Shiraz University 13th Iranian Physical Chemistry Seminar Shiraz University of Technology

DFT study of gas-solid interaction in oxidative coupling of methane reactions: CH4 + BaTiO3 perovskite catalyst
Mahtab Gharibi *1,2, Maryam Motalebipour1
1
National Petrochemical Company, Research & Technology Co. (NPC-RT), Tehran center- Iran
2
Department of Chemistry, Tarbiat Moallem University,49 Mofateh Avenue, Tehran-Iran
(E-mail: m.gharibi@npc-rt.ir)

Keywords: DFT calculations, BaTiO3 catalyst, Oxidative coupling of methane (OCM), Bond energy.
1. Introduction
A vast variety of metal oxides has been tested as potential catalysts. Rare-earth compounds, alkali and alkaline-earth metal
compounds, and multivalent metal oxides such as Mn/Na2WO4/SiO2 have been reported as catalysts effective in exothermic
OCM process: CH4 ´ CH3º Catalytic activation-hydrogen abstraction, CH3º ´ C2H6 Rapid gas-phase coupling, C2H6 ´ C2H5º
Catalytic activation and activation by various radicals, C2H5º ´ C2H4 Rapid gas-phase reactions, C2H4 ´ CO Catalytic activation
and activation by various radicals ,CO ´ CO2 Mainly catalytic oxidation.
The theoretical efforts on BaTiO3 towards an understanding of elastic constants, phase transfer, oxygen vacancies,
relaxation, optical band gaps and Ferro electricity, bulk modulus and band structure [1-2]. However, in this work we attempt to
find optimized bulk model BaTiO3 catalyst on OCM process by using hybrid DFT (B3PW, B3LYP) as a new screening and suggest
a catalytic cycle mechanism over BaTiO3 that is more consistent with Ito-Lunsford mechanism on Li/MgO oxide catalyst. Fig. 1
shows the good catalytic performance on BaTiO3 for OCM process [3].

B TiO i
BaTiO3 unit cell

Fig. 1. Activity of methane conversion with various perovskite catalysts. The optimized geometry for 1×1×1 cubic BaTiO3 unit
cell is also shown.
2. Methods
The Gaussian 98 program package has been used for all calculations. The strategy employed in this work is first optimizing
catalyst geometries by making use of ab initio density functional theory (DFT) applying a number of different exchange-
correlation functional, which describes well the lattice structure of perovskite crystals, including hybrid B3LYP or B3PW with the
SSD and LANL2DZ basis sets and then obtaining bulk properties. For calculation of bulk crystal, the BaTiO3 catalyst was modeled
as a finite lattice BanTinO3n (n=8) molecular cluster. This cluster size is significantly larger than the molecular sizes of CH4, O2
and OCM products, so that the chemisorption's properties of the surface should be minimally altered.

3. Results and discussion

We investigated methane adsorption on different reaction sites of its surface while considering lattice fixed during
adsorption via calculation of energies. In Fig. 2 the relative energy of the BaTiO3+CH4 complex is plotted as a function of the C-
H distance to illustrate the dissociation and migration of the CH4 molecule upon adsorption.

Fig. 2. Relative energy of the BaTiO3+CH4 complex as a function of the C-H distance.

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 Shiraz University 13th Iranian Physical Chemistry Seminar Shiraz University of Technology

Table 1 gives the calculated properties for bulk crystal BaTiO3 and CH4 at the B3PW level, together with experimental data.
Standard DFT functional (LDA, BLYP, B3LYP, PW) and uncorrected HF are also added for comparison. Our results confirm that
B3PW/LANL2DZ can be confidently used, the agreement with experiment being of the same order as that achieved by using the
more extended theoretical levels.

Table 1. Comparison of the results for bond lengths and lattice parameter on cubic BaTiO3 (a Ref. [5],b Ref. [6], d Ref. [4].)

Bond Lengths (Å) Lattice Parameter (Å)

This work Expt.b Cubic (a=b=c)
Ba-O 2.8453 2.8365 This work 4.0145
Ti-O 2.0069 2.0057 LDAa, PW91d 3.96, 3.996
Ti-Ba 3.4767 3.4739 BLYP, PBEa, B3LYP, HFa 4.08, 4.03, 4.01, 4.01
CH3-H 1.08 1.08 Expt. 4.0185 b

As an indication of the quality of the chosen correlation method, pseudo potential, and basis sets, in Table 2 the calculated
bond energies (kcal/mol) of relevant gas phase molecules, such as CH4 ´ CH3 + H, C2H6 ´ CH3 + CH3, O2 ´ O + O, with
experimental or series of ab inito data at the HF, MP2, BLYP, G2, and G3MP2B3 levels are compared. Experimentally, the
reaction 4CH4 + O2 ´ 2C2H6+2H2O is exothermic by -84.5 kcal/mol. Using DFT/B3PW level we get -76.23 kcal/mol which is
good agreement with experimental data. We investigated methane adsorption on different reaction sites of its surface while
considering lattice fixed during adsorption via calculation of energies. We investigated methane adsorption on different reaction
sites of its surface while considering lattice fixed during adsorption via calculation of energies.
Table 2. Bond energies (kcal/mol) for some gas phase molecules and reaction energy for methane conversion to ethane.
Reaction Step Theoretical Refs. This work Expt.
O2 ´ O + O 22 (HF)a , 113 (MP2) a 116.74 119.106 ± 0.048 b

a a c b
H2O ´ OH + H 89 (HF) , 119 (MP2) ,123.0 (B3LYP) 98.09 119 ± 1
OH ´ O + H 68 (HF)a , 96 (MP2) a,102.39 ( B3LYp)d 100.45 101.0 ± 0.2
CH4 ´ CH3 + H 88 (HF)a , 107 (MP2) a,104.76(G3MP2B3)b 103.7 104 ± 1 b
C2H6 ´ CH3 + CH3 67 (HF)a , 92 (MP2) a, 90.81 (G2)b 90.65 90.2 ± 0.2
4CH4 + O2 ´ 2C2H6 + 2H2O -74 (HF)a , -73 (MP2) a -76.23 -84.5 b
a b c d
Ref.[7], Ref.[10], Ref. [9], Ref. [8].
References
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