The Impact of Post-Synthetic Linker Functionalization of MOFs on Methane Storage: The Role of Defects

Szilágyi, Petra Ágota; Serra‐Crespo, Pablo; Gascón, Jorge; Geerlings, Hans; Dam, B.

doi:10.3389/fenrg.2016.00009

Cited by 23 publications

(15 citation statements)

References 49 publications

(67 reference statements)

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“…In 2016 Szilágyi et al reported on enhanced methane adsorption properties of postsynthetically treated MIL‐101(Cr) by 33% compared to the pristine MOF . In their work, they introduced NH 2 ‐BDC 2− (BDC 2− = 1,4‐dicarboxylate) via SALE and were able to exchange up to 20% of the original BDC 2− linkers.…”

Section: Function and Properties Of Mofsmentioning

confidence: 99%

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Defective Metal‐Organic Frameworks

et al. 2018

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The targeted incorporation of defects into crystalline matter allows for the manipulation of many properties and has led to relevant discoveries for optimized and even novel technological applications of materials. It is therefore exciting to see that defects are now recognized to be similarly useful in tailoring properties of metal-organic frameworks (MOFs). For instance, heterogeneous catalysis crucially depends on the number of active catalytic sites as well as on diffusion limitations. By the incorporation of missing linker and missing node defects into MOFs, both parameters can be accessed, improving the catalytic properties. Furthermore, the creation of defects allows for adding properties such as electronic conductivity, which are inherently absent in the parent MOFs. Herein, progress of the rapidly evolving field of the past two years is overviewed, putting a focus on properties that are altered by the incorporation and even tailoring of defects in MOFs. A brief account is also given on the emerging quantitative understanding of defects and heterogeneity in MOFs based on scale-bridging computational modeling and simulations.

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Section: Function and Properties Of Mofsmentioning

confidence: 99%

“…The orange polyhedra represent the cationic units, whereas C and O atoms are depicted in black and blue, respectively. Reproduced under the terms of the CC‐BY License . Copyright 2016, P. Á. Szilágyi, P. Serra‐Crespo, J. Gascon, H. Geerlings, B. Dam, Frontiers.…”

Section: Function and Properties Of Mofsmentioning

confidence: 99%

Defective Metal‐Organic Frameworks

et al. 2018

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“…A segunda abordagem visa promover a funcionalização pós-sintética de MOFs com grupamentos sítio-específicos que auxiliem na adsorção do gás metano. 217,218 Uso do biogás como fonte de metano. Uma etapa crítica da utilização do biogás como combustível renovável é a sua purificação, que consiste basicamente na remoção de dióxido de carbono.…”

Section: Mofs Energia E Meio-ambienteunclassified

MOFs (METAL-ORGANIC FRAMEWORKS): UMA FASCINANTE CLASSE DE MATERIAIS INORGÂNICOS POROSOS

Frem¹,

Arroyos²,

Flor³

et al. 2018

Quim. Nova

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MOFs (METAL-ORGANIC FRAMEWORKS): A FASCINATING CLASS OF POROUS INORGANIC MATERIALS. Metal-Organic Frameworks (MOFs) are, according to IUPAC, coordination polymers with an open framework containing potential voids, which can be accessible after activation processes. These materials have aroused interest in the academic environment-and more recently in industry-because their properties such as high crystallinity, permanent microporosity, high surface areas, and the possibility of functionalization. This has enabled applications in different areas, such as gas adsorption, catalysis, drug delivery, photonics and others. Depending on the judicious choice of the metals and the organic linkers, MOFs with different topologies and functions can be created. Synthetic routes for the preparation of these materials will be discussed, highlighting those in consonance with the Green Inorganic Chemistry. Strategies for controlling the size and morphology of the crystals will also be presented, as well the most recent methodologies for the large-scale production. This review will also discuss the use of MOFs in the context of energy and environment, particularly referring to the adsorption and/or transformation of CO 2 , storage of H 2 and CH 4 as well potable water capture.

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“…This makes MOFs very attractive materials for applications: e.g. gas storage, [2][3][4] carbon dioxide capture, [5][6][7][8] sensor applications, [9] luminescence, [10][11][12] catalysis, [13] and many more. [14][15][16][17][18] Also from the fundamental point of view, MOFs show many interesting properties.…”

Section: Introductionmentioning

confidence: 99%

Linker Functionalization in MIL-47(V)-R Metal–Organic Frameworks: Understanding the Electronic Structure

Vanpoucke

2017

J. Phys. Chem. C

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For the series of structures under study we perform ab-initio density functional theory (DFT) calculations within the projector augmented wave (PAW) method as implemented in the Vienna ab-initio Package (VASP) program using the generalized gradient approximation (GGA) functional as constructed by Perdew, Burke and Ernzerhof (PBE). 1-5 The plane wave kinetic energy cutoff is set to 500 eV. Due to the large difference in lattice vector lengths for the structures a Monkhorst-Pack special k-point grid of 2 × 2 × 6 k-points is used to sample the Brillouin zone. 6,7 Dispersive interactions, which play an important role in the flexibility of the crystal structure of MOFs, are included through the DFT-D method as suggested by Grimme et al., including Becke-Johnson damping. 8-11. To obtain an accurate picture of the electronic structure, hybrid functional, HSE06+D, 12-14 calculations are performed on the PBE optimized geometries, as this was previously shown to give very accurate estimates of the experimental band gap in MOFs. 15 The atomistic model used in our DFT calculations consisted of a conventional unit cell containing four formula units (i.e. containing 72 to 88 atoms). Figure 1 shows a ball-and-stick representation of the large pore MIL-47(V) structure (a super cell is shown). Starting from the experimental lattice parameters and volumes the structures are optimized under the constraint of constant volume to allow for direct comparison to the experimental results. 7 Ionic positions and cell shape are optimized simultaneously using a conjugate gradient method, and convergence is set to the difference in energy between subsequent steps becoming smaller than 1.0 × 10 −7 eV. After full relaxation, the forces on the ions were found to be below 0.002 eV/Å. As each of the four vanadium atoms (two V atoms on each vanadyl chain in the conventional unit cell) contributes one unpaired electron to the system, and it is known that the configuration of these unpaired spins has a strong influence on the electronic structure and mechanical properties of flexible MOFs, 16 we considered two different spin configurations for each of the structures: the anti-ferromagnetic (AF) ground state configuration 17 and the ferromagnetic (FM) configuration. The presence of both configurations in experimental samples has been derived from X-Ray Diffraction data. 18 The different spin configurations are manually imposed upon initialization of the structure optimization by setting the initial magnetic moment for each atom in the cell (MAGMOM keyword). For each following calculation the atomic magnetic moments are checked, and it is verified that the imposed spin configuration is retained. If this is not the case, the magnetic moment is reinitialized and the structure optimization is continued from this point. The atomic charges of the systems are calculated using the iterative Hirshfeld-I approach 19 as implemented in our in house developed code HIVE. 20-22 Our implementation makes use of the grid stored (pseudo) electron density distributions w...

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The Impact of Post-Synthetic Linker Functionalization of MOFs on Methane Storage: The Role of Defects

Cited by 23 publications

References 49 publications

Defective Metal‐Organic Frameworks

Defective Metal‐Organic Frameworks

MOFs (METAL-ORGANIC FRAMEWORKS): UMA FASCINANTE CLASSE DE MATERIAIS INORGÂNICOS POROSOS

Linker Functionalization in MIL-47(V)-R Metal–Organic Frameworks: Understanding the Electronic Structure

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