Density Functional Methods for Fast Screening of Metal–Organic Frameworks for Hydrogen Storage

2015 ◽  
Vol 119 (10) ◽  
pp. 5374-5385 ◽  
Author(s):  
Jia Fu ◽  
Yu Liu ◽  
Yun Tian ◽  
Jianzhong Wu
Keyword(s):  
Hydrogen Storage ◽  
Density Functional ◽  
Metal Organic Frameworks ◽  
Density Functional Methods ◽  
Fast Screening ◽  
Functional Methods ◽  
Metal Organic

scholarly journals Hydrogen storage on metal oxide model clusters using density-functional methods and reliable van der Waals corrections

2014 ◽  
Vol 16 (11) ◽  
pp. 5382 ◽  
Author(s):  
Julian Gebhardt ◽  
Francesc Viñes ◽  
Patrick Bleiziffer ◽  
Wolfgang Hieringer ◽  
Andreas Görling
Keyword(s):  
Metal Oxide ◽  
Hydrogen Storage ◽  
Density Functional ◽  
Van Der Waals ◽  
Density Functional Methods ◽  
Functional Methods

Hydrogen Storage in Metal-Organic Frameworks

2013 ◽  
Vol 316-317 ◽  
pp. 946-949 ◽  
Author(s):  
Yue Huang ◽  
San Huang Ke
Keyword(s):  
Crystal Structure ◽  
Hydrogen Storage ◽  
First Principles ◽  
Density Functional ◽  
Good Accuracy ◽  
Metal Organic Frameworks ◽  
Small Fragment ◽  
First Principles Calculations ◽  
Metal Organic ◽  
Vdw Interaction

Understanding of the physisorption of H2 in metal-organic frameworks (MOFs) is critical to improving its performance for hydrogen storage. By using first-principles calculations employing the van der Waals density functional (vdW-DF) method which can properly describe the vdW interaction, we investigate the binding energy of H2 in MOF-5 crystal. The accuracy of this methodology is first examined and good accuracy comparable to the correlated wavefunction methods is found. Calculations for the true crystal structure show that the small fragment models used in previous calculations cannot represent well the property of the crystal. The good accuracy and the ability to deal with the true crystal structure make the vdW-DF method a good candidate for investigating hydrogen storage in MOFs.

Molecular Modeling Studies on a series of Metal-Organic Frameworks

2004 ◽  
Vol 837 ◽  
Author(s):  
Tae-Bum Lee ◽  
Daejin Kim ◽  
Seung-Hoon Choi ◽  
Eungsung Lee ◽  
Youjin Oh ◽  
...  
Keyword(s):  
Monte Carlo ◽  
Hydrogen Storage ◽  
Density Functional ◽  
Storage Capacity ◽  
Metal Organic Frameworks ◽  
Adsorbed Hydrogen ◽  
Grand Canonical Monte Carlo ◽  
Hydrogen Storage Capacity ◽  
Metal Organic ◽  
Grand Canonical

ABSTRACTIn order to explore rational designs and synthetic strategies toward efficient hydrogen storage materials, quantum mechanical calculations and grand canonical Monte Carlo simulations have been carried out on a series of the Metal-Organic Frameworks containing various organic linkers. The calculations for specific surface areas and the shape of frontier orbitals for various frameworks indicate that the hydrogen storage capacity is largely dependent on the effective surface area of the material, rather than the free volume. Based on the iso-electrostatic potential surface from density functional calculations and the theoretical amount of adsorbed hydrogen from the grand canonical Monte Carlo calculations, it was also found that the electron localization around the organic linker plays an important role in the hydrogen storage capacity of Metal-Organic Frameworks. The prediction of the modeling study is supported by the hydrogen adsorption experiments with IRMOF-1 and -3, revealing the more enhanced hydrogen storage capacity of IRMOF-3 compared with that of IRMOF-1 at 77 K and H2 1 atm.

HYDROGEN STORAGE ENHANCEMENT VIA TRANSITION METAL DECORATION ON METAL ORGANIC FRAMEWORKS: A FIRST-PRINCIPLES STUDY

NANO ◽  
2012 ◽  
Vol 07 (06) ◽  
pp. 1250044 ◽  
Author(s):  
JEONGWOON HWANG ◽  
CHANGWON PARK ◽  
KEUNSU CHOI ◽  
MOON-HYUN CHA ◽  
RAJEEV AHUJA ◽  
...  
Keyword(s):  
Transition Metal ◽  
Hydrogen Storage ◽  
Density Functional ◽  
Metal Organic Frameworks ◽  
Density Functional Theory Calculations ◽  
Hydrogen Uptake ◽  
Level Shift ◽  
Ligand Field ◽  
Metal Organic ◽  
The Stability

We investigate the hydrogen storage capacity of the light transition metal (TM)-decorated metal organic frameworks (MOFs) by performing ab initio density functional theory calculations. We find that among all the light TM elements, divalent Ti and Fe are suitable for decorating MOFs to enhance the hydrogen uptake, considering the H2 binding energy on the TM atom and the reversibly usable number of H2 molecules attached to the metal site. In general, the magnetization of metal atoms undergoes a high-spin to low-spin state transition when H2 molecules are adsorbed, which helps to stabilize the system energetically. By analyzing the projected density of states on each TM atom, it is shown that the d-level shift induced by the ligand field of the adsorbed H2 molecules contributes substantially to the H2 binding strength. We also study the stability of selected TM-decorated nanostructures against the attack of foreign molecules by examining the energetics of those contaminating molecules around the metal sites.

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>

Sign in / Sign up

Export Citation Format

Share Document