7 The Role of Cation-Templating, Co-Templating, or No Templating

96



N



3 Ionothermal Synthesis of Zeolites and Other Porous Materials



Br

+

N



Br

+

N



Br

+

N



N



Br

+

N



N



Br

+

N



Br

+

N



Figure 3.4 The effect of changing the size of the IL cation

on the resulting metal organic framework structure. The materials prepared in this study are Ni (blue) or cobalt (purple)

terephthalate MOFs.



EMIM-templated materials SIZ-1 and SIZ-4 have closely related structures to the

EMIM-‘‘templated’’ layer in this material.

Up to now, the cation in the IL has only acted as a template in the synthesis.

However, like any other solvent, including water, there is also the possibility

of bonding interactions with the frameworks. Most of the ILs that are based on

di-alkylated imidazolium cations have no obvious sites through which to coordinate

to the metal sites in the way that water does. However, some ILs, under specific

conditions, can breakdown to leave the monoalkylated imidazole species that can

coordinate to metals [63]. As in hydrothermal synthesis, controlling how the solvent

interacts with the framework materials is therefore important in determining the

exact nature of the final material. A similar example where the solvent can

coordinate to the metal in a metal organic framework comes when using choline

chloride/urea-based DES ILs. Normally, this type of solvent is regarded as being

relatively unstable, especially the urea portion which can break up and deliver

smaller templates into the reaction. However, under conditions where the urea is

stable, it is possible to keep this intact, and in the case of ionothermally prepared

lanthanum-based MOFs the urea coordinates to the metal [64].

In addition to the templating cations, ILs also contain an anion, and these

turn out to be extremely important in controlling the properties of the solvents

(Section 3.8). The anions can, in certain circumstances, also be occluded in the

structure as a template, most often in combination with the IL cation. Bu et al.

recently showed that in a series of MOFs (called ALF-n) the IL displayed several

different types of behavior, including templating by only the cation and templating



3.8 The Role of the Anion – Structure Induction



by both the cation and anion simultaneously, illustrating the multiple functions

that ILs can play even in the same systems [56].

Finally, of course, the ILs can only play the role as solvent and not be occluded

in the final structure at all. For species like aluminophosphate zeolites and MOFs

where the chemistry of the cation is similar to that of commonly used templates

one would expect them to be occluded in the final structure. However, there are

certain situations where this does not happen. Perhaps the most striking of these

is when a very hydrophobic IL is used. In the case of aluminophosphate and MOF

synthesis, the more hydrophobic the IL used the less likely the IL cation is to be

occluded [32]. Of course, as the chemistry of the system is changed (e.g., by trying

to make different types of inorganic material), the balance between the solvent and

templating actions of ILs also changes.



3.8

The Role of the Anion – Structure Induction



As we have seen above, the common organic cations in ILs are chemically very

similar to zeolite templates. However, ILs also contain an anion, and the nature

of the anion plays an extremely important part in controlling the nature of the IL.

Figure 3.5 demonstrates this dependence of property on anion very clearly. Two

low melting ILs that are solid at room temperature can be prepared from the same

cation (EMIM) but with two different anions – bromide and triflimide (NTf2 ). The

two ILs have very different properties, especially when it comes to their interaction

with water. Figure 3.6 shows what happens when the two compounds are left out

in the air for 20 minutes. EMIM NTf2 is a relatively hydrophobic material and there

is no change in its properties on exposure to the moisture in the air. EMIM Br, on

the other hand, is highly hygroscopic and turns liquid on reaction with moisture

in the air.

Clearly, this change in IL chemistry on alteration of the IL anion is bound

to have a significant effect on the products of any reaction carried out in such

solvents. One example of this is given in Section 3.7, where in the synthesis of

aluminophosphates EMIM Br solvents lead to incorporation of the EMIM cation

to form zeotype materials, whereas the use of the EMIM NTf2 IL leads to no

occlusion of the IL cation [32]. More interesting, however, and potentially extremely

useful, is the possibility of mixing the two types of liquid to form solvents with

different chemistries from the end member liquids. Figure 3.6 illustrates this for

the synthesis of cobalt bezenetricarboxylate MOFs [65]. The two end member ILs,

EMIM Br and EMIM NTf2 , form two different types of material, while a 50 : 50

mixture of the two ILs, which are miscible, forms a third structure type. This type

of result opens up the possibility of mixing ILs to form solvents whose chemistry

is different from the end members, giving rise to much more control over the

properties of the solvent. In a similar example, a mixed anion IL (50% bromide 50%

triflimide) leads to the formation of coordination polymers containing fluorinated



97



98



3 Ionothermal Synthesis of Zeolites and Other Porous Materials



A



B



A



B



Figure 3.5 The effect of moist air on hydrophobic EMIM

triflimide (sample A) and hydrophilic EMIM Br (sample B).

After 20 minutes exposure to normal air at room temperature, the EMIM Br has absorbed enough moisture from the

atmosphere to turn from a solid into a liquid.



ligands when ILs containing only one anion (either bromide or triflimide) does not

produce any crystalline solid [66].

It is clearly the nature of the anion that determines the final material in these

examples. However, the anions themselves are not generally occluded into the

structure, and so this is an induction effect rather than a templating of the structure

directing effect. It is perhaps not too surprising that changing the chemistry of the

solvent will change the type of product in such a manner. In the example illustrated

in Figure 3.6, there is no obvious correspondence between the nature of the anions

and the nature of the final material. However, in 2007, we published an example

of an anion induction using a chiral anion as part of an IL to induce a chiral

coordination polymer that contains only achiral building blocks [67] (Figure 3.7).

In this example, a chiral IL prepared from the butyl methyl imidazolium (BMIM)

cation in combination with l-aspartate as the anion, when used to prepare a cobalt

bezenetricarboxylate MOF produced a chiral structure, with all indications that the

bulk solid produced was homochiral. Where some specific property of the IL anion

manifests itself in the resulting material, despite the fact that it is not actually

occluded, the potential for ‘‘designer’’ structure induction becomes very attractive,

and one would hope that such properties of ionothermal synthesis will be explored

and exploited more thoroughly in the near future.



3.9 The Role of Water and Other Mineralizers



N



Br

+

N



100% bromide



50% bromide 50% triflimide



100% triflimide



Figure 3.6 The effect of the anion on the

final structure of the material produced in

an ionothermal synthesis. The top reaction

shows uses EMIM Br as the solvent, and

produces one particular cobalt-trimesic acid



MOF. A 50 : 50 mixture of EMIM Br and

EMIM triflimide produces a different MOF,

while using only the EMIM triflimide produces yet another material.



3.9

The Role of Water and Other Mineralizers



One of the very first questions asked about ionothermal synthesis was whether the

ILs used were sufficient in their own right to promote the synthesis of zeolites

and other inorganic materials, particularly those oxides where water might catalyze

the condensation reactions needed to form the required bonds. One of the first

things noted about ionothermal synthesis was that too much water was detrimental

to the formation of zeolites. At low concentrations of water, zeolites were the

main products, but as more water was added to the IL solvents so that they were

about equimolar in concentration only dense phases could be prepared. Wragg

and coworkers studied this effect in more detail and confirmed through several

hundred high-throughput reactions that larger amounts of water did indeed lead

to dense phases [63]. The origin of this effect is still under investigation but it

is known that the microstructure of water in ILs changes with concentration.

At low concentrations, the water is hydrogen bonded relatively strongly to the

anion, and exists either as isolated water molecules or as very small clusters [68].

However, as the concentration of water increases, larger clusters and eventually



99



100



3 Ionothermal Synthesis of Zeolites and Other Porous Materials

O

N



+



N



HO



O

O



−



NH2



Figure 3.7 The use of an ionic liquid with a chiral anion

induces a chiral MOF structure. Use of an achiral anion

produces achiral structures.



hydrogen-bonded networks start to appear, which change the properties of the

liquid markedly. Eventually, of course, as more and more water is added, it

becomes the dominant chemical component (and therefore the solvent) and the

system becomes hydrothermal rather than ionothermal.

The strong binding of isolated water molecules in ILs leads to another interesting

effect that can be used in ionothermal synthesis – so-called water deactivation. At

low concentrations of water, this strong hydrogen bonding leads to water being

less reactive than similar amounts in other solvents. This effect is so strong

that highly hydrolytically sensitive compounds such as PCl3 can be stored for

relatively long periods, whereas they react quickly, and often violently, in other

‘‘wet’’ solvents [69]. Such water deactivation is probably the reason why some of

the materials prepared using ILs can have unusual features. For instance SIZ-13, a

cobalt aluminophosphate material, has a layered structure that is closely related to a

zeolite, but has Co–Cl bonds. Normally such bonds are hydrolytically unstable and,

under hydrothermal conditions, it is unlikely that this material would be stable [27].

In zeolite (and other) synthetic procedures, mineralizers, such as fluoride or

hydroxide ions, added to the reaction mixtures in the correct quantities are often

vital for crystallization of the desired molecular sieve products. Fluoride in particular

has recently been an extremely useful mineralizer for aluminophosphate [70] and

silicate [71, 72] synthesis. In addition to helping solubilize the starting materials

under the reaction conditions, there is evidence that fluoride itself can play a

structure directing role [73] and is intimately involved in template ordering in

certain materials [74, 75]. In ionothermal synthesis, the addition of fluoride also

seems to be important in determining the phase selectivity of the reaction [9]. It may

also help catalyze the bond-forming reactions in zeolite synthesis, as suggested by

Camblor and coworkers [71]. For instance, in the synthesis of aluminophosphates,



3.11 Summary and Outlook



the addition of fluoride leads to the formation of SIZ-4 and SIZ-3, which are both

fully four-connected zeolite frameworks, SIZ-1, which is an interrupted structure

with some unconnected P–OH bonds.

Tian and coworkers have recently completed an extremely useful kinetic study

of the effect of both water and fluoride added to ionothermal systems in zeolite

synthesis [76]. It is clear from their results that both small amounts of water, and

particularly fluoride, increase the crystallization rate. If the reactions are carried

out carefully to exclude as much water as possible, the crystallization of the zeolites

becomes very slow indeed, suggesting that for all practical purposes a small

reactant amount of water (probably in the IL) is vital if ionothermal synthesis is to

be successful.

3.10

Unstable Ionic Liquids



In many publications, one often sees the mention of the high thermal and chemical

stability of ILs. Bearing in mind of course that it is difficult to generalize across all

the possible ILs, this is true under many conditions. However, under ionothermal

conditions, some quite common ILs can breakdown. Even some that are often

relatively stable such as BMIM bromide can breakdown, especially in the presence

of fluoride ions [77]. One possible reaction is the transalkylation reaction that swaps

the alkyl groups, leading to the formation of dimethylimidazolium cations, which

then templates a zeolite structure [77].

DES ILs based on choline chloride/urea mixtures are also unstable under

ionothermal conditions. The urea portion of the IL breaks up to release ammonium

ions into the mixture, which then templates the SIZ-2 aluminophosphate material.

This type of instability in the ILs is actually extremely repeatable. Deep eutectic

ILs made from functionized ureas all break down in the same way to produce the

expected functionalized ammonium or diammonium cations that then go on to

template many different structures [78]. Such reproduction ability in the reactions of

these ILs opens up interesting possibilities for the delivery of small amounts of template to the reaction mixture, as opposed to having the whole IL made up of the

template.

3.11

Summary and Outlook



Normally, ILs are classed as ‘‘green’’ chemicals because they are most often used

to replace volatile organic solvents. However, when preparing the materials, this

perspective has been discussed and, in particular, all inorganic framework solids

such as zeolites and ILs are more often than not replacing water. In these situations,

ionothermal synthesis cannot be called a green technology compared to that which

it replaces. When replacing organic solvents in, for example, the synthesis of

metal organic frameworks there is more justification for using the ‘‘green’’ tag.



101



102



3 Ionothermal Synthesis of Zeolites and Other Porous Materials



However, even in these syntheses, the success of the methodology has to rely

on the ILs introducing new chemistry into the system that is not possible using

other systems. Fortunately, over recent years, ionothermal synthesis has been

recognized as a highly flexible methodology that does indeed bring new chemistry

to the system. Features like water deactivation and chiral induction offer many

possibilities for the preparation of materials that are unlikely or even impossible to

make in other solvents.

One of the most interesting features of ILs for ionothermal synthesis is the sheer

number of possible liquids available. There are an estimated 1 million binary ILs

available, compared to only a few hundred molecular solvents. The wide range of

accessible properties of the liquids provides huge opportunities for matching the

chemistry of the solvent system to that of the reactants. However, this also presents

huge challenges – it is at the moment extremely difficult to predict a priori the

properties of the solvent and how they will behave in combination with the reactants.

Up to now, only a few of the easily available ILs have been studied, leaving many

potentially interesting solvents completely unexplored. One particularly interesting

feature of ionothermal synthesis is the use of mixed ILs to tailor the solvent toward a

particular reaction chemistry by mixing two different miscible ILs to produce a new

solvent with different properties (Section 3.8). Once again the issue of predicting

the properties of the mixed ILs is a problem. However, this type of approach is

particularly suited to high-throughput methodologies because new solvents can

be prepared simply by mixing two ILs in various amounts, and the ‘‘brute force’’

approach afforded by high-throughput instrumentation can at least identify areas

of interest in the compositional fields.

The use of ILs in the synthesis of solids has, of course, not been limited to

new hybrid and inorganic framework solids. Work in the nanomaterials area and

increasingly in other areas, such as the organic solid state, has increased steadily

over the last few years. However, there is still much scope to develop the synthesis

methodology further.

In the field of zeolite science, the challenges are clear, particularly for the

synthesis of silica-based zeolites. Here the plethora of possible ILs is both a

blessing and a challenge as we really need to understand more fully the speciation

of silicate ions in particular when they are dissolved in ILs. It is clear that the

change from molecular to ionic solvents significantly affects the chemistry, and

that new zeolite-type structures will inevitably arise from ionothermal preparations.

We hope that as we discover ever more about the interesting properties of ILs the

field of ionothermal synthesis will develop into an even more useful addition to the

armory of synthetic zeolite chemists.

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