Synthesis and Characterization of Films and Membranes of Metal-Organic Framework (MOF) for Gas Separation Applications

Synthesis and Characterization of Films and Membranes of Metal-Organic Framework (MOF) for Gas Separation Applications PDF Author: Miral Naresh Shah
Publisher:
ISBN:
Category :
Languages : en
Pages : 170

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Book Description
Metal-Organic Frameworks (MOFs) are nanoporous framework materials with tunable pore size and functionality, and hence attractive for gas separation membrane applications. Zeolitic Imidazolate Frameworks (ZIFs), a subclass of MOFs, are known for their high thermal and chemical stability. ZIF-8 has demonstrated potential to kinetically separate propane/propene in powder and membrane form. ZIF-8 membranes propane-propene separation performance is superior in comparison to polymer, mixed matrix and carbon membranes. The overarching theme of my research is to address challenges that hinder fabrication of MOF membranes on a commercial scale and in a reproducible and scalable manner. 1. Current approaches, are specific to a given ZIF, a general synthesis route is not available. Use of multiple steps for surface modification or seeding causes reproducibility and scalability issues. 2. Conventional fabrication techniques are batch processes, thereby limiting their commercialization. Here we demonstrate two new approaches that can potentially address these challenges. First, we report one step in situ synthesis of ZIF-8 membranes on more commonly used porous [alpha]-alumina supports. By incorporating sodium formate in the in situ growth solution, well intergrown ZIF-8 membranes were synthesized on unmodified supports. The mechanism by which sodium formate promotes heterogeneous nucleation was investigated. Sodium formate reacts with zinc source to form zinc oxide layer, which in turn promotes heterogeneous nucleation. Sodium formate promotes heterogeneous nucleation in other ZIF systems as well, leading to ZIF-7, Zn(Im)2 (ZIF-61 analogue), ZIF-90, and SIM-1 films. Thus one step in situ growth using sodium formate provides a simplified, reproducible and potentially general route for ZIF film fabrication. One step in situ route, although advantageous; is still conventional in nature and batch process with long synthesis time. This limits commercialization, due to scalability and manufacturing cost issues. Taking advantage of coordination chemistry of MOFs and using temperature as driving force, continuous well-intergrown membranes of HKUST-1 and ZIF-8 in relatively short time (15 min) using Rapid Thermal Deposition (RTD). With minimum precursor consumption and simplified synthesis protocol, RTD provides potential for a continuous, scalable, reproducible and commercializable route for MOF membrane fabrication. RTD-prepared MOF membranes show improved separation performances, indicating improved microstructure. The electronic version of this dissertation is accessible from http://hdl.handle.net/1969.1/148212

Synthesis and Characterization of Films and Membranes of Metal-Organic Framework (MOF) for Gas Separation Applications

Synthesis and Characterization of Films and Membranes of Metal-Organic Framework (MOF) for Gas Separation Applications PDF Author: Miral Naresh Shah
Publisher:
ISBN:
Category :
Languages : en
Pages : 170

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Book Description
Metal-Organic Frameworks (MOFs) are nanoporous framework materials with tunable pore size and functionality, and hence attractive for gas separation membrane applications. Zeolitic Imidazolate Frameworks (ZIFs), a subclass of MOFs, are known for their high thermal and chemical stability. ZIF-8 has demonstrated potential to kinetically separate propane/propene in powder and membrane form. ZIF-8 membranes propane-propene separation performance is superior in comparison to polymer, mixed matrix and carbon membranes. The overarching theme of my research is to address challenges that hinder fabrication of MOF membranes on a commercial scale and in a reproducible and scalable manner. 1. Current approaches, are specific to a given ZIF, a general synthesis route is not available. Use of multiple steps for surface modification or seeding causes reproducibility and scalability issues. 2. Conventional fabrication techniques are batch processes, thereby limiting their commercialization. Here we demonstrate two new approaches that can potentially address these challenges. First, we report one step in situ synthesis of ZIF-8 membranes on more commonly used porous [alpha]-alumina supports. By incorporating sodium formate in the in situ growth solution, well intergrown ZIF-8 membranes were synthesized on unmodified supports. The mechanism by which sodium formate promotes heterogeneous nucleation was investigated. Sodium formate reacts with zinc source to form zinc oxide layer, which in turn promotes heterogeneous nucleation. Sodium formate promotes heterogeneous nucleation in other ZIF systems as well, leading to ZIF-7, Zn(Im)2 (ZIF-61 analogue), ZIF-90, and SIM-1 films. Thus one step in situ growth using sodium formate provides a simplified, reproducible and potentially general route for ZIF film fabrication. One step in situ route, although advantageous; is still conventional in nature and batch process with long synthesis time. This limits commercialization, due to scalability and manufacturing cost issues. Taking advantage of coordination chemistry of MOFs and using temperature as driving force, continuous well-intergrown membranes of HKUST-1 and ZIF-8 in relatively short time (15 min) using Rapid Thermal Deposition (RTD). With minimum precursor consumption and simplified synthesis protocol, RTD provides potential for a continuous, scalable, reproducible and commercializable route for MOF membrane fabrication. RTD-prepared MOF membranes show improved separation performances, indicating improved microstructure. The electronic version of this dissertation is accessible from http://hdl.handle.net/1969.1/148212

Membranes For Gas Separations

Membranes For Gas Separations PDF Author: Moises A Carreon
Publisher: World Scientific
ISBN: 9813207728
Category : Technology & Engineering
Languages : en
Pages : 376

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Book Description
This book aims at illustrating several examples of different membrane compositions ranging from inorganic, polymeric, metallic, metal organic framework, and composite which have been successfully deployed to separate industrially relevant gas mixtures including hydrogen, nitrogen, methane, carbon dioxide, olefins/parafins among others. Each book chapter highlights some of the current and key fundamental and technological challenges for these membranes that must be overcome in order to envision its application at industrial level.

Synthesis and Characterization of Iso-reticular Metal-organic Frameworks and Their Applications for Gas Separations

Synthesis and Characterization of Iso-reticular Metal-organic Frameworks and Their Applications for Gas Separations PDF Author: Yeonshick Yoo
Publisher:
ISBN:
Category :
Languages : en
Pages :

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Book Description
Nanoporous metal-organic frameworks (MOFs) have attracted tremendous interest due to their potential applications in gas-storage, gas separation, gas sensing, and catalysis. MOFs consist of metal-oxygen polyhedera interconnected with a variety of organic linker molecules, resulting in tailored nanoporous materials. With a judicious choice of organic linker groups, it is possible to fine-tune size, shape, and chemical functionality of the cavities and the internal surfaces. This unique structural feature offers unprecedented opportunities in small-molecule separations as well as chiral separations and catalysis. Prototypical iso-reticular metal-organic frameworks (IRMOFs) have been extensively studied among MOFs due to the simplicity of their synthesis and the variety of their potential applications. IRMOFs are a specific series of metal-organic frameworks developed by Yaghi and his coworkers. All IRMOFs are composed of oxygen-centered Zn4O tetrahedra interconnected with dicarboxylate linkers, forming a cubic type three dimensional (3D) porous network with high surface area. Despite a great deal of research in the synthesis and characterization of MOFs, there have been relatively few reports on the development of their applications, such as the fabrication of MOF thin films and membranes for gas separations. This is mainly due to the challenges associated with relatively difficult heterogeneous nucleation (seeding) and growth of MOFs on supports, and crack formation compared to their counterparts. Thin films and membranes of MOFs have great potentials for applications in membranebased gas separations, reactors, chemical sensors, and nonlinear optical devices. In this dissertation, the fabrication of IRMOF-1 membrane using a novel seeding method and its gas diffusion properties has been demonstrated. Introduction of the new seeding method for MOFs using microwaves resulted in well inter-grown IRMOF membranes showing Knudsen type transport of small gases through its pore. The heteroepitaxial growth of one IRMOF on another produced multi-layered IRMOF membranes. In addition, postsynthetic modification (PSM) of IRMOFs created functionalized membranes with enhanced stability against water as well as reduced crack formation during membrane fabrication. Lastly, hierarchical IRMOFs with improved CO2 adsorption properties were synthesized via PSM with cyanuric chloride.

Metal-organic Framework Membranes For Molecular Gas Separations

Metal-organic Framework Membranes For Molecular Gas Separations PDF Author: Moises A Carreon
Publisher: World Scientific
ISBN: 1786346745
Category : Technology & Engineering
Languages : en
Pages : 283

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Book Description
This unique compendium describes research progress on metal-organic framework (MOF) membranes for different relevant industrial gas separations. Specifically, the book focuses mainly on gas separations which are important in flue gas treatment, natural gas purification, hydrogen purification, and nuclear reprocessing. The advantages of using MOFs in mixed matrix membranes are discussed. Some of the pressing challenges in the field, and strategies to potentially overcome them are also distinctly outlined.This volume is a useful reference materials for professionals, academics, researchers and postgraduate students in chemical engineering and materials engineering.

Thin film MOFs (SURMOFs) for application in gas separation

Thin film MOFs (SURMOFs) for application in gas separation PDF Author: Valadez Sánchez, Elvia Patricia
Publisher: KIT Scientific Publishing
ISBN: 3731508834
Category : Biology (General)
Languages : en
Pages : 180

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Book Description
In this work, the deposition of ZIF-8 surface-anchored metal-organic framework (SURMOF) films was systematically studied. A proper characterization and optimization of the synthesized films was performed and their separation performance was determined. Furthermore, a general description of the system was achieved using the Maxwell-Stefan surface diffusion model.

Metal Organic Frameworks

Metal Organic Frameworks PDF Author: Victoria Samanidou
Publisher: MDPI
ISBN: 303928486X
Category : Science
Languages : en
Pages : 198

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Book Description
Metal–organic frameworks are among the most promising novel materials. The concept of MOFs was first introduced in 1990. They were actually initially used in catalysis, gas separation, membranes, electrochemical sensors. Later on, they were introduced as SPE sorbents for PAHs (Polycyclic Aromatic Hydrocarbons) in environmental water samples, then the range expanded to the field of analytical chemistry, both in chromatographic separation and sample preparation, with great success in, e.g., SPE and SPME (Solid Phase Mico-extraction). Since then, the number of analytical applications implementing MOFs as sorbents in sorptive sample preparation approaches is increasing. Τhis is reinforced by the fact that, at least theoretically, an infinite number of structures can be designed and synthesized, thus making tuneability one of the most unique characteristics of MOF materials. Moreover, they have been designed in various shapes, such as columns, fibers, and films, so that they can meet more analytical challenges with improved analytical features.Their exceptional properties attracted the interest of analytical chemists who have taken advantage of the unique structures and properties and have already introduced them in several sample pretreatment techniques, such as solid phase extraction, dispersive SPE, magnetic solid phase extraction, solid phase microextraction, stir bar sorptive extraction, etc.

Metal-Organic Frameworks

Metal-Organic Frameworks PDF Author: David Farrusseng
Publisher: John Wiley & Sons
ISBN: 3527635866
Category : Science
Languages : en
Pages : 415

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Book Description
An international and interdisciplinary team of leading experts from both academia and industry report on the wide range of hot applications for MOFs, discussing both the advantages and limits of the material. The resulting overview covers everything from catalysis, H2 and CH4 storage and gas purification to drug delivery and sensors. From the Contents: - Design of Porous Coordination Polymers/Metal-Organic Frameworks: Past, Present and Future - Design of Functional Metal-Organic Frameworks by Post-Synthetic Modification - Thermodynamic Methods for Prediction of Gas Separation in Flexible Frameworks - Separation and purification of gases by MOFs - Opportunities for MOFs in CO2 capture from flue gases, natural gas and syngas by adsorption - Manufacture of MOF thin films on structured supports for separation and catalysis - Research status of Metal-Organic Frameworks for on-board cryo-adsorptive hydrogen storage applications - Separation of xylene isomers - Metal-Organic Frameworks as Catalysts for Organic Reactions - Biomedical applications of Metal Organic Frameworks - Metal Organic Frameworks for Biomedical Imaging - Luminescent Metal-Organic Frameworks - Deposition of thin films for sensor applications - Industrial MOF Synthesis - MOF shaping and immobilisation A must-have for every scientist in the field.

Gas Separation Membranes

Gas Separation Membranes PDF Author: Ahmad Fauzi Ismail
Publisher: Springer
ISBN: 3319010956
Category : Science
Languages : en
Pages : 340

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Book Description
This book describes the tremendous progress that has been made in the development of gas separation membranes based both on inorganic and polymeric materials. Materials discussed include polymer inclusion membranes (PIMs), metal organic frameworks (MOFs), carbon based materials, zeolites, as well as other materials, and mixed matrix membranes (MMMs) in which the above novel materials are incorporated. This broad survey of gas membranes covers material, theory, modeling, preparation, characterization (for example, by AFM, IR, XRD, ESR, Positron annihilation spectroscopy), tailoring of membranes, membrane module and system design, and applications. The book is concluded with some perspectives about the future direction of the field.

Development of Metal-organic Framework Thin Films and Membranes for Low-energy Gas Separation

Development of Metal-organic Framework Thin Films and Membranes for Low-energy Gas Separation PDF Author: Michael McCarthy
Publisher:
ISBN:
Category :
Languages : en
Pages :

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Book Description
Metal-organic frameworks (MOFs) are hybrid organic-inorganic micro- or mesoporous materials that exhibit regular crystalline lattices with rigid pore structures. Chemical functionalization of the organic linkers in the structures of MOFs affords facile control over pore size and physical properties, making MOFs attractive materials for application in gas-separating membranes. A wealth of reports exist discussing the synthesis of MOF structures, however relatively few reports exist discussing MOF membranes. This disparity owes to challenges associated with fabricating films of hybrid materials, including poor substrate-film interactions, moisture sensitivity, and thermal instability. Since even nanometer scale cracks and defects can affect the performance of a membrane for gas separation, these challenges are particularly acute for MOF membranes. The focus of this work is the development of novel methods for MOF film and membrane fabrication with a view to overcoming these challenges. The MOF film production methods discussed herein include in situ synthesis using ligand-modified or metal-modified supports and rapid thermal deposition (RTD).

Thin Film MOFs (SURMOFs) for Application in Gas Separation

Thin Film MOFs (SURMOFs) for Application in Gas Separation PDF Author: Elvia Patricia Valadez Sánchez
Publisher:
ISBN: 9781013281457
Category : Science
Languages : en
Pages : 176

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Book Description
In this work, the deposition of ZIF-8 surface-anchored metal-organic framework (SURMOF) films was systematically studied. A proper characterization and optimization of the synthesized films was performed and their separation performance was determined. Furthermore, a general description of the system was achieved using the Maxwell-Stefan surface diffusion model. This work was published by Saint Philip Street Press pursuant to a Creative Commons license permitting commercial use. All rights not granted by the work's license are retained by the author or authors.