XRD-DSC: a screening tool for identifying effective MOFs for selective gas sorption from humid gas streams

2019 ◽  
Vol 34 (1) ◽  
pp. 3-12
Author(s):  
John B Parise ◽  
Xianyin Chen ◽  
Anna M. Plonka ◽  
William R. Woerner ◽  
Debasis Banerjee ◽  
...  
Keyword(s):  
Structural Changes ◽  
Variable Pressure ◽  
Gas Sorption ◽  
Scanning Calorimetry ◽  
Zeolitic Imidazolate Framework ◽  
Humid Atmosphere ◽  
Humidity Generator ◽  
Gas Streams ◽  
Vacuum Atmosphere ◽  
Metal Organic

A commercially available combined X-ray diffraction – differential scanning calorimetry (XRD-DSC) stage was adapted for studies of gas loading in microporous materials, including metal organic frameworks (MOFs). Insertion of a custom-built humid atmosphere swing chamber (HASC) between a humidity generator and the XRD-DSC stage facilitates both humid atmosphere and vacuum swing gas loading. The HASC is necessary to buffer between the humidity generator and the XRD-DSC stage, allowing the gas mixture to homogenize prior to sample exposure, so that both humid atmosphere and vacuum swings could be performed. The changes in XRD can be used to follow structural changes, including collapse, which is indicative of a lack of microporosity upon activation, and the flexibity of frameworks upon gas sorption–desorption cycles. Measurements of the area under the DSC curve allows for calculation of the isosteric heat of adsorption (Qst; kJ molGAS−1). Vacuum-atmosphere swing experiments performed at different pressure steps allow for the reconstruction of the enthalpy of gas adsorption before and after a phase transition. These modes of operation are illustrated in three case studies from a program of exploratory MOF synthesis used to discover novel materials for selective gas sorption from humid gas streams: (1) gas binding in Stony Brook metal organic framework-1, (2) zeolitic imidazolate framework-7 response to variable pressure vacuum-atmosphere swing, and (3) high throughput evaluation of the selectivity of novel MOFs synthesized from customized linkers.

Tuning the Electric Field Response of MOFs by Rotatable Dipolar Linkers

2019 ◽  
Author(s):  
Johannes P. Dürholt ◽  
Babak Farhadi Jahromi ◽  
Rochus Schmid
Keyword(s):  
Electric Field ◽  
Electric Fields ◽  
Structural Changes ◽  
Dielectric Behavior ◽  
Two Dimensions ◽  
Dielectric Constants ◽  
Electric Response ◽  
Dipole Strength ◽  
Metal Organic ◽  
Dynamics Simulations

Recently the possibility of using electric fields as a further stimulus to trigger structural changes in metal-organic frameworks (MOFs) has been investigated. In general, rotatable groups or other types of mechanical motion can be driven by electric fields. In this study we demonstrate how the electric response of MOFs can be tuned by adding rotatable dipolar linkers, generating a material that exhibits paralectric behavior in two dimensions and dielectric behavior in one dimension. The suitability of four different methods to compute the relative permittivity κ by means of molecular dynamics simulations was validated. The dependency of the permittivity on temperature T and dipole strength μ was determined. It was found that the herein investigated systems exhibit a high degree of tunability and substantially larger dielectric constants as expected for MOFs in general. The temperature dependency of κ obeys the Curie-Weiss law. In addition, the influence of dipolar linkers on the electric field induced breathing behavior was investigated. With increasing dipole moment, lower field strength are required to trigger the contraction. These investigations set the stage for an application of such systems as dielectric sensors, order-disorder ferroelectrics or any scenario where movable dipolar fragments respond to external electric fields.

Effect of new metal–organic framework (zeolitic imidazolate framework [ZIF-12]) in mixed matrix membranes on structure, morphology, and gas separation properties

2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Mehtap Safak Boroglu ◽  
Ismail Boz ◽  
Busra Kaya
Keyword(s):  
Gas Separation ◽  
Gas Permeability ◽  
Metal Organic Framework ◽  
Thermomechanical Analysis ◽  
Variable Pressure ◽  
Mixed Matrix Membranes ◽  
Mixed Matrix ◽  
Sem Images ◽  
Zeolitic Imidazolate Framework ◽  
Matrix Membranes

Abstract In our study, the synthesis of zeolitic imidazolate framework (ZIF-12) crystals and the preparation of mixed matrix membranes (MMMs) with various ZIF-12 loadings were targeted. The characterization of ZIF-12 and MMMs were carried out by Fourier transform infrared spectroscopy analysis, thermogravimetric analysis, scanning electron microscopy (SEM), and thermomechanical analysis. The performance of MMMs was measured by the ability of binary gas separation. Commercial polyetherimide (PEI-Ultem® 1000) polymer was used as the polymer matrix. The solution casting method was utilized to obtain dense MMMs. In the SEM images of ZIF-12 particles, the particles with a rhombic dodecahedron structure were identified. From SEM images, it was observed that the distribution of ZIF-12 particles in the MMMs was homogeneous and no agglomeration was present. Gas permeability experiments of MMMs were measured for H2, CO2, and CH4 gases at steady state, at 4 bar and 35 °C by constant volume-variable pressure method. PEI/ZIF-12-30 wt% MMM exhibited high permeability and ideal selectivity values for H2/CH4 and CO2/CH4 were P H 2 / CH 4 = 331.41 ${P}_{{\text{H}}_{2}/{\text{CH}}_{4}}=331.41$ and P CO 2 / CH 4 = 53.75 ${P}_{{\text{CO}}_{2}/{\text{CH}}_{4}}=53.75$ gas pair.

scholarly journals Dynamic Single-Fiber Pull-Out of Polypropylene Fibers Produced with Different Mechanical and Surface Properties for Concrete Reinforcement

Materials ◽  
2021 ◽  
Vol 14 (4) ◽  
pp. 722
Author(s):  
Enrico Wölfel ◽  
Harald Brünig ◽  
Iurie Curosu ◽  
Viktor Mechtcherine ◽  
Christina Scheffler
Keyword(s):  
Tensile Strength ◽  
Dynamic Loading ◽  
Melt Spinning ◽  
Structural Changes ◽  
High Surface ◽  
Single Fiber ◽  
Scanning Calorimetry ◽  
Matrix Interaction ◽  
Pull Out ◽  
Fiber Matrix

In strain-hardening cement-based composites (SHCC), polypropylene (PP) fibers are often used to provide ductility through micro crack-bridging, in particular when subjected to high loading rates. For the purposeful material design of SHCC, fundamental research is required to understand the failure mechanisms depending on the mechanical properties of the fibers and the fiber–matrix interaction. Hence, PP fibers with diameters between 10 and 30 µm, differing tensile strength levels and Young’s moduli, but also circular and trilobal cross-sections were produced using melt-spinning equipment. The structural changes induced by the drawing parameters during the spinning process and surface modification by sizing were assessed in single-fiber tensile experiments and differential scanning calorimetry (DSC) of the fiber material. Scanning electron microscopy (SEM), atomic force microscopy (AFM) and contact angle measurements were applied to determine the topographical and wetting properties of the fiber surface. The fiber–matrix interaction under quasi-static and dynamic loading was studied in single-fiber pull-out experiments (SFPO). The main findings of microscale characterization showed that increased fiber tensile strength in combination with enhanced mechanical interlocking caused by high surface roughness led to improved energy absorption under dynamic loading. Further enhancement could be observed in the change from a circular to a trilobal fiber cross-section.

Microporous Heptazine Functionalized (3,24)-Connected rht-Metal–Organic Framework: Synthesis, Structure, and Gas Sorption Analysis

2014 ◽  
Vol 14 (2) ◽  
pp. 414-418 ◽  
Author(s):  
Ryan Luebke ◽  
Łukasz J. Weseliński ◽  
Youssef Belmabkhout ◽  
Zhijie Chen ◽  
Łukasz Wojtas ◽  
...  
Keyword(s):  
Metal Organic Framework ◽  
Gas Sorption ◽  
Metal Organic ◽  
Organic Framework

scholarly journals Templated interfacial synthesis of metal-organic framework (MOF) nano- and micro-structures with precisely controlled shapes and sizes

2021 ◽  
Vol 4 (1) ◽  
Author(s):  
Lingyao Meng ◽  
Binyu Yu ◽  
Yang Qin
Keyword(s):  
Crystal Growth ◽  
Metal Organic Framework ◽  
Reaction Conditions ◽  
Zeolitic Imidazolate Framework ◽  
Crystallographic Preferred Orientation ◽  
Metal Organic ◽  
Interfacial Synthesis ◽  
Oil Water ◽  
Synthesis Methodology ◽  
Micro Structures

AbstractMetal-organic frameworks (MOF) are an emerging class of microporous materials with promising applications. MOF nanocrystals, and their assembled super-structures, can display unique properties and reactivities when compared with their bulk analogues. MOF nanostructures of 0-D, 2-D, and 3-D dimensions can be routinely obtained by controlling reaction conditions and ligand additives, while formation of 1-D MOF nanocrystals (nanowires and nanorods) and super-structures has been relatively rare. We report here a facile templated interfacial synthesis methodology for the preparation of a series of 1-D MOF nano- and micro-structures with precisely controlled shapes and sizes. Specifically, by applying track-etched polycarbonate (PCTE) membranes as the templates and at the oil/water interface, we rapidly and reproducibly synthesize zeolitic imidazolate framework-8 (ZIF-8) and ZIF-67 nano- and micro structures of sizes ranging from 10 nm to 20 μm. We also identify a size confinement effect on MOF crystal growth, which leads to single crystals under the most restricted conditions and inter-grown polycrystals at larger template pore sizes, as well as surface directing effects that influence the crystallographic preferred orientation. Our findings provide a potentially generalizable method for controlling the size, morphology, and crystal orientations of MOF nanomaterials, as well as offering fundamental understanding into MOF crystal growth mechanisms.

scholarly journals Comparative Study of Structural Changes of Polylactide and Poly(ethylene terephthalate) in the Presence of Trichoderma viride

2021 ◽  
Vol 22 (7) ◽  
pp. 3491
Author(s):  
Grażyna B. Dąbrowska ◽  
Zuzanna Garstecka ◽  
Ewa Olewnik-Kruszkowska ◽  
Grażyna Szczepańska ◽  
Maciej Ostrowski ◽  
...  
Keyword(s):  
Structural Changes ◽  
Ethylene Terephthalate ◽  
Molecular Mechanisms ◽  
Blot Hybridization ◽  
Trichoderma Viride ◽  
Cost Effective ◽  
Plastic Pollution ◽  
Scanning Calorimetry ◽  
Poly Ethylene Terephthalate ◽  
Poly Ethylene

Plastic pollution is one of the crucial global challenges nowadays, and biodegradation is a promising approach to manage plastic waste in an environment-friendly and cost-effective way. In this study we identified the strain of fungus Trichoderma viride GZ1, which was characterized by particularly high pectinolytic activity. Using differential scanning calorimetry, Fourier-transform infrared spectroscopy techniques, and viscosity measurements we showed that three-month incubation of polylactide and polyethylene terephthalate in the presence of the fungus lead to significant changes of the surface of polylactide. Further, to gain insight into molecular mechanisms underneath the biodegradation process, western blot hybridization was used to show that in the presence of poly(ethylene terephthalate) (PET) in laboratory conditions the fungus produced hydrophobin proteins. The mycelium adhered to the plastic surface, which was confirmed by scanning electron microscopy, possibly due to the presence of hydrophobins. Further, using atomic force microscopy we demonstrated for the first time the formation of hydrophobin film on the surface of aliphatic polylactide (PLA) and PET by T. viride GZ1. This is the first stage of research that will be continued under environmental conditions, potentially leading to a practical application.

scholarly journals Metastable Intermediates as Stepping Stones on the Maturation Pathways of Viral Capsids

mBio ◽  
2014 ◽  
Vol 5 (6) ◽  
Author(s):  
Giovanni Cardone ◽  
Robert L. Duda ◽  
Naiqian Cheng ◽  
Lili You ◽  
James F. Conway ◽  
...  
Keyword(s):  
Conformational Changes ◽  
Large Scale ◽  
Structural Changes ◽  
Energy Landscape ◽  
Potential Hazard ◽  
Stepping Stones ◽  
Scanning Calorimetry ◽  
Conformational Effects ◽  
Capsid Maturation ◽  
Capsid Integrity

ABSTRACT As they mature, many capsids undergo massive conformational changes that transform their stability, reactivity, and capacity for DNA. In some cases, maturation proceeds via one or more intermediate states. These structures represent local minima in a rich energy landscape that combines contributions from subunit folding, association of subunits into capsomers, and intercapsomer interactions. We have used scanning calorimetry and cryo-electron microscopy to explore the range of capsid conformations accessible to bacteriophage HK97. To separate conformational effects from those associated with covalent cross-linking (a stabilization mechanism of HK97), a cross-link-incompetent mutant was used. The mature capsid Head I undergoes an endothermic phase transition at 60°C in which it shrinks by 7%, primarily through changes in its hexamer conformation. The transition is reversible, with a half-life of ~3 min; however, >50% of reverted capsids are severely distorted or ruptured. This observation implies that such damage is a potential hazard of large-scale structural changes such as those involved in maturation. Assuming that the risk is lower for smaller changes, this suggests a rationalization for the existence of metastable intermediates: that they serve as stepping stones that preserve capsid integrity as it switches between the radically different conformations of its precursor and mature states. IMPORTANCE Large-scale conformational changes are widespread in virus maturation and infection processes. These changes are accompanied by the release of conformational free energy as the virion (or fusogenic glycoprotein) switches from a precursor state to its mature state. Each state corresponds to a local minimum in an energy landscape. The conformational changes in capsid maturation are so radical that the question arises of how maturing capsids avoid being torn apart. Offering proof of principle, severe damage is inflicted when a bacteriophage HK97 capsid reverts from the (nonphysiological) state that it enters when heated past 60°C. We suggest that capsid proteins have been selected in part by the criterion of being able to avoid sustaining collateral damage as they mature. One way of achieving this—as with the HK97 capsid—involves breaking the overall transition down into several smaller steps in which the risk of damage is reduced.

Systematic and Dramatic Tuning on Gas Sorption Performance in Heterometallic Metal–Organic Frameworks

2016 ◽  
Vol 138 (8) ◽  
pp. 2524-2527 ◽  
Author(s):  
Quan-Guo Zhai ◽  
Xianhui Bu ◽  
Chengyu Mao ◽  
Xiang Zhao ◽  
Pingyun Feng
Keyword(s):  
Metal Organic Frameworks ◽  
Gas Sorption ◽  
Metal Organic

Metal–organic framework-derived CoSe2/(NiCo)Se2 box-in-box hollow nanocubes with enhanced electrochemical properties for sodium-ion storage and hydrogen evolution

2017 ◽  
Vol 5 (35) ◽  
pp. 18823-18830 ◽  
Author(s):  
Seung-Keun Park ◽  
Jin Koo Kim ◽  
Yun Chan Kang
Keyword(s):  
Electrochemical Properties ◽  
Hydrogen Evolution ◽  
Metal Organic Framework ◽  
Sodium Ion ◽  
Zeolitic Imidazolate Framework ◽  
Box Structures ◽  
Ion Storage ◽  
Metal Organic ◽  
Sodium Ion Storage ◽  
Organic Framework

Multishell structured metal selenide nanocubes, namely, Co/(NiCo)Se2 box-in-box structures with different shell compositions, were successfully synthesized by applying zeolitic imidazolate framework-67 (ZIF-67) as a template.

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