Chapter 7
Catalysis by Metal Nanoparticles
Encapsulated Within Metal–Organic
Frameworks
Amarajothi Dhakshinamoorthy and Hermenegildo Garcia
Abstract Supported metal nanoparticles (NPs) are a class of heterogeneous catalysts widely used to promote hydrogenations, chemical reductions, oxidations, and
coupling reactions. The metal–support interaction is crucial to determine not only
the catalytic activity of these materials, but also their stability. Since high catalytic
activity requires small size metal NPs, the most common deactivation mechanism
occurs by agglomeration of these NPs and increase of their particle size. One general
strategy to minimize particle growth in encapsulation inside porous hosts and MOFs
(MOFs) have been used for this purpose. This chapter describes the use of MOFs as
hosts to encapsulate metal NPs, covering the main properties of MOFs, encapsulation procedures and the most important reactions. Special attention has been paid to
describe the use of metal NPs supported on MOFs to promote coupling reactions,
since particularly for these type of reactions, MOFs have shown a clear superiority
respect to alternative supports. The final sections show some directions on the current
development of the field.
Keywords Heterogeneous catalysis · Porous supports · Metal–organic frameworks
as hosts · Coupling reactions · Alcohol oxidation
7.1 Introduction
Metal nanoparticles (NPs) exhibit general catalytic activity in a large variety of
reaction types including hydrogenation, aerobic oxidation, and cross-coupling reactions [1, 2]. It has been found that the activity of these metal NPs in catalysis is
due to the atoms located on the external surface having coordinatively unsaturated
positions [3]. In general, experimental and theoretical studies have shown that the
A. Dhakshinamoorthy
School of Chemistry, Madurai Kamaraj University, Madurai 625021, India
e-mail: admguru@gmail.com
H. Garcia (B)
Departamento de Quimica, Instituto Universitario de Tecnologia Quimica (CSIC-UPV),
Universitat Politecnica de Valencia, Valencia 46022, Spain
e-mail: hgarcia@qim.upv.es
© Springer Nature Switzerland AG 2020
P. W. N. M. van Leeuwen and C. Claver (eds.), Recent Advances in Nanoparticle Catalysis,
Molecular Catalysis 1, https://doi.org/10.1007/978-3-030-45823-2_7
221
Catalysis by Metal Nanoparticles
Encapsulated Within Metal–Organic
Frameworks
Amarajothi Dhakshinamoorthy and Hermenegildo Garcia
Abstract Supported metal nanoparticles (NPs) are a class of heterogeneous catalysts widely used to promote hydrogenations, chemical reductions, oxidations, and
coupling reactions. The metal–support interaction is crucial to determine not only
the catalytic activity of these materials, but also their stability. Since high catalytic
activity requires small size metal NPs, the most common deactivation mechanism
occurs by agglomeration of these NPs and increase of their particle size. One general
strategy to minimize particle growth in encapsulation inside porous hosts and MOFs
(MOFs) have been used for this purpose. This chapter describes the use of MOFs as
hosts to encapsulate metal NPs, covering the main properties of MOFs, encapsulation procedures and the most important reactions. Special attention has been paid to
describe the use of metal NPs supported on MOFs to promote coupling reactions,
since particularly for these type of reactions, MOFs have shown a clear superiority
respect to alternative supports. The final sections show some directions on the current
development of the field.
Keywords Heterogeneous catalysis · Porous supports · Metal–organic frameworks
as hosts · Coupling reactions · Alcohol oxidation
7.1 Introduction
Metal nanoparticles (NPs) exhibit general catalytic activity in a large variety of
reaction types including hydrogenation, aerobic oxidation, and cross-coupling reactions [1, 2]. It has been found that the activity of these metal NPs in catalysis is
due to the atoms located on the external surface having coordinatively unsaturated
positions [3]. In general, experimental and theoretical studies have shown that the
A. Dhakshinamoorthy
School of Chemistry, Madurai Kamaraj University, Madurai 625021, India
e-mail: admguru@gmail.com
H. Garcia (B)
Departamento de Quimica, Instituto Universitario de Tecnologia Quimica (CSIC-UPV),
Universitat Politecnica de Valencia, Valencia 46022, Spain
e-mail: hgarcia@qim.upv.es
© Springer Nature Switzerland AG 2020
P. W. N. M. van Leeuwen and C. Claver (eds.), Recent Advances in Nanoparticle Catalysis,
Molecular Catalysis 1, https://doi.org/10.1007/978-3-030-45823-2_7
221