Tuning the functional sites in metal–organic frameworks to modulate CO2 heats of adsorption

CrystEngComm ◽  
2015 ◽  
Vol 17 (4) ◽  
pp. 706-718 ◽  
Author(s):  
Anita Das ◽  
Deanna M. D'Alessandro
Keyword(s):  
Metal Organic Frameworks ◽  
Isosteric Heat ◽  
Performance Criterion ◽  
Heat Of Adsorption ◽  
Adsorption Properties ◽  
Isosteric Heat Of Adsorption ◽  
Functional Sites ◽  
Heats Of Adsorption ◽  
Metal Organic ◽  
Insight Into

Tuning the functional sites in metal–organic frameworks provides one strategy to vary the CO2 adsorption properties – this highlight article provides insight into modulation of another key performance criterion, namely the isosteric heat of adsorption, and its influence on CO2 capture.

Pore with Gate: Enhancement of the Isosteric Heat of Adsorption of Dihydrogen via Postsynthetic Cation Exchange in Metal−Organic Frameworks

2011 ◽  
Vol 50 (19) ◽  
pp. 9374-9384 ◽  
Author(s):  
Sihai Yang ◽  
Gregory S. B. Martin ◽  
Jeremy J. Titman ◽  
Alexander J. Blake ◽  
David R. Allan ◽  
...  
Keyword(s):  
Cation Exchange ◽  
Metal Organic Frameworks ◽  
Isosteric Heat ◽  
Heat Of Adsorption ◽  
Isosteric Heat Of Adsorption ◽  
Metal Organic

Microporous rod metal–organic frameworks with diverse Zn/Cd–triazolate ribbons as secondary building units for CO2 uptake and selective adsorption of hydrocarbons

2017 ◽  
Vol 46 (3) ◽  
pp. 836-844 ◽  
Author(s):  
Jian-Wei Zhang ◽  
Man-Cheng Hu ◽  
Shu-Ni Li ◽  
Yu-Cheng Jiang ◽  
Quan-Guo Zhai
Keyword(s):  
Selective Adsorption ◽  
Metal Organic Frameworks ◽  
Isosteric Heat ◽  
Heat Of Adsorption ◽  
Co2 Uptake ◽  
Isosteric Heat Of Adsorption ◽  
Secondary Building Units ◽  
Metal Organic

Three rod MOFs exhibiting remarkable CO2 uptake and high CO2 and C2-hydrocarbons over CH4 selectivity, as well as high isosteric heat of adsorption for C2H2.

scholarly journals Gas adsorption and structural diversity in a family of Cu(II) pyridyl-isophthalate metal–organic framework materials

2017 ◽  
Vol 375 (2084) ◽  
pp. 20160334 ◽  
Author(s):  
Jamie A. Gould ◽  
Harprit Singh Athwal ◽  
Alexander J. Blake ◽  
William Lewis ◽  
Peter Hubberstey ◽  
...  
Keyword(s):  
Dicarboxylic Acid ◽  
Gas Adsorption ◽  
Metal Organic Framework ◽  
Metal Organic Frameworks ◽  
Structural Diversity ◽  
Isosteric Heat ◽  
Adsorption Properties ◽  
Framework Materials ◽  
Materials By Design ◽  
Metal Organic

A family of Cu(II)-based metal–organic frameworks (MOFs) has been synthesized using three pyridyl-isophthalate ligands, H 2 L 1 (4′-(pyridin-4-yl)biphenyl-3,5-dicarboxylic acid), H 2 L 2 (4′′-(pyridin-4-yl)-1,1′:4′,1′′-terphenyl-3,5-dicarboxylic acid) and H 2 L 3 (5-[4-(pyridin-4-yl)naphthalen-1-yl]benzene-1,3-dicarboxylic acid). Although in each case the pyridyl-isophthalate ligands adopt the same pseudo-octahedral [Cu 2 (O 2 CR) 4 N 2 ] paddlewheel coordination modes, the resulting frameworks are structurally diverse, particularly in the case of the complex of Cu(II) with H 2 L 3 , which leads to three distinct supramolecular isomers, each derived from Kagomé and square nets. In contrast to [Cu(L 2 )] and the isomers of [Cu(L 3 )], [Cu(L 1 )] exhibits permanent porosity. Thus, the gas adsorption properties of [Cu(L 1 )] were investigated with N 2 , CO 2 and H 2 , and the material exhibits an isosteric heat of adsorption competitive with leading MOF sorbents for CO 2 . [Cu(L 1 )] displays high H 2 adsorption, with the density in the pores approaching that of liquid H 2 . This article is part of the themed issue ‘Coordination polymers and metal–organic frameworks: materials by design’.

scholarly journals An experimental and computational study of CO2adsorption in the sodalite-type M-BTT (M = Cr, Mn, Fe, Cu) metal–organic frameworks featuring open metal sites

2018 ◽  
Vol 9 (20) ◽  
pp. 4579-4588 ◽  
Author(s):  
Mehrdad Asgari ◽  
Sudi Jawahery ◽  
Eric D. Bloch ◽  
Matthew R. Hudson ◽  
Roxana Flacau ◽  
...  
Keyword(s):  
Molecular Level ◽  
Computational Study ◽  
Metal Organic Frameworks ◽  
Adsorption Properties ◽  
Open Metal Sites ◽  
Metal Organic ◽  
Insight Into

The work provides molecular level insight into the CO2adsorption properties of an isostructural series of MOFs, known as M-BTT.

Quantum Mechanical Interpretation of the Ultra-Low Energy Methyl-Rotation Dynamics in Porous Metal-Organic Frameworks Probed by Low-Frequency Vibrational Spectroscopy and ab initio Simulations

2018 ◽  
Author(s):  
Qi Li ◽  
Adam J. Zaczek ◽  
Timothy M. Korter ◽  
J. Axel Zeitler ◽  
Michael T. Ruggiero
Keyword(s):  
Ab Initio ◽  
Metal Organic Frameworks ◽  
Low Frequency ◽  
Rotor Dynamics ◽  
Quantum Mechanical ◽  
Valuable Insight ◽  
Void Space ◽  
Ab Initio Simulations ◽  
Metal Organic ◽  
Insight Into

<div>Understanding the nature of the interatomic interactions present within the pores of metal-organic frameworks</div><div>is critical in order to design and utilize advanced materials</div><div>with desirable applications. In ZIF-8 and its cobalt analogue</div><div>ZIF-67, the imidazolate methyl-groups, which point directly</div><div>into the void space, have been shown to freely rotate - even</div><div>down to cryogenic temperatures. Using a combination of ex-</div><div>perimental terahertz time-domain spectroscopy, low-frequency</div><div>Raman spectroscopy, and state-of-the-art ab initio simulations,</div><div>the methyl-rotor dynamics in ZIF-8 and ZIF-67 are fully charac-</div><div>terized within the context of a quantum-mechanical hindered-</div><div>rotor model. The results lend insight into the fundamental</div><div>origins of the experimentally observed methyl-rotor dynamics,</div><div>and provide valuable insight into the nature of the weak inter-</div><div>actions present within this important class of materials.</div>

Green Synthesis and Enhanced CO2 Capture Performance of Perfluorinated Cerium-Based Metal-Organic Frameworks with UiO-66 and MIL-140 Topology

2018 ◽  
Author(s):  
Roberto D’Amato ◽  
Anna Donnadio ◽  
Mariolino Carta ◽  
Claudio Sangregorio ◽  
Riccardo Vivani ◽  
...  
Keyword(s):  
Photoelectron Spectroscopy ◽  
Metal Organic Frameworks ◽  
Isosteric Heat ◽  
Experimental Conditions ◽  
Cerium Ammonium Nitrate ◽  
Ideal Adsorbed Solution Theory ◽  
Metal Organic ◽  
Adsorbed Solution ◽  
Better Than ◽  
The Ideal

Reaction of cerium ammonium nitrate and tetrafluoroterephthalic acid in water afforded two new metal-organic frameworks with UiO-66 [F4_UiO-66(Ce)] and MIL-140 [F4_MIL-140A(Ce)] topologies. The two compounds can be obtained in the same experimental conditions, just by varying the amount of acetic acid used as crystallization modulator in the synthesis. Both F4_UiO-66(Ce) and F4_MIL-140A(Ce) feature pores with size < 8 Å, which classifies them as ultramicroporous. Combination of X-ray photoelectron spectroscopy and magnetic susceptibility measurements revealed that both compounds contain a small amount of Ce(III), which is preferentially accumulated near the surface of the crystallites. The CO<sub>2</sub> sorption properties of F4_UiO-66(Ce) and F4_MIL-140A(Ce) were investigated, finding that they perform better than their Zr-based analogues. F4_MIL-140A(Ce) displays an unusual S-shaped isotherm with steep uptake increase at pressure < 0.2 bar at 298 K. This makes F4_MIL-140A(Ce) exceptionally selective for CO<sub>2</sub> over N<sub>2</sub>: the calculated selectivity, according to the ideal adsorbed solution theory for a 0.15:0.85 mixture at 1 bar and 293 K, is higher than 1900, amongst the highest ever reported for metal-organic frameworks. The calculated isosteric heat of CO<sub>2 </sub>adsorption is in the range of 38-40 kJ mol<sup>-1</sup>, indicating a strong physisorptive character.

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