EMCHiE topic Abdul Hannan Khan

First Principle study on Methane Adsorption in Metal-Organic Framework.

Abdul Hannan Khan

M10506819 Department of Chemical Engineering, Taiwan Tech

Abstract
A Density Functional Theory (DFT) approach was employed using VASP to study an organometallic system for
Methane (CH4) adsorption. CPO-27-Ni containing Nickle as a central metal and 2,5-dihydroxyterephthalic acid as
a linker site was chosen for study purpose because it is commercially available for CH4 and CO2 capture as well
as it shows so far highest adsorption capacity. However very less DFT study for this system is published so far. So
far 9 molecules of CH4 in a single pore of unit cell has been successfully adsorbed, however literature review
suggests that total number of molecules that a single pore can adsorb successfully is 18 CH4 molecules, (6 on
metal site, 6 on all linker site and 6 on above monolayer when all 12 molecules are adsorbed on Metal and linker
site.). So far the calculation is running because system contains 167 atoms so it takes almost one month to run a
single calculation. In future I will try to adsorb as much molecule as literature predicts.

Introduction
Methane contains highest C/H ration in all fuels and it gives relatively less CO2 emission, thus to meet
environmental standards as well as to reduce the dependence on oil-based petroleum, natural gas (which mainly
consists of methane) is considered as alternative fuel for transport applications. It seems more efficient to adsorb
methane into porous solids, which, because of the gas−solid interactions, store more gas molecules than an empty
container would under the same conditions. This excess adsorption is proportional to the specific surface area of
the adsorbents and depends on the strength of the interaction between the gas molecules and the surface. (Sun, Y.,
2009). Among the porous materials, the crystalline metal−organic frameworks (MOFs) have exceptionally high
surface areas (even exceeding 5000 or 6000 m2/g), (Düren, T.,2004) and high methane storage capacities have
been reported (Getzschmann, J., 2010). In particular, for MOFs with a high density of accessible strong adsorption
sites at the pore surfaces, typically under-coordinated metal cations. (Bourrelly, S., 2005). By now the highest
methane storage capacity11 (195 cm3(STP)/cm3) at 298 K has been reported for CPO-27- Ni, the Ni2+-containing
member of the CPO-27-M series of isostructural compounds. On the basis of composition, these framework
structures are also named M2(dhtp), where M is a divalent metal and dhtp refers to the fully deprotonated form of
2,5-dihydroxyterephthalic acid (H4dhtp). (Rosi, N., 2006). Due to defects in crystal structure and restriction in site
availability only 96% of active sites are available for CPO-27 with Ni2+ strong adsorption sites. Thus, the evaluation
of adsorption properties of the fully activated, i.e., ideal material by computational means is very desirable. This will
be done in the present study for adsorption of CH4 in CPO-27-Ni, which is of interest also from a fundamental
surface science point of view. This structure when fully understood using computational means will set as a basis
for further modification of Linker as well as Metal site to search for more strong adsorber for Methane.
 First Principle study on Methane Adsorption in Metal-Organic Framework.

Structure Development

A unit cell of CPO-27-Ni contains two pores, each pore containing 6 metal sites (oxidation no 2+) and 6 linkers
which combines metal sites together and develop a stable structure. Material studio was used to develop the .cif
file of system. A diagram of structure is given below.

Calculations.

VASP code was used for calculation of adsorption energy, Step by step molecules of CH4 were adsorbed on active
sites. First one molecule was adsorbed on metal site and adsorption energy was calculated, the procedure was
continued until all the Metal sites were occupied. In the similar fashion Linker site was saturated with Methane
molecules step by step. Up till now the calculations are running and after all the 6 linkers sites will become saturated
with CH4 molecules a complete monolayer will be formed. After complete monolayer formation another site is
recognised as the adsorption site in literature which is above monolayer. The molecules will fill the sites in the
following order.

1- 6 molecules on Ni 2+ sites
2- 6 molecules on Linker (L) sites
3- 6 molecules on above monolayer (2L) sites

This approach will be proved using computational study. The adsorption Equation employed is given as follows.

E Adsorption = E (A+B)-[E(A)+E(B)]
 EMCHiE topic Abdul Hannan Khan

Results and Discussion.

DFT study so far shows the adsorption is not that much strong on Metal site. The adsorption energy on average is
around -0.3 ev.. The following graph gives adsorption energy curve for different sites.

Adosrption Curve
-0.23000
-0.24000 1-CH4-Ni 2-Ch4-Ni 3-CH4-Ni 4-CH4-Ni 5-CH4-Ni 6-CH4-Ni

-0.25000
-0.26000
-0.25962
Ead (ev)

-0.27000
-0.28000
-0.29000
-0.30000 -0.29047
-0.29669
-0.31000
-0.30820 -0.30597 -0.30557
-0.32000

Molecule A (ev) B (ev) AB (ev) Ead=AB-(A+B) (ev)

112-CPO-27-Ni -947.7718
CH4-Molecule -22.3454
1-CH4-Ni -947.7718 -22.3454 -970.4139 -0.29669
2-Ch4-Ni -970.4139 -22.3454 -993.0190 -0.25962
3-CH4-Ni -993.0190 -22.3454 -1015.67 -0.30820
4-CH4-Ni -1015.6726 -22.3454 -1038.31 -0.29047
5-CH4-Ni -1038.3085 -22.3454 -1060.96 -0.30597
6-CH4-Ni -1060.9599 -22.3454 -1083.61 -0.30557
Avg Ead -0.29442

Data clearly indicates that the adsorption mode is Physisorption.

Future Work.

Future plan for this work is to study the system and try to make in-situ conversion of Methane into some valuable
product, i.e. Formalin etc. this requires chemisorption instead of Physisorption. A lot of transition metals candidates
are available that shows stronger affinity towards methane i.e. Iridium which in previous studies at lab had shown
great affinity towards Methane. In future I will try to replace Ni with Ir metal so that in-situ conversion to valuable
product can be achieved. However, the search for suitable and best MOF is tedious work because of long
calculations period. Currently there are thousands of Linkers that can be suitable with different transition metals.
One cannot calculate all and conclude the best one it will take forever, however statistics approach will be applied
in search for suitable candidate, The CPO-27-Ni will be kept as a base reference molecule and a library of other
Molecules will be developed and a Statistics Model using Python will be developed. The calculation will be run on
small and less expensive theory that will give the candidates which are above the reference molecule in desirable
properties. Therefore, calculation on high level of theory will be done on specifically on those molecules, and best
possible candidate will be preferred, based on stability as well as adsorbing affinity.
 First Principle study on Methane Adsorption in Metal-Organic Framework.

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