Dynamic Article LinksC<Journal ofMaterials Chemistry

Cite this: J. Mater. Chem., 2011, 21, 7582

www.rsc.org/materials PAPER

Publ

ishe

d on

26

Apr

il 20

11. D

ownl

oade

d by

St.

Pete

rsbu

rg S

tate

Uni

vers

ity o

n 09

/12/

2013

12:

26:3

3.

View Article Online / Journal Homepage / Table of Contents for this issue

Engineering structured MOF at nano and macroscales for catalysis andseparation†

Sonia Aguado,* Jerome Canivet and David Farrusseng

Received 22nd February 2011, Accepted 28th March 2011

DOI: 10.1039/c1jm10787a

Here, we present for the first time the combination of the postfunctionalization of a MOF with its

shaping as structured bodies. This study deals with the porous zinc carboxylimidazolate material

known as SIM-1. A great advantage of this method is that the aldehyde moieties present on the

structure walls allow organic modifications in the solid state, such as imine synthesis by condensation

with primary amines to give the corresponding imino-functionalized SIM-2. We show that this

postfunctionalization can be carried out on shaped SIM-1 bodies and films. The parent SIM-1

structured materials are prepared by direct in situ synthesis on a variety of supports for catalysis such as

alumina beads and cordierite monoliths, and for separation applications using supports such as

alumina tubes, fibers and anodic alumina disks. The hydrophobic SIM-2(C12) prepared on alumina

beads is found to be an active catalyst for the Knoevenagel condensation, while its analogous supported

membrane on alumina tube is efficient for CO2/N2 separation under humid conditions.

Introduction

Metal–organic frameworks (MOFs) are inorganic–organic

hybrid materials which are often compared with zeolites with

regard to their microporous structures. They are attractive for

many applications such as gas storage1 and separation,2–4

sensors5 and catalysis.6–9 In contrast to zeolites, they can be

engineered at the molecular scale through postsynthetic modifi-

cation (PSM).10–16 This deals with the grafting of desired organic

groups or complexes into the MOF framework, usually through

the formation of covalent bonds. In this way, tailor-made

materials have been prepared for catalysis15–19 and gas adsorp-

tion.20–25 Another example is the hydrophobization of amino-

containing IRMOF-3 and MIL-53 by the grafting of fatty chains

through amide coupling in order to increase their moisture

resistance.26

At early stages of R&D, the testing of MOFs is generally

carried out through their use as a bulk powder. Technological

solutions must therefore be developed to shapeMOFs in order to

fulfill requirements for chemical or physical processes. From

a practical point of view, the shaping of inorganic materials (e.g.,

zeolites) as structured bodies is classically performed by mixing

the powder-form material with inorganic (metal oxides,27 silica,28

kaolin,29 .) or organic binders (tetramethylorthosilicate,

Universit�e Lyon 1, IRCELYON, Institut de Recherches sur la Catalyse etl’Environnement de Lyon, UMR CNRS 5256, 2 avenue Albert Einstein,69626 Villeurbanne, France. E-mail: sonia.aguado@ircelyon.univ-lyon1.fr; Fax: +33 04 72 44 54 36; Tel: +33 04 72 44 53 84

† Electronic supplementary information (ESI) available: Synthesis ofsupported materials, XRDs, NMR spectra, catalysis and separationdetails. See DOI: 10.1039/c1jm10787a

7582 | J. Mater. Chem., 2011, 21, 7582–7588

methylsiloxane,30 .). The resulting ‘‘paste’’ is then used for the

embodiment process (e.g., extrusion). Finally, a thermal treat-

ment allows the hardening process and the stabilization of the

shape. Classical shaping processes are not applicable to MOFs,

since the thermal treatment will ultimately result in the destruc-

tion of the structure.

Generally, the choice of the material shape depends on the

target application. For catalytic applications, the shaping of

materials as structured bodies should mainly ensure mechanical

strength in order to avoid attrition issues. It should also facilitate

mass transport by avoiding external diffusion limitation.31 When

the activity of a catalyst is very high, its shaping as thin supported

layers, such as coatings on beads or monoliths, is ideal for

operation with low pressure drops.32 For separation applications

using membrane processes, the materials have to be prepared as

thin films supported on porous structured bodies. Ideally, the

supports exhibit high surface-to-volume ratio, as is the case for

multitubular geometries or fibers.

Despite its industrial relevance, the shaping of MOFs for

catalytic and separation applications has been little reported so

far. Kapteijn et al. have carried out the coating of MIL-101

slurry on monolith for the selective oxidation of tetralin in the

liquid phase.33 For adsorption, the tableting of MIL-53(Al) with

a polyvinyl alcohol as a binder,34 and HKUST-1 with Alox C and

graphite as additives,35 was performed for CO2/CH4 separation.

Regarding films, there are reports using various substrates and

support materials including stainless steel fibers,36 graphited

anodic alumina,37 copper net38 and ceramic discs.39,40 For real

applications, however, methods must be developed to deposit or

grow MOF films on substrates, ideally in a homogeneous and

oriented manner.41

This journal is ª The Royal Society of Chemistry 2011

Fig. 1 Anodic alumina-supported SIM-1. (a–c) SEM image of the cross-

section and (d) EDXSmapping of the cross-section (color code: cyan, Zn;

red, Al).

Publ

ishe

d on

26

Apr

il 20

11. D

ownl

oade

d by

St.

Pete

rsbu

rg S

tate

Uni

vers

ity o

n 09

/12/

2013

12:

26:3

3.

View Article Online

Here, we present for the first time the combination of the

postfunctionalization of a MOF with its shaping as structured

bodies. This study deals with the porous substituted imidazolate

material SIM-1, discovered at IRCELYON.42 It belongs to the

class of ZIF materials also known as ZMOFs.43 The zinc imi-

dazolate SIM-1 is isostructural to ZIF-8 (SOD), which is

commercialized under the name Basolite Z-1200�.44,45 The SIM-

1 solid consists of Zn tetrahedra linked by carboxylimidazolates.

A great advantage of this material is that the aldehyde moieties

present on the structure walls allow organic modifications in the

solid state, such as imine synthesis by condensation with primary

amines to give the corresponding imino-functionalized SIM-2.46

We show here that this postfunctionalization can be carried out

on shaped SIM-1 bodies and films. The parent SIM-1 structured

materials are prepared by direct in situ synthesis on a variety of

supports for catalysis such as alumina beads and cordierite

monoliths, and for separation applications using supports such

as alumina tubes, fibers and anodic alumina disks.

General procedure

Shaping

In all cases, the support on which the SIM-1 is grown is based on

alumina bodies or at least contains a layer of alumina. The

general procedure for growing SIM-1 on structured supports is

as follows. The support is immersed vertically in a vial containing

a DMF solution of Zn(NO3)2$4H2O (0.136 M) and 4-methyl-5-

imidazolecarboxaldehyde (0.55 M). After a solvothermal treat-

ment at 358 K for 48 h, the resulting supported material is

washed with ethanol to remove unreacted precursors and fine

SIM-1 unsupported particles. The supported SIM-1 is then dried

at room temperature. Note that in the case of tubular supports,

the external surface of the tube is wrapped with Teflon tape prior

to immersion in the mother solution.

All supports were characterized by SEM to determine the

thickness and homogeneity of the membrane, as well as the grade

of attachment of the SIM-1 top layer to the support.

XRD diffractograms of the SIM-1/support composites clearly

show the signals of SIM-1 combined with those of the support,

confirming that we obtain in all cases the same crystalline

structure (see the ESI†).

Film postfunctionalization

In a typical experiment, a sample of approximately 50 mg of

SIM-1 supported on alumina-based support is immersed in 5 mL

of an anhydrous methanol solution containing 1 mmol of the

desired amine. The alumina-supported SIM-1 is allowed to react

at room temperature for 48 hours without stirring in order to

avoid attrition. After reaction, the support is washed several

This journal is ª The Royal Society of Chemistry 2011

times with ethanol, soaked in hot ethanol overnight and then

dried under vacuum, providing the corresponding alumina-sup-

ported SIM-2 as a crystalline off-white powder. The alumina-

supported SIM-1 can therefore react with primary amines such

as dodecylamine to give the Al2O3-supported SIM-2(C12).

All supports were characterized by NMR to determine the

yield of postmodification. XRD diffractograms of the SIM-2

(C12)/support composites clearly show the signals of SIM-1

combined with those of the support, confirming that we obtain in

all cases the same crystalline structure (see the ESI†).

Surface hydrophobization

In nature, many components such as lotus leaves or water

strider’s legs exhibit water repellence in that water droplets roll

off their surface. Applications of superhydrophobic surfaces are

interesting for industrial and biological applications.47

SIM-1 on alumina disks

In order to characterize the surface tension of the SIM-1 and

SIM-2 materials, films were prepared on anodic alumina disks.

Anodic alumina discs have a smooth surface with an abundance

of OH groups that facilitate nucleation. We used symmetric

anodic alumina disks (13 mm diameter, 60 mm thickness, pore

size 200 nm, supplied by Whatman) as the support, and followed

the synthesis procedure described above. Fig. 1 shows the SIM-1

crystals, averaged up to 10 mm, forming a dense layer and

covering the support without any gap. The cross-section of the

SIM-1 film on anodic alumina indicates a layer thickness of

about 20 mm, strongly bonded to and anchored into the anodic

alumina, as also verified by EDXS.

Fig. 2 shows the powder XRD patterns of both SIM materials

as powder and supported on anodic alumina disks.

The patterns of the supported SIMs clearly show signals of

SIM-1, similar to those of SIM-2(C12), combined with those of

the alumina support, confirming the preservation of the crys-

talline structure throughout the procedures of film growth and

film postfunctionalization. In addition, we can conclude that

J. Mater. Chem., 2011, 21, 7582–7588 | 7583

Fig. 2 XRD patterns of SIM-1 and SIM-2(C12) as powder and sup-

ported on the anodic alumina disk.

Publ

ishe

d on

26

Apr

il 20

11. D

ownl

oade

d by

St.

Pete

rsbu

rg S

tate

Uni

vers

ity o

n 09

/12/

2013

12:

26:3

3.

View Article Online

there is no preferential orientation of the crystal when supported.

With respect to gas diffusion properties, this is not a drawback

for SIM-1, since its 3D porous structure allows the same diffu-

sion properties regardless of dimensions.

SIM-2 on alumina disks

In a previous work, we reported that the SIM-1 powder can

undergo postsynthetic functionalization to give the imino-func-

tionalized SIM-2(C12).46 In this study, we apply the PSMmethod

developed to SIM-1 films supported on Al2O3 (Fig. 3). The C12

Fig. 3 Postsynthetic modification of SIM-1 film with dodecylamine. (a)

Schematic representation of the SIM-2(C12) film synthesis. (b) Photo-

graphs of a water drop deposited on anodic alumina-supported SIMs

(SIM-1: left and SIM-2(C12): right). (c) SEM image of the cross-section of

anodic alumina-supported SIMs (SIM-1: left and SIM-2(C12): right).

7584 | J. Mater. Chem., 2011, 21, 7582–7588

aliphatic chains present at the surface of the material create

a hydrophobic shell surrounding the framework.

In line with the results reported for the SIM-2(C12) powder,46

the water repellence of the SIM-2(C12) supported on a anodic

alumina disk is highlighted by the behavior of a water drop

deposited on its surface, the Al2O3-supported SIM-2(C12)

showing the so-called ‘‘lotus leaf effect’’ (Fig. 3b and the ESI†).

Moreover, according to cross-section SEM analysis, the integrity

and the morphology of the SIM layer remain after functionali-

zation (Fig. 3c and the ESI†).

Liquid 1H NMR analysis after digestion in acidic DCl–D2O–

DMSO-d6 solution shows a 50% modification according to the

signal integration in the case of the anodic alumina disk (Fig. 4).

The presence in the NMR spectrum of a new typical peak at

8.09 ppm, corresponding to the imino proton, confirms the effi-

ciency of the organic transformation.

Powder XRD analysis of the Al2O3-supported SIM-2(C12)

sample shows a slight loss of crystallinity despite maintenance of

the initial structure (Fig. 2).

Catalyst upgrading

Heterogeneously catalyzed reactions can often be hindered or the

reaction rate limited due to poisoning effects originating from

moisture in the air or from the water formed during the organic

transformation. This water can be adsorbed, blocking the cata-

lytic sites and leading to their deactivation.48–50 It is therefore

worthwhile to design and engineer catalytic materials with

hydrophobic features—such as the hydrophobic outer shell of

enzymes—in order to prevent water-induced catalyst poisoning.

We therefore designed a bead-shaped water-repellent catalyst

based on our SIM materials.

SIM-1 on alumina beads: core–shell and composites

We used a- and g-alumina beads (1.5 mm diameter, BET area 2

and 100 m2 g�1, respectively) supplied by Saint-Gobain NorPro.

Fig. 4 1H NMR spectra of alumina disk-supported SIM-1 and SIM-2

after digestion in a deuterated acidic solution.

This journal is ª The Royal Society of Chemistry 2011

Fig. 5 SIM-1 supported on alumina beads (2). (a) SEM image of g-

alumina/SIM-1 and (b) SEM image of a-alumina/SIM-1.

Publ

ishe

d on

26

Apr

il 20

11. D

ownl

oade

d by

St.

Pete

rsbu

rg S

tate

Uni

vers

ity o

n 09

/12/

2013

12:

26:3

3.

View Article Online

Fig. 5 shows the morphology of the bead-supported SIM-1/

Al2O3. We observe an interesting difference depending on

whether the SIM-1 is supported on a- or g-alumina beads. In the

SIM-1/g-Al2O3 composite, crystals are embedded in cavities of

the support and some crystals grow on the surface of the bead,

but do not form a continuous film (Fig. 5a). This implies a good

mechanical strength and abrasive resistance for the embedded

SIM-1 particles. On the other hand, only scattered small crystals

appear inside the a-alumina beads, while the formation of

a homogeneous layer of 15 mm takes place on the outer surface

(Fig. 5b).

Scheme 1 Knoevenagel condensation catalyzed by SIMs on beads.

SIM-2 on alumina beads: designing water-repellent spheres

Following the procedure described above, beads of SIM-1/Al2O3

were allowed to react with a methanolic solution of dodecyl-

amine to give the corresponding SIM-2(C12)/Al2O3. NMR

analyses of the crushed beads show that 29% and 22% of the

aldehyde moieties are converted into dodecylimine for a- and g-

alumina beads, respectively. Moreover, the framework structure

is preserved during the modification in both cases, as confirmed

by PXRD patterns (ESI†). In order to assess the water repellence

of our alumina bead-supported SIM-2(C12), beads were dropped

into a vial filled with pure water. Beyond our expectations, the

SIM-1/a-Al2O3 bead sinks to the bottom of the vial, whereas the

SIM-2(C12)/a-Al2O3 bead floats at the surface (Fig. 6 and

the ESI†). It is noteworthy that the SIM-2(C12)/a-Al2O3 bead

remains floating for weeks.

SIM-catalyzed Knoevenagel condensation

The SIM-1/g-Al2O3 composite was already found to be active as

a catalyst for the reduction of ketones by transfer

Fig. 6 Photograph of a-alumina/SIM-1 (left) and a-alumina/SIM-2

(C12) (right) after being dropped into pure water.

This journal is ª The Royal Society of Chemistry 2011

hydrogenation.51 Here, we show the application of the SIM-1/g-

Al2O3 composite in base catalysis, which is known to be very

water sensitive. The Knoevenagel reaction, which produces water

as a secondary product, is usually catalyzed with bases that can

be poisoned by the water. Our new supported material being

hydrophobic, the catalytic behavior of the SIM-2(C12)/g-Al2O3

composite was evaluated for the Knoevenagel reaction under

solvent-free conditions (Scheme 1).

A typical catalytic run consists of 20 mmol of benzaldehyde

reacting with 20 mmol of ethyl cyanoacetate, with catalysis by

0.1 mol% of SIM material (6 to 7 mg of catalytic material, or

about 5 beads) to give the corresponding Knoevenagel adduct,

ethyl a-cyanocinnamate, at 323 K. Both alumina-supported

SIM-1 and SIM-2(C12) show catalytic activity, while almost no

conversion is observed using alumina beads alone (Fig. 7). Even

using magnetic stirring (400 rpm), there is no notable weathering

of the alumina beads. Once the reaction is finished, beads can be

easily separated from the reaction mixture by removing the

solution. After washings with ethanol and drying, these beads

were introduced in a second catalytic run under the same

conditions without loss of activity, ensuring the possibility of

recycling the catalyst.

In order to prove the stability of our new heterogeneous

catalyst, a leaching test was performed. After 30 minutes, the

SIM-2(C12)/g-Al2O3 beads were removed by filtration and the

evolution of the ethyl a-cyanocinnamate was followed with

the same reaction conditions maintained. No further reaction

takes place after the removal of the catalyst, which demonstrates

the absence of the leaching of active sites.

Fig. 7 Catalyst screening for the Knoevenagel condensation using

powder and alumina-supported SIM materials (TOF ¼ initial turnover

frequencies calculated after 30 min) and expressed in mol of product/(mol

of MOF catalyst � h).

J. Mater. Chem., 2011, 21, 7582–7588 | 7585

Publ

ishe

d on

26

Apr

il 20

11. D

ownl

oade

d by

St.

Pete

rsbu

rg S

tate

Uni

vers

ity o

n 09

/12/

2013

12:

26:3

3.

View Article Online

The catalytic activities observed for the supported SIM

materials are 30% lower than those found for their powder

analogs.46 This is likely due to diffusion limitations of the reac-

tants into the intergrown SIM-1 layer. This could be optimized

by reducing the thickness of the layer and increasing the number

of beads in the reaction, keeping the amount of the active SIM

phase the same.

Although the actual identity of the catalytic centers is currently

unknown, we may suggest that surface species are responsible for

catalytic activity. Indeed, recent studies performed on ZIF-8

show that crystalline defects (i.e., monocoordinated imidazoles

or imidazolates) or zinc hydroxide surface species, which are

Brønsted bases, are involved in acid/base catalysis.52 Moreover,

in the case of SIM-2(C12), we suggest that the hydrophobic

chains at the surface of the solid, i.e., in the vicinity of the

catalytic centers, hinder or limit water adsorption, making the

centers free to adsorb the substrates.

Gas separation

SIM membrane on porous tubular supports

We prepared SIM-1 membrane on a tubular support to achieve

gas separation. Asymmetric a-alumina tubes (10 mm outer

diameter, 7 mm inner diameter, 15 cm length, top layer pore size

200 nm) supplied by Pall Exekia and asymmetric a-alumina

fibers (1.65 mm outer diameter, 1.44 mm inner diameter, 15 cm

length, top layer pore size 200 nm) supplied by the Fraunhofer

Institute were used for this purpose.

Recently, we reported that a SIM-1 membrane was synthe-

sized in situ on a tubular asymmetric alumina support. We

illustrated a very reproducible one-step process operating at

atmospheric pressure to prepare a thin MOF, which meets the

first criterion enabling the scale-up for the preparation of a large

membrane surface. We showed how the SIM-1 crystals merge

compactly and proved the absence of defects over a long

distance.53

In order to obtain a membrane showing hydrophobic features,

the SIM-1 on Al2O3 tube is allowed to react with a methanolic

solution of dodecylamine to give the corresponding SIM-2(C12)

membrane following the procedure described above. NMR

analysis of the crushed tube shows that 33% of the aldehyde

moieties are converted into the dodecylimine. Moreover, the

PXRD pattern shows that the framework structure is preserved

during the modification (ESI†).

Fig. 8 CO2 adsorption isotherms of SIM-1 (-), SIM-1/alumina

composite (B) and SIM-2(C12)/alumina composite (O) at 303 K.

CO2/N2 separation

In the case of postcombustion capture, membranes could

potentially compete with chemical absorption in terms of energy

demands, even at low CO2 concentration. Although promising

CO2/N2 separation results have been reported in the literature,

care should be taken when analyzing these data due to a lack of

tests carried out under ‘‘real’’ flue gases.54–59 Most of the post-

combustion CO2 capture applications at the industrial level

involve CO2 separation from humid flue gases. Despite this

requirement, most of the gas permeation and separation data

reported have been obtained for dry (often equimolar) simulated

flue gases that omit the effect of water.

7586 | J. Mater. Chem., 2011, 21, 7582–7588

Adsorption properties of the material remain invariable when

SIM-1 is supported. Fig. 8 shows no significant change in

adsorption uptake of CO2 at 303 K at isoloading of SIM-1. The

postmodified SIM-2(C12) also shows CO2 adsorption properties;

however, its capacity remains lower than that of SIM-1, in line

with the decrease of BET area from 471 to 112 m2 g�1, for SIM-1

and SIM-2(C12), respectively.46

Moreover, we measured the single gas permeance of N2 using

a SIM-1 membrane, obtaining 0.21 m3(STP) m�2 h�1 bar�1. This

value is in line with data reported by Caro for ZIF-8

membrane.60 Fig. 9 shows the permeance profiles of different

gases as a function of the transmembrane pressure.

Ideal selectivity data calculated from single gas permeances at

303 K are slightly deviated from Knudsen values for H2/N2 ¼ 2.5

(3.7) but are reversed for CO2/N2 ¼ 1.1 (0.78), thereby indicating

an adsorption–diffusion based mechanism.

As already reported, the separation factor found for a SIM-1

membrane is 4.5 for the ternary mixture CO2/N2/H2O.53 In the

case of a SIM-2(C12) membrane, tuned to show hydrophobic

features, the separation factor found for the same ternary

mixture is 5.5. Even if better separation is obtained, however, the

resulting CO2 permeation flux is lowered. This might be due to

the lower capacity of the SIM-2(C12), which remains a critical

issue for efficient membrane performance.

Outlook

SIM-1 layer on monoliths

Among all the SIM-supported geometries, the cordierite mono-

lith is of particular interest in terms of catalytic applications,

because of its facile mass transport and low pressure drop

operability.

On the basis of our previous results, we have developed a SIM-

1/monolith material in order to obtain an efficient catalytic

reactor with a higher surface-to-volume ratio. For this, we used

400 cpsi cordierite monoliths supplied by Corning, washcoated

with a thin layer of g-alumina. Regarding the SIM-1 growth on

cordierite monolith, SEM investigation across the entire film

shows a continuous crack-free membrane (Fig. 10). The cross-

section image of the film shows a thickness of about 5 mm for the

washcoated alumina layer and 5 mm for the SIM-1 film, with an

excellent attachment of the crystals to the support. In this case,

we obtain a largely intergrown polycrystalline film with

This journal is ª The Royal Society of Chemistry 2011

Fig. 9 Permeance of gas molecules through an activated SIM-1

membrane at room temperature as a function of the partial pressure

difference across the membrane.

Fig. 10 Monolith-supported SIM-1. (a) SEM image of the surface. (b

and c) SEM image of the cross-section. (d) EDXS mapping of the cross-

section (color code: blue, Zn; red, Al; green, Si).

Fig. 11 Fiber-supported SIM-1. (a) SEM image of the surface. (b and c)

SEM image of the cross-section. (d) EDXS mapping of the cross-section

(color code: cyan, Zn; red, Al).

Publ

ishe

d on

26

Apr

il 20

11. D

ownl

oade

d by

St.

Pete

rsbu

rg S

tate

Uni

vers

ity o

n 09

/12/

2013

12:

26:3

3.

View Article Online

a columnar structure, indicating some kind of orientation of

crystals in the film.

Following the above procedure, SIM-1 on monolith was

allowed to react with dodecylamine to give the corresponding

SIM-2(C12). NMR analysis of the crushed monolith shows 25%

postfunctionalization. Moreover, the framework structure is

preserved during the modification, as confirmed by the PXRD

pattern (ESI†).

SIM-1 layer on fibers

On the other hand, the possibility of growing SIMmembranes on

fibers would be useful for practical separation applications.

The cross-section of the fiber shows a 15 mm continuous, well-

intergrown layer of SIM-1 crystals on top of the support

(Fig. 11). Energy-dispersive X-ray spectroscopy (EDXS) proves

that there is a sharp transition between the SIM-1 layer (Zn

signal) and the alumina support (Al signal).

As with the other supports, a SIM-2(C12) layer was obtained

on fiber following our PSM method using dodecylamine. NMR

analysis of the crushed fiber shows 30% postfunctionalization,

This journal is ª The Royal Society of Chemistry 2011

and the PXRD pattern confirms that the structure remains intact

(ESI†).

Conclusions

We demonstrate in this study that it is possible to achieve mul-

tiscale engineering of a MOF for catalytic and separation

applications. At micron or millimetre scale, a new imidazolate-

based MOF (SIM-1) can be prepared on or in different ceramic

support morphologies of various compositions and shapes. In

addition to the advantages of hydrodynamics and secure

handling for catalytic applications, the core–shell-like structure

(SIM/alumina) allows a drastic reduction of the cost of raw

material (e.g., linkers), which is a strong asset when considering

sophisticated linkers together with an application at the ton

scale.

We have shown, for the first time, that a postmodification

technique can be applied to a supported MOF, regardless of the

shape of the body. At the nanometre scale, we have demon-

strated the benefits of the hydrophobization of the MOF surface.

The hydrophobic SIM-2(C12) prepared on alumina beads is

found to be an active catalyst for the Knoevenagel condensation,

while its analogous film on alumina tube is efficient for CO2/N2

separation under humid conditions.

We believe that this study contributes to bridging the gap

between initial stages of R&D and the application of MOFs at

the industrial scale.

Acknowledgements

The authors thank the French National Research Agency (ANR)

for financial support through the MECAFI project (ANR-07-

PCO2-003) and the ACACIA 31 project (ANR-08-PCO2-001-

02).

Notes and references

1 M. Eddaoudi, J. Kim, N. Rosi, D. Vodak, J. Wachter, M. O’Keefeand O. M. Yaghi, Science, 2002, 295, 469–472.

J. Mater. Chem., 2011, 21, 7582–7588 | 7587

Publ

ishe

d on

26

Apr

il 20

11. D

ownl

oade

d by

St.

Pete

rsbu

rg S

tate

Uni

vers

ity o

n 09

/12/

2013

12:

26:3

3.

View Article Online

2 L. Alaerts, C. Kirschhock, M. Maes, M. van der Veen, V. Finsy,A. Depla, J. Martens, G. Baron, P. Jacobs, J. Denayer and D. DeVos, Angew. Chem., Int. Ed., 2007, 46, 4293–4297.

3 J. R. Li, R. J. Kuppler and H. C. Zhou, Chem. Soc. Rev., 2009, 38,1477–1504.

4 P. L. Llewellyn, S. Bourrelly, C. Serre, A. Vimont, M. Daturi,L. Hamon, G. De Weireld, J.-S. Chang, D.-Y. Hong, Y. KyuHwang, S. Hwa Jhung and G. Ferey, Langmuir, 2008, 24, 7245–7250.

5 B. Harbuzaru, A. Corma, F. Rey, P. Atienzar, J. Jord�a, H. Garc�ıa,D. Ananias, L. Carlos and R. Rocha, Angew. Chem., Int. Ed., 2008,47, 1080–1083.

6 F. Xamena, A. Abad, A. Corma and H. Garcia, J. Catal., 2007, 250,294–298.

7 A. Corma, H. Garcia and F. X. L. Xamena, Chem. Rev., 2010, 110,4606–4655.

8 D. Farrusseng, S. Aguado and C. Pinel, Angew. Chem., Int. Ed., 2009,48, 7502–7513.

9 J. Lee, O. K. Farha, J. Roberts, K. A. Scheidt, S. T. Nguyen andJ. T. Hupp, Chem. Soc. Rev., 2009, 38, 1450–1459.

10 S. M. Cohen, Chem. Sci., 2010, 1, 32–36.11 K. K. Tanabe and S. M. Cohen, Chem. Soc. Rev., 2011, 40, 498–519.12 Z. Q. Wang and S. M. Cohen, Chem. Soc. Rev., 2009, 38, 1315–1329.13 S. Chavan, J. G. Vitillo, M. J. Uddin, F. Bonino, C. Lamberti,

E. Groppo, K. P. Lillerud and S. Bordiga, Chem. Mater., 2010, 22,4602–4611.

14 M. Savonnet, D. Bazer-Bachi, N. Bats, J. Perez-Pellitero,E. Jeanneau, V. Lecocq, C. Pinel and D. Farrusseng, J. Am. Chem.Soc., 2010, 132, 4518–4519.

15 C. J. Doonan, W. Morris, H. Furukawa and O. M. Yaghi, J. Am.Chem. Soc., 2009, 131, 9492–9493.

16 W. Morris, C. J. Doonan, H. Furukawa, R. Banerjee andO. M. Yaghi, J. Am. Chem. Soc., 2008, 130, 12626–12627.

17 M. J. Ingleson, J. P. Barrio, J. B. Guilbaud, Y. Z. Khimyak andM. J. Rosseinsky, Chem. Commun., 2008, 2680–2682.

18 X. Zhang, F. Llabres and A. Corma, J. Catal., 2009, 265, 155–160.19 K. K. Tanabe and S. M. Cohen, Angew. Chem., Int. Ed., 2009, 48,

7424–7427.20 Y. S. Bae, O. K. Farha, J. T. Hupp and R. Q. Snurr, J. Mater. Chem.,

2009, 19, 2131–2134.21 Z. Q.Wang, K. K. Tanabe and S. M. Cohen,Chem.–Eur. J., 2010, 16,

212–217.22 M. Dinca, W. S. Han, Y. Liu, A. Dailly, C. M. Brown and J. R. Long,

Angew. Chem., Int. Ed., 2007, 46, 1419–1422.23 G. Ferey and C. Serre, Chem. Soc. Rev., 2009, 38, 1380–1399.24 K. L. Mulfort, O. K. Farha, C. L. Stern, A. A. Sarjeant and

J. T. Hupp, J. Am. Chem. Soc., 2009, 131, 3866–3868.25 Z. Q. Wang and S. M. Cohen, J. Am. Chem. Soc., 2009, 131, 16675–

16677.26 J. G. Nguyen and S. M. Cohen, J. Am. Chem. Soc., 2010, 132, 4560–

4561.27 W. Hoelderich, W. Himmel, W. D. Mross and M. Schwarmann, US

Pat. 4616098, 1986.28 D. S. Shihabi, W. E. Garwood, P. Chu, J. N. Miale, R. M. Lago,

C. T. W. Chu and C. D. Chang, J. Catal., 1985, 93, 471–474.29 W. Flank, W. Fethke and M. Peekskill, US Pat. 4818508, 1989.30 H. Frintz, C. Trefzger and H. Hofer, US Pat. 6458187, 2002.

7588 | J. Mater. Chem., 2011, 21, 7582–7588

31 H. Zhou, Y. Wang, F. Wei, D. Wang and Z. Wang, Appl. Catal., A,2008, 341, 112–118.

32 A. E. W. Beers, T. A. Nijhuis, N. Aalders, F. Kapteijn andJ. A. Moulijn, Appl. Catal., A, 2003, 243, 237–250.

33 E. V. Ramos-Fernandez, M. Garcia-Domingos, J. Juan-Alca~niz,J. Gascon and F. Kapteijn, Appl. Catal., A, 2010, 391, 261–267.

34 V. Finsy, L. Ma, L. Alaerts, D. E. De Vos, G. V. Baron andJ. F. M. Denayer, Microporous Mesoporous Mater., 2009, 120, 221–227.

35 S. Cavenati, C. A. Grande, A. E. Rodrigues, C. Kiener andU. Mu�Iller, Ind. Eng. Chem. Res., 2008, 47, 6333–6335.

36 X.-Y. Cui, Z.-Y. Gu, D.-Q. Jiang, Y. Li, H.-F. Wang and X.-P. Yan,Anal. Chem., 2009, 81, 9771–9777.

37 Y. Yoo and H. K. Jeong, Chem. Commun., 2008, 2441–2443.38 H. Guo, G. Zhu, I. J. Hewitt and S. Qiu, J. Am. Chem. Soc., 2009, 131,

1646–1647.39 H. Bux, F. Liang, Y. Li, J. Cravillon, M. Wiebcke and J. Caro, J. Am.

Chem. Soc., 2009, 131, 16000–16001.40 R. Ranjan and M. Tsapatsis, Chem. Mater., 2009, 21, 4920–4924.41 S. Kitagawa and R. Matsuda, Coord. Chem. Rev., 2007, 251, 2490–

2509.42 D. Farrusseng, S. Aguado and J. Canivet, FR Pat., FR09/04488, 2009.43 Y. Liu, V. C. Kravtsov, R. Larsen and M. Eddaoudi, Chem.

Commun., 2006, 14, 1488–1490.44 X. Huang, Y. Lin, J. Zhang and X. Chen, Angew. Chem., Int. Ed.,

2006, 45, 1557–1559.45 X.Huang, J. Zhang andX.Chen,Chin. Sci. Bull., 2003, 48, 1531–1534.46 J. Canivet, S. Aguado, C. Daniel and D. Farrusseng, ChemCatChem,

2011, 3, 675–678.47 X. M. Li, D. Reinhoudt and M. Crego-Calama, Chem. Soc. Rev.,

2007, 36, 1350–1368.48 G. Di Carlo, G. Melaet, N. Kruse, L. F. Liotta, G. Pantaleo and

A. M. Venezia, Chem. Commun., 2010, 46, 6317–6319.49 J. Y. Park, Z. M. Wang, D. K. Kim and J. S. Lee, Renewable Energy,

2010, 35, 614–618.50 H. Y. Wang and W. F. Schneider, Surf. Sci., 2009, 603, L91–L94.51 S. Aguado, J. Canivet and D. Farrusseng, Chem. Commun., 2010, 46,

7999–8001.52 C. Chizallet and N. Bats, J. Phys. Chem. Lett., 2010, 1, 349–353.53 S. Aguado, C. H. Nicolas, V. Moizan-Basl�e, C. Nieto, H. Amrouche,

N. Bats, N. Audebrand and D. Farrusseng, New J. Chem., 2011, 35,41–44.

54 M. P. Bernal, J. Coronas, M.Men�endez and J. Santamar�ıa,AIChE J.,2004, 50, 127–135.

55 M. A. Carreon, S. G. Li, J. L. Falconer and R. D. Noble, J. Am.Chem. Soc., 2008, 130, 5412–5413.

56 S. Li, J. L. Falconer and R. D. Noble, J. Membr. Sci., 2004, 241, 121–135.

57 S. Li, J. L. Falconer and R. D. Noble, Adv. Mater., 2006, 18, 2601–2603.

58 J. C. Poshusta, V. A. Tuan, J. L. Falconer and R. D. Noble, Ind. Eng.Chem. Res., 1998, 37, 3924–3929.

59 J. van den Bergh, W. Zhu, J. Gascon, J. A. Moulijn and F. Kapteijn,J. Membr. Sci., 2008, 316, 35–45.

60 Y. Li, F. Liang, H. Bux, A. Feldhoff, W. Yang and J. Caro, Angew.Chem., Int. Ed., 2010, 49, 548–551.

This journal is ª The Royal Society of Chemistry 2011