Ionothermal synthesis using a hydrophobic ionic liquid as solvent in the

preparation of a novel aluminophosphate chain structure

Emily R. Parnham and Russell E. Morris*
Received 26th July 2006, Accepted 23rd August 2006
First published as an Advance Article on the web 4th September 2006
DOI: 10.1039/b610774e
A novel aluminophosphate chain structure, Al(H
2
PO
4
)
2
F, has
been synthesised ionothermally using the hydrophobic ionic
liquid 1-ethyl-3-methylimidazolium bis((trifluoromethyl)sulfo-
nyl)amide as the solvent.
Ionothermal synthesis
1
is the use of an ionic liquid
2
as solvent, and
in many cases the template provider, in materials synthesis.
36
A
major advantage over hydrothermal and traditional solvothermal
reaction conditions is that ionothermal synthesis takes place at
ambient pressures due to the ionic liquids vanishingly low vapour
pressure, thus avoiding the high autogenous pressures (up to
15 atm at 200 uC) and associated safety concerns that accompany
hydrothermal/solvothermal synthesis.
7
The different chemistry of the ionothermal solvent system, as
compared to that of the traditionally used hydrothermal and
solvothermal systems, produces conditions under which novel
structure types appear to be accessible. These include SIZ-1, the
first material reported using the ionothermal method which
displays some unusual hanging PO bonds and contains alumi-
nium in both 4- and 5-coordination;
1
SIZ-6, a layered material
displaying aluminium with 4-, 5- and 6-coordination;
4
SIZ-7, a
novel Co-AlPO zeolite framework;
3
and (EMIm)
2
[Ni
3
(TMA)
2
-
(OAc)
2
], a metalorganic framework (MOF) synthesised using
microwave heating.
6
To date much of the work on ionothermal synthesis has
concentrated on the use of 1-ethyl-3-methylimidazolium bromide
(EMIBr) as solvent. Whilst this ionic liquid has produced some
interesting results, it has several disadvantages. The hygroscopic
nature of EMIBr makes the handling of the ionic liquid difficult
and even after a moderate drying process it will still contain up to
about 2200 ppm water.
8
The thermal stability of EMIBr is perhaps
not as high as would be liked with studies showing that heating
EMIBr to temperatures of 220260 uC for 0.51.5 h under vacuum
produces 1-substituted imidazoles.
9
A recent study by Parnham
and Morris reports the use of several 1-alkyl-3-methylimidazolium
bromide ionic liquids as solvent in the ionothermal synthesis of
AlPO CHA.
10
In all cases where the alkyl group has a carbon
chain length of 3, 4 or 5 the template is the 1,3-dimethylimida-
zolium cation produced by degradation of the 1-alkyl-3-methyl-
imidazolium cation.
To overcome these disadvantages of the EMIBr ionic liquid, the
anion can be changed to bis((trifluoromethyl)sulfonyl)amide
(Tf
2
N). The Tf
2
N family of ionic liquids are highly stable against
hydrolysis, have high thermal stability to well over 500 uC,
11
low
viscosity and are easily prepared in halogen-free forms due to the
miscibility gap with water.
12
The downside to these seemingly
excellent properties is that the hydrophobic nature of the solvents
results in poor solubilisation of inorganic cations and anions. This
makes them far from ideal as solvents for inorganic materials
synthesis and there are no previous reports of successful prepara-
tion of crystalline materials using such hydrophobic ionic liquids.
One method of improving the solubility of inorganic species is the
use of mineralisers. Mineralisers, such as fluoride or hydroxide
ions, added to the reaction mixtures in the correct quantities are
often vital for crystallisation of the desired molecular sieve
products. Fluoride in particular has recently been an extremely
useful mineraliser for aluminophosphate
13
and silicate
14,15
synthesis. In addition to helping solubilise the starting materials
under the reaction conditions there is evidence that fluoride itself
can play a structure directing role
1619
and is intimately involved
in structure directing agent ordering in certain materials.
20,21
In
ionothermal synthesis the addition of fluoride also seems to be
important in determining the phase selectivity of the reaction.
1
Here we report the synthesis of a novel chain structure
Al(H
2
PO
4
)
2
F produced by ionothermal synthesis using the
hydrophobic ionic liquid EMITf
2
N as the solvent and fluoride
as a mineraliser. A Teflon-lined autoclave (volume 23 ml) was
charged with EMITf
2
N (4.0 g),
22
Al[OCH(CH
3
)
2
]
3
(0.103 g,
Aldrich), H
3
PO
4
(0.176 g, 85 wt% in H
2
O, Aldrich) and HF
(0.015 g, 48 wt% in H
2
O, Aldrich). This gives the ratio of
Al[OCH(CH
3
)
2
]
3
: H
3
PO
4
: HF : EMITf
2
N : H
2
O (from the
aqueous H
3
PO
4
and HF) as 1.0 : 2.9 : 0.69 : 27 : 3.6. The stainless
steel autoclave was then heated in an oven to 170 uC for 96 hours.
The colourless crystals were washed in methanol, suspended in
water, sonicated then filtered under suction and washed with water
and acetone.
The Al(H
2
PO
4
)
2
F crystals were very small (40 620 6 1 mm),
so diffraction data were collected using a Bruker AXS SMART
CCD area detector diffractometer on the high flux microcrystal-
diffraction facility (Station 9.8) of the SRS at Daresbury, UK. The
structure was solved using standard direct methods and refined
using least-squares minimisation techniques against F
2
. The
hydrogen atoms were located using difference Fourier maps and
the OH bond distances fixed at 0.85 A

. The single crystal X-ray

diffraction analysis gives for AlFH
4
O
8
P
2
, M = 239.95, monoclinic,
space group P2
1
/c, a = 8.449(2) A

, b = 4.783(1), c = 15.767(3) A

,
b = 99.491(3)u, Z = 4, m = 0.730 mm
21
, 4222 reflections measured,
1001 unique (R
int
= 0.0656), wR(F
2
) = 0.1240, R(F) = 0.0552.
CCDC reference number 616055. For crystallographic data in CIF
or other electronic format see DOI: 10.1039/b610774e
EaSt Chem School of Chemistry, University of St Andrews, Purdie
Building, St Andrews, Scotland, UK KY16 9ST.
E-mail: rem1@st-andrews.ac.uk; Fax: +44 1334 463808;
Tel: +44 1334 463818
COMMUNICATION www.rsc.org/materials | Journal of Materials Chemistry
3682 | J. Mater. Chem., 2006, 16, 36823684 This journal is The Royal Society of Chemistry 2006
The asymmetric unit of Al(H
2
PO
4
)
2
F (Fig. 1) consists of one
aluminium, two phosphorus, eight oxygen, one fluorine and four
hydrogen atoms. The structure is made up of chains running
parallel to the b-axis, joined together through a hydrogen bonding
network (Fig. 2). The absence of template was confirmed via
CHN analysis which gave C = 0.12, H = 1.23 and N = 0.0%; the
calculated H = 1.67%. The crystals were analysed using EDX to
confirm the presence of fluorine. The reported atomic percentages
are O = 68.43, F = 7.74, Al = 8.60 and P = 15.23%. These values
are comparable with the calculated values of O = 66.67, F = 8.33,
Al = 8.33, P = 16.67%.
The chains are made up of phosphorus atoms tetrahedrally
bonded to four oxygens, two of which are terminal POH. The
other two oxygens are bonded to octahedrally co-ordinated
aluminium (AlO
4
F
2
). These units are reminiscent of units found
in other aluminium
23
and other metal phosphates.
24
There exists an infinite zigzagging AlFAl linkage in the chain
parallel to the b-axis, represented in Fig. 3 as a thicker line. The
chain structure is made up of corner-sharing squares joined
together running parallel to the b-axis. The corners of these
squares consist of three aluminium and one phosphorus. Along the
AlFAl zigzagging linkage are triangles. These are situated
alternately above and below the AlFAl chain running parallel
to the b-axis. The corners of these triangles consist of two
aluminium and one phosphorus. Under similar conditions the
same material can be prepared using a 4-dimethyl-aminopyridi-
nium bis((trifluoromethyl)sulfonyl)amide ionic liquid as the
solvent, but changing the anion to Br
2
or PF
6
2
leads to other
phases. This indicates that perhaps the anion is the controlling
feature of the reaction.
Interestingly the Al(H
2
PO
4
)
2
F material is not templated i.e.
there is no incorporation of the EMI cation into the structure.
This is in contrast to that previously reported using the ionic
liquid EMIBr for the synthesis of SIZ-1, SIZ-3 and SIZ-4.
1
EMITf
2
N is not as polar as EMIBr hence the starting materials
of Al[OCH(CH
3
)
2
]
3
, H
3
PO
4
(85 wt% in H
2
O) and HF (48 wt%
in H
2
O) form a gel at the bottom of the autoclave, which does
not dissolve into the EMITf
2
N. It would appear that this synthesis
may predominantly be a solid-phase transformation rather than
a solution-mediated transformation as seen for SIZ-1, SIZ-3
and SIZ-4.
The original idea behind ionothermal synthesis is to remove the
competition between templateframework and solventframework
interactions that are present in hydrothermal preparations.
However if the anion in the ionic liquid is large and bulky,
leading to hydrophobic ionic liquids, this alters the balance of
chemistry preventing favourable templateframework interactions
hence hindering the formation of a three-dimensional framework.
This work demonstrates the dramatic effect that changing the
anion of the ionic liquid can have on the results produced. Whilst
there is a vast array of ionic liquids available with many different
properties, not all will be immediately suitable for ionothermal
synthesis of porous materials. The Tf
2
N family of ionic liquids
have many favourable properties such as high stability against
hydrolysis and high thermal stability, however the lack of polarity
is evidently a drawback in their use for ionothermal synthesis of
Fig. 1 The asymmetric unit of Al(H
2
PO
4
)
2
F. Note that H3A and H3B
are a statistically disordered pair.
Fig. 2 (Top) Ball and stick (left) and polyhedral representation of the
Al(H
2
PO
4
)
2
F chain down the b-axis. H atoms are omitted for clarity.
(Bottom) Polyhedral representation down the b-axis showing the
H-bonding network (black dashed lines) between donor and acceptor
atoms.
Fig. 3 (Left) Polyhedral representation of Al(H
2
PO
4
)
2
F chain. (Right)
Ball and stick representation of the Al(H
2
PO
4
)
2
F chain omitting the O, F
and H for clarity.
This journal is The Royal Society of Chemistry 2006 J. Mater. Chem., 2006, 16, 36823684 | 3683
zeolites but it is clear from this work that new inorganic materials
are accessible from such solvents.
An alternative strategy to optimise the properties of the ionic
liquid is to use mixtures of anions to provide solvents of
intermediate properties, which would combine the advantages of
the hydrophobic and hydrophilic classes of ionic liquids. This
work is in the early stages but again demonstrates the versatility
of ionothermal synthesis.
We acknowledge the EPSRC for funding of this work and
REM thanks the Royal Society for provision of a University
Research Fellowship.
Notes and references
1 E. R. Cooper, C. D. Andrews, P. S. Wheatley, P. B. Webb, P. Wormald
and R. E. Morris, Nature, 2004, 430, 1012.
2 P. Wasserscheid and W. Keim, Angew. Chem., Int. Ed., 2000, 39, 3773.
3 E. R. Parnham and R. E. Morris, J. Am. Chem. Soc., 2006, 128, 2204.
4 E. R. Parnham, P. S. Wheatley and R. E. Morris, Chem. Commun.,
2006, 380.
5 Y. P. Xu, Z. J. Tian, S. J. Wang, Y. Hu, L. Wang, Y. C. Ma, J. Y. Yu
and L. W. Lin, Angew. Chem., 2006, 118, 4069.
6 Z. Lin, D. S. Wragg and R. E. Morris, Chem. Commun., 2006, 2021.
7 H. Robson, in Verified Synthesis of Zeolite Materials, ed. H. Robson,
Elsiever, Amsterdam, 2001, pp. 4546.
8 J. G. Huddleston, A. E. Visser, W. M. Reichert, E. D. Willauer,
G. A. Broker and R. D. Rogers, Green Chem., 2001, 3, 156.
9 B. K. M. Chan, N.-H. Chang and M. R. Grimmett, Aust. J. Chem.,
1977, 30, 2005.
10 E. R. Parnham and R. E. Morris, Chem. Mater., 2006, in press.
11 J. M. Crosthwaite, M. J. Muldoon, J. K. Dixon, J. L. Anderson and
J. F. Brennecke, J. Chem. Thermodyn., 2005, 37, 559.
12 P. Wasserscheid and M. Haumann, in Catalyst Separation, Recovery
and Recycling, ed. D. J. Cole-Hamilton and R. P. Tooze, Springer,
Dordrecht, 2006, pp. 183210.
13 R. E. Morris, A. Burton, L. M. Bull and S. I. Zones, Chem. Mater.,
2004, 16, 2844.
14 C. A. Fyfe, D. H. Brouwer, A. R. Lewis, L. A. Villaescusa and
R. E. Morris, J. Am. Chem. Soc., 2002, 124, 7770.
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2005, 109, 652.
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Trans., 2004, 820.
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2220.
18 D. S. Wragg and R. E. Morris, J. Am. Chem. Soc., 2000, 122, 11246.
19 D. S. Wragg, A. M. Z. Slawin and R. E. Morris, J. Mater. Chem., 2001,
11, 1850.
20 I. Bull, L. A. Villaescusa, S. J. Teat, M. A. Camblor, P. A. Wright,
P. Lightfoot and R. E. Morris, J. Am. Chem. Soc., 2000, 122, 7128.
21 L. A. Villaescusa, P. S. Wheatley, I. Bull, P. Lightfoot and R. E. Morris,
J. Am. Chem. Soc., 2001, 123, 8797.
22 Synthesis of EMITf
2
N: Under inert atmosphere conditions, degassed
ethylbromide (86.04 g, 0.790 mol, Avacado) was added to the redistilled
N-methylimidazole (49.86 g, 0.607 mol, Aldrich), with constant stirring.
This was refluxed at 40 uC for 3 h then allowed to cool to room
temperature. Ethyl acetate was added and the product crashed out of
solution. This was filtered, washed with ethyl acetate and dried under
vacuum at 25 uC for 10 h to give 1-ethyl-3-methylimidazolium bromide
(EMIBr) as a white solid. The product was stored under an inert
atmosphere. Yield 94%. Mp = 8183 uC.
1
H NMR (D
2
O): d 1.41 (t, 3H,
J = 7.3 Hz), 3.81 (s, 3H), 4.15 (q, 2H, J = 7.3 Hz), 7.38 (d, 2H, J =
21.0 Hz), 8.66 (s, 1H). EMIBr (15 g, 0.079 mol) was placed in a plastic
container and dissolved in about 30 ml distilled water. LiTf
2
N (25 g,
0.087 mol) was dissolved in about 40 ml distilled water and added
dropwise to the EMIBr solution. A colourless oil was produced and the
top aqueous phase decanted. The oil was washed vigorously several
times with distilled water until the washings showed the presence of no
Br
2
when tested with AgNO
3
. The EMITf
2
N was dried at 50 uC on a
vacuum line for 3 hours and stored under argon. Yield 70%.
23 M. P. Attfield, R. E. Morris, I. Burshtein, C. F. Campana and
A. K. Cheetham, J. Solid State Chem., 1995, 118, 412.
24 S. J. Crennell, R. E. Morris, A. K. Cheetham and R. H. Jarman, Chem.
Mater., 1992, 4, 82.
3684 | J. Mater. Chem., 2006, 16, 36823684 This journal is The Royal Society of Chemistry 2006