Zeolites and Mofs: What They Are and Their Use in Sensing Applications

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Zeolites and MOFs: what they are and their use in sensing applications
Conference Paper · July 2016
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Vincent Blay Alejandro Cabrera-García

University of Valencia Universidad Europea de Valencia
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Zeneida Díaz Betancor

Universitat Politècnica de València
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Zeolites and MOFs: what they are and their use in sensing applications
1,2 2 3 1 2
V. Blay , A. Cabrera-García , Z. Díaz-Betancor , P. J. Miguel , A. Corma
1
Departamento de Ingeniería Química, Universitat de València, Burjassot, España
2
Instituto de Tecnología Química (UPV-CSIC), Universitat Politècnica de València, Consejo Superior
de Investigaciones Científicas, Valencia, España
3
Instituto Interuniversitario de Reconocimiento Molecular y Desarrollo Tecnológico, Valencia, España
vblayr@itq.upv.es, zediabe@upv.es
Abstract
In this contribution we present zeolites and metal organic frameworks (MOFs) as

valuable materials for sensing applications thanks to their special properties. Zeolites
are a class of crystalline microporous materials whose basic building blocks are SiO 4
tetrahedra, although Si atoms can be substituted by other elements to affect the
properties of the material. In its turn, MOFs are a class of crystalline hybrid materials
composed of metal ions or clusters bridged by organic linkers. Both zeolites and metal
organic frameworks can be designed with pore apertures of molecular sizes, leading to
materials with shape selectivity or molecular sieve properties that allow the design of
novel sensors and the improvement of existing ones.
1. Zeolites and their properties
Zeolites are a class of crystalline tectosilicates. This means that their basic building
blocks are SiO 4 tetrahedra, each oxygen being shared by two Si atoms. Very
interestingly, these tetrahedra arrange to leave void channels of molecular sizes
(microporosity). In addition, silicon atoms in the framework can be substituted by
different metals (such as Al, Ti, B, Fe, Sn, Ge…), thus changing their properties and
behaviour in their different applications.
Micropores in zeolites allow them to act as molecular sieves: they select which
molecules can access or leave the crystal, and even through which transition states a
reaction or signalling process can or cannot proceed. Simultaneously, they offer an
2
enormous surface area (50-1000 m /g) for surface phenomena such as sensing,
1
catalysis or gas storage. Moreover, the substitution, exchange or confinement of
different metals in the network can give rise to different reactivity (such as acid-base or
redox catalysis, or functionalization capabilities) as well as adsorption properties (such
as ion-exchange properties). Furthermore, zeolites are highly appreciated from an
industrial standpoint because of their high thermal and hydrothermal stablility under high
severity reaction conditions.
2. Sensing with zeolites
Most zeolite sensors have been developed for the environmental industry and
combustion processes. However, the use of zeolites as selective filters and sensor
amplifiers continues to find new applications thanks to their preconcentration effect. In
fact, zeolites are often referred to as solid solvents. Newer sensing paradigms, such as
catalysis leading to products with a higher sensitivity than the analyte itself or interfacial
effects in composites have also emerged. Nanometric thin films and oriented films hold
2
promise to improve response and recovery times .
A selected example is summarized in Figure 1, in which zeolite-induced catalysis
3
promotes sensor selectivity . The work presents a potentiometric sensor of total NO x
(NO + NO 2 ) by a new sensing paradigm in which the zeolite layer is separated from the
sensor. Many potentiometric devices cannot be calibrated for NO x mixtures because
NO gets oxidized and NO 2 gets reduced, leading to signal cancellation. The authors
propose to equilibrate the NO x mixture in a Pt-Y zeolite filter at a particular temperature,
say 450 °C. The mixture will then encounter a YSZ sensor at a different temperature,
such as 600 °C, with a measurable signal for total NO x . The use of zeolite also reduced
interference with CO, C 3 H 8 and ammonia, which are present in combustion processes.
This sensor has a sensitivity in the ppm range, and has been improved further to the
ppb range by stringing 10-20 sensors in series, with the goal of developing a hand-held
4
asthma monitor .
Figure 1. a) Scheme of a total NOx sensor based on a zeolite filter and YSZ sensor at differing temperatures. b)
The resulting sensorr shows equivalent responses to NO and NO 2 . From S.S P.
P Mondal,
Mondal et al.
al Sensors
Se Actuators
B: Chem. 2011, 158, 292.
3. MOFs and their properties
Metal-organic frameworks (MOFs) are an attractive class of hybrid materials composed

5
by metal ions or clusters bridged by organic linkers . MOF structures have been
proposed as new materials for gas storage and separation, sensing, catalysis, nonlinear
optics and ferroelectrics, light-harvesting and photocatalysis, drug delivery devices and
6-8
MRI contrast agents thanks to its varied properties.
MOFs are molecularly tunable porous solids with permanent porosity. This porosity is
determined by the selection of the metal (secondary building unit) and the organic linker
in the crystalline structure. As it is the case with zeolites, the pore dimension controls
the size of the molecules that may enter the pores, which provide the surface and space
to carry out the adsorption, signaling or catalysis. MOFs pore sizes lie in the micropore
and mesopore ranges (an outstanding pore diameter of 98 angstroms was reported by
9-11
Yaghi and coworkers for the IRMOF-74-XI material ). The possibilities of MOFs can
be extended by adding new functionalities through chemical reaction on the reactive
12
parts of the material .
4. Sensing with MOFs
Lots of MOFs devices for sensing applications have been described, we will mention
two examples developed at our institute. Corma et al. reported two new MOFs for
13
sensing applications: ITQMOF-1 and ITQMOF-2 (Figure 2). Both structures were
3+
obtained by the reaction between the Ln salt or oxide with 4,4’-
(hexafluoroisopropylidene)-bis(benzoic acid). ITQMOF-1 containing Europium (III) as
the metal secondary building unit was shown very useful to determine ethanol
concentration in air by monitoring the photoluminescent emission of the material at 619
nm. Another example of this class of materials reported by Corma et al. is ITQMOF-3-
Eu (Figure 3), which was synthesized with europium (III) and 1,10-phenanthroline-2,9-
14
dicarboxylic acid . This material was used as a component of a miniaturized pH sensor
that functions in the pH range of biological interest (5-7.5).
Figure 2. a) ITQMOF-2-Eu UV Figure 3. a) ITQMOF-3-Eu optical microscopy

light optical microscopy image. image. b) and c) Eu coordination environments.
b) and c) Solid structure solved From B.V. Harbuzaru, et al. Angew. Chem. Int.
by XRD. From B.V. Harbuzaru, et Ed. 2009, 48, 6476.
al. Angew. Chem. Int. Ed. 2008,
47, 1080.
5. Conclusions
MOFs and zeolites have very valuable properties that can be exploited for sensor
applications, particularly a pore topology that can be finely tuned to achieve shape
selectivity or sieving at the molecular scale. Their use can remarkably enhance the
sensitivity, selectivity and stability of existing sensors and allow for novel sensing
paradigms.
6. References
1. B. Yilmaz, N. Trukhan, U. Müller, Chinese Journal of Catalysis, 2012, 33, 3.

2. Y. Zheng, X. Li, P.K. Dutta, Sensors, 2012, 12.
3. J. Yang, P.K. Dutta, Sensors Actuators B:Chem.,2007,125,30.
4. S. P. Mondal, P. K. Dutta, G. W. Hunter, B. J. Ward, D. Laskowski, R. A. Dweik. Sensors
Actuators B: Chem. 2011,158,292.
5. O.K. Farha, A.Ö. Yazaydin, I. Eryazici, C.D. Malliakas, B.G. Hauser, M.G. Kanatzidis, S.T.
Nguyen, R.Q. Snurr, J.T. Hupp, Nature Chemistry 2010, 2, 944.
6. C. He, J. Lu, W. Lin, Journal of Controlled Release, 2015, 219, 224.
7. M. Giménez-Marqués, T. Hidalgo, C. Serre, P. Horcajada, Coordination Chemistry
Reviews, 2016, 307, 342.
8. P. Horcajada, T. Chalati, C. Serre, B. Gillet, C. Sebrie, T. Baati, J.F. Eubank, D. Heurtaux,
P. Clayette, C. Kreuz, J.-S. Chang, Y.K. Hwang, V. Marsaud, P.-N. Bories, L. Cynober, S.
Gil, G. Férey, P. Couvreur, R. Gref, Nature Materials, 2010, 9, 172.
9. C. Wang, W. Lin, J. Am. Chem. Soc., 2011, 133, 4232.
10. H. Furukawa, K.E. Cordova, M. O’Keeffe, O.M. Yaghi, Science, 2013, 341, 974.
11. H. Deng, S. Grunder, K.E. Cordova, C. Valente, H. Furukawa, M. Hmadeh, F. Gándara,
A.C. Whalley, Z. Liu, S. Asahina, H. Kazumori, M. O’Keeffe, O. Terasaki, J.F. Stoddart,
O.M. Yaghi, Science, 2012, 336, 1018.
12. J. Park, D. Feng, H.-C.Zhou, J. Am. Chem. Soc., 2015, 137, 1663.
13. B.V. Harbuzaru, A. Corma, F. Rey, P. Atienzar, J.L. Jordá, H. García, D. Ananias, L.D.
Carlos, João Rocha, Angew. Chem. Int. Ed. 2008, 47, 1080.
14. B.V. Harbuzaru, A. Corma, F. Rey, J.L. Jordá, D. Ananias, L.D. Carlos, João Rocha,
Angew. Chem. Int. Ed. 2009, 48, 6476.
Acknowledgments
V. Blay thanks the support from the Valencian Ministry of Education. A. Cabrera thanks the “La
Caixa” Foundation for his Ph.D. scholarship. Z. Díaz-Betancor thanks the Spanish Ministry of
Economy and Competitiveness for her scholarship.
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See discussions, stats, and author profiles for this publication at: https://www.researchgate.

Conference Paper · July 2016

Vincent Blay Alejandro Cabrera-García

SEE PROFILE SEE PROFILE

Zeneida Díaz Betancor

Zeolites and Metal-Organic Frameworks. From Lab to Industry View project

PHOCNOSIS View project

The user has requested enhancement of the downloaded file.

In this contribution we present zeolites and metal organic frameworks (MOFs) as

1. Zeolites and their properties

2. Sensing with zeolites

3. MOFs and their properties

Metal-organic frameworks (MOFs) are an attractive class of hybrid materials composed

4. Sensing with MOFs

Figure 2. a) ITQMOF-2-Eu UV Figure 3. a) ITQMOF-3-Eu optical microscopy

1. B. Yilmaz, N. Trukhan, U. Müller, Chinese Journal of Catalysis, 2012, 33, 3.

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