Accelerating Applications of Metal–Organic Frameworks for Gas Adsorption and Separation by Computational Screening of Materials

Porous metal-organic frameworks are a class of materials with great promise in gas separation and gas storage applications. Due to the large material space, computational screening techniques have long been an important part of the scientific toolbox. However, a broad validation of molecular simulations in these materials is hampered by the lack of a connection between databases of gas adsorption experiments and databases of the atomic crystal structure of corresponding materials. This work aims to connect the gas adsorption isotherms of metal-organic frameworks collected in the NIST/ARPA-E Database of Novel and Emerging Adsorbent Materials to a corresponding crystal structure in the Cambridge Structural Database. With tens of thousands of isotherms and crystal structures reported to date, an automatic approach is needed to establish this link, which we describe in this paper. As a first application and consistency check, we compare the pore volume deduced from low-temperature argon or nitrogen isotherms to the geometrical pore volume computed from the crystal structure. Overall, 545 argon or nitrogen isotherms could be matched to a corresponding crystal structure. We find that the pore volume computed via the two complementary methods shows acceptable agreement only in about 35% of these cases. We provide the subset of isotherms measured on these materials as a seed for a future, more complete reference data set for computational studies.

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Data-driven matching of experimental crystal structures and gas adsorption isotherms of metal-organic frameworks

10.26434/chemrxiv-2021-gs0wj ◽

2021 ◽

Author(s):

Daniele Ongari ◽

Leopold Talirz ◽

Kevin M. Jablonka ◽

Daniel W. Siderius ◽

Berend Smit

Keyword(s):

Crystal Structure ◽

Crystal Structures ◽

Adsorption Isotherms ◽

Pore Volume ◽

Gas Adsorption ◽

Metal Organic Frameworks ◽

Great Promise ◽

Data Set ◽

Computational Screening ◽

Metal Organic

Porous metal-organic frameworks are a class of materials with great promise in gas separation and gas storage applications. Due to the large material space, computational screening techniques have long been an important part of the scientific toolbox. However, a broad validation of molecular simulations in these materials is hampered by the lack of a connection between databases of gas adsorption experiments and databases of the atomic crystal structure of corresponding materials. This work aims to connect the gas adsorption isotherms of metal-organic frameworks collected in the NIST/ARPA-E Database of Novel and Emerging Adsorbent Materials to a corresponding crystal structure in the Cambridge Structural Database. With tens of thousands of isotherms and crystal structures reported to date, an automatic approach is needed to establish this link, which we describe in this paper. As a first application and consistency check, we compare the pore volume deduced from low-temperature argon or nitrogen isotherms to the geometrical pore volume computed from the crystal structure. Overall, 545 argon or nitrogen isotherms could be matched to a corresponding crystal structure. We find that the pore volume computed via the two complementary methods shows acceptable agreement only in about 35% of these cases. We provide the subset of isotherms measured on these materials as a seed for a future, more complete reference data set for computational studies.

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Tuning the Redox Activity of Metal−Organic Frameworks for Enhanced, Selective O2 Binding

10.26434/chemrxiv.10316681.v1 ◽

2019 ◽

Author(s):

Andrew Rosen ◽

M. Rasel Mian ◽

Timur Islamoglu ◽

Haoyuan Chen ◽

Omar Farha ◽

...

Keyword(s):

Density Functional ◽

Metal Organic Frameworks ◽

Redox Activity ◽

Screening Methods ◽

Bridging Ligands ◽

Metal Centers ◽

Computational Screening ◽

Open Metal Sites ◽

Metal Organic ◽

Unsaturated Metal Sites

Metal−organic frameworks (MOFs) with coordinatively unsaturated metal sites are appealing as adsorbent materials due to their tunable functionality and ability to selectively bind small molecules. Through the use of computational screening methods based on periodic density functional theory, we investigate O2 and N2 adsorption at the coordinatively unsaturated metal sites of several MOF families. A variety of design handles are identified that can be used to modify the redox activity of the metal centers, including changing the functionalization of the linkers (replacing oxido donors with sulfido donors), anion exchange of bridging ligands (considering μ-Br-, μ-Cl-, μ-F-, μ-SH-, or μ-OH- groups), and altering the formal oxidation state of the metal. As a result, we show that it is possible to tune the O2 affinity at the open metal sites of MOFs for applications involving the strong and/or selective binding of O2. In contrast with O2 adsorption, N2 adsorption at open metal sites is predicted to be relatively weak across the MOF dataset, with the exception of MOFs containing synthetically elusive V2+ open metal sites. As one example from the screening study, we predict that exchanging the μ-Cl- ligands of M2Cl2(BBTA) (H2BBTA = 1H,5H-benzo(1,2-d:4,5-d′)bistriazole) with μ-OH- groups would significantly enhance the strength of O2 adsorption at the open metal sites without a corresponding increase in the N2 affinity. Experimental investigation of Co2Cl2(BBTA) and Co2(OH)2(BBTA) confirms that the former exhibits only weak physisorption, whereas the latter is capable of chemisorbing O2 at room temperature. The chemisorption behavior is attributed to the greater electron-donating character of the μ-OH- ligands and the presence of H-bonding interactions between the μ-OH- bridging ligands and the O2 adsorbate.

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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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High-Throughput Computational Screening of Metal–Organic Frameworks for the Separation of Methane from Ethane and Propane

The Journal of Physical Chemistry C ◽

10.1021/acs.jpcc.0c09117 ◽

2021 ◽

Vol 125 (3) ◽

pp. 1839-1854

Author(s):

Yadava Krishnan Ponraj ◽

Bhaskarjyoti Borah

Keyword(s):

High Throughput ◽

Metal Organic Frameworks ◽

Computational Screening ◽

Metal Organic

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Predictive Acid Gas Adsorption in Rare Earth DOBDC Metal–Organic Frameworks via Complementary Cluster and Periodic Structure Models

The Journal of Physical Chemistry C ◽

10.1021/acs.jpcc.0c08282 ◽

2020 ◽

Vol 124 (49) ◽

pp. 26801-26813

Author(s):

Dayton J. Vogel ◽

Zachary R. Lee ◽

Caitlin A. Hanson ◽

Susan E. Henkelis ◽

Caris M. Smith ◽

...

Keyword(s):

Rare Earth ◽

Periodic Structure ◽

Gas Adsorption ◽

Metal Organic Frameworks ◽

Acid Gas ◽

Metal Organic

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Non-Interpenetrated Metal–Organic Frameworks Based on Copper(II) Paddlewheel and Oligoparaxylene-Isophthalate Linkers: Synthesis, Structure, and Gas Adsorption

Journal of the American Chemical Society ◽

10.1021/jacs.5b12312 ◽

2016 ◽

Vol 138 (10) ◽

pp. 3371-3381 ◽

Cited By ~ 78

Author(s):

Yong Yan ◽

Michal Juríček ◽

François-Xavier Coudert ◽

Nicolaas A. Vermeulen ◽

Sergio Grunder ◽

...

Keyword(s):

Gas Adsorption ◽

Metal Organic Frameworks ◽

Metal Organic

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Screening the Effect of Water Vapour on Gas Adsorption Performance: Application to CO2Capture from Flue Gas in Metal-Organic Frameworks

ChemSusChem ◽

10.1002/cssc.201601816 ◽

2017 ◽

Vol 10 (7) ◽

pp. 1543-1553 ◽

Cited By ~ 40

Author(s):

Nicolas Chanut ◽

Sandrine Bourrelly ◽

Bogdan Kuchta ◽

Christian Serre ◽

Jong-San Chang ◽

...

Keyword(s):

Water Vapour ◽

Flue Gas ◽

Gas Adsorption ◽

Metal Organic Frameworks ◽

Adsorption Performance ◽

Effect Of Water ◽

Metal Organic

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Enhanced performance in gas adsorption and Li ion batteries by docking Li+ in a crown ether-based metal–organic framework

Chemical Communications ◽

10.1039/c5cc09935h ◽

2016 ◽

Vol 52 (14) ◽

pp. 3003-3006 ◽

Cited By ~ 38

Author(s):

Linyi Bai ◽

Binbin Tu ◽

Yi Qi ◽

Qiang Gao ◽

Dong Liu ◽

...

Keyword(s):

Crown Ether ◽

Metal Ions ◽

Gas Adsorption ◽

Metal Organic Framework ◽

Metal Organic Frameworks ◽

Li Ion Batteries ◽

Metal Organic ◽

Li Ion ◽

Organic Framework

Incorporating supramolecular recognition units, crown ether rings, into metal–organic frameworks enables the docking of metal ions through complexation for enhanced performance.

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Metal–organic frameworks with the gyroid surface: structures and applications

Dalton Transactions ◽

10.1039/d0dt04234j ◽

2021 ◽

Vol 50 (14) ◽

pp. 4757-4764

Author(s):

Yan Yan Li ◽

Dong Luo ◽

Kun Wu ◽

Xiao-Ping Zhou

Keyword(s):

Gas Adsorption ◽

Metal Organic Frameworks ◽

Review Article ◽

Surface Structures ◽

Luminescent Materials ◽

Metal Organic

This review article summarizes the assembly, structures, and topologies of gyroidal metal–organic frameworks. Their applications in gas adsorption, catalysis, sensors, and luminescent materials are also discussed in detail.

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