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

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.

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

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.

scholarly journals The effect of atomic point charges on adsorption isotherms of CO2 and water in metal organic frameworks

Adsorption ◽  
2019 ◽  
Vol 26 (5) ◽  
pp. 663-685 ◽  
Author(s):  
Kristina Sladekova ◽  
Christopher Campbell ◽  
Calum Grant ◽  
Ashleigh J. Fletcher ◽  
José R. B. Gomes ◽  
...  
Keyword(s):  
Adsorption Isotherms ◽  
Point Charge ◽  
Carbon Capture ◽  
Gas Adsorption ◽  
Periodic Structures ◽  
Metal Organic Frameworks ◽  
Large Variability ◽  
Wide Range ◽  
Open Metal Sites ◽  
Metal Organic

AbstractThe interactions between metal–organic frameworks (MOFs) and adsorbates have been increasingly predicted and studied by computer simulations, particularly by Grand-Canonical Monte Carlo (GCMC), as this method enables comparing the results with experimental data and also provides a degree of molecular level detail that is difficult to obtain in experiments. The assignment of atomic point charges to each atom of the framework is essential for modelling Coulombic interactions between the MOF and the adsorbate. Such interactions are important in adsorption of polar gases like water or carbon dioxide, both of which are central in carbon capture processes. The aim of this work is to systematically investigate the effect of varying atomic point charges on adsorption isotherm predictions, identify the underlying trends, and based on this knowledge to improve existing models in order to increase the accuracy of gas adsorption prediction in MOFs. Adsorption isotherms for CO2 and water in several MOFs were generated with GCMC, using the same computational parameters for each material except framework point charge sets that were obtained through a wide range of computational approaches. We carried out this work for 6 widely studied MOFs; IRMOF-1, MIL-47, UiO-66, CuBTC, Co-MOF-74 and SIFSIX-2-Cu-I. We included both MOFs with and without open metal sites (OMS), specifically to investigate whether this property affects the predicted adsorption behaviour. Our results show that point charges obtained from quantum mechanical calculations on fully periodic structures are generally more consistent and reliable than those obtained from either cluster-based QM calculations or semi-empirical approaches. Furthermore, adsorption in MOFs that contain OMS is much more sensitive to the point charge values, with particularly large variability being observed for water adsorption in such MOFs. This suggests that particular care must be taken when simulating adsorption of polar molecules in MOFs with open metal sites to ensure that accurate results are obtained.

An investigation of a series of layered Zn-1,4-diazabicyclo[2.2.2]octane metal–organic frameworks: local structure and adsorption properties of mixed-metal centre

2020 ◽  
Vol 77 (1) ◽  
Author(s):  
Chang-Chun Ding ◽  
Xiao-Hong Chu ◽  
Meng-Jia Zhang ◽  
Jia Fu
Keyword(s):  
Adsorption Isotherms ◽  
Gas Adsorption ◽  
Metal Organic Frameworks ◽  
Adsorption Properties ◽  
Paramagnetic Resonance ◽  
Mixed Metal ◽  
Local Structures ◽  
Different Temperatures ◽  
Metal Organic ◽  
Epr Parameters

The mixed-metal pillar-layered metal–organic frameworks of Zn(bdc)(DABCO)0.5, Zn0.5Cu0.5(bdc)(DABCO)0.5 and Cu(bdc)(DABCO)0.5 (bdc = 1,4-benzenedicarboxylate, DABCO = 1,4-diazabicyclo[2.2.2]octane) are investigated for their local structures and gas adsorption properties. According to the obtained electron paramagnetic resonance (EPR) spectra, the distorted structures around Cu2+ are proposed to be tetragonally and orthorhombically elongated [CuO4N] with the well fitted high-order perturbation formulae of the EPR parameters. Due to the doped Cu2+, the adsorption isotherms of industrially relevant gases (CO2, CO, CH4 and N2) and lower alkanes (CH4, C2H6, C3H8, C4H10 and C5H12) are different, especially at different temperatures. By combining the structural properties and adsorption isotherms, a comprehensive study suggests that the ZnDABCO series can be a controllable tool in gas storage and separation.

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

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

<p>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 O<sub>2</sub> and N<sub>2</sub> 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<sup>-</sup>, μ-Cl<sup>-</sup>, μ-F<sup>-</sup>, μ-SH<sup>-</sup>, or μ-OH<sup>-</sup> groups), and altering the formal oxidation state of the metal. As a result, we show that it is possible to tune the O<sub>2</sub> affinity at the open metal sites of MOFs for applications involving the strong and/or selective binding of O<sub>2</sub>. In contrast with O<sub>2</sub> adsorption, N<sub>2</sub> adsorption at open metal sites is predicted to be relatively weak across the MOF dataset, with the exception of MOFs containing synthetically elusive V<sup>2+</sup> open metal sites. As one example from the screening study, we predict that exchanging the μ-Cl<sup>-</sup> ligands of M<sub>2</sub>Cl<sub>2</sub>(BBTA) (H<sub>2</sub>BBTA = 1<i>H</i>,5<i>H</i>-benzo(1,2-d:4,5-d′)bistriazole) with μ-OH<sup>-</sup> groups would significantly enhance the strength of O<sub>2</sub> adsorption at the open metal sites without a corresponding increase in the N<sub>2</sub> affinity. Experimental investigation of Co<sub>2</sub>Cl<sub>2</sub>(BBTA) and Co<sub>2</sub>(OH)<sub>2</sub>(BBTA) confirms that the former exhibits only weak physisorption, whereas the latter is capable of chemisorbing O<sub>2</sub> at room temperature. The chemisorption behavior is attributed to the greater electron-donating character of the μ-OH<sup>-</sup><sub> </sub>ligands and the presence of H-bonding interactions between the μ-OH<sup>-</sup> bridging ligands and the O<sub>2</sub> adsorbate.</p>

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

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.<br>

Synthesis, crystal structure, luminescence, and photocatalytic properties of a 2D Cu(II) metal-organic frameworks based on 3,5-di(1H-benzimidazol-1-yl)pyridine and 4,4′-oxybis(benzoate) ligands

2020 ◽  
Vol 75 (8) ◽  
pp. 727-732
Author(s):  
Chen Zhang ◽  
Jian-Qing Tao
Keyword(s):  
Crystal Structure ◽  
Thermal Analysis ◽  
Uv Light ◽  
Metal Organic Framework ◽  
Metal Organic Frameworks ◽  
X Ray Diffraction ◽  
X Ray ◽  
Uv Light Irradiation ◽  
Photocatalytic Activities ◽  
Metal Organic

AbstractA new Cu(II) metal-organic framework, [Cu(L)(OBA)·H2O]n (1) [H2OBA = 4,4′-oxybis(benzoic acid), L = 3,5-di(1H-benzimidazol-1-yl)pyridine] was hydrothermally synthesized and characterized through IR spectroscopy, elemental and thermal analysis and single-crystal X-ray diffraction. Complex 1 is a four-connected uni-nodal 2D net with a (44·62) topology which shows an emission centered at λ ∼393 nm upon excitation at λ = 245 nm. Moreover, complex 1 possesses high photocatalytic activities for the decomposition of Rhodamine B (RhB) under UV light irradiation.

Negative linear compressibility in nanoporous metal-organic frameworks rationalized by the empty channel structural mechanism

2021 ◽  
Author(s):  
Francisco Colmenero
Keyword(s):  
Crystal Structures ◽  
Metal Organic Frameworks ◽  
Structural Mechanism ◽  
Nanoporous Metal ◽  
Metal Organic ◽  
Linear Compressibility

Cobalt squarate hydroxide (Co3(C4O4)2(OH)2), zinc squarate tetrahydrate (ZnC4O4·4 H2O) and titanium oxalate trioxide dihydrate (Ti2(C2O4)O3·2 H2O) are nanoporous metal-organic frameworks possessing empty channels in their crystal structures. The crystal structures...

Sign in / Sign up

Export Citation Format

Share Document