Gas Adsorption Selectivity in Topologically Disordered Metal–Organic Frameworks

<div>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 C3H6 and C3H8 in Fe‑BTC, with over a twofold increase in the amount of C3H6 being adsorbed than C3H8. 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.</div>

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Two tetranuclear Cd-based metal–organic frameworks for sensitive sensing of TNP/Fe3+ in aqueous media and gas adsorption

CrystEngComm ◽

10.1039/d0ce01193b ◽

2020 ◽

Vol 22 (41) ◽

pp. 6927-6934

Author(s):

Ruihong Guo ◽

Lingling Gao ◽

Jinxia Liang ◽

Zhikai Zhang ◽

Jie Zhang ◽

...

Keyword(s):

Gas Adsorption ◽

Metal Organic Frameworks ◽

Aqueous Media ◽

Soil Samples ◽

Mixed Ligand ◽

Adsorption Selectivity ◽

Metal Organic

Two Cd-MOFs were solvothermally synthesized by mixed-ligand strategy. 1 has the largest adsorption selectivity for CO2. Furthermore, 1 and 2 present sensitive sensing for TNP/Fe3+ in water or soil samples.

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Gas adsorption in the topologically disordered Fe-BTC framework

Journal of Materials Chemistry A ◽

10.1039/d1ta08449f ◽

2021 ◽

Author(s):

Adam Sapnik ◽

Christopher W. Ashling ◽

Lauren Macreadie ◽

Seok J. Lee ◽

Timothy Johnson ◽

...

Keyword(s):

Gas Adsorption ◽

Metal Organic Frameworks ◽

Functional Materials ◽

Gas Storage ◽

Metal Organic

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...

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

Chemical Science ◽

10.1039/c6sc05012c ◽

2017 ◽

Vol 8 (3) ◽

pp. 2373-2380 ◽

Cited By ~ 72

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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Gas adsorption applications of porous metal–organic frameworks

Pure and Applied Chemistry ◽

10.1351/pac-con-09-07-09 ◽

2009 ◽

Vol 81 (12) ◽

pp. 2235-2251 ◽

Cited By ~ 75

Author(s):

Shengqian Ma

Keyword(s):

Hydrogen Storage ◽

Recent Progress ◽

Gas Adsorption ◽

Metal Organic Frameworks ◽

Porous Metal ◽

Functional Materials ◽

Research Field ◽

Methane Storage ◽

Metal Organic ◽

New Type

Porous metal–organic frameworks (MOFs) represent a new type of functional materials and have recently become a hot research field due to their great potential in various applications. In this review, recent progress of gas adsorption applications of porous MOFs, mainly including hydrogen storage, methane storage, and selective gas adsorption will be briefly summarized.

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High performance gas adsorption and separation of natural gas in two microporous metal–organic frameworks with ternary building units

Chemical Communications ◽

10.1039/c4cc03729d ◽

2014 ◽

Vol 50 (63) ◽

pp. 8648-8650 ◽

Cited By ~ 76

Author(s):

Dongmei Wang ◽

Tingting Zhao ◽

Yu Cao ◽

Shuo Yao ◽

Guanghua Li ◽

...

Keyword(s):

Natural Gas ◽

High Performance ◽

Gas Adsorption ◽

Metal Organic Frameworks ◽

High Adsorption ◽

Adsorption Selectivity ◽

Metal Organic

Two MMOFs were assembled by the ternary SBU strategy and exhibited high adsorption selectivity for CO2, C2H6 and C3H8 over CH4.

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Message Passing Neural Networks for Partial Charge Assignment to Metal-Organic Frameworks

10.26434/chemrxiv.12298487 ◽

2020 ◽

Author(s):

Ali Raza ◽

Arni Sturluson ◽

Cory Simon ◽

Xiaoli Fern

Keyword(s):

Electronic Structure ◽

Message Passing ◽

Gas Adsorption ◽

Metal Organic Frameworks ◽

Computational Cost ◽

Electronic Structure Calculations ◽

High Fidelity ◽

Partial Charges ◽

Metal Organic ◽

Structure Calculations

Virtual screenings can accelerate and reduce the cost of discovering metal-organic frameworks (MOFs) for their applications in gas storage, separation, and sensing. In molecular simulations of gas adsorption/diffusion in MOFs, the adsorbate-MOF electrostatic interaction is typically modeled by placing partial point charges on the atoms of the MOF. For the virtual screening of large libraries of MOFs, it is critical to develop computationally inexpensive methods to assign atomic partial charges to MOFs that accurately reproduce the electrostatic potential in their pores. Herein, we design and train a message passing neural network (MPNN) to predict the atomic partial charges on MOFs under a charge neutral constraint. A set of ca. 2,250 MOFs labeled with high-fidelity partial charges, derived from periodic electronic structure calculations, serves as training examples. In an end-to-end manner, from charge-labeled crystal graphs representing MOFs, our MPNN machine-learns features of the local bonding environments of the atoms and learns to predict partial atomic charges from these features. Our trained MPNN assigns high-fidelity partial point charges to MOFs with orders of magnitude lower computational cost than electronic structure calculations. To enhance the accuracy of virtual screenings of large libraries of MOFs for their adsorption-based applications, we make our trained MPNN model and MPNN-charge-assigned computation-ready, experimental MOF structures publicly available.

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

10.26434/chemrxiv.6876749.v1 ◽

2018 ◽

Cited By ~ 1

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 CO2 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 CO2 over N2: 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 CO2 adsorption is in the range of 38-40 kJ mol-1, indicating a strong physisorptive character.

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