrylate (EDMA), butyl methacrylate (BMA), and an imidazolium-based ionic liquid as porogenic solvent followed by microwave-assisted polymerization with the addition of 25 % MOF. This novel hybrid MOF-polymer was used to extract penicillin (penicillin G, penicillin V, oxacillin, cloxacillin, nafcillin, dicloxacillin) under different conditions. Quantitative analysis of the extracted penicillin samples using the MOF-organic polymer for SPME was conducted by using capillary electrochromatography (CEC) coupled with UV analysis. The penicillin recovery was 63-96.2 % with high reproducibility, sensitivity, and reusability. The extraction time with the proposed fabricated SPME was only 34 min.

  3. Metal organic framework-mediated synthesis of highly active and stable Fischer-Tropsch catalysts.

    PubMed

    Santos, Vera P; Wezendonk, Tim A; Jaén, Juan José Delgado; Dugulan, A Iulian; Nasalevich, Maxim A; Islam, Husn-Ubayda; Chojecki, Adam; Sartipi, Sina; Sun, Xiaohui; Hakeem, Abrar A; Koeken, Ard C J; Ruitenbeek, Matthijs; Davidian, Thomas; Meima, Garry R; Sankar, Gopinathan; Kapteijn, Freek; Makkee, Michiel; Gascon, Jorge

    2015-03-05

    Depletion of crude oil resources and environmental concerns have driven a worldwide research on alternative processes for the production of commodity chemicals. Fischer-Tropsch synthesis is a process for flexible production of key chemicals from synthesis gas originating from non-petroleum-based sources. Although the use of iron-based catalysts would be preferred over the widely used cobalt, manufacturing methods that prevent their fast deactivation because of sintering, carbon deposition and phase changes have proven challenging. Here we present a strategy to produce highly dispersed iron carbides embedded in a matrix of porous carbon. Very high iron loadings (>40 wt %) are achieved while maintaining an optimal dispersion of the active iron carbide phase when a metal organic framework is used as catalyst precursor. The unique iron spatial confinement and the absence of large iron particles in the obtained solids minimize catalyst deactivation, resulting in high active and stable operation.

  4. Adsorption and diffusion of carbon dioxide on metal-organic framework (MOF-5)

    SciTech Connect

    Zhao, Z.X.; Li, Z.; Lin, Y.S.

    2009-11-15

    Adsorption equilibrium and diffusion of CO{sub 2} on microporous metal-organic frameworks (MOF-5, or IRMOF-1) crystals were experimentally studied by the gravimetric method in the pressure range up to 1 atm. The MOF-5 crystal cubes of about 40-60 {mu} m in sizes were synthesized by the solvothermal method. Freundlich adsorption isotherm equation can fit well CO{sub 2} adsorption isotherms on MOF-5, with isosteric heat of adsorption of about 34 kJ/mol. Diffusion coefficient of CO{sub 2} in the MOF-5 is in the range of 8.1-11.5 x 10{sup -9} cm{sup 2}/s in 295-331K with activation energy of 7.61 kJ/mol. MOF-5 offers attractive adsorption properties as an adsorbent for separation of CO{sub 2} from flue gas.

  5. Detection of Volatile Organic Compounds by Weight-Detectable Sensors coated with Metal-Organic Frameworks

    PubMed Central

    Yamagiwa, Hiroki; Sato, Seiko; Fukawa, Tadashi; Ikehara, Tsuyoshi; Maeda, Ryutaro; Mihara, Takashi; Kimura, Mutsumi

    2014-01-01

    Detection of volatile organic compounds (VOCs) using weight-detectable quartz microbalance and silicon-based microcantilever sensors coated with crystalline metal-organic framework (MOF) thin films is described in this paper. The thin films of two MOFs were grown from COOH-terminated self-assembled monolayers onto the gold electrodes of sensor platforms. The MOF layers worked as the effective concentrators of VOC gases, and the adsorption/desorption processes of the VOCs could be monitored by the frequency changes of weight-detectable sensors. Moreover, the MOF layers provided VOC sensing selectivity to the weight-detectable sensors through the size-selective adsorption of the VOCs within the regulated nanospace of the MOFs. PMID:25175808

  6. Stable metal-organic frameworks containing single-molecule traps for enzyme encapsulation

    NASA Astrophysics Data System (ADS)

    Feng, Dawei; Liu, Tian-Fu; Su, Jie; Bosch, Mathieu; Wei, Zhangwen; Wan, Wei; Yuan, Daqiang; Chen, Ying-Pin; Wang, Xuan; Wang, Kecheng; Lian, Xizhen; Gu, Zhi-Yuan; Park, Jihye; Zou, Xiaodong; Zhou, Hong-Cai

    2015-01-01

    Enzymatic catalytic processes possess great potential in chemical manufacturing, including pharmaceuticals, fuel production and food processing. However, the engineering of enzymes is severely hampered due to their low operational stability and difficulty of reuse. Here, we develop a series of stable metal-organic frameworks with rationally designed ultra-large mesoporous cages as single-molecule traps (SMTs) for enzyme encapsulation. With a high concentration of mesoporous cages as SMTs, PCN-333(Al) encapsulates three enzymes with record-high loadings and recyclability. Immobilized enzymes that most likely undergo single-enzyme encapsulation (SEE) show smaller Km than free enzymes while maintaining comparable catalytic efficiency. Under harsh conditions, the enzyme in SEE exhibits better performance than free enzyme, showing the effectiveness of SEE in preventing enzyme aggregation or denaturation. With extraordinarily large pore size and excellent chemical stability, PCN-333 may be of interest not only for enzyme encapsulation, but also for entrapment of other nanoscaled functional moieties.

  7. Preparation of Pickering emulsions stabilized by metal organic frameworks using oscillatory woven metal micro-screen.

    PubMed

    Sabouni, R; Gomaa, H G

    2015-06-14

    Uniform Pickering emulsions stabilized by metal organic frameworks (MOFs) MIL-101 and ZIF-8 nanoparticles (NPs) were successfully prepared using an oscillatory woven metal microscreen (WMMS) emulsification system in the presence and the absence of surfactants. The effects of operating and system parameters including the frequency and amplitude of oscillation, the type of nano-particle and/or surfactant on the droplet size and coefficient of variance of the prepared emulsions are investigated. The results showed that both the hydrodynamics of the system and the hydrophobic/hydrophilic nature of the NP influenced the interfacial properties of the oil-water interface during droplet formation and after detachment, which in turn affected the final droplet size and distribution. Comparison between the measured and predicted droplet size using a simple torque balance (TB) model is discussed.

  8. Adsorption of volatile organic compounds in porous metal-organic frameworks functionalized by polyoxometalates

    NASA Astrophysics Data System (ADS)

    Ma, Feng-Ji; Liu, Shu-Xia; Liang, Da-Dong; Ren, Guo-Jian; Wei, Feng; Chen, Ya-Guang; Su, Zhong-Min

    2011-11-01

    The functionalization of porous metal-organic frameworks (Cu 3( BTC) 2) was achieved by incorporating Keggin-type polyoxometalates (POMs), and further optimized via alkali metal ion-exchange. In addition to thermal gravimetric analysis, IR, single-crystal X-ray diffraction, and powder X-ray diffraction, the adsorption properties were characterized by N 2 and volatile organic compounds (VOCs) adsorption measurements, including short-chain alcohols ( C<4), cyclohexane, benzene, and toluene. The adsorption enthalpies estimated by the modified Clausius-Clapeyron equation provided insight into the impact of POMs and alkali metal cations on the adsorption of VOCs. The introduction of POMs not only improved the stability, but also brought the increase of adsorption capacity by strengthening the interaction with gas molecules. Furthermore, the exchanged alkali metal cations acted as active sites to interact with adsorbates and enhanced the adsorption of VOCs.

  9. Understanding H2- H2 interactions in Metal Organic Frameworks (MOFs) with unsaturated metal centers

    NASA Astrophysics Data System (ADS)

    Nijem, Nour; Veyan, Jean F.; Kong, Lingzhu; Zhao, Yonggang; Li, Jing; Langreth, David; Chabal, Yves J.

    2011-03-01

    Unsaturated Metal Organic Frameworks (MOFs) are particularly interesting due to their high H2 uptakes with relatively large isosteric heats of adsorption (Qst > 8 kJ / mol) . ThisworkexploresH 2 - H 2 interactionsbetweenadsorbedH 2 atthedifferentsitesinMOF - 74 (M 2 (dhtp) , dhtp = 2 , 5 - dihydroxyterephthalate) andcombinesIRspectroscopywithvdW - DFTcalculations . TheadsorptionsitesinMOF - 74 arefromhighesttolowestbindingenergiesthemetal , oxygen , benzeneandpore - centersites . ThefrequencyofadsorbedH 2 atthemetalsitesuffersanadditional ~ - 30 cm -1 redshift (forMgandZn) and ~ - 84 cm -1 (forCo) whentheneighboringoxygensiteisoccupied . ThedipolemomentofadsorbedH 2 isalsoaffected . TheseinteractionsextendtothebenzenesitesforMOF - 74 - Co . AdecreaseindipolemomentofH 2 adsorbedatthemetalsiteisobservedwiththepartialoccupationofthebenzenesites . However , thecompleteoccupationofthebenzenesitesinducesanadditional ~ - 10 cm -1 red shift. DOE Grant No. DE-FG02-08ER46491.

  10. Regulating the spatial distribution of metal nanoparticles within metal-organic frameworks to enhance catalytic efficiency

    PubMed Central

    Yang, Qiu; Liu, Wenxian; Wang, Bingqing; Zhang, Weina; Zeng, Xiaoqiao; Zhang, Cong; Qin, Yongji; Sun, Xiaoming; Wu, Tianpin; Liu, Junfeng; Huo, Fengwei; Lu, Jun

    2017-01-01

    Composites incorporating metal nanoparticles (MNPs) within metal-organic frameworks (MOFs) have broad applications in many fields. However, the controlled spatial distribution of the MNPs within MOFs remains a challenge for addressing key issues in catalysis, for example, the efficiency of catalysts due to the limitation of molecular diffusion within MOF channels. Here we report a facile strategy that enables MNPs to be encapsulated into MOFs with controllable spatial localization by using metal oxide both as support to load MNPs and as a sacrificial template to grow MOFs. This strategy is versatile to a variety of MNPs and MOF crystals. By localizing the encapsulated MNPs closer to the surface of MOFs, the resultant MNPs@MOF composites not only exhibit effective selectivity derived from MOF cavities, but also enhanced catalytic activity due to the spatial regulation of MNPs as close as possible to the MOF surface. PMID:28195131

  11. Exploration of Gate-Opening and Breathing Phenomena in a Tailored Flexible Metal-Organic Framework.

    PubMed

    Hyun, Sung-min; Lee, Jae Hwa; Jung, Gwan Yeong; Kim, Yun Kyeong; Kim, Tae Kyung; Jeoung, Sungeun; Kwak, Sang Kyu; Moon, Dohyun; Moon, Hoi Ri

    2016-02-15

    Flexible metal-organic frameworks (MOFs) show the structural transition phenomena, gate opening and breathing, upon the input of external stimuli. These phenomena have significant implications in their adsorptive applications. In this work, we demonstrate the direct capture of these gate-opening and breathing phenomena, triggered by CO2 molecules, in a well-designed flexible MOF composed of rotational sites and molecular gates. Combining X-ray single crystallographic data of a flexible MOF during gate opening/closing and breathing with in situ X-ray powder diffraction results uncovered the origin of this flexibility. Furthermore, computational studies revealed the specific sites required to open these gates by interaction with CO2 molecules.

  12. Mechanized azobenzene-functionalized zirconium metal-organic framework for on-command cargo release

    PubMed Central

    Meng, Xiangshi; Gui, Bo; Yuan, Daqiang; Zeller, Matthias; Wang, Cheng

    2016-01-01

    Stimuli-responsive metal-organic frameworks (MOFs) have gained increasing attention recently for their potential applications in many areas. We report the design and synthesis of a water-stable zirconium MOF (Zr-MOF) that bears photoresponsive azobenzene groups. This particular MOF can be used as a reservoir for storage of cargo in water, and the cargo-loaded MOF can be further capped to construct a mechanized MOF through the binding of β-cyclodextrin with the azobenzene stalks on the MOF surface. The resulting mechanized MOF has shown on-command cargo release triggered by ultraviolet irradiation or addition of competitive agents without premature release. This study represents a simple approach to the construction of stimuli-responsive mechanized MOFs, and considering mechanized UiO-68-azo made from biocompatible components, this smart system may provide a unique MOF platform for on-command drug delivery in the future. PMID:27493996

  13. Metal-organic framework based highly selective fluorescence turn-on probe for hydrogen sulphide

    PubMed Central

    Nagarkar, Sanjog S.; Saha, Tanmoy; Desai, Aamod V.; Talukdar, Pinaki; Ghosh, Sujit K.

    2014-01-01

    Hydrogen sulphide (H2S) is known to play a vital role in human physiology and pathology which stimulated interest in understanding complex behaviour of H2S. Discerning the pathways of H2S production and its mode of action is still a challenge owing to its volatile and reactive nature. Herein we report azide functionalized metal-organic framework (MOF) as a selective turn-on fluorescent probe for H2S detection. The MOF shows highly selective and fast response towards H2S even in presence of other relevant biomolecules. Low cytotoxicity and H2S detection in live cells, demonstrate the potential of MOF towards monitoring H2S chemistry in biological system. To the best of our knowledge this is the first example of MOF that exhibit fast and highly selective fluorescence turn-on response towards H2S under physiological conditions. PMID:25394493

  14. Fabrication of the microchannel by metal-organic framework, copper benzenetricarboxylate.

    PubMed

    Lim, Mikyung; Seo, You-Kyong; Park, Hyoun Hyang; Kim, Jin-Ha; Chang, Jong-San; Hwang, Young Kyu; Lee, Seung S

    2013-04-01

    We successfully fabricated the metal-organic framework (MOF), copper benzenetricarboxylate on a microchannel system, which was able to solve the problems created by increased heat dissipation in small electronic equipment. The microchannel system was designed to make an entrance part that can control the reaction temperature, which was predicted through a heat transfer analysis and the finite element method with COMSOL Multiphysics. Synthetic conditions, synthesis time, temperature and microchannel size were systematically tuned for the selective fabrication of copper benzenetricarboxylate on a microchannel surface. Scanning electron microscope (SEM) images, selected area electron diffraction (SAED) pattern and Fourier transform infrared (FT-IR) data clearly demonstrated that copper benzenetricarboxylate was strongly adhered to the bottom surfaces of the microchannels. Moreover, the synthesis of MOF in the microchannel system provided a much faster growth rate and better crystallinity compared to a conventional synthesis method.

  15. Anodized Aluminum Oxide Templated Synthesis of Metal-Organic Frameworks Used as Membrane Reactors.

    PubMed

    Yu, Yifu; Wu, Xue-Jun; Zhao, Meiting; Ma, Qinglang; Chen, Junze; Chen, Bo; Sindoro, Melinda; Yang, Jian; Han, Shikui; Lu, Qipeng; Zhang, Hua

    2017-01-09

    The incorporation of metal-organic frameworks (MOFs) into membrane-shaped architectures is of great importance for practical applications. The currently synthesized MOF-based membranes show many disadvantages, such as poor compatibility, low dispersity, and instability, which severely limit their utility. Herein, we present a general, facile, and robust approach for the synthesis of MOF-based composite membranes through the in situ growth of MOF plates in the channels of anodized aluminum oxide (AAO) membranes. After being used as catalysis reactors, they exhibit high catalytic performance and stability in the Knoevenagel condensation reaction. The high catalytic performance might be attributed to the intrinsic structure of MOF-based composite membranes, which can remove the products from the reaction zone quickly, and prevent the aggregation and loss of catalysts during reaction and recycling process.

  16. Tunable catalytic activity of solid solution metal-organic frameworks in one-pot multicomponent reactions.

    PubMed

    Aguirre-Díaz, Lina María; Gándara, Felipe; Iglesias, Marta; Snejko, Natalia; Gutiérrez-Puebla, Enrique; Monge, M Ángeles

    2015-05-20

    The aim of this research is to establish how metal-organic frameworks (MOFs) composed of more than one metal in equivalent crystallographic sites (solid solution MOFs) exhibit catalytic activity, which is tunable by virtue of the metal ions ratio. New MOFs with general formula [InxGa1-x(O2C2H4)0.5(hfipbb)] were prepared by the combination of Ga and In. They are isostructural with their monometal counterparts, synthesized with Al, Ga, and In. Differences in their behavior as heterogeneous catalysts in the three-component, one pot Strecker reaction illustrate the potential of solid solution MOFs to provide the ability to address the various stages involved in the reaction mechanism.

  17. Nano Metal-Organic Framework-Derived Inorganic Hybrid Nanomaterials: Synthetic Strategies and Applications.

    PubMed

    Mai, Hien Duy; Rafiq, Khezina; Yoo, Hyojong

    2016-11-11

    Nano- (or micro-scale) metal-organic frameworks (NMOFs), also known as coordination polymer particles (CPPs), have received much attention because of their structural diversities and tunable properties. Besides the direct use, NMOFs can be alternatively used as sacrificial templates/precursors for the preparation of a wide range of hybrid inorganic nanomaterials in straightforward and controllable manners. Distinct advantages of using NMOF templates are correlated to their structural and functional tailorability at molecular levels that is rarely acquired in any other conventional template/precursor. In addition, NMOF-derived inorganic nanomaterials with distinct chemical and physical properties are inferred to dramatically expand the scope of their utilization in many fields. In this review, we aim to provide readers with a comprehensive summary of recent progress in terms of synthetic approaches for the production of diverse inorganic hybrid nanostructures from as-synthesized NMOFs and their promising applications.

  18. Highly sensitive detection of dipicolinic acid with a water-dispersible terbium-metal organic framework.

    PubMed

    Bhardwaj, Neha; Bhardwaj, Sanjeev; Mehta, Jyotsana; Kim, Ki-Hyun; Deep, Akash

    2016-12-15

    The sensitive detection of dipicolinic acid (DPA) is strongly associated with the sensing of bacterial organisms in food and many types of environmental samples. To date, the demand for a sensitive detection method for bacterial toxicity has increased remarkably. Herein, we investigated the DPA detection potential of a water-dispersible terbium-metal organic framework (Tb-MOF) based on the fluorescence quenching mechanism. The Tb-MOF showed a highly sensitive ability to detect DPA at a limit of detection of 0.04nM (linear range of detection: 1nM to 5µM) and also offered enhanced selectivity from other commonly associated organic molecules. The present study provides a basis for the application of Tb-MOF for direct, convenient, highly sensitive, and specific detection of DPA in the actual samples.

  19. Regulating the spatial distribution of metal nanoparticles within metal-organic frameworks to enhance catalytic efficiency

    NASA Astrophysics Data System (ADS)

    Yang, Qiu; Liu, Wenxian; Wang, Bingqing; Zhang, Weina; Zeng, Xiaoqiao; Zhang, Cong; Qin, Yongji; Sun, Xiaoming; Wu, Tianpin; Liu, Junfeng; Huo, Fengwei; Lu, Jun

    2017-02-01

    Composites incorporating metal nanoparticles (MNPs) within metal-organic frameworks (MOFs) have broad applications in many fields. However, the controlled spatial distribution of the MNPs within MOFs remains a challenge for addressing key issues in catalysis, for example, the efficiency of catalysts due to the limitation of molecular diffusion within MOF channels. Here we report a facile strategy that enables MNPs to be encapsulated into MOFs with controllable spatial localization by using metal oxide both as support to load MNPs and as a sacrificial template to grow MOFs. This strategy is versatile to a variety of MNPs and MOF crystals. By localizing the encapsulated MNPs closer to the surface of MOFs, the resultant MNPs@MOF composites not only exhibit effective selectivity derived from MOF cavities, but also enhanced catalytic activity due to the spatial regulation of MNPs as close as possible to the MOF surface.

  20. Site-selective synthesis of Janus-type metal-organic framework composites.

    PubMed

    Yadnum, Sudarat; Roche, Jérome; Lebraud, Eric; Négrier, Philippe; Garrigue, Patrick; Bradshaw, Darren; Warakulwit, Chompunuch; Limtrakul, Jumras; Kuhn, Alexander

    2014-04-07

    Herein, bipolar electrochemistry is applied in a straightforward way to the site-selective in situ synthesis of metal-organic framework (MOF) structures, which have attracted tremendous interest in recent years because of their significant application potential, ranging from sensing to gas storage and catalysis. The novelty of the presented work is that the deposit can be intentionally confined to a defined area of a substrate without using masks or templates. The intrinsic site-selectivity of bipolar electrochemistry makes it a method of choice to generate, in a highly controlled way, hybrid particles that may have different functionalities combined on the same particle. The wireless nature of electrodeposition allows the potential for mass production of such Janus-type objects.

  1. Chemoselective single-site Earth-abundant metal catalysts at metal-organic framework nodes.

    PubMed

    Manna, Kuntal; Ji, Pengfei; Lin, Zekai; Greene, Francis X; Urban, Ania; Thacker, Nathan C; Lin, Wenbin

    2016-08-30

    Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal-organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C-H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals.

  2. Metal-organic framework based highly selective fluorescence turn-on probe for hydrogen sulphide.

    PubMed

    Nagarkar, Sanjog S; Saha, Tanmoy; Desai, Aamod V; Talukdar, Pinaki; Ghosh, Sujit K

    2014-11-14

    Hydrogen sulphide (H2S) is known to play a vital role in human physiology and pathology which stimulated interest in understanding complex behaviour of H2S. Discerning the pathways of H2S production and its mode of action is still a challenge owing to its volatile and reactive nature. Herein we report azide functionalized metal-organic framework (MOF) as a selective turn-on fluorescent probe for H2S detection. The MOF shows highly selective and fast response towards H2S even in presence of other relevant biomolecules. Low cytotoxicity and H2S detection in live cells, demonstrate the potential of MOF towards monitoring H2S chemistry in biological system. To the best of our knowledge this is the first example of MOF that exhibit fast and highly selective fluorescence turn-on response towards H2S under physiological conditions.

  3. Nickel(II) oxide nanostructure derived from metal-organic frameworks and its adsorption capability

    NASA Astrophysics Data System (ADS)

    Ru, Shuai; Xu, Lina; Xiao, Hongping; Li, Xinhua

    2016-11-01

    Nanosized nickel(II) oxide (NiO) was obtained by oxidation of ([(Ni2(nic)4(H2O)] n , nic = nicotinic acid), a metal-organic framework (MOF), at 350 °C. Nanosized NiO assembled to form block NiO having a mesoporous structure similar to the porous structure of activated carbon block. This bulk NiO exhibits excellent adsorbing capability, with 100% higher adsorption capacities than the [(Ni2(nic)4(H2O)] n MOF towards toluene and water steam; therefore, it can find potential application in gas adsorption. Moreover, this bulk NiO can be synthesized using a facile, environment-friendly, and cost-effective method, and exhibits excellent hydrothermal stability, which is not commonly observed for MOFs.

  4. Mixed-Lanthanoid Metal-Organic Framework for Ratiometric Cryogenic Temperature Sensing.

    PubMed

    Liu, Xue; Akerboom, Sebastiaan; de Jong, Mathijs; Mutikainen, Ilpo; Tanase, Stefania; Meijerink, Andries; Bouwman, Elisabeth

    2015-12-07

    A ratiometric thermometer based on a mixed-metal Ln(III) metal-organic framework is reported that has good sensitivity in a wide temperature range from 4 to 290 K and a quantum yield of 22% at room temperature. The sensing mechanism in the europium-doped compound Tb0.95Eu0.05HL (H4L = 5-hydroxy-1,2,4-benzenetricarboxylic acid) is based not only on phonon-assisted energy transfer from Tb(III) to Eu(III) centers, but also on phonon-assisted energy migration between neighboring Tb(III) ions. It shows good performance in a wide temperature range, especially in the range 4-50 K, reaching a sensitivity up to 31% K(-1) at 4 K.

  5. Selectively catalytic micro- and nanocrystals of metal-organic framework [Co(4-bpdh)(HIA)]∝

    NASA Astrophysics Data System (ADS)

    Ye, Jing; Gou, Yongxia; Xu, Zhen-Liang; Xu, Haitao

    2015-03-01

    Metal-organic framework micro-crystals [Co(4-bpdh)(HIA)]∝ (1Co), crystallized in the monoclinic system (space group P12/n1, a=10.0009(16) Å, b=15.472(3) Å, c=18.563(3) Å, β=91.81(0)°, and Z=4), were controllably synthesized through the adjustment of the solvent system. The Co2+ ion center located in a six-coordinated environment combined with 5-hydroxyisophthalic acid (HIA) to produce ladder-like structures, which again linked with 2,5-bis(4-pyridyl)-3,4-diaza-2,4-hxadiene (4-bpdh) to yield a double-layer network. Micro-crystals 1Co exhibited selectively oxidation-catalytic properties for the degradation of methyl orange (conversion 90%) owing to ligand to metal charge transfer. Our work determined that the synthesized catalyst is not only highly selective for degradation of organic dyes, but also very efficient.

  6. One-dimensional magnetic order in the metal-organic framework Tb(HCOO ) 3

    NASA Astrophysics Data System (ADS)

    Harcombe, Daniel R.; Welch, Philip G.; Manuel, Pascal; Saines, Paul J.; Goodwin, Andrew L.

    2016-11-01

    Variable-temperature neutron scattering measurements, reverse Monte Carlo analysis, and direct Monte Carlo simulation are used to characterize magnetic order in the metal-organic framework (MOF) Tb (HCOO) 3 over the temperature range 100 to 1.6 K =TN . The magnetic transition at TN is shown to involve one-dimensional ferromagnetic ordering to a partially ordered state related to the triangular Ising antiferromagnet and distinct from the canonical partially disordered antiferromagnet model. In this phase, the direction of magnetization of ferromagnetic chains tends to alternate between neighboring chains but this alternation is frustrated and is not itself ordered. We suggest the existence of low-dimensional magnetic order in Tb (HCOO) 3 is stabilized by the contrasting strength of inter- and intrachain magnetic coupling, itself a consequence of the underlying MOF architecture. Our results demonstrate how MOFs may provide an attractive if as yet underexplored platform for the realization and investigation of low-dimensional physics.

  7. Metal-organic framework nanoparticles decorated with graphene: A high-performance electromagnetic wave absorber

    NASA Astrophysics Data System (ADS)

    Wang, Yan; Zhang, Wenzhi; Wu, Xinming; Luo, Chunyan; Liang, Tan; Yan, Gang

    2016-10-01

    A novel metal organic framework (MOF) coated RGO was fabricated by a one-step method. The morphology and microstructure of MOF-53(Fe)/RGO composite were characterized by XRD and TEM. The electromagnetic parameters indicate that MOF-53(Fe)/RGO composite shows enhanced electromagnetic absorption properties compared with MOF-53(Fe). The maximum RL can reach -25.8 dB at 15.4 GHz and the absorption bandwidth with the reflection loss exceeding -10 dB is 5.9 GHz (from 12.1 to 18 GHz) with the thickness of 2 mm. The possible absorption mechanism was also investigated in detail. Our results indicate the potential application of MOF/RGO composite as a more efficient microwave absorber.

  8. Dubinin-Astakhov model for acetylene adsorption on metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Cheng, Peifu; Hu, Yun Hang

    2016-07-01

    Acetylene (C2H2) is explosive at a pressure above 29 psi, causing a safety issue for its storage and applications. C2H2 adsorption on metal-organic frameworks (MOFs) has been explored to solve the issue. However, a suitable isotherm equation for C2H2 adsorption on various MOFs has not been found. In this paper, it was demonstrated that Dubinin-Astakhov equation can be exploited as a general isotherm model to depict C2H2 adsorption on MOF-5, ZIF-8, HKUST-1, and MIL-53. In contrast, commonly used Langmuir and BET models exhibited their inapplicability for C2H2 adsorption on those MOFs.

  9. Tailoring metal-organic frameworks for CO2 capture: the amino effect.

    PubMed

    Vitillo, Jenny G; Savonnet, Marie; Ricchiardi, Gabriele; Bordiga, Silvia

    2011-09-19

    Carbon dioxide capture from processes is one of the strategies adopted to decrease anthropogenic greenhouse gas emissions. To lower the cost associated with the regeneration of amine-based scrubber systems, one of the envisaged strategies is the grafting of amines onto high-surface-area supports and, in particular, onto metal-organic frameworks (MOFs). In this study, the interaction between CO(2) and aliphatic and aromatic amines has been characterized by quantum mechanical methods (MP2), focusing attention both on species already reported in MOFs and on new amine-based linkers, to inspire the rational synthesis of new high-capacity MOFs. The calculations highlight binding-site requisites and indicate that CO(2) vibrations are independent of the adsorption energy and monitoring them in probe-molecule experiments is not a suitable marker of efficient adsorption.

  10. Stable metal-organic frameworks containing single-molecule traps for enzyme encapsulation.

    PubMed

    Feng, Dawei; Liu, Tian-Fu; Su, Jie; Bosch, Mathieu; Wei, Zhangwen; Wan, Wei; Yuan, Daqiang; Chen, Ying-Pin; Wang, Xuan; Wang, Kecheng; Lian, Xizhen; Gu, Zhi-Yuan; Park, Jihye; Zou, Xiaodong; Zhou, Hong-Cai

    2015-01-19

    Enzymatic catalytic processes possess great potential in chemical manufacturing, including pharmaceuticals, fuel production and food processing. However, the engineering of enzymes is severely hampered due to their low operational stability and difficulty of reuse. Here, we develop a series of stable metal-organic frameworks with rationally designed ultra-large mesoporous cages as single-molecule traps (SMTs) for enzyme encapsulation. With a high concentration of mesoporous cages as SMTs, PCN-333(Al) encapsulates three enzymes with record-high loadings and recyclability. Immobilized enzymes that most likely undergo single-enzyme encapsulation (SEE) show smaller Km than free enzymes while maintaining comparable catalytic efficiency. Under harsh conditions, the enzyme in SEE exhibits better performance than free enzyme, showing the effectiveness of SEE in preventing enzyme aggregation or denaturation. With extraordinarily large pore size and excellent chemical stability, PCN-333 may be of interest not only for enzyme encapsulation, but also for entrapment of other nanoscaled functional moieties.

  11. Interactive Thermal Effects on Metal-Organic Framework Polymer Composite Membranes.

    PubMed

    Cacho-Bailo, Fernando; Téllez, Carlos; Coronas, Joaquín

    2016-07-04

    Polymeric membranes are important tools for intensifying separation processes in chemical industries, concerning strategic tasks such as CO2 sequestration, H2 production, and water supply and disposal. Mixed-matrix and supported membranes have been widely developed; recently many of them have been based on metal-organic frameworks (MOFs). However, most of the impacts MOFs have within the polymer matrix have yet to be determined. The effects related to thermal behavior arising from the combination of MOF ZIF-8 and polysulfone have now been quantified. The catalyzed oxidation of the polymer is strongly affected by the MOF crystal size and distribution inside the membrane. A 16 wt % 140 nm-sized ZIF-8 loading causes a 40 % decrease in the observed activation energy of the polysulfone oxidation that takes place at a temperature (545 °C) 80 °C lower than in the raw polymer (625 °C).

  12. Heterometallic Metal-Organic Frameworks That Catalyze Two Different Reactions Sequentially.

    PubMed

    Saha, Debraj; Hazra, Dipak K; Maity, Tanmoy; Koner, Subratanath

    2016-06-20

    A series of copper- and alkaline-earth-metal-based multidimensional metal-organic frameworks, {[CuMg(pdc)2(H2O)4]·2H2O}n (1), [CuCa(pdc)2]n (2), [CuSr(pdc)2(H2O)3]n (3), and {[CuBa(pdc)2(H2O)5]·H2O}n (4), where H2Pdc = pyridine-2,5-dicarboxylic acid, were hydrothermally synthesized and characterized. Two different metals act as the active center to catalyze two kinds of reactions, viz., olefin to its epoxide followed by epoxide ring opening to afford the corresponding vicinal diol in a sequential manner.

  13. Electronic and magnetic properties of a conductive metal-organic framework from first principles

    NASA Astrophysics Data System (ADS)

    Hamed, Samia M.; Reyes-Lillo, Sebastian E.; Neaton, Jeffrey B.

    Motivated by the recent synthesis of a mixed-valence metal-organic framework (MOF) displaying high electron mobilities upon reduction, we undertake a computational study of its electronic, structural, and magnetic properties, utilizing ab initio density functional theory. We model the reduced system through charge doping, and the local ligand environment through finite cluster calculations. Molecular orbitals near the Fermi level are found to display mixtures of localized iron d and delocalized ligand p states suggesting strong charge carrier delocalization. Furthermore, we extend our study to one dimensional and three dimensional periodic systems and discuss possible transport mechanisms. Finally, the static correlation effects due to the presence of partially filled iron d orbitals requires an especially careful choice of exchange correlation functional, and the consequence of this choice is demonstrated.

  14. Separation membranes. Interfacial microfluidic processing of metal-organic framework hollow fiber membranes.

    PubMed

    Brown, Andrew J; Brunelli, Nicholas A; Eum, Kiwon; Rashidi, Fereshteh; Johnson, J R; Koros, William J; Jones, Christopher W; Nair, Sankar

    2014-07-04

    Molecular sieving metal-organic framework (MOF) membranes have great potential for energy-efficient chemical separations, but a major hurdle is the lack of a scalable and inexpensive membrane fabrication mechanism. We describe a route for processing MOF membranes in polymeric hollow fibers, combining a two-solvent interfacial approach for positional control over membrane formation (at inner and outer surfaces, or in the bulk, of the fibers), a microfluidic approach to replenishment or recycling of reactants, and an in situ module for membrane fabrication and permeation. We fabricated continuous molecular sieving ZIF-8 membranes in single and multiple poly(amide-imide) hollow fibers, with H2/C3H8 and C3H6/C3H8 separation factors as high as 370 and 12, respectively. We also demonstrate positional control of the ZIF-8 films and characterize the contributions of membrane defects and lumen bypass.

  15. Centimetre-scale micropore alignment in oriented polycrystalline metal-organic framework films via heteroepitaxial growth

    NASA Astrophysics Data System (ADS)

    Falcaro, Paolo; Okada, Kenji; Hara, Takaaki; Ikigaki, Ken; Tokudome, Yasuaki; Thornton, Aaron W.; Hill, Anita J.; Williams, Timothy; Doonan, Christian; Takahashi, Masahide

    2016-12-01

    The fabrication of oriented, crystalline films of metal-organic frameworks (MOFs) is a critical step toward their application to advanced technologies such as optics, microelectronics, microfluidics and sensing. However, the direct synthesis of MOF films with controlled crystalline orientation remains a significant challenge. Here we report a one-step approach, carried out under mild conditions, that exploits heteroepitaxial growth for the rapid fabrication of oriented polycrystalline MOF films on the centimetre scale. Our methodology employs crystalline copper hydroxide as a substrate and yields MOF films with oriented pore channels on scales that primarily depend on the dimensions of the substrate. To demonstrate that an anisotropic crystalline morphology can translate to a functional property, we assembled a centimetre-scale MOF film in the presence of a dye and showed that the optical response could be switched `ON’ or `OFF’ by simply rotating the film.

  16. Metal-organic frameworks with high capacity and selectivity for harmful gases

    PubMed Central

    Britt, David; Tranchemontagne, David; Yaghi, Omar M.

    2008-01-01

    Benchmarks have been established for the performance of six metal-organic frameworks (MOFs) and isoreticular MOFs (IRMOFs, which have the same underlying topology as MOF-5), MOF-5, IRMOF-3, MOF-74, MOF-177, MOF-199, and IRMOF-62, as selective adsorbents for eight harmful gases: sulfur dioxide, ammonia, chlorine, tetrahydrothiophene, benzene, dichloromethane, ethylene oxide, and carbon monoxide. Kinetic breakthrough measurements are used to determine the calculated dynamic adsorption capacity of each “benchmark” MOF for each gas. The capacity of each MOF is compared to that of a sample of Calgon BPL activated carbon. We find that pore functionality plays a dominant role in determining the dynamic adsorption performance of MOFs. MOFs featuring reactive functionality outperform BPL carbon in all but one case and exhibit high dynamic adsorption capacities up to 35% by weight. PMID:18711128

  17. Metal organic framework-mediated synthesis of highly active and stable Fischer-Tropsch catalysts

    NASA Astrophysics Data System (ADS)

    Santos, Vera P.; Wezendonk, Tim A.; Jaén, Juan José Delgado; Dugulan, A. Iulian; Nasalevich, Maxim A.; Islam, Husn-Ubayda; Chojecki, Adam; Sartipi, Sina; Sun, Xiaohui; Hakeem, Abrar A.; Koeken, Ard C. J.; Ruitenbeek, Matthijs; Davidian, Thomas; Meima, Garry R.; Sankar, Gopinathan; Kapteijn, Freek; Makkee, Michiel; Gascon, Jorge

    2015-03-01

    Depletion of crude oil resources and environmental concerns have driven a worldwide research on alternative processes for the production of commodity chemicals. Fischer-Tropsch synthesis is a process for flexible production of key chemicals from synthesis gas originating from non-petroleum-based sources. Although the use of iron-based catalysts would be preferred over the widely used cobalt, manufacturing methods that prevent their fast deactivation because of sintering, carbon deposition and phase changes have proven challenging. Here we present a strategy to produce highly dispersed iron carbides embedded in a matrix of porous carbon. Very high iron loadings (>40 wt %) are achieved while maintaining an optimal dispersion of the active iron carbide phase when a metal organic framework is used as catalyst precursor. The unique iron spatial confinement and the absence of large iron particles in the obtained solids minimize catalyst deactivation, resulting in high active and stable operation.

  18. A new method to position and functionalize metal-organic framework crystals

    PubMed Central

    Falcaro, Paolo; Hill, Anita J.; Nairn, Kate M.; Jasieniak, Jacek; Mardel, James I.; Bastow, Timothy J.; Mayo, Sheridan C.; Gimona, Michele; Gomez, Daniel; Whitfield, Harold J.; Riccò, Raffaele; Patelli, Alessandro; Marmiroli, Benedetta; Amenitsch, Heinz; Colson, Tobias; Villanova, Laura; Buso, Dario

    2011-01-01

    With controlled nanometre-sized pores and surface areas of thousands of square metres per gram, metal-organic frameworks (MOFs) may have an integral role in future catalysis, filtration and sensing applications. In general, for MOF-based device fabrication, well-organized or patterned MOF growth is required, and thus conventional synthetic routes are not suitable. Moreover, to expand their applicability, the introduction of additional functionality into MOFs is desirable. Here, we explore the use of nanostructured poly-hydrate zinc phosphate (α-hopeite) microparticles as nucleation seeds for MOFs that simultaneously address all these issues. Affording spatial control of nucleation and significantly accelerating MOF growth, these α-hopeite microparticles are found to act as nucleation agents both in solution and on solid surfaces. In addition, the introduction of functional nanoparticles (metallic, semiconducting, polymeric) into these nucleating seeds translates directly to the fabrication of functional MOFs suitable for molecular size-selective applications. PMID:21407203

  19. NMR relaxation and exchange in metal-organic frameworks for surface area screening

    SciTech Connect

    Chen, JJ; Mason, JA; Bloch, ED; Gygi, D; Long, JR; Reimer, JA

    2015-03-15

    We describe a robust screening technique that correlates the surface area of metal organic frameworks to the proton T-2 relaxation behavior of imbibed solvent at low field (13 MHz). In frameworks with small pore sizes (<1 nm) or strong solvent-framework interactions, diffusional exchange between the pore-confined and inter-particle solvent populations remains slow compared to the T-2 of the pore-confined solvent, allowing for a direct porosity analysis of the T-2 spectrum obtained from Laplace inversions. Increases in framework pore-size (>1 nm) lead to corresponding increases in the rate of solvent exchange, as confirmed by T-2 relaxation exchange (REXSY) experiments; increases in the pore size also increases the T-2 of the pore-confined solvent. The combination of these two effects results in comparable rates of relaxation and exchange, which precludes the direct analysis of Laplace inversions. Thus, two- and three-site kinetics models were applied to extract porosity from relaxation decays, thereby improving the utility of the porosity screening tool. (C) 2014 Elsevier Inc. All rights reserved.

  20. Toward Metal-Organic Framework-Based Solar Cells: Enhancing Directional Exciton Transport by Collapsing Three-Dimensional Film Structures.

    PubMed

    Goswami, Subhadip; Ma, Lin; Martinson, Alex B F; Wasielewski, Michael R; Farha, Omar K; Hupp, Joseph T

    2016-11-16

    Owing to their ability to act as light-harvesting scaffolds, porphyrin-containing metal-organic frameworks (MOFs) are in the forefront of research on the application of highly ordered molecular materials to problems in solar-energy conversion. In this work, solvent-assisted linker exchange (SALE) is performed on a pillared paddlewheel porphyrin containing MOF thin film to collapse a 3D framework to a 2D framework. The change in dimensionality of the framework is confirmed by a decrease in the film thickness, the magnitude of which is in agreement with crystallographic parameters for related bulk materials. Furthermore, NMR spectroscopy performed on the digested sample suggests a similar change in geometry is achieved in bulk MOF samples. The decreased distance between the porphyrin chromophores in the 2D MOF film compared to the 3D film results in enhanced energy transfer through the film. The extent of energy transport was probed by assembling MOF thin film where the outermost layers are palladium porphyrin (P2) units, which act as energy traps and fluorescence quenchers. Steady-state emission spectroscopy together with time-resolved emission spectroscopy indicates that excitons can travel through about 9-11 layers (porphyrin layers) in 2D films, whereas in 3D films energy transfer occurs through no more than about 6-8 layers. The results are difficult to understand if only changes in MOF interlayer spacing are considered but become much more understandable if dipole-dipole coupling distances are considered.