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

2009 ◽  
pp. 77-113 ◽  
Author(s):  
Felicitas Schröder ◽  
Roland A. Fischer
Keyword(s):  
Metal Organic Frameworks ◽  
Guest Molecules ◽  
Metal Organic

scholarly journals Gas Adsorption Selectivity in Topologically Disordered Metal–Organic Frameworks

2021 ◽  
Author(s):  
Adam Sapnik ◽  
Christopher W. Ashling ◽  
Lauren K. Macreadie ◽  
Seok J. Lee ◽  
Tim Johnson ◽  
...  
Keyword(s):  
Gas Adsorption ◽  
Metal Organic Frameworks ◽  
Interaction Strength ◽  
Functional Materials ◽  
Adsorption Selectivity ◽  
Guest Molecules ◽  
Sorption Behaviour ◽  
Ideal Adsorbed Solution Theory ◽  
Industrial Gases ◽  
Metal Organic

<div><p>Disordered metal–organic frameworks are emerging as an attractive class of functional materials, however their applications in gas storage and separation have yet to be fully explored. Here, we investigate gas adsorption in the topologically disordered Fe-BTC framework and its crystalline counterpart, MIL‑100. Despite their similar chemistry and local structure, they exhibit very different sorption behaviour towards a range of industrial gases, noble gases and hydrocarbons. Virial analysis reveals that Fe-BTC has enhanced interaction strength with guest molecules compared to MIL‑100. Most notably, we observe striking discrimination between the adsorption of C<sub>3</sub>H<sub>6</sub> and C<sub>3</sub>H<sub>8</sub> in Fe‑BTC, with over a twofold increase in the amount of C<sub>3</sub>H<sub>6</sub> being adsorbed than C<sub>3</sub>H<sub>8</sub>. Thermodynamic selectivity towards a range of industrially relevant binary mixtures is probed using ideal adsorbed solution theory (IAST). Together, this suggests the disordered material may possess powerful separation capabilities that are rare even amongst crystalline frameworks.</p></div>

scholarly journals Power of Infrared and Raman Spectroscopies to Characterize Metal-Organic Frameworks and Investigate Their Interaction with Guest Molecules

2020 ◽  
Author(s):  
Konstantin I. Hadjiivanov ◽  
Dimitar A. Panayotov ◽  
Mihail Y. Mihaylov ◽  
Elena Z. Ivanova ◽  
Kristina K. Chakarova ◽  
...  
Keyword(s):  
Metal Organic Frameworks ◽  
Guest Molecules ◽  
Metal Organic

scholarly journals Simulation Meets Experiment: Unraveling the Properties of Water in Metal-Organic Frameworks Through Vibrational Spectroscopy

2021 ◽  
Author(s):  
Kelly M. Hunter ◽  
Jackson Wagner ◽  
Mark Kalaj ◽  
Wei Xiong ◽  
Paesani Lab
Keyword(s):  
Metal Organic Frameworks ◽  
Nanoporous Materials ◽  
Chemical Diversity ◽  
Guest Molecules ◽  
Host Interactions ◽  
Metal Organic ◽  
Computational Spectroscopy ◽  
And Function ◽  
Nuclear Quantum Effects ◽  
Fermi Resonances

<div> <div> <div> <p>In nanoporous materials, guest–host interactions affect the properties and function of both adsorbent and adsorbate molecules. Due to their structural and chemical diversity, metal-organic frameworks (MOFs), a common class of nanoporous materials, have been shown to be able to efficiently and, often, selectively adsorb various types of guest molecules. In this study, we characterize the structure and dynamics of water confined in ZIF-90. Through the integration of experimental and computational infrared (IR) spectroscopy, we probe the structure of heavy water (D<sub>2</sub>O) adsorbed in the pores, disentangling the fundamental framework–water and water–water interactions. The experimental IR spectrum of D<sub>2</sub>O in ZIF-90 displays a blue-shifted OD-stretch band compared to liquid D<sub>2</sub>O. The analysis of the IR spectra simulated at both classical and quantum levels indicates that the D<sub>2</sub>O molecules preferentially interact with the carbonyl groups of the framework and highlights the importance of including nuclear quantum effects and taking into account Fermi resonances for a correct interpretation of the OD-stretch band in terms of the underlying hydrogen-bonding motifs. Through a systematic comparison with the experimental spectra, we demonstrate that computational spectroscopy can be used to gain quantitative, molecular-level insights into framework–water interactions that determine the water adsorption capacity of MOFs as well as the spatial arrangements of the water molecules inside the MOF pores which, in turn, are key to the design of MOF-based materials for water harvesting.</p> </div> </div> </div>

scholarly journals Harnessing Electrostatic Interactions for Enhanced Conductivity in Metal-Organic Frameworks

Research ◽  
2021 ◽  
Vol 2021 ◽  
pp. 1-11
Author(s):  
An-An Zhang ◽  
Xiyue Cheng ◽  
Xu He ◽  
Wei Liu ◽  
Shuiquan Deng ◽  
...  
Keyword(s):  
Electrostatic Interaction ◽  
Electrostatic Interactions ◽  
Metal Organic Frameworks ◽  
Electron Conduction ◽  
Guest Molecules ◽  
Type Semiconductor ◽  
Metal Organic ◽  
Application Potential ◽  
Enhanced Conductivity

The poor electrical conductivity of metal-organic frameworks (MOFs) has been a stumbling block for its applications in many important fields. Therefore, exploring a simple and effective strategy to regulate the conductivity of MOFs is highly desired. Herein, anionic guest molecules are incorporated inside the pores of a cationic MOF (PFC-8), which increases its conductivity by five orders of magnitude while maintaining the original porosity. In contrast, the same operation in an isoreticular neutral framework (PFC-9) does not bring such a significant change. Theoretical studies reveal that the guest molecules, stabilized inside pores through electrostatic interaction, play the role of electron donors as do in semiconductors, bringing in an analogous n-type semiconductor mechanism for electron conduction. Therefore, we demonstrate that harnessing electrostatic interaction provides a new way to regulate the conductivity of MOFs without necessarily altering the original porous structure. This strategy would greatly broaden MOFs’ application potential in electronic and optoelectronic technologies.

scholarly journals Disappeared supramolecular isomer reappears with perylene guest

IUCrJ ◽  
2020 ◽  
Vol 7 (2) ◽  
pp. 324-330
Author(s):  
In-Hyeok Park ◽  
Atanu Dey ◽  
Kenta Sasaki ◽  
Masaaki Ohba ◽  
Shim Sung Lee ◽  
...  
Keyword(s):  
Coordination Polymers ◽  
Guest Molecule ◽  
Metal Organic Frameworks ◽  
Guest Molecules ◽  
Supramolecular Isomerism ◽  
The World ◽  
Different Types ◽  
Metal Organic ◽  
The Disappeared ◽  
Kinetic Form

Among different types of polymorphism, disappearing polymorphism deals with the metastable kinetic form which can not be reproduced after its first isolation. In the world of coordination polymers (CPs) and metal–organic frameworks (MOFs), despite the fact that many types of supramolecular isomerism exist, we are unaware of disappearing supramolecular isomerism akin to disappearing polymorphism. This work reports a MOF with dia topology that could not be reproduced, but subsequent synthesis yielded another supramolecular isomer, a double-pillared-layer MOF. When perylene was added in the same reaction, the disappeared dia MOF reappeared with perylene as a guest in the channels. Interestingly, the photoluminescence of the dia MOF with a perylene guest is dominated by the emission of the guest molecule. The influence of guest molecules on the stabilization of the supramolecular isomers of a MOF opens up a strategy to access MOFs with different structures.

scholarly journals London Dispersion Governs the Interaction Mechanism of Small Polar and Non-Polar Molecules in Metal-Organic Frameworks

2020 ◽  
Author(s):  
Patrick Melix ◽  
Thomas Heine
Keyword(s):  
Dipole Moments ◽  
Metal Organic Framework ◽  
Metal Organic Frameworks ◽  
Interaction Mechanism ◽  
Ligand Field ◽  
Dispersion Interactions ◽  
Guest Molecules ◽  
Metal Organic ◽  
London Dispersion ◽  
Chlorinated Methanes

<div>In this work we investigate the adsorption of chlorinated methanes (CH<sub>x</sub>Cl<sub>4-x</sub>, x=0-4) in a representative layer-pillar Metal-Organic Framework (MOF), the flexible MOF Ni<sub>2</sub>(ndc)<sub>2</sub>(dabco) (ndc = 2,6-naphthalene-dicarboxylate, dabco = 1,4-diazabicyclo-[2.2.2]-octane), also known as DUT-8(Ni). The guest molecules show a systematic increase of polarizability with increasing number of chlorine atoms, while the dipole moment exceeds 2 Debye for x = 2 and 3. Our ligand field molecular mechanics (LFMM) simulations show that, counter-intuitively, the host-guest interactions are mainly characterized by London dispersion, despite the molecular dipole moments reaching magnitudes as large as water. This highlights the importance of London dispersion interactions in the description of host-guest interactions.<br></div>

Metal-Organic Frameworks for Asymmetric Catalysis and Chiral Separations

MRS Bulletin ◽  
2007 ◽  
Vol 32 (7) ◽  
pp. 544-548 ◽  
Author(s):  
Wenbin Lin
Keyword(s):  
Asymmetric Catalysis ◽  
Active Sites ◽  
Heterogeneous Catalysts ◽  
Metal Organic Frameworks ◽  
Building Blocks ◽  
Chiral Separations ◽  
Bridging Ligands ◽  
Guest Molecules ◽  
Pure Compounds ◽  
Metal Organic

Metal-organic frameworks (MOFs) are an interesting class of molecule-based hybrid materials built from metal-connecting points and bridging ligands. MOFs have received much attention, owing to their potential impact on many technological areas, including gas storage, separation, and heterogeneous catalysis. The modular nature of MOFs endows them with facile tunability, and as a result, properly designed MOFs can yield ideal heterogeneous catalysts with uniform active sites through judicious choice of the building blocks. Homochiral MOFs, which can be prepared by numerous approaches (construction from achiral components by seeding with a chiral single crystal, templating with coordinating chiral co-ligands, and building from metal-connecting nodes and chiral bridging ligands), represent a unique class of materials for the economical production of optically pure compounds, whether through asymmetric catalysis or enantioselective inclusion of chiral guest molecules in their porous frameworks. As such, homochiral MOFs promise new opportunities for developing chirotechnology. This contribution provides a brief overview of recent progress in the synthesis of homochiral porous MOFs and their applications in asymmetric catalysis and chiral separations.

scholarly journals Effect of ring rotation upon gas adsorption in SIFSIX-3-M (M = Fe, Ni) pillared square grid networks

2017 ◽  
Vol 8 (3) ◽  
pp. 2373-2380 ◽  
Author(s):  
Sameh K. Elsaidi ◽  
Mona H. Mohamed ◽  
Cory M. Simon ◽  
Efrem Braun ◽  
Tony Pham ◽  
...  
Keyword(s):  
Gas Adsorption ◽  
Metal Organic Frameworks ◽  
Gas Separations ◽  
Guest Molecules ◽  
Grid Networks ◽  
Ring Rotation ◽  
Metal Organic ◽  
Flexible Metal ◽  
As Stress ◽  
External Stimuli

Dynamic and flexible metal–organic frameworks (MOFs) that respond to external stimuli, such as stress, light, heat, and the presence of guest molecules, hold promise for applications in chemical sensing, drug delivery, gas separations, and catalysis.

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