[upgrade] my account ·

Post New Content Invite People logout

Inbox Contacts Groups • Inbox • Search
Media Locker atp cooperative • Media Locker • Invite
Shop Search • atp • Post
cooperative

"atpcorporation" Website: GODSEND Products- Fulvic

Acid ("Miracle Molecule") & Natural ZEOLITES , * * * "
F R E E " in the P H I L I P P I N E S ! ! ! . with
"ORGANIC GERMANIUM" - SYNTHESIZED by ATP with
the DIVINE PROVIDENCE of our CREATOR ****
CONTACT US / JOIN US . . . . TOGETHER LET'S MAKE
A BEAUTIFUL WOLD * * * *

HomeNotesBlogPhotosVideoMusicCalendarReviewsLinks

Process for making a germanium-zeolite. Atp Medical Jun 14, atpcoop

'09 1:49
Literature - Series # 017. Source: AM
atp
cooperat
http://www.sciencemag.org/cgi/content/full/304/5673/9 for
everyon ive
90 e
Online
... now

Reports ( We report the Quezon

City, NCR
• U

synthesis and some

p
gr
a
d
characterizations of IM-
e
A
cc
o

12, a thermally stable

u
nt
• C

germanium-containing us
to
mi

. . . .)
ze

zeolite M
y
Si
te
• Pr
o
Extra-Large-Pore Zeolites with Two- m
ot

Dimensional Channels Formed by e

M
y

14 and 12 Rings Si
te

Jean-Louis Paillaud,1* Bogdan • M

y
C
Harbuzaru,1 Joël Patarin,1 Nicolas o
nt

Bats2 ac
ts
(8
2
9)

Stable zeolites that have

• M
y
G

larger pore apertures and a three- ro

u
ps
dimensional pore topology are of (4
7)

interest because they couldbe

• P
h
ot
os

used to adsorb larger

of
M
e
•
molecules, particularly for
R
S
S
F

application in oil
e
e
d
refining.
[?
]
•

Several large-pore zeolitic

materials with channels formed by
openings of more than 12 rings are
known, but all of them have a one-
dimensional channel system that
limits their use in catalysis.
We report the synthesis and
some characterizations of IM-12, a
thermally stable
germanium-containing
zeolite that contains the first
two-dimensional channel system
with extra-large pores formed by 14-
and 12-ring channels.
1
Laboratoire de Matériaux
Minéraux, UMR-CNRS 7016, Ecole
Nationale Supérieure de Chimie de
Mulhouse, Université de Haute
Alsace, 3 rue Alfred Werner, 68093
Mulhouse Cedex, France.
2
Institut Français du Pétrole, IFP-
Lyon, Boîte Postale 3, 69390
Vernaison, France.
*
To whom correspondence should
be addressed. E-mail:
jl.paillaud@uha.fr <!-- var u =
"jl.paillaud", d = "uha.fr";
document.getElementById("em0").in
nerHTML = '<a href="mailto:' + u +
'@' + d + '">' + u + '@' + d +
'<\/a>'//-->
Because of their high
thermal stability, new
zeolites are of interest in
petroleum refining, especially those
with larger pores and systems of
intersecting channels that could
potentially process
larger hydrocarbon
molecules. Two approaches
have led to larger pore systems.
One is the use of fluoride
–
ions in place of OH
species (1–3), because the
fluoride appears to act
as a structure-
directing agent (SDA)
that plays a templating role (4–6).
The other is the use
of two
sources of framework
atoms.
For example, the
silicogermanates ITQ-12 (7), ITQ-17
(8), ITQ-21 (9), and ITQ-22 (10)
present new topologies that include
F–-containing double four-ring (D4R)
cubic units in their structures
(Scheme 1), thus confirming the
template role of the F– ion toward the
formation of these D4R units.
Interestingly, ITQ-17 (11) and ITQ-
21 (12) can also be prepared in a
fluoride-free medium, but at a slower
crystallization rate.
The formation of
such porous
structures is also related
to the presence of Ge-
O-Ge angles, which are
smaller than the Si-O-
Si angles that change the
geometric constraints in the D4R
units and thus stabilize the resulting
structures (13).
Theoretical calculations
confirm this interpretation (14),
together with the reported
preferential occupation of the
tetrahedral (T) sites of the D4R by
Ge in the zeolites obtained from Si-
and Ge-containing synthetic gels
(14–16), and also with the
observed faster
crystallization rate of
the ITQ-7 zeolite in its
Si- and Ge-containing
form (14).
Scheme 1. One F-
containing D4R
cubic unit of
formula T8O20, in
which each T atom
 is at the center of a
tetrahedron and the
oxygen's atoms are
at the vertices.
[View Larger
Version of this
Image (32K GIF
file)]

We prepared the extra-large

pore zeolite IM-12 (Institut Français
du Pétrole/Mulhouse–12), a Ge-
containing zeolite, from a
fluoride-free synthesis medium in
the presence of organic (6R,10S)-
6,10-dimethyl-5-
azoniaspiro[4,5]decane cations as
SDA. This zeolitic
material
displays a high
thermal stability and
high adsorption
capacity.
Depending on the
crystallization conditions (17), the
silicogermanate IM-12
shows two different
crystal morphologies.
Under static conditions,
aggregates of size 150 by 150 by
200 µm (Fig. 1A) resulting from the
superposition of thin
platelet-
like crystals are
formed.
Under stirring conditions,
gypsum flower-type
aggregates are
produced with more
isolated crystals, with
sizes of 5 by 5 µm and thicknesses
of about 300 nm (Fig. 1B).
The chemical and the thermal
gravimetric and differential thermal
analyses of IM-12
synthesized in this way
indicated a Si/Ge
atomic ratio of about
4.5 and a total weight
loss of 15.7%, respectively,
which are consistent with the unit
cell formula: |
(C11H22N)4(H2O;OH)16|
[Ge13.8Si62.2O152].
Fig. 1. Scanning
electron
microscopy pictures
show two different
morphologies of the
IM-12 zeolite
synthesized under
(A) static and (B)
stirring conditions.
[View Larger
Version of this
Image (47K GIF
file)]

The three-dimensional (3D)

structure of IM-12 (17) may be
described as layers
stacked
in the [100] direction,
connected to each
other by their four-
membered rings and
thereby forming D4R
units (Fig. 2, left).
From the structure
determination and the Rietveld
refinement, the Ge atoms can only
be localized at T sites of the D4R
unit.
According to the
chemical analysis, the
average Si/Ge atomic
ratio in the D4R units
is 1 Ge to 7 Si atoms.
Such a distribution is in
agreement with those previously
reported for the microporous
silicogermanates with the topologies
ISV, ITH, and AST (14–16, 18).
Thus, each layer is essentially
siliceous and constructed of fused
small [415462] and [5262] cages.
The topology of IM-12 is that
of a 2D channel system formed by
14- and 12-ring intersecting
channels parallel to the c and b
axes, respectively (Fig. 2). The
framework density of
IM-12 is 15.2 T atoms
3
per 1000 Å .
This value is lower than that of
other zeolitic materials containing
14-ring channels, such as UTD-1
(19), CIT-5 (20), SSZ-53, and SSZ-
59 (18, 21) but higher than those
recently reported for ECR-34 (18-
ring pores) (22) and OSB-1 (a
beryllosilicate with 14- and 8-ring
intersecting channels) (18).
The crystallographic data of
IM-12 led to a free-pore diameter of
9.5 by 7.1 Å and 8.5 by 5.5 Å for the
straight elliptical 14- and 12-ring
channels, respectively; these values
are comparable to 9.3 by 7.6 Å,
which was observed for the 14-ring
opening of the borosilicate SSZ-59
(21).
A calcination
at
550°C under air for
several hours was sufficient
to empty the pore volume of IM-12.
Moreover, after several cycles of
calcination at 600°C, the structure of
IM-12 remained intact.
We evaluated the
adsorption capacity of
this highly thermally stable material
by N2 adsorption
measurements. The N 2
adsorption isotherm of IM-12, of type
Ia, according to the International
Union of Pure and Applied
Chemistry nomenclature (fig. S2)
(17), is characteristic
of a
microporous material
that lacks secondary
micropores and
mesopores.
The corresponding
Brunauer-Emmet-
Teller surface area of
2 –1
670 m g and the
microporous volume of 0.26 cm3 g–1
are similar to those of wellknown
highly porous
zeolites of
topology FAU or EMT
(18).
The pore-size distribution is
rather narrow and centered on 10 Å
(fig. S3) (17). This value is slightly
higher than the one calculated from
the crystallographic data; the
disparity may reflect the
noncylindrical shape of the pores or
the effect of the side pockets of the
12-ring channel, which the model
does not take into account (Fig. 3).

Fig. 2. The 3D
structure and the
2D channel system
of the IM-12 zeolite.
The connection
between the
silicogermanate
layers lying in the
(100) plane shows
the 14-ring channel
along [001] (left)
and the 12-ring
channel along [010]
(right). The dark
gray circles are the
Ge atoms. There
are no openings
down [100]. [View
Larger Version of
this Image (60K
GIF file)]

Fig. 3. View down a

direction close to
[001] reveals the
tie-shaped
 pseudocage formed
in combination with
the side pockets.
[View Larger
Version of this
Image (16K GIF
file)]

The incorporation
of heteroatoms in the
framework of the
thermally stable
zeolite IM-12 is also
possible by direct or
postsynthesis.
The highest Al/(Si + Ge)
molar ratio obtained is close to 0.2.
The ability
to
incorporate Al
suggests that this
material may have
catalytic applications
as well.
References and Notes
• 1. E. M. Flaningen, R. L. Patton,

U.S. Patent 4, 073, 865 (1978).

• 2. J.-L. Guth, H. Kessler, R. Wey,

Stud. Surf. Sci. Catal. 28, 121

(1986).
• 3. J. Patarin, J.-L. Paillaud, H.

Kessler, in Handbook of Porous

Solids, F. Schüth, K. S. W. Sing,
J. Weitkamp, Eds. (Wiley,
Weinheim, Germany, 2002), vol.
2, pp. 815–876.
• 4. P. Caullet, J.-L. Guth, J.
 Hazm, J.-M. Lamblin, H. Gies,
Eur. J. Solid State Inorg. Chem.
28, 345 (1991).
• 5. A. Corma, M. Puche, F. Rey,
G. Sankar, S. J. Teat, Angew.
Chem. Int. Ed. Engl. 42, 1156
(2003).[Medline]
• 6. E. Aubert, F. Porcher, M.
Souhassou, V. Petricek, C.
Lecomte, J. Phys. Chem. B 106,
1110 (2002).[CrossRef]
• 7. P. A. Barrett et al., Chem.
Commun. 2003, 2114 (2003).
[CrossRef]
• 8. A. Corma, M. T. Navarro, F.
Rey, J. Rius, S. Valencia,
Angew. Chem. Int. Ed. Engl. 40,
2277 (2001).[CrossRef][Medline]
• 9. A. Corma, M. J. Diaz-
Cabanas, J. Martinez-Triguero,
F. Rey, J. Rius, Nature 418, 514
 (2002).[CrossRef][Medline]
• 10. A. Corma, F. Rey, S.
Valencia, J. L. Jorda, J. Rius,
Nature Mater. 2, 493 (2003).
[CrossRef][ISI][Medline]
• 11. A. Corma, M. Navarro, F.
Rey, S. Valencia, Chem.
Commun. 2001, 1486 (2001).
[CrossRef]
• 12. A. Corma, M. J. Diaz-
Cabanas, F. Rey, Chem.
Commun. 2003, 1050 (2003).
[CrossRef]
• 13. M. O'Keeffe, O. M. Yaghi,
Chem. Eur. J. 5, 2796 (1999).
[CrossRef]
• 14. T. Blasco et al., J. Phys.
Chem. B 106, 2634 (2002).
[CrossRef]
• 15. J. A. Vidal-Moya, T. Blasco,
F. Rey, A. Corma, M. Puche,
 Chem. Mater. 15, 3921 (2003).
• 16. Y. Wang, J. Song, H. Gies,
Solid State Sci. 5, 1421 (2003).
[CrossRef]
• 17. Materials and methods are
available as supporting material
on Science Online.
• 18. All framework type codes are
derived from the names of the
type materials and consist of
three capital Roman letters. For
more information, see Ch.
Baerlocher, W. M. Meier, D. H.
Olson, Atlas of Zeolite
Framework Types (Elsevier,
Amsterdam, ed. 5, 2001); also
available at www.iza-
structure.org/databases.
• 19. C. C. Freyhardt, M.
Tsapatsis, R. F. Lobo, K. J.
Balkus, M. E. Davis, Nature 381,
 295 (1996).[CrossRef][ISI]
• 20. M. Yoshikawa et al., J. Phys.

Chem. B 102, 7139 (1998).

[CrossRef]
• 21. A. Burton et al., Chem. Eur.

J. 9, 5737 (2003).[CrossRef]
• 22. K. G. Strohmaier, D. E. W.

Vaughan, J. Am. Chem. Soc.

125, 16035 (2003).[CrossRef]
[ISI][Medline]
• 23. We thank the Institut

Français du Pétrole for providing

the germanium source. B.H.
thanks the Ministère de
l'Education Nationale, de la
Recherche et de la Technologie
for financial support.
Supporting Online Material
www.sciencemag.org/cgi/content/full
/304/5673/990/DC1
Tags: medical literature
Prev: USES OF ATP's ZEOLITE. "God Created Men From DusT (Zeolites) ... from Dust (Zeolites)
He Shall Return".. ATP Medical Literature - series #016
Next: Medical use of Organic Germanium(Ge-132) . ATP Medical Literature - Series - #018.
edit delete
reply share

audio reply video reply

Add a Comment
Top of Form
U2FsdGVkX1-X6 reply 1

reply

6169:U2FsdGVkX
F
o Add a comment to this blog entry, for
r: everyone
Send atpcoop a personal message

S
u
b
j Re: Process for m
e
c
t:

Quote original message

Submit (Ctrl+Enter) Preview & Spell Check

submitted
Bottom of Form

navydiverjlm

lorraineszone

ayene88
Viewing History
This Blog Entry has been viewed 3 times by 3 people, most recently on Jun 14, '09
See Detailed Viewing History
View This Page as Another User

© 2009 Multiply, Inc. About · Blog · Terms · Privacy · Corporate · Advertise · Contact · Help