ModeIing of surface properties of IameIIar zeoIites

1an Hermann, MichaI 7rachta, and Ota 8Iudsky

|nstltute of Organlc Chemlstry and 8lochemlstry, Academy of Sclences of the Czech Pepubllc, Plemlngovo nam. 2, !66 !0 Praha 6, Czech Pepubllc
Introduction
3D zeolltes UTL or |TH can be broken down
to 2Dlamellae by dlssolvlng thelr D4P brldg-
lng unlts.
!,2
Proper treatment of van der waals forces ls
cruclal ln modellng physlsorptlon of small
molecules on 2D zeolltes.
we use the emplrlcal DPT/CC method
3
slm-
plled by a physlcal model for dlsperslon.
Studied systems
!T and 2T models of the slllca framework are
used for parametrlzatlon of our method.
8lndlng energles of molecules at several
speclc sltes of 2D-UTL, 2D-|TH and 3D-|TH
were calculated.
Z
B
A
C
D
U
Deformation energy
1
5
1
1
1
5
10
15
1
C
H
4
C
O
2
H
2
H
2
O
N
2
A B C D U Z
Site
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e
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a
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J
/
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o
l
)
Dimension
2D
3D
Deformatlon energy ls slgnlcant for water
lnteractlng wlth sllanol groups vla hydro-
gen bonds.
Comparison of dispersion-corrected DI7 methods
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1
3
10
30
1 3 10 30
vdWDF/CC binding energy (kJ/mol)
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/
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o
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Method
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CCSD(T)
DFTD2
vdWDF2
PBE
20
10
0
10
Passage through the pore
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vdWDF/CC
vdWDF2
DFTD2
PBE
DPT-D2 and vdw-DP2 predlct an energy
mlnlmum ln the mlddle of the cross-
lamellar pore ln |TH.
Our methodpredlcts a barrler whlchpre-
vents the passage through the pore.
Two wldely used methods for dlsperslon ln-
teractlon, DPT-D2 and vdw-DP2, overestlmate
blndlng energles ln the studled systems.
The error can be as much as !00% ln case of
CH
4
or N
2
.
Our method provldes blndlng energles wlth
the accuracy of ! k1/mol (several percent).
The behavlour of the methods ls conslstent be-
tween the 2T model and a full zeollte, lndlrectly
provlng the transferablllty of our method.
ects of 3D to 2D transformation of I7H on binding energies
0
10
0
10
0
0
10
50
0
10
C
H
4
C
O
2
H
2
H
2
O
N
2
A B C D U Z
Site
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o
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)
Dimension
2D
3D
Sltes 8, C, D and U are present ln both
2D- and 3D-|TH, whlle sltes Aand Z are
unlque for 2D-|TH (on sllanol hllls
formed after dlssolvlng the D4Ps).
Several enects contrlbute to the
changes ln blndlng energles:
Hydrogen-bond and electrostatlc ln-
teractlons wlth sllanol groups of the
2D zeollte (H
2
O, CO
2
).
Conned space enect enhances dls-
perslon lnteractlon ln the 3D zeollte.
2D zeollte ls more nexlble to accom-
modate larger molecules (lnner sltes,
CH
4
).
ConcIusions
Standard methods for descrlblng van der
waals forces ln DPT are not only lnaccurate,
but can provlde qualltatlvely wrong results.
8oth the framework and surface of 2D zeo-
lltes are more nexlble than those of thelr 3D
counterparts.
The domlnant feature of the surface of 2D ze-
olltes ls the presence of sllanol groups, whlch
strongly lnteract wlth polar molecules, espe-
clally water.
References
!. Poth, w. 1. et al. J. Am. Chem. Soc. I33, 6!30 (20!!).
2. Gra[clar, L., 8ludsky, O., Poth, w. 1. & Nachtlgall, P.
Catal. Today 204, !5 (20!2).
3. 8ludsky, O., Pube, M., Soldan, P. & Nachtlgall, P.
J. Chem. Phys. I28, !!4!02 (2008).
AcknowIedgment
Thls work was supported by the Czech Sclence Pounda-
tlon Grant No. P!06/!2/G0!5.
Iurther information
ota.bludskyQuochb.cas.cz