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N
RING 1
RING 2
Molecule
Ring 1
N atom
Ring 2
Diffusion tracks
EVALUATION OF SDA MOBILITY
EVALUATION OF SDA MOBILITY
MD SIMULATIONS
MD SIMULATIONS
Molecule
Ring 1
N atom
Ring 2
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M
S
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[4,5] IN MTW
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[4,5] IN MOR
MD SIMULATIONS
MD SIMULATIONS
RESULTS
RESULTS
!NO TRUE MOLECULAR DIFFUSION PROCESS (D
~110
-11
m
2
s
-1
) SDA MOTION LOCALIZED AROUND
PREFERRED SITES
!THE SDA MOBILITY DECREASES IN THE ORDER:
[5,5]-MOR ) [4,5]-MOR > [5,6]-MOR > [5,5]-MTW ) [4,5]-MTW >
[5,6]-MTW, IN AGREEMENT WITH THE
13
C MAS NMR
DATA
!AZONIA-SPIRO COMPOUNDS DISPLAY HIGHER
TEMPLATING EFFECT FOR MTW THAN MOR
ARE THESE RESULTS USEFUL FOR
DESIGNING NEW SDAS?
OBSERVATION
SDA [5,5] FITS BETTER MWT THAN MOR
HYPOTHESIS
DIFFERENT ZEOLITE PHASES CAN BE OBTAINED IF WE
INCREASE THE STERIC HINDRANCE OF THE SDA AND WE
USE THE NEW SDAS IN THE SAME CONDITIONS WHICH
GIVE MTW (e.g. IN THE PURE SILICA SYSTEM)
MD SIMULATIONS
MD SIMULATIONS
RESULTS
RESULTS
*-Me-[5,5] *,*-di-Me-[5,5]
+,+-di-Me-[5,5] +-Me-[5,5]
+-Et-[5,5]
NEW
NEW
SDAS
SDAS
ZEOLITE SYNTHESIS WITH THE NEW
ZEOLITE SYNTHESIS WITH THE NEW
SDAS
SDAS
+,+-di-Me-[5,5] *-Me-[5,5] +-Me-[5,5]
MTW
MOR
*,*-di-Me-[5,5] +-Et-[5,5]
MEL
MEL
DOCKING CALCULATIONS
DOCKING CALCULATIONS
RESULTS
RESULTS
ZEOLITE VAN DER WAALS ENERGY (kJmol
-1
)
[5,5] +-Me-[5,5] +,+-di-Me-[5,5] *-Me-[5,5] *,*-di-Me-[5,5] +-Et-[5,5]
MEL -109.0 -119.4 -98.8 -121.3 -129.6 -132.2
MFI -87.0 -88.8 -83.6 -71.2 -89.6 -86.2
MOR -100.3 -104.9 -103.2 -103.9 -101.8 -98.3
MTW -103.6 -114.1 -104.4 -111.9 -105.1 -98.1
ZEOLITE RELATIVE VAN DER WAALS ENERGY (kJmol
-1
)
[5,5] +-Me-[5,5] +,+-di-Me-[5,5] *-Me-[5,5] *,*-di-Me-[5,5] +-Et-[5,5]
MEL 0 0 +5.6 0 0 0
MFI +22.0 +30.6 +20.8 +50.1 +40.0 +46.0
MOR +8.7 +14.5 +1.2 +17.4 +27.8 +33.9
MTW +5.4 +5.3 0 +9.4 +24.5 +34.1
&TBA favors the crystallization of MFI/MEL intergrowth with 75%
probability of i-type of stacking (MFI) and 25% probability of #-type
of stacking (MEL) [1]
&The first synthesis of defect-free MEL was reported in 1995, using
N,N-diethyl-3,5-dimethylpiperidinium (DDP) [2]
[1] G. Perego et al., J . Appl. Cryst. 17 (1984) 403
[2] Y. Nakagawa, WO Patent 95/09812
+-Et-[5,5] *,*-di-Me-[5,5]
SIMILAR
DDP
SYNTHESIS OF DEFECT
SYNTHESIS OF DEFECT
-
-
FREE MEL
FREE MEL
i
a
c
b
c
m
a
c
b
c
a
c
MFI
MEL
MFI/MEL
SBU
5-1
PerBU
THE PENTASIL FAMILY
THE PENTASIL FAMILY
Standard laboratory XRD
Sharp 110 reflection indicates
the lack of intergrowth
SXPD (GILDA -BM08, ESRF)
I4m2 space group
a = 20.0777(3), c = 13.4154(2)
Rwp = 0.0276, R(F
2
) = 0.0703,
Red. ,
2
= 1.213
R. Millini et al., 2
nd
FEZA Conf. (2002)
IS IT REALLY DEFECT
IS IT REALLY DEFECT
-
-
FREE MEL?
FREE MEL?
IS IT REALLY DEFECT
IS IT REALLY DEFECT
-
-
FREE MEL?
FREE MEL?
MEL/+-Et-[5,5]
E
vdW
= -132.2 kJmol
-1
MFI/+-Et-[5,5]
E
vdW
= -86.2 kJmol
-1
MEL/DDP
E
vdW
= -120.5 kJmol
-1
MFI/DDP
E
vdW
= -111.3 kJmol
-1
BASE SDA
STRUCTURE
MODIFICATION
Feasibility
Costs
Stability
.
DOCKING
MINIMIZATION
Compatibility With
The Porous Systems
Obtained With The
Parent SDA
SDA
SYNTHESIS
ZEOLITE
SYNTHESIS
DESIGN OF NEW
DESIGN OF NEW
SDAS
SDAS