Synthesis and Characterization of Alkylamine-Functionalized Metal-Organic Frameworks as Adsorbents for Carbon Dioxide

Synthesis and Characterization of Alkylamine-Functionalized Metal-Organic Frameworks as Adsorbents for Carbon Dioxide PDF Author: Thomas Michael McDonald
Publisher:
ISBN:
Category :
Languages : en
Pages : 101

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Book Description
The work herein describes an investigation of metal-organic frameworks as adsorbents for selectively removing carbon dioxide (CO2) from low-pressure gas mixtures. Metal-organic frameworks are permanently porous, crystalline solid phase materials composed of organic molecules connected together by metal-based nodes into ordered structures. Generally exhibiting very high gravimetric surface areas, the pore surfaces of metal-organic frameworks can be rationally designed to allow for highly specific interactions between the adsorbent and guest species. Through chemical modifications of the pore surfaces, metal-organic frameworks were designed to adsorb CO2 over other small molecules. Chapter 1 begins with background information on carbon capture and sequestration (CCS) and the role it can potentially play in slowing anthropogenic CO2 emissions. An analysis of desirable metal-organic frameworks properties is presented along with a summary of the most significant work in the field of developing new metal-organic frameworks as CO2 adsorbents. Finally, a summary of amine-functionalized solid adsorbents that have directly influenced the synthesis and characterization methods reported in this investigation is presented. Chapter 2 reports the synthesis and characterization of the metal-organic framework mmen-CuBTTri. At the time it was first synthesized, mmen-CuBTTri exhibited some of the best CO2 adsorption properties of any metal-organic framework, including the highest selectivity for CO2 over N2 yet measured. The sorbent was the first to demonstrate that aliphatic amines could significantly improve the CO2 adsorption properties of metal-organic frameworks with open metal sites. Furthermore, despite an enthalpy of CO2 adsorption of nearly -100 kJ/mol at zero coverage, it was shown that the sorbent could be effectively cycled with modest temperature swings. Chapter 3 reports the original synthesis and characterization of mmen-Mg2(dobpdc). Utilizing the same diamine as the sorbent in Chapter 2, it was demonstrated that the nature of metal-organic framework support, and not just the amine functional groups, affects the CO2 adsorption properties. In this case, the high density of amines within the pores resulted in a material that could effectively remove CO2 at very low concentrations; it was the first metal-organic framework studied for its ability to remove CO2 directly from air. Furthermore, mmen-Mg2(dobpdc) was the first amine-functionalized solid sorbent to exhibit steps in its pure component CO2 isotherm. Finally, it was shown that the adsorption properties of the material, especially the regeneration energy, make it competitive with aqueous amine solutions. Chapter 4 builds upon the work of Chapter 3. The adsorption mechanism of mmen-Mg2(dobpdc), which was studied by infrared spectroscopy, solid state NMR spectroscopy, and in situ powder X-ray diffraction measurements was revealed to be a previously unprecedented cooperative insertion mechanism. The origin of the unusual isotherm steps was revealed to be a phase transition of the amines attached to the pore surface. In Chapter 4, a method of controlling the position of isotherm steps is described. Finally, the superior carbon capture characteristics of phase change adsorbents are enumerated. Chapter 5 is a departure from the previous chapters and describes a simple and convenient method of utilizing a commercially available thermogravimetric analyzer to assess the porosity and activation conditions of metal-organic frameworks. The importance of identifying proper activation is discussed and a suggested protocol for researchers to use is given. Lastly, the ability of the method to improve the reported gas adsorption properties of the metal-organic framework Mn-BTT is reported.

Synthesis and Characterization of Alkylamine-Functionalized Metal-Organic Frameworks as Adsorbents for Carbon Dioxide

Synthesis and Characterization of Alkylamine-Functionalized Metal-Organic Frameworks as Adsorbents for Carbon Dioxide PDF Author: Thomas Michael McDonald
Publisher:
ISBN:
Category :
Languages : en
Pages : 101

Get Book Here

Book Description
The work herein describes an investigation of metal-organic frameworks as adsorbents for selectively removing carbon dioxide (CO2) from low-pressure gas mixtures. Metal-organic frameworks are permanently porous, crystalline solid phase materials composed of organic molecules connected together by metal-based nodes into ordered structures. Generally exhibiting very high gravimetric surface areas, the pore surfaces of metal-organic frameworks can be rationally designed to allow for highly specific interactions between the adsorbent and guest species. Through chemical modifications of the pore surfaces, metal-organic frameworks were designed to adsorb CO2 over other small molecules. Chapter 1 begins with background information on carbon capture and sequestration (CCS) and the role it can potentially play in slowing anthropogenic CO2 emissions. An analysis of desirable metal-organic frameworks properties is presented along with a summary of the most significant work in the field of developing new metal-organic frameworks as CO2 adsorbents. Finally, a summary of amine-functionalized solid adsorbents that have directly influenced the synthesis and characterization methods reported in this investigation is presented. Chapter 2 reports the synthesis and characterization of the metal-organic framework mmen-CuBTTri. At the time it was first synthesized, mmen-CuBTTri exhibited some of the best CO2 adsorption properties of any metal-organic framework, including the highest selectivity for CO2 over N2 yet measured. The sorbent was the first to demonstrate that aliphatic amines could significantly improve the CO2 adsorption properties of metal-organic frameworks with open metal sites. Furthermore, despite an enthalpy of CO2 adsorption of nearly -100 kJ/mol at zero coverage, it was shown that the sorbent could be effectively cycled with modest temperature swings. Chapter 3 reports the original synthesis and characterization of mmen-Mg2(dobpdc). Utilizing the same diamine as the sorbent in Chapter 2, it was demonstrated that the nature of metal-organic framework support, and not just the amine functional groups, affects the CO2 adsorption properties. In this case, the high density of amines within the pores resulted in a material that could effectively remove CO2 at very low concentrations; it was the first metal-organic framework studied for its ability to remove CO2 directly from air. Furthermore, mmen-Mg2(dobpdc) was the first amine-functionalized solid sorbent to exhibit steps in its pure component CO2 isotherm. Finally, it was shown that the adsorption properties of the material, especially the regeneration energy, make it competitive with aqueous amine solutions. Chapter 4 builds upon the work of Chapter 3. The adsorption mechanism of mmen-Mg2(dobpdc), which was studied by infrared spectroscopy, solid state NMR spectroscopy, and in situ powder X-ray diffraction measurements was revealed to be a previously unprecedented cooperative insertion mechanism. The origin of the unusual isotherm steps was revealed to be a phase transition of the amines attached to the pore surface. In Chapter 4, a method of controlling the position of isotherm steps is described. Finally, the superior carbon capture characteristics of phase change adsorbents are enumerated. Chapter 5 is a departure from the previous chapters and describes a simple and convenient method of utilizing a commercially available thermogravimetric analyzer to assess the porosity and activation conditions of metal-organic frameworks. The importance of identifying proper activation is discussed and a suggested protocol for researchers to use is given. Lastly, the ability of the method to improve the reported gas adsorption properties of the metal-organic framework Mn-BTT is reported.

Carbon-Capture by Metal-Organic Framework Materials

Carbon-Capture by Metal-Organic Framework Materials PDF Author: David J. Fisher
Publisher: Materials Research Forum LLC
ISBN: 1644900858
Category : Technology & Engineering
Languages : en
Pages : 140

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Book Description
Metal-Organic Framework Materials (MOFs) are well suited for absorbing carbon dioxide. MOFs can form highly-porous structures with great adsorption capacities. They also offer good catalytic properties and much research refers to the relationship between catalytic performance and framework structure. In addition to simple CO2 absorption, there are other interesting applications, such as the direct electrochemical reduction into useful chemicals and fuels, the conversion of CO2 into methanol, the electrochemical reduction of CO2, or electrocatalytic hydrogen evolution (thus boosting the ‘hydrogen economy’). The book references 295 original resources and includes their direct web link for in-depth reading. Keywords: Global Warming, Carbon Dioxide Capture, Metal-Organic Frameworks MOFs, Adsorbents for CO2, Porous Solids, Catalytic Performance, Synthesis of MOFs, Conversion of CO2 into Methanol, Electrocatalytic Hydrogen Evolution, Hydrogen Economy, Gas Adsorption, Gas Separation, Organic Ligands, Metal Ion Clusters.

Metal-Organic Framework Materials

Metal-Organic Framework Materials PDF Author: Leonard R. MacGillivray
Publisher: John Wiley & Sons
ISBN: 1118931580
Category : Science
Languages : en
Pages : 1210

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Book Description
Metal-Organic Frameworks (MOFs) are crystalline compounds consisting of rigid organic molecules held together and organized by metal ions or clusters. Special interests in these materials arise from the fact that many are highly porous and can be used for storage of small molecules, for example H2 or CO2. Consequently, the materials are ideal candidates for a wide range of applications including gas storage, separation technologies and catalysis. Potential applications include the storage of hydrogen for fuel-cell cars, and the removal and storage of carbon dioxide in sustainable technical processes. MOFs offer the inorganic chemist and materials scientist a wide range of new synthetic possibilities and open the doors to new and exciting basic research. Metal-Organic Frameworks Materials provides a solid basis for the understanding of MOFs and insights into new inorganic materials structures and properties. The volume also reflects progress that has been made in recent years, presenting a wide range of new applications including state-of-the art developments in the promising technology for alternative fuels. The comprehensive volume investigates structures, symmetry, supramolecular chemistry, surface engineering, recognition, properties, and reactions. The content from this book will be added online to the Encyclopedia of Inorganic and Bioinorganic Chemistry: http://www.wileyonlinelibrary.com/ref/eibc

Metal-Organic Frameworks (MOFs) as Catalysts

Metal-Organic Frameworks (MOFs) as Catalysts PDF Author: Shikha Gulati
Publisher: Springer Nature
ISBN: 9811679592
Category : Science
Languages : en
Pages : 785

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Book Description
This book highlights the state-of-the-art research and discovery in the use of MOFs in catalysis, highlighting the scope to which these novel materials have been incorporated by the community. It provides an exceptional insight into the strategies for the synthesis and functionalization of MOFs, their use as CO2 and chemical warfare agents capture, their role in bio-catalysis and applications in photocatalysis, asymmetric catalysis, nano-catalysis, etc. This book will also emphasize the challenges with previous signs of progress and way for further research, details relating to the current pioneering technology, and future perspectives with a multidisciplinary approach. Furthermore, it presents up-to-date information on the economics, toxicity, and regulations related to these novel materials.

Metal-Organic Frameworks

Metal-Organic Frameworks PDF Author: Hermenegildo García
Publisher: John Wiley & Sons
ISBN: 352734313X
Category : Science
Languages : en
Pages : 530

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Book Description
Focusing on applications in separation, adsorption and catalysis, this handbook underlines the importance of this hot and exciting topic. It provides an excellent insight into the synthesis and modification of MOFs, their synthesis on an industrial scale, their use as CO2 and chemical warfare adsorbers, and the role of defects in catalysis. In addition, the authors treat such new aspects as biocatalysis and applications in photocatalysis and optoelectronic devices.

Advanced Materials for Sustainable Environmental Remediation

Advanced Materials for Sustainable Environmental Remediation PDF Author: Dimitrios A Giannakoudakis
Publisher: Elsevier
ISBN: 0323904866
Category : Technology & Engineering
Languages : en
Pages : 652

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Book Description
Advanced Materials for Sustainable Environmental Remediation: Terrestrial and Aquatic Environments presents detailed, comprehensive coverage of novel and advanced materials that can be applied to address the growing global concern of the pollution of natural resources in waters, the air and soil. It provides fundamental knowledge on available materials and treatment processes, as well as applications, including adsorptive remediation and catalytic remediation. Organized clearly by type of material, this book presents a consistent structure for each chapter, including characteristics of the materials, basic and important physicochemical features for environmental remediation applications, routes of synthesis, recent advances as remediation medias, and future perspectives. This book offers an interdisciplinary and practical examination of available materials and processes for environmental remediation that will be valuable to environmental scientists, materials scientists, environmental chemists, and environmental engineers alike. - Highlights a wide range of synthetic methodologies, physicochemical and engineered features of novel materials and composites/hybrids for environmental purposes - Provides comprehensive, consolidated coverage of advanced materials for environmental remediation applications for researchers in environmental science, materials science, and industry to identify in-depth solutions to pollution - Presents up-to-date details of advanced materials, including descriptions and characteristics that impact their applications in environmental remediation processes

Metal-Organic Frameworks for Carbon Capture and Energy

Metal-Organic Frameworks for Carbon Capture and Energy PDF Author: Pooja Ghosh
Publisher:
ISBN: 9780841298088
Category : Carbon sequestration
Languages : en
Pages :

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Book Description


Functional Metal-Organic Frameworks

Functional Metal-Organic Frameworks PDF Author: Ali Morsali
Publisher: John Wiley & Sons
ISBN: 1119640431
Category : Science
Languages : en
Pages : 256

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Book Description
Owing to the extensive interest in construction of functional metal organic frameworks (FMOFs), this book discusses the roles of functional groups on the structure and application of metal organic frameworks (MOFs). The contents of the book are classified based on the structural and chemical properties of organic functions, in order to make readers able to compare the different effects of each function on the structure and application of the MOFs. In each chapter, the chemical properties of applied functional groups are gathered to give deeper insight into the roles of organic functions in the structure and application of MOFs. In the function-application properties, the authors discuss how a functional group can dominate the host-guest chemistry of the MOFs and how this host-guest chemistry can expand the effectiveness and efficiency of the material in different fields of applications. Finally, function-structure properties are discussed. In function-application properties, it is discussed how a functional group can affect the topology, porosity, flexibility and stability of the framework. The features of this subject are novel and are presented for the first time.

Membrane Contactor Technology

Membrane Contactor Technology PDF Author: Mohammad Younas
Publisher: John Wiley & Sons
ISBN: 3527348611
Category : Technology & Engineering
Languages : en
Pages : 372

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Book Description
An eye-opening exploration of membrane contactors from a group of industry leaders In Membrane Contactor Technology: Water Treatment, Food Processing, Gas Separation, and Carbon Capture, an expert team of researchers delivers an up-to-date and insightful explanation of membrane contactor technology, including transport phenomena, design aspects, and diverse process applications. The book also includes explorations of membrane synthesis, process, and module design, as well as rarely discussed process modeling and simulation techniques. The authors discuss the technical and economic aspects of this increasingly important technology and examine the geometry, flow, energy and mass transport, and design aspects of membrane contactor modules. They also cover a wide range of application opportunities for this technology, from the materials sciences to process engineering. Membrane Contactor Technology also includes: A thorough introduction to the membrane contactor extraction process, including dispersion-free membrane extraction processes and supported liquid membrane processes Comprehensive explorations of membrane transport theory, including discussions of diffusional mass and heat transfer modeling, as well as numerical modeling In-depth examinations of module configuration and geometry, including design and flow configuration Practical discussions of modes or operation, including membrane distillation, osmotic evaporation, and forward osmosis Perfect for process engineers, biotechnologists, water chemists, and membrane scientists, Membrane Contactor Technology also belongs in the libraries of chemical engineers, polymer chemists, and chemists working in the environmental industry.

Synthesis of Amine-modified Aerogel Sorbents and Metal-organic Framework-5 (MOF-5) Membranes for Carbon Dioxide Separation

Synthesis of Amine-modified Aerogel Sorbents and Metal-organic Framework-5 (MOF-5) Membranes for Carbon Dioxide Separation PDF Author: Teresa M. Rosa
Publisher:
ISBN:
Category : Aerogels
Languages : en
Pages : 85

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Book Description
Amine-modified solid sorbents and membrane separation are promising technologies for separation and capture of carbon dioxide (CO2) from combustion flue gas. Amine absorption processes are mature, but still have room for improvement. This work focused on the synthesis of amine-modified aerogels and metal-organic framework-5 (MOF-5) membranes for CO2 separation. A series of solid sorbents were synthesized by functionalizing amines on the surface of silica aerogels. This was done by three coating methods: physical adsorption, magnetically assisted impact coating (MAIC) and atomic layer deposition (ALD). CO2 adsorption capacity of the sorbents was measured at room temperature in a Cahn microbalance. The sorbents synthesized by physical adsorption show the largest CO2 adsorption capacity (1.43-1.63 mmol CO2/g). An additional sorbent synthesized by ALD on hydrophilic aerogels at atmospheric pressures shows an adsorption capacity of 1.23 mmol CO2/g. Studies on one amine-modified sorbent show that the powder is of agglomerate bubbling fluidization (ABF) type. The powder is difficult to fluidize and has limited bed expansion. The ultimate goal is to configure the amine-modified sorbents in a micro-jet assisted gas fluidized bed to conduct adsorption studies. MOF-5 membranes were synthesized on α-alumina supports by two methods: in situ synthesis and secondary growth synthesis. Characterization by scanning electron microscope (SEM) imaging and X-ray diffraction (XRD) show that the membranes prepared by both methods have a thickness of 14-16 μm, and a MOF-5 crystal size of 15-25 μm with no apparent orientation. Single gas permeation results indicate that the gas transport through both membranes is determined by a combination of Knudsen diffusion and viscous flow. The contribution of viscous flow indicates that the membranes have defects.