Adsorption (2018) 24:691–701

https://doi.org/10.1007/s10450-018-9978-6

Adsorption of propane and propylene in zeolitic imidazolate

framework ZIF-8 pore: periodic SCC-DFTB method
Benjawan Kaewruksa1 · Viwat Vchirawongkwin1 · Vithaya Ruangpornvisuti1 

Received: 27 June 2018 / Revised: 9 September 2018 / Accepted: 18 September 2018 / Published online: 22 September 2018
© Springer Science+Business Media, LLC, part of Springer Nature 2018

Abstract
Adsorptions of propane and propylene in the ZIF-8 pore, were studied using periodic SCC-DFTB method. Six and
eleven adsorption configurations for propane and propylene molecules in the ZIF-8 pore, were respectively found. The
adsorption energies based on the most stable configurations of propane (− 1.38 kcal/mol) and propylene (− 1.25 kcal/
mol) in the ZIF-8 pore were obtained. Due to adsorption abilities of the ZIF-8 pore which can adsorb propane bet-
ter than propylene, the ZIF-8 therefore differentiate diffusion flux of propane and propylene via hexagonal aperture.
These results agree with ability of the ZIF-8 pore to separate propane/propylene mixture based on the principle of
gas–solid partition. All the adsorption configurations of propane and propylene molecules and their adsorption ener-
gies are reported.

Keywords  ZIF-8 · Propane · Adsorption energy · SSC-DFTB computations · Propylene

1 Introduction

Electronic supplementary material  The online version of this
article (https​://doi.org/10.1007/s1045​0-018-9978-6) contains
supplementary material, which is available to authorized users.
* Vithaya Ruangpornvisuti
vithaya.r@chula.ac.th
1
Department of Chemistry, Faculty of Science,
Chulalongkorn University, Bangkok 10330, Thailand
Metal organic frameworks (MOFs) are fascinating porous
materials which were widely utilized for gas separa-
tion (Ingole et al. 2018; Jia et al. 2014; Lee et al. 2014),
adsorptions for small gases (Fan et al. 2018; Ramsahye
et al. 2014; Bentley et al. 2016) including hydrogen stor-
age (Ozer et al. 2018) and light hydrocarbons. MOFs were
also used as heterogeneous catalyst (Ravon et al. 2008;

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692
Zhang et al. 2014; Hu et al. 2018). MOFs were rapidly
growing as versatile nanoporous materials (Meek et al.
2011). Due to definition of MOF which is composed of
coordination bonds between inorganic metal ions and
polydentate organic linker ligands, several kinds of MOF
have therefore been mentioned such as zeolite imidazolate
frameworks (ZIFs) (Wu et al. 2018a), dioxybenzenedicar-
boxylate (DOBDC) (Gholami and Yeganegi 2017; Borycz
et al. 2014), materials institute lavoisier (MILs) (Wu et al.
2018b), porous coordination networks (PCNs) (Ozturk and
Keskin 2014), and iso-reticular metal–organic frameworks
(IRMOFs) (Bryant et al. 2017).
Hydrogen adsorptions in various types of ZIFs such as
ZIF-8 (Assfour et al. 2010; Pérez-Pellitero et al. 2010),
ZIF-11 (Assfour et al. 2010), ZIF-7 (Dixit et al. 2016) were
widely studied. Hydrogen permeations through different
porous membranes of ZIF-8 (Friebe et al. 2014), ZIF-90
(Friebe et al. 2014), ZIF-7 (Go et al. 2016; Li et al. 2010)
and hydrogen separation using ZIF-8 (Yin et al. 2016) were
remarkably investigated. Adsorption of ­CO2, ­N2 and ­CH4 in
ZIF-8 (Pérez-Pellitero et al. 2010), ZIF-78 (Li et al. 2011)
and ZIF-79 (Li et al. 2011) was theoretically studied by dif-
ferent theoretical approaches for gas storage applications.
Adsorption of small gas in ZIF-8 (Pérez-Pellitero et  al.
2010) was studied and found that their uptakes are in order:
­CO2 > CH4 > N2 > H2. ZIF-7 (Ebrahimi and Mansournia
2017), ZIF-8 (Kolmykov et al. 2017; Yan et al. 2016; Lai
et al. 2017; Jomekian et al. 2016), ZIF-11 (Reif et al. 2017)
and ZIF-67 (Zhang et al. 2017) were synthesized and studied
in various phases. Studies for kinetic transformation (Feng
et al. 2016) and dye adsorption (Li et al. 2016) on ZIF-8
and ZIF-67, separation of n-hexane/2-methylpentan (Chen
et al. 2016) by ZIF-69 and hydrogen separation by ZIF-90
(Yang and Chung 2013) were made. Other types of ZIFs
were synthesized and studied for ­CO2 capture (Banerjee
et al. 2009, 2008).
ZIF-8 has demonstrated wide applications for the adsorp-
tion of various gases (­ CH4, ­CO2, ­N2, etc.) (Nune et al. 2010;
Nugent et al. 2013a, b; Liao et al. 2015; Wang et al. 2015),
gas storages (Rowsell and Yaghi 2005; Wu et al. 2010;
Himsl and Hartmann 2010) and catalysts (Schlichte et al.
2004; Wu et al. 2005; Lee et al. 2009). Due to high surface
area, large pore size, relatively high thermal and chemi-
cal stability of ZIF-8, it was therefore, used in applica-
tions for drug delivery systems (Vallet-Regí et al. 2007;
Zhuang et al. 2014; Sun et al. 2012) and separations (Pan
et al. 2006; Eriksson et al. 2009; Shimomura et al. 2010).
Applications of petrochemicals, ZIFs were used in purifica-
tion of propylene from propylene/propane mixture (Demir
and Ahunbay 2014) and the purity of propylene primar-
ily depends on the removal of propane in dehydrogenation
reaction (Wȩgrzyniak et al. 2017). Kinetic separation of
13
Adsorption (2018) 24:691–701
propylene/propane (Li et al. 2009), their transport prop-
erties and characteristics in ZIF-8 membranes (Liu et al.
2014) were studied and activation energies for their diffu-
sions were reported. ZIF-8 membrane prepared by a facile
hydrothermal seeded growth method (Pan et al. 2012) and
ultrathin ZIF-8 membranes supported on polymeric hollow
fibers (Lee et al. 2018) were found to show excellent separa-
tion performances for a wide range of propylene/propane
mixtures.
Nevertheless, separation performances depend on several
factors and adsorption of propylene and propane gases in
the ZIF-8 is one of the most effective factor which has never
been studied. Therefore, the ZIF-8 has become more specific
MOF for purification in terms of separation and adsorption
of propane and propylene molecules.
Although, numerous works on propane and propylene
adsorption, storage and separation of their mixtures in ZIFs,
the physical insight of propane and propylene gases in ZIFs
has been not elucidated. In present work, adsorption of pro-
pane and propylene molecules in the ZIF-8 has therefore
been investigated using the self-consistent charge density
functional tight-binding (SCC-DFTB) periodic method. All
adsorption configurations of propane and propylene in the
ZIF-8 pore and their locations have been investigated and
revealed, respectively. Adsorption energies of all adsorption
configurations are reported.
2 Computational methodology
2.1 Geometry optimization of the ZIF‑8
The ZIF-8 unit cell size, based on the X-ray diffraction
structure (Novaković et al. 2015) which is a cubic space
group I43m and unit cell dimension of a = 16.9386  Å,
V = 4860.0 Å3, was as initial structure in geometrical opti-
mization. The geometry of ZIF-8 (Fig. S1, Supplementary
data) was geometrically optimized using self-consistent
charge density functional tight-binding (SCC-DFTB) peri-
odic calculations. All SCC-DFTB calculations were per-
formed with the code of DFTB+ version 1.3 (Aradi et al.
2007). Parameter sets “mio–0–1” for H, C, N atoms (Elstner
et al. 1998) and “znorg–0–1” for Zn atom (Moreira et al.
2009) were employed in SCC-DFTB calculations. Solid-
state cubic ZIF-8 properties were calculated using PBC and
converged (1 × 1 × 1) MP k-points. In all SCC-DFTB calcu-
lations, the atomic positions were relaxed until the forces in
the system became smaller than 1.9 × 10−5 eV/Å which SCC
tolerance were smaller than 1.0 × 10−5 e. The periodic struc-
ture of the ZIF-8 pore based on ­(Zn12N48C96H120) periodic
formula is defined as a supercell size.
Adsorption (2018) 24:691–701 693

Fig. 1  The SCC-DFTB optimized structure of ZIF-8 unit-cell depicted by tube model, shown its a tetragonal aperture (TA), b hexagonal aper-
ture (HA) and c propane (left) and propylene (right) molecules, shown by ball–stick model

2.2 Adsorption of propylene/propane in the ZIF‑8
Adsorption energy (ΔEads) of propylene (PPE)/propane
(PPA) guest molecule (G) in ZIF-8 host molecule is defined
by
(1)
[ ( )]
ΔEads = EG∕ZIF-8 − EZIF-8 + EG
where EG/ZIF-8, EZIF-8, and EG are the total energies of guest
molecule (propylene/propane) in the host (ZIF-8), ZIF-8
host, and propylene/propane guest molecule, respectively.
3 Results and discussions
equation of E = ar2 + br + c which is the curve fit as shown
in Fig. S2, Supplementary data. Tetragonal and hexagonal
apertures of the SCC-DFTB-optimized structure of ZIF-8
unit-cell, are shown in Fig. 1. Nevertheless, the gate size,
size of hexagonal aperture for the optimized ZIF-8 structure
(3.27 Å), computed using a model introduced by Zheng et al.
(2016) being smaller than the X-ray structure (Novaković
et al. 2015) (3.53 Å) was found.
ZIF-8 is a sodalite (SOD) topology and a sub-class of
MOFs consisting of zinc ions and 2-methyl imidazolate link-
ers and crystallizes in a cubic lattice with I43m space group
(Yao and Wang 2014). It contains cavities with a diameter
of 11.6 Å connected with tetragonal aperture and flexible
hexagonal aperture with a diameters of 3.3 Å and 2.2 Å,
respectively (Huang et al. 2006).

3.1 Geometry optimization of the ZIF‑8 3.2 Interaction energy of propane on windows

The optimized structures of ZIF-8 unit-cell obtained by
the SCC-DFTB method with different conditions are
shown in Fig. S1, and the unit cell parameter a = 16.705 Å
at 298.15 K, was found. The optimized a parameter was
obtained by taking the minimum point of the quadratic
of the ZIF‑8 pore
The SCC-DFTB-optimized structures of propane interacting
with atoms of the ZIF-8 pore are shown in Fig. 2. Six con-
figurations of propane adsorbed on wall of the ZIF-8 were
found. All the configurations named as PPA/ZIF-8_H, PPA/

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694
Fig. 2  Adsorption structures of propane in the ZIF-8 pore, which the
propane molecule is located close to the tetragonal aperture as con-
figuration a PPA/ZIF-8_H, b PPA/ZIF-8_T, c PPA/ZIF-8_H/T_1, d
PPA/ZIF-8_h-H, e PPA/ZIF-8_H/T_2 and f PPA/ZIF-8_h-T. “H”
and “T” stand for hexagonal and tetragonal apertures, respectively,
ZIF-8_T, PPA/ZIF-8_H/T_1, PPA/ZIF-8_h-H, PPA/ZIF-
8_H/T_2 and PPA/ZIF-8_h-T are defined. The first (PPA/
ZIF-8_H) and second (PPA/ZIF-8_T) configurations are
structures of which propane is located near the hexagonal
aperture (H) and tetragonal aperture (T), respectively. The
third (PPA/ZIF-8_H/T_1) is the structure of which propane
is located in between the hexagonal and tetragonal apertures.
PPA/ZIF-8_h-H is the structure of which propane is located
at the center of the hexagonal aperture. PPA/ZIF-8_H/T_2
is quite similar to the PPA/ZIF-8_H/T_1. PPA/ZIF-8_h-T is
the structure of which propane is located at the center of the
tetragonal aperture. Adsorption energies (ΔEads) of propane
on the ZIF-8 cage are shown in Table 1. Adsorption strengths
are in order: PPA/ZIF-8_H/T_1 (ΔEads  =  − 1.38  kcal/
mol) > PPA/ZIF-8_h-H (ΔE ads   =  − 1.08  kcal/
mol) > PPA/ZIF-8_H (ΔEads  =  − 0.95  kcal/mol) > PPA/
ZIF-8_H/T_2 (ΔE ads   =  − 0.90  kcal/mol) > PPA/
ZIF-8_h-T (ΔE ads  =  − 0.66  kcal/mol) > PPA/ZIF-8_T
(ΔEads = − 0.39 kcal/mol).
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Adsorption (2018) 24:691–701
and h means at hollow position. Atoms in ZIF apertures and propane
molecule, shown by tube model are the main adsorption interaction.
The left and right graphics are side and top views, respectively. The
adsorption energies (ΔEads), in kcal/mol are shown
The shortest bond-distances between propane’s atoms and
atoms of the ZIF-8 of all the (six) adsorption configurations
are shown in Table 2 of which all locations of propane mol-
ecule in the ZIF-8 are specified. The shortest bond-distances
between hydrogen atoms (ether methyl or ethylene group)
of propane and hydrogen atoms of either methyl or ethylene
group of imidazolate unit of the ZIF-8 are within the range of
2.14–2.66 Å.
3.3 Interaction energy of propylene on windows
of the ZIF‑8 pore
The SCC-DFTB-optimized structures of propylene inter-
acting with atoms of the ZIF-8 pore are shown in Fig. 3.
Eleven configurations of propylene adsorbed on wall of
the ZIF-8 were found. All the configurations named as
PPE/ZIF-8_H_1, PPE/ZIF-8_h-H, PPE/ZIF-8_H/T_1,
PPE/ZIF-8_H/T_2, PPE/ZIF-8_T_1, PPE/ZIF-8_T_2,
PPE/ZIF-8_h-H(CH 2), PPE/ZIF-8_H_2, PPE/ZIF-8_h-
H_2(CH3), PPE/ZIF-8_h-H_3(CH2) and PPE/ZIF-8_center
Adsorption (2018) 24:691–701 695

Table 1  Total energies of the SCC-DFTB-optimized structure of Table 2  The shortest bond-distances between specific atoms of pro-
propane and propylene adsorbed on wall of the ZIF-8 pore and their pane and the ZIF-8
components, and its corresponding adsorption energies
Configuration/bondsa Bond
Configuration/system Etotal (au) ΔEads (kcal/mol) distances
(Å)
ZIF-8 − 379.2730472 –
Propane − 8.178396288 – PPA/ZIF-8_H
Propylene − 7.388266617 –  H6(G)⋯H1(H) 2.26
Propane/ZIF-8  H6(G)⋯C2(H) 3.31
 PPA/ZIF-8_H − 387.4529502 − 0.95 PPA/ZIF-8_T
 PPA/ZIF-8_T − 387.4520560 − 0.39  H5(G)⋯H1(H) 2.34
 PPA/ZIF-8_H/T_1 − 387.4536361 − 1.38  H5(G)⋯C2(H) 3.18
 PPA/ZIF-8_h-H − 387.4531617 − 1.08 PPA/ZIF-8_H/T_1b
 PPA/ZIF-8_H/T_2 − 387.4528811 − 0.90  H6(G)⋯H1(H) 2.66
 PPA/ZIF-8_h-T − 387.4524916 − 0.66  H5(G)⋯H2(H) 2.63
Propylene/ZIF-8  H2(G)⋯H3(H) 2.14
 PPE/ZIF-8_H_1 − 386.6626219 − 0.82 PPA/ZIF-8_h-H
 PPE/ZIF-8_h-H_1 − 386.6626177 − 0.82  H6(G)⋯H1(H) 2.19
 PPE/ZIF-8_H/T_1 − 386.6621387 − 0.52  H5(G)⋯H2(H) 2.44
 PPE/ZIF-8_H/T_2 − 386.6618589 − 0.34  H7(G)⋯H3(H) 2.30
 PPE/ZIF-8_T_1 − 386.6632995 − 1.25 PPA/ZIF-8_H/T_2
 PPE/ZIF-8_T_2 − 386.6630932 − 1.12  H6(G)⋯H1(H) 2.19
 PPE/ZIF-8_h-H_2(CH2) − 386.6632341 − 1.20  H5(G)⋯H2(H) 2.44
 PPE/ZIF-8_H_2 − 386.6629239 − 1.01  H7(G)⋯H3(H) 2.30
 PPE/ZIF-8_h-H_3(CH3) − 386.6632785 − 0.83 PPA/ZIF-8_h-T
 PPE/ZIF-8_h-H_4(CH2) − 386.6625597 − 0.78  H6(G)⋯H1(H) 5.43
 PPE/ZIF-8_center − 386.6623603 − 0.66  H5(G)⋯H2(H) 6.34
 H7(G)⋯H3(H) 6.20
a
 A(G)⋯B(H) represents atom A of guest (G) bonding to atom B of
host (H) and labels for all atoms are defined in Fig. 1
are defined. These configurations can be categorized into b
 The most stable configuration
four groups as follows. The first group is collected of PPE/
ZIF-8_H_1, PPE/ZIF-8_H_2, PPE/ZIF-8_h-H_1, PPE/
ZIF-8_h-H_2(CH 2), PPE/ZIF-8_h-H_3(CH 3) and PPE/ ZIF-8_H/T_1 (ΔE ads   =  − 0.52  kcal/mol) > PPE/ZIF-
ZIF-8_h-H_4(CH2) of which propylene is located close to 8_H/T_2 (ΔEads = − 0.34 kcal/mol).
the hexagonal apertures. The second group is composed The shortest bond-distances between propylene’s atoms
of PPE/ZIF-8_T_1 and PPE/ZIF-8_T_2 of which propyl- and atoms of the ZIF-8 of all the (eleven) adsorption con-
ene is located close to the tetragonal aperture. The PPE/ figurations are shown in Table 3 of which all locations of
ZIF-8_H/T_1 and PPE/ZIF-8_H/T_2, the third group, are propylene molecule in the ZIF-8 are specified. The shortest
configurations of which propylene is located in between bond-distances between hydrogen atoms (ether methyl or
hexagonal and tetragonal apertures. The last group, PPE/ ethylene group) of propylene and hydrogen atoms of either
ZIF-8_center is the configuration of which propylene methyl or ethylene group of imidazolate unit of the ZIF-8 are
is located at center of the cage. Adsorption strengths within the wide range of 1.56–3.25 Å, except the adsorption
are in order: PPE/ZIF-8_T_1 (ΔE ads   =  − 1.25  kcal/ at center of the pore.
mol) > PPE/ZIF-8_h-H_2(CH 2) (ΔE ads  =  − 1.20  kcal/
mol) > PPE/ZIF-8_T_2 (ΔEads = − 1.12 kcal/mol) > PPE/ 3.4 Effect of adsorption configurations
ZIF-8_H_2 (ΔE ads   =  −  1.01  kcal/mol) > PPE/ZIF- on separation of propane and propylene
8_h-H_3(CH 3 ) (ΔE ads   =  − 0.83  kcal/mol) > PPE/ mixture
ZIF -8_H_1 (ΔE ads   =  − 0.82  kcal/mol) ~ PPE/
ZIF-8_h-H_1 (ΔE ads   =  − 0.82  kcal/mol) > PPE/ZIF- The most stable adsorption-structures of propane and pro-
8_h-H_4(CH 2 ) (ΔE ads   =  − 0.78  kcal/mol) > PPE/ pylene in the ZIF-8 are illustrated in Fig. 4. It shows that
ZIF-8_center (ΔE ads   =  − 0.66  kcal/mol) > PPE/ propane points its methyl hydrogen atoms towards ethylene

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Fig. 3  Adsorption structures of propene in the ZIF-8 pore, which the
propene molecule located close to the tetragonal aperture as configu-
ration a PPE/ZIF-8_H_1, b PPE/ZIF-8_h-H c PPE/ZIF-8_H/T_1, d
PPE/ZIF-8_H/T_2, e PPE/ZIF-8_T_1, f PPE/ZIF-8_T_2, close to the
hexagonal aperture as g PPE/ZIF-8_h-H(CH2), h PPE/ZIF-8_H_2, i
and methyl hydrogen atoms of imidazolate unit belonging
to the hexagonal aperture of the ZIF-8 of which bond dis-
tances are 2.66, 2.63 and 2.14 Å, respectively. For propyl-
ene adsorption, propylene points its methyl hydrogen atoms
towards hydrogen atoms of two methyl groups of imida-
zolate unit belonging to the tetragonal aperture of the ZIF-8
of which bond distances are 2.43 and 3.14 Å, respectively.
Based on the separation of propane/propylene mixture and
partition theory, the adsorption configurations of propane
or propylene in the ZIF-8 located close to the hexagonal
aperture has more effect on its moving rate through the
hexagonal aperture than further location. As consideration
of adsorption configuration, PPE/ZIF-8_h-H_2(CH 2) for
13
Adsorption (2018) 24:691–701
PPE/ZIF-8_h-H_2(CH3), j PPE/ZIF-8_h-H_3(CH2) and close to the
center as k PPE/ZIF-8_center. Atoms of apertures and the propane
molecule, shown by tube are the main adsorption interaction. The left
and right graphics are side and top views, respectively. The adsorp-
tion energies (ΔEads), in kcal/mol are shown
propylene adsorption of which adsorption is the strongest
(ΔEads = − 1.20 kcal/mol), must be taken into considera-
tion of moving rate through the hexagonal aperture. Bond-
distance data shown in Tables 2 and 3 were used to confirm
locations of propane and propylene molecules of rerated
adsorption configurations.
4 Conclusions
Adsorption of propane and propylene in the ZIF-8 pore,
was studied using periodic SCC-DFTB method. Six and
eleven adsorption configurations for propane and propylene
Adsorption (2018) 24:691–701 697

Fig. 3  (continued)

molecules in the ZIF-8 pore, were found respectively.
Adsorption energies of propane and propylene are within
the ranges of − 0.39 to − 1.38  kcal/mol and − 0.34 to
− 1.25 kcal/mol, respectively. Adsorption energies of the
most stable configurations of propane and propylene mol-
ecules in the ZIF-8 pore are − 1.38 and − 1.25 kcal/mol,
respectively. As trend of adsorption abilities of the ZIF-8
pore for adsorption of propane better than propylene, the
ZIF-8 cage can differentiate diffusion fluxes of propane and
propylene via hexagonal aperture. Therefore, lower diffusion
flux of propane gas via hexagonal aperture of the ZIF-8,
compared with propylene gas, is expected.

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698 Adsorption (2018) 24:691–701

Table 3  The shortest bond-distances between specific atoms of pro-

pylene and the ZIF-8

Configuration/bondsa Bond
distances
(Å)

PPE/ZIF-8_H_1
 H7(G)⋯H1(H) 2.32
 H7(G)⋯C2(H) 3.20
PPE/ZIF-8_h-H_1
 H9(G)⋯H1(H) 2.44
 H9(G)⋯C1(H) 2.62
PPE/ZIF-8_H/T_1
 H8(G)⋯H1(H) 2.73
 H8(G)⋯C2(H) 3.34
PPE/ZIF-8_H/T_2b
 H5(G)⋯H1(H) 2.76
 H5(G)⋯C2(H) 3.25
PPE/ZIF-8_T_1
 H4(G)⋯H1(H) 2.43
 H4(G)⋯H2(H) 3.14
PPE/ZIF-8_T_2
 H8(G)⋯H1(H) 1.56
 H8(G)⋯H2(H) 2.22
PPE/ZIF-8_h-H_2(CH2)
 H6(G)⋯H1(H) 2.47
 H6(G)⋯H1(H) 2.45
 H7(G)⋯H2(H) 2.52
PPE/ZIF-8_H_2
 H9(G)⋯H1(H) 2.90
 H9(G)⋯H2(H) 3.00
 H10(G)⋯H3(H) 2.27
PPE/ZIF-8_h-H_3(CH3)
 H6(G)⋯H4(H) 2.47
 H6(G)⋯H1(H) 2.47
 H7(G)⋯H2(H) 2.52
PPE/ZIF-8_h-H_4(CH2)
 H10(G)⋯H4(H) 2.37
 H10(G)⋯H1(H) 2.80
 H9(G)⋯H2(H) 2.66 Fig. 4  The most stable adsorption-structures of a propane and b pro-
pylene in ZIF-8 pore as configurations PPA/ZIF-8_H/T_1 and PPE/
PPE/ZIF-8_center ZIF-8_T_1, respectively. Bond distances between nearest atoms of
 H5(G)⋯H1(H) 6.22 guest molecule (propane or propylene) and ZIF-8 pore are illustrated
 H6(G)⋯H2(H) 6.42
 H6(G)⋯H3(H) 5.17
Acknowledgements  This Research is funded by Chulalongkorn Uni-
a versity, Thailand. The 100th Anniversary Chulalongkorn University
 A(G)⋯B(H) represents atom A of guest (G) bonding to atom B of
host (H) and labels for all atoms are defined in Fig. 1 Fund for Doctoral Scholarship is also acknowledged.
b
 The most stable configuration
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