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Review
. 2023;135(2):19.
doi: 10.1007/s12039-022-02130-5. Epub 2023 Mar 14.

Role of molecular modelling in the development of metal-organic framework for gas adsorption applications

Reshma Jose  1 , Garima Bangar  1 , Sourav Pal  2 , Gopalan Rajaraman  1
Affiliations
Review

Role of molecular modelling in the development of metal-organic framework for gas adsorption applications

Reshma Jose et al. J Chem Sci (Bangalore). 2023.

Abstract

More than 47,000 articles have been published in the area of Metal-Organic Framework since its seminal discovery in 1995, exemplifying the intense research carried out in this short span of time. Among other applications, gas adsorption and storage are perceived as central to the MOFs research, and more than 10,000 MOFs structures are reported to date to utilize them for various gas storage/separation applications. Molecular modeling, particularly based on density functional theory, played a key role in (i) understanding the nature of interactions between the gas and the MOFs geometry (ii) establishing various binding pockets and relative binding energies, and (iii) offering design clues to improve the gas uptake capacity of existing MOF architectures. In this review, we have looked at various MOFs that are studied thoroughly using DFT/periodic DFT (pDFT) methods for CO2, H2, O2, and CH4 gases to provide a birds-eye-view on how various exchange-correlation functionals perform in estimating the binding energy for various gases and how factors such as nature of the (i) metal ion, (ii) linkers, (iii) ligand, (iv) spin state and (v) spin-couplings play a role in this process with selected examples. While there is still room for improvement, the rewards offered by the molecular modelling of MOFs were already substantial that we advocate experimental and theoretical studies to go hand-in-hand to undercut the trial-and-error approach that is often perceived in the selection of MOFs and gas partners in this area.

Graphical abstract: The importance of density functional theory-based molecular modeling studies in offering design clues to improve the gas adsorption and storage capacity of existing MOF architectures is discussed here. The use of DFT-based investigation in conjunction with experimental synthesis is an imperative tool in designing new-generation MOFs with enhanced uptake capacity.

Keywords: DFT calculations; Metal-Organic Frameworks; gas storage and adsorption; molecular modelling; spin-coupling; spin-state.

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Figures

Figure 1
Figure 1
The distribution of MOFs as per CSD database (2020).
Figure 2
Figure 2
The representative structures of MOF chosen for the investigation of modelling of CO2 adsorption in MOFs. (a) Co-DOBDC, (b)Cr-BTT, and (c) Cu-BTTri. Co, Cr, Cu, O, N, Cl, C, and H are denoted as light green, dark green, orange, red, blue, purple, gray, and white, respectively.
Figure 3
Figure 3
CO2 adsorption energies in M/DOBDC (M = Mg, Ni, Co) and HKUST-1 calculated using standard density functional methods. Reproduced with permission from Ref. 71. Copyright 2012 American Chemical Society.
Figure 4
Figure 4
CO2 charge gain and loss as it is adsorbed to the CPO-27-Mg cluster in a linear configuration. The blue and cyan surfaces represent charge gain and loss, respectively, at an isosurface value of 0.003. White, gray, red, yellow, purple spheres represent H, C, O, Mg, Li atoms, respectively. (a) M–O–C angle is 145.9°; (b) M–O–C angle is 180°. Reproduced with permission from Ref. 85. Copyright 2013 from Royal Society of Chemistry.
Figure 5
Figure 5
Various binding pockets identified for CO2 adsorption for Cu-BTT and Cu-BTTri MOF by the DFT calculations. Reproduced with permission from Ref. 88. Copyright 2020 American Chemical Society. The Cu, C, N, are denoted as cyan, gray, and blue spheres, respectively. Yellow spheres represent mixed sites containing both C and N.
Figure 6
Figure 6
Relaxed structure of Ca-decorated B-substituted MOF-5 with 8H2's adsorbed per linker. The gray, pink, white, red, green and dark violet balls represent carbon, boron, hydrogen, oxygen, calcium and zinc atoms, respectively. Reproduced with permission from Ref.104. Copyright 2009 Elsevier.
Figure 7
Figure 7
(a) The repeating unit of MOF-5*, (b) The optimized structures of Li-, Be-, Mg- and Al-decorated primitive cells of MOF-5** (c) Frontier molecular orbitals of metals and MOF-5**. *Reproduced with permission from Ref. 107. Copyright 2016 Wiley. **Reproduced with permission from Ref. 105. Copyright 2011 Elsevier.
Figure 8
Figure 8
Charge density difference plots of (a) MOF-5:Li2:2H2 and MOF-5:Li2 and 2H2 molecules and (b) MOF-5:Li2:4H2 and MOF-5:Li2 and 4H2 molecules, at an iso-value of 0.01. Reproduced with permission from Ref. 105. Copyright 2011 Elsevier.
Figure 9
Figure 9
Structural model taken for MOF with added H2 molecules with first at site I and then at site II. The M (M= Cu, Mn, Fe, Zn), N, Cl, C, and H are denoted as black, blue, purple, gray, and white, respectively.
Figure 10
Figure 10
A ball and stick model of the Cu-BTTri framework dosed with 3.11 D2/Cu2+. The Cu, C, N, and H are denoted as cyan, gray, blue, and white spheres, respectively. Yellow spheres represent mixed sites containing both C and N. The pink dotted lines represent nearest-neighbor interactions. Reproduced with permission from Ref.110. Copyright 2019 Wiley.
Figure 11
Figure 11
The representative MOF structures were chosen for the modelling studies of O2 adsorption in MOFs, (a) Periodic unit of Cr3(BTC)2, (b) Periodic unit of Fe2(DOBDC), (c) tetrameric model of Co-BTTri, (d) Periodic unit of Co-BTTri, (e) tetrameric model of Co-BDTrip, (f) periodic unit of Co2Cl2(BBTA)2,and (g) periodic unit of Co2(OH)2(BBTA)2. The Cr, Fe, Co, N, Cl, O, C, and H are denoted as dark green, orange, light green, blue, purple, red, gray, and white, respectively.
Figure 12
Figure 12
The difference in binding energies (ΔΔE) between oxygen and nitrogen binding (bars) and binding energies for nitrogen (open circles) and oxygen (closed circles), for variants of M3(BTC)2 (orange) and M2(DOBDC) (purple) containing first-row transition metals. Reproduced with permission from Ref.111. Copyright 2015 American Chemical Society.
Figure 13
Figure 13
(a) Comparison of O2 adsorption isotherms collected for Co-BTTri (red) and Co-BDTriP (purple) at 195 K. Filled circles and solid lines represent experimental data, and their corresponding Langmuir fits, respectively. Inset: Low-pressure region of 195 K O2 isotherms. The Co-BDTriP–O2 uptake is significantly steeper at these low pressures than Co-BTTri. (b) Comparison of Co-BTTri (filled with red and blue circles, respectively) and Co-BDTriP (open red and blue circles, respectively) O2 and N2 isosteric heats. Reproduced with permission from Ref. 50. Copyright 2016 American Chemical Society.
Figure 14
Figure 14
(a) Geometry and representation of J1–4, bond parameters of GS (in black) and HS in [(Cr4(O2)4Cl)3(BTT)8]3− MOF. (Cr: green, Cl: purple, N: blue, C: gray, H: white). b) GS spin-density plot of [(Cr4(O2)4Cl)3(BTT)8]3−. c) Estimated spin-state ladder based on DFT J values for O2-bound (black) and unbound MOF. d) The partial DOS plot for the [(Cr4(O2)4Cl)3(BTT)8]3− MOF. Reproduced with permission from Ref. 119. Copyright 2020 Wiley.
Figure 15
Figure 15
The energy level diagram depicts different spin states comparative energies [kJ/mol] before and after oxygen binding. Reproduced with permission from Ref. 119. Copyright 2020 Wiley.
Figure 16
Figure 16
(a) Computed adsorption isotherm for successive O2 binding. b) Comparative adsorption isotherm for O2 and N2 in GS and HS states. c) Computed BE for successive addition of oxygen in GS (black, S=0) and HS (blue) states. d) Rigid scan of N−N bond distance in N2-bound MOFs. Here the blue circled regions indicate the formation of radical at the N2 moiety and corresponding spin density. Reproduced with permission from Ref. 119. Copyright 2020 Wiley.
Figure 17
Figure 17
The representative MOF structures are taken for the investigation of CH4 modelling studies in MOFs, (a-c) different binding sites in Zn2(DHTP)*, (d) bare structure of the Zn2(DHTP)*, (e) UTSA-76a, and (f) Crystal structures of HKUST-1, PCN-11, and PCN-14**. * Reproduced with Permission Ref. 70. Copyright 2009 American Chemical Society, ** Reproduced with Permission Ref. 125. Copyright 2010 Wiley.
Figure 18
Figure 18
The representative structure of MOF taken for the investigation of M-MOF–74. Reproduced with permission from Ref. 128. Copyright 2014 American Chemical Society.
Figure 19
Figure 19
M-MOF-74 binding energies for a row of different small compounds on the periodic table. Reproduced with permission from Ref. 128. Copyright 2014 American Chemical Society.
Figure 20
Figure 20
The computed (with different functionals) vs experimental binding energy (kJ/mol) plot for various MOFs studied here with CO2.
Figure 21
Figure 21
The computed (with different functionals) vs experimental binding energy (kJ/mol) plot for various MOFs studied here with H2 (left) and CH4.
See this image and copyright information in PMC

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