Synthesis And Phtoluminescence Sic Study Of Microporous Metal Organic Frameworks Mmofs For Sensing And Detection Of Nitroexplosives And Aromatic Compounds
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Synthesis And Phtoluminescence Sic Study Of Microporous Metal Organic Frameworks Mmofs For Sensing And Detection Of Nitroexplosives And Aromatic Compounds
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Author : Sanhita Pramanik
language : en
Publisher:
Release Date : 2011
Synthesis And Phtoluminescence Sic Study Of Microporous Metal Organic Frameworks Mmofs For Sensing And Detection Of Nitroexplosives And Aromatic Compounds written by Sanhita Pramanik and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 2011 with Chemical detectors categories.
Due to the increased terrorist activity worldwide and the use of modern bombs in those attacks, the development of a new method capable of rapidly and cost-efficiently detecting trace vapor of explosives is highly desirable. Chemical explosives composed of a diverse group of compounds, including nitroaromatics, nitramines, nitrate esters as well as some inorganic/organic nitrates and peroxides. Current methodologies include use of well trained dogs and sophisticated instrumentation such as gas chromatography coupled with a mass spectrometer, nuclear quadruple resonance, ionization mass spectrometry (IMS). These methods are highly sensitive and selective, but often expensive, not always easily accessible, and require intense training for operation. As a complementary method, chemical sensors can provide new ways to the rapid detection of ultra trace explosives, and can be easily incorporated into inexpensive and portable microelectronic devices. Fluorescence based sensors utilizing conjugated polymers have attracted enormous attention in the recent years for their excellent performance. In this thesis, a systematic study was performed in a series of luminescent MMOFs and their behavior upon exposure to the vapor of different analytes. For example, [Zn2(oba)2(bpy)]'DMA, one of the MMOFs made of paddle-wheel SBU, selectively responds to nitroaromatics (with electron-withdrawing groups) and other aromatic compounds, like benzene, toluene (with electron-donating groups) via fluorescent quenching and enhancement respectively. The study also shows that nitro-containing non-aromatic analytes (nitroaliphatics) make negligible effect on the fluorescence of [Zn2(oba)2(bpy)]'DMA . The results demonstrate the exceptional ability of this particular MMOF to selectively detect explosives of different types (e.g. aromatic DNT vs. non-aromatic or aliphatic DMNB). Another series of highly luminescent MMOFs made of the same metal center (Zn) and similar ligands (bpdc, bpy, 2,2'dmbpy and bpe) but different structures have also been investigated. Photoluminescence studies show that the guest-free samples of these compounds also exhibit quenching or enhancement phenomena, when exposed to the vapors of two different types of analyte molecules having electron rich and electron deficient functional groups. The origin of such effect can be well understood and explained based on molecular orbital and band structure calculations, as well as the comparison of their redox potentials. In addition, synthesis and characterization of some new MMOFs, composed of V-shaped dicarboxylic acid and selected diamine ligands are briefly discussed. Clearly, ligands play an important role in the crystal structure formation as well as pore characteristics of the resultant MMOFs.
Metal Organic Frameworks Based Hybrid Materials For Environmental Sensing And Monitoring
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Author : Ram K. Gupta
language : en
Publisher: CRC Press
Release Date : 2022-06-22
Metal Organic Frameworks Based Hybrid Materials For Environmental Sensing And Monitoring written by Ram K. Gupta and has been published by CRC Press this book supported file pdf, txt, epub, kindle and other format this book has been release on 2022-06-22 with Science categories.
With an unprecedented population boom and rapid industrial development, environmental pollution has become a severe problem for the ecosystem and public health. Classical techniques for sensing and determining environmental contaminants often require complex pretreatments, expensive equipment, and longer testing times. Therefore, new, and state-of-the-art sensing technologies possessing the advantages of excellent sensitivity, rapid detection, ease of use, and suitability for in situ, real-time, and continuous monitoring of environmental pollutants, are highly desirable. Metal-Organic Frameworks-based Hybrid Materials for Environmental Sensing and Monitoring covers the current-state-of-the-art hybrid nanomaterials based on metal-organic frameworks for electrochemical monitoring purposes. Accomplished authors cover various synthetic routes, methods, and theories behind enhancing the electrochemical properties and applications of metal-organic frameworks-based hybrid nanomaterials for electrochemical sensing of environmental pollutants under one roof. This book is essential reading for all academic and industrial researchers working in the fields of materials science and nanotechnology.
Metal Organic Framework Mof Based Materials
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Author : Xiang He
language : en
Publisher:
Release Date : 2019
Metal Organic Framework Mof Based Materials written by Xiang He and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 2019 with Nuclear engineering categories.
Metal-organic frameworks (MOFs) have been attracting great attention in the past several decades mainly because of their amazing properties, including tunable surface chemistry, flexible structure, large surface area, and huge porosity. Endorsed by those merits, MOFs have been applied in a wide range of applications, such as catalysis, gas separation, drug delivery, and sensing. Typically, MOFs are synthesized via the hydrothermal method, which, however, is difficult to scale up and requires long reaction durations (e.g., from hours to days). To achieve the full potentials of MOFs, the exploration of a novel strategy is necessary for the facile and fast synthesis of MOFs. Here in this dissertation, the aerosol route was presented as a facile route to synthesize MOFs and MOF-based composites. The aerosol route not only enabled fast crystallization of MOFs (i.e., within seconds), but also allowed continuous tuning of MOF's properties by simply adjusting the operating parameters (e.g., temperature, pressure, and precursor conditions). To map out the formation mechanism of MOFs inside the microdroplets, systematic experimental and simulation work were carried out, which demonstrated that the fast heat and mass transfer during the aerosol route played a vital role in the rapid synthesis of MOFs. Beyond the synthesis of MOFs, the photocatalytic applications of MOF-based materials for energy and environmental sustainability were also studied in detail. More specifically, several efficient MOF-based composite photocatalysts were designed, including HKUST-1/TiO2, HKUST-1/TiO2/Cu2O, ZIF-8/ZnO, and MIL-100(Fe)/TiO2. The composite photocatalysts exhibited remarkable efficiencies towards either CO2 photoreduction or water remediation. In-depth exploration of the photocatalytic mechanism was carried out with the aid of several advanced techniques, such as in situ diffuse reflectance infrared Fourier spectroscopy (DRIFTS), photoluminescence spectroscopy, grazing-incidence wide-angle X-ray scattering, and ultrafast transient absorption spectroscopy. Meanwhile, the density functional theory (DFT) calculation was also applied to provide further mechanistic insights. The results demonstrated that MOFs acted as excellent co-catalysts, which not only facilitated molecule adsorption and activation, but also promoted the separation of the photo-induced charge carriers, leading to increased charge carrier densities in the photocatalytic systems for significantly enhanced efficiencies. The work from this dissertation is expected to broaden the synthesis strategies for the synthesis of MOF-based materials and advance the fundamental understanding of MOFs' roles in photocatalytic applications, which should have a great impact on the rational design of MOF-based composite photocatalysts for energy and environmental sustainability.
Metal Organic Frameworks Of Pyrazolate Derivatives
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Author : Charlie Eric William Kivi
language : en
Publisher:
Release Date : 2017
Metal Organic Frameworks Of Pyrazolate Derivatives written by Charlie Eric William Kivi and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 2017 with categories.
In this work we examine the structure and applications of metal-organic frameworks (MOFs) synthesized from pyrazolate derivatives. In total, six pyrazolate ligands were examined: 4-(4-(3,5-dimethyl-1H-pyrazol-4-yl)phenyl)pyridine (HL), 1,1'-methylenebis(3,5-dimethyl-1H-pyrazolyl-4-carboxylic acid) (H2BPM), triethyl-1,1',1''-methanetriyltris(3,5-dimethyl-1H-pyrazole-4-carboxylate) (TPM-1), triethyl-4,4',4''-(methanetriyltris[3,5-dimethyl-1H-pyrazole-1,4-diyl])tribenzoate (TPM-2), 1,1',1'',1'''-(propane-1,1,3,3-tetrayl)tetrakis(3,5-dimethyl-1H-pyrazole-4-carboxylic acid) (H4TPP), tetraethyl-1,1',1'',1'''-(1,4-phenylenebis[methanetriyl]) tetrakis(3,5-dimethyl-1H-pyrazole-4-carboxylate)pyridinephenylpyrazole (TPX). These ligands were used to synthesize a variety of MOFs that were subsequently investigated for luminescent sensing, gas storage, and catalytic performance. In Chapter 2, three MOFs synthesized from the reaction of HL and CuX (X = Br, I) were investigated. These materials were found to form MOFs which contained the luminescent trinuclear Cu(I) pyrazolate unit. Only CuBr and HL alone resulted in a MOF of sufficient purity and stability to permit evaluation as a luminescent sensor. Experiments with various volatile organic compounds revealed turn-on (luminescence enhancement) behaviour for ethyl acetate, pentane, and benzene and turn-off (luminescence quenching) behaviour for diethyl ether and chloroform for this material. In Chapters 3 and 4, ten MOFs are described. These were synthesized from H2BPM and metal-acetate salts. Chapter 3 encompassed two MOFs: [Ni(BPM)]n∙xDMSO and [Cd(BPM)]n∙xDMSO. These MOFs are isostructural, microporous materials. Evacuation of the pores led to collapse of the [Cd(BPM)]n∙xDMSO material but [Ni(BPM)]n∙xDMSO proved to be permanently porous. Further investigations revealed [Ni(BPM)]n∙xDMSO selectively adsorbed methane over nitrogen indicating it may serve as a porous material for coal mine methane capture. Chapter 4 investigated the many other structures H2BPM can assume in the presence of manganese, cobalt, iron, copper, and europium. Cobalt in particular proved highly tunable with 4 separate structures being synthesized such as [Co2(BPM)2(H2O)4(Bpy)0.5]n∙2DMF∙2(H2O). This was achieved through varying the synthetic conditions. [Co2(BPM)2(H2O)4(Bpy)0.5]n∙2DMF∙2(H2O)and [Eu(BPM)(OAc)]n were further investigated for the oxidation of olefins and luminescence respectively. In Chapter 5, metal complexes Mo(TPM-1)(CO)3, Mo(TPM-2)(CO)3, Pd2(H4TPP)Cl4, and Pd2(TPX)Cl4 were synthesized. The catalytic performance of Mo(TPM-1)(CO)3 was evaluated and found to be effective for the oxidation of olefins. MOF synthesis was attempted with all four compounds but was ultimately unsuccessful. Although one MOF was produced from Mo(TPM-1)(CO)3, large scale synthesis was not possible preventing full investigation of its properties.
From Design To Application
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Author : Jinfeng Zhang
language : en
Publisher:
Release Date : 2018
From Design To Application written by Jinfeng Zhang and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 2018 with categories.
Metal-organic frameworks (MOFs) are a series of porous materials made of wellorganized inorganic metal nodes linked via organic ligands (linkers). MOFs have gained particular attention due to their applications in gas adsorption and separation, selective sorption of harmful chemicals, catalysis, energy, sensing, bioscience, and electronics. The thesis will focus on two different aspects of MOFs. Briefly, in the first portion of the thesis, a less-toxic solvent than N,N-dimethylformamide (DMF) can be used to make MOFs will be demonstrated. In the latter portion of the thesis, my efforts to incorporate organic moieties into MOFs for sulfur dioxide sequestration will be described. With regard to the use of less-toxic solvents, it should be noted that with notable exceptions (e.g., mechanochemical, water-based, and electrochemical), the synthesis of MOFs is often carried out at elevated temperature using DMF or N,Ndiethylformamide (DEF) as the solvent. However, the industrial-scale synthesis of MOFs from DMF/DEF may generate significant amounts of DMF waste, which can exhibit reprotoxicity and end-of-life issues associated with the formation of NOx upon incineration. With the introduction of the Registration, Evaluation and Authorization of Chemicals (REACH) legislation in the European Union, there is a growing trend towards safer production and use of chemicals by industry. As such, it is crucial to develop green/sustainable methods of synthesizing MOFs. Dihydrolevoglucosenone (Cyrene), a green bioderived solvent from waste cellulose, was applied to the synthesis of MOFs. The MOF, HKUST-1, exhibited a larger Brunauer-Emmett-Teller (BET) surface area than HKUST-1 synthesized with DMF. Four additional archetypal MOFs were also synthesized to verify the universal application of Cyrene in the synthesis of MOFs. However, their BET surface areas were lower than DMF-made MOFs. It was observed that an aldol-condensation product of two Cyrene molecules, in addition to Cyrene trapped within the pores, were responsible for the lower-than expected surface areas. The use of Cyrene has led to a series of design principles that eliminate the need for problematic solvents such as DMF and can be applied to the synthesis of a wide range of MOFs. With regard to sulfur dioxide sequestration, it should be noted that sulfur dioxide, a colorless gas belonging to SOx family, yields detrimental effects via inhalation or absorption. Since MOFs are ideal sorbents for toxic gases, in Chapter 3, I will continue along the theme of reprotoxicity and end-of-life issues by designing MOFs which have the potential to chemically react with sulfur dioxide. Unlike the de novo synthetic pathways in the Chapter 2, the Chapter 3 will demonstrate how solvent-assisted linker exchange (SALE) and solvent-assisted linker incorporation (SALI) can be used to make MOFs with the ideal functionalities for sulfur dioxide sequestration. In Chapter 3, the main focus of the work was to introduce the butadiene functional groups into different MOFs, namely UiO-66, UiO-66-MA (muconic-acid-functionalized UiO-66), MOF-808, MOF-808-BS (butadiene-sulfone-functionalized MOF-808) and MOF-808-BD (butadiene-functionalized MOF-808), the SALI method was vitalized to determine if the butadiene group could undergo a cheletropic reaction in the presence of sulfur dioxide inside the MOF. All MOFs were exposed to a constant flow of sulfur dioxide, the UiO-66-MA was observed to take up three times more sulfur dioxide than the unfunctionalized parent UiO-66. For the MOF-808 series, surprisingly, the unfuctionalized MOF-808 was able to absorb more than two times the sulfur dioxide than MOF-808-BD, and five times higher than MOF-808-BS, respectively. This suggests that the terminal waters and hydroxide groups are responsible for the enhanced uptake. Despite the improved uptake of sulfur dioxide in UiO-66-MA and MOF-808, nuclear magnetic resonance (NMR) and infrared (IR) data indicate that no chemical change occurred to the butadiene-functionalized group, which suggests that a cheletropic reaction did not occur.
A Multifunctional 3d Cd Based Metal Organic Frameworks For The Highly Luminescence Sensitive Detection Of Cro42 Cr2o72 And Nitro Aromatic Compounds
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Author : Wen-Kui Xi
language : en
Publisher:
Release Date : 2020
A Multifunctional 3d Cd Based Metal Organic Frameworks For The Highly Luminescence Sensitive Detection Of Cro42 Cr2o72 And Nitro Aromatic Compounds written by Wen-Kui Xi and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 2020 with categories.
A novel 3D cadmium-based luminescent metal-organic framework {[Cd(L)(bpe) 0.5 ]·H 2 O} n ( 1 ) [L = 6-(3-pyridyl)isophthalic acid and 1,2-bis(4-pyridyl)ethane], has been successfully assembled by a solvothermal method. Luminescence sensing suggest that compound 1 displays excellent sensitivity and selectivity to detect CrO 4 2- /Cr 2 O 7 2- and a wide range of nitro aromatic compounds (NACs).
Fabrication Of Metal Organic Framework Derived Nanomaterials And Their Electrochemical Applications
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Author : Wei Xia
language : en
Publisher: Springer
Release Date : 2018-04-03
Fabrication Of Metal Organic Framework Derived Nanomaterials And Their Electrochemical Applications written by Wei Xia and has been published by Springer this book supported file pdf, txt, epub, kindle and other format this book has been release on 2018-04-03 with Technology & Engineering categories.
This thesis systematically introduces readers to a new metal-organic framework approach to fabricating nanostructured materials for electrochemical applications. Based on the metal-organic framework (MOF) approach, it also demonstrates the latest ideas on how to create optimal MOF and MOF-derived nanomaterials for electrochemical reactions under controlled conditions. The thesis offers a valuable resource for researchers who want to understand electrochemical reactions at nanoscale and optimize materials from rational design to achieve enhanced electrochemical performance. It also serves as a useful reference guide to fundamental research on advanced electrochemical energy storage materials and the synthesis of nanostructured materials.
Recent Progress In Strategies For Preparation Of Metal Organic Frameworks And Their Hybrids With Different Dimensions
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Author : Yichun Su
language : en
Publisher: OAE Publishing Inc.
Release Date : 2023-01-01
Recent Progress In Strategies For Preparation Of Metal Organic Frameworks And Their Hybrids With Different Dimensions written by Yichun Su and has been published by OAE Publishing Inc. this book supported file pdf, txt, epub, kindle and other format this book has been release on 2023-01-01 with Science categories.
As a new kind of organic-inorganic hybrid porous material, metal-organic frameworks (MOFs) exhibit a wide application prospect in gas storage and separation, catalysis and sensing due to their characteristics of large specific surface area, high porosity and coordination unsaturation. As more and more types of MOFs were reported, the synthetic strategies of MOFs-based materials have become a hot research topic. According to the morphological dimension, MOFs can be roughly divided into one-dimensional, two-dimensional and three-dimensional structures. Herein, we summarize the synthetic methods and principles of MOFs from multi-dimensional perspectives, and explore the growth mechanism of MOFs with different morphologies based on dynamic and thermodynamic tuning. Finally, based on the above summaries, the challenges and opportunities of MOFs in the future are discussed.
Hierarchical Metal Organic Framework Hybrids
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Author :
language : en
Publisher:
Release Date : 2015
Hierarchical Metal Organic Framework Hybrids written by and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 2015 with categories.
Metal-organic frameworks (MOFs) represent a new family of microporous materials; however, microporous-mesoporous hierarchical MOF materials have been less investigated because of the lack of simple, reliable methods to introduce mesopores to the crystalline microporous particles. State-of-the-art MOF hierarchical materials have been prepared by ligand extension methods or by using a template, resulting in intrinsic mesopores of longer ligands or replicated pores from template agents, respectively. However, mesoporous MOF materials obtained through ligand extension often collapse in the absence of guest molecules, which dramatically reduces the size of the pore aperture. Although the template-directed strategy allows for the preparation of hierarchical materials with larger mesopores, the latter requires a template removal step, which may result in the collapse of the implemented mesopores. Recently, a general template-free synthesis of hierarchical microporous crystalline frameworks, such as MOFs and Prussian blue analogues (PBAs), has been reported. Our new method is based on the kinetically controlled precipitation (perturbation), with simultaneous condensation and redissolution of polymorphic nanocrystallites in the mother liquor. This method further eliminates the use of extended organic ligands and the micropores do not collapse upon removal of trapped guest solvent molecules, thus yielding hierarchical MOF materials with intriguing porosity in the gram scale. The hierarchical MOF materials prepared in this way exhibited exceptional properties when tested for the adsorption of large organic dyes over their corresponding microporous frameworks, due to the enhanced pore accessibility and electrolyte diffusion within the mesopores. As for PBAs, the pore size distribution of these materials can be tailored by changing the metals substituting Fe cations in the PB lattice. For these, the textural mesopores increased from approximately 10 nm for Cu analogue (mesoCuHCF), to 16 nm in Co substituted compound (mesoCoHCF), and to as large as 30 nm for the Ni derivative (mesoNiHCF). And while bulk PB and analogues have a higher capacitance than hierarchical analogues for Na-batteries, the increased accessibility to the microporous channels of PBAs allow for faster intercalated ion exchange and diffusion than in bulk PBA crystals. Therefore, hierarchical PBAs are promising candidates for electrodes in future electrochemical energy storage devices with faster charge-discharge rates than batteries, namely pseudocapacitors. Finally, this new synthetic method opens the possibility to prepare hierarchical materials having bimodal distribution of mesopores, and to tailor the structural properties of MOFs for different applications, including contrasting agents for MRI, and drug delivery.
Sensing And Biosensing With Optically Active Nanomaterials
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Author : Suban K. Sahoo
language : en
Publisher: Elsevier
Release Date : 2021-10-21
Sensing And Biosensing With Optically Active Nanomaterials written by Suban K. Sahoo and has been published by Elsevier this book supported file pdf, txt, epub, kindle and other format this book has been release on 2021-10-21 with Technology & Engineering categories.
Sensing and Biosensing with Optically Active Nanomaterials summarizes the potential sensing applications of optically (chromogenic and fluorogenic) active, nano-sized, organic, and inorganic materials for the selective detection of ionic analytes (such as metal ions and anions) in various environmental and biological samples. Sections cover design, synthesis, sensing mechanisms and applications for detecting ionic analytes. Each chapter deals with the sensing applications of one kind of nanomaterial. This book is an important reference source for materials scientists and engineers seeking to increase their understanding on how nanomaterials are being used for sensing applications. - Provides information on the various types of optically active inorganic and organic nanomaterials, including quantum dots, SPR active noble metal nanoparticles, metal nanoclusters, organic nanoparticles and carbon dots - Summarizes the synthesis, design and development of sensors, along with their mechanisms - Explains major sensing applications and manufacturing challenges