Chapter 1
Ligand-Free Sub-Nanometer Metal
Clusters in Catalysis
Judit Oliver–Meseguer and Antonio Leyva–Pérez
Abstract Recent advances in the synthesis and characterization of ligand-free subnanometer metal clusters, either in solution or supported on solids, have enabled their
rational use as catalysts in new reactions. These clusters expose all their metal atoms
to outer molecules without the potential steric/electronic interferences of ligands,
while, at the same time, show defined molecular orbitals to ultimately control the
catalytic reaction. Therefore, these clusters somehow combine the advantages of
single atom and metal nanoparticles for molecular activation and catalysis. This
chapter aims at describing how to prepare, better characterize and apply, on a realistic
scale, ligand-free sub-nanometer metal clusters for catalytic processes (many of them
of industrial interest) during the last ten years.
Keywords Sub-nanometer metal clusters · Catalysis · Ligand-free · Industrial
reactions
1.1 Introduction
1.1.1 History and Nanotechnology Projection
The prefix nano gives the name to a discipline that is considered the scientific sign
of our generation, the nanotechnology, although this is not a novelty for humanity.
The book written by the philosopher and medical doctor Francisci Antonii in 1618,
Aurea–Auro Potabile, is considered as the first book on colloidal Au. The reputation
of soluble Au until the Middle Ages was to disclose fabulous curative powers for
various diseases, such as heart and venereal problems, dysentery, epilepsy and tumors
and for diagnosis of syphilis. Also, this book includes considerable information on
the formation of colloidal Au solutions and their medical uses, including successful
practical cases (Fig. 1.1), whereas the extraction of Au started in the 5th millennium
J. Oliver–Meseguer · A. Leyva–Pérez (B)
Instituto de Tecnología Química (UPV–CSIC), Universitat Politècnica de València–Consejo
Superior de Investigaciones Científicas, Avda. de Los Naranjos s/n, 46022 València, Spain
e-mail: anleyva@itq.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_1
1
Ligand-Free Sub-Nanometer Metal
Clusters in Catalysis
Judit Oliver–Meseguer and Antonio Leyva–Pérez
Abstract Recent advances in the synthesis and characterization of ligand-free subnanometer metal clusters, either in solution or supported on solids, have enabled their
rational use as catalysts in new reactions. These clusters expose all their metal atoms
to outer molecules without the potential steric/electronic interferences of ligands,
while, at the same time, show defined molecular orbitals to ultimately control the
catalytic reaction. Therefore, these clusters somehow combine the advantages of
single atom and metal nanoparticles for molecular activation and catalysis. This
chapter aims at describing how to prepare, better characterize and apply, on a realistic
scale, ligand-free sub-nanometer metal clusters for catalytic processes (many of them
of industrial interest) during the last ten years.
Keywords Sub-nanometer metal clusters · Catalysis · Ligand-free · Industrial
reactions
1.1 Introduction
1.1.1 History and Nanotechnology Projection
The prefix nano gives the name to a discipline that is considered the scientific sign
of our generation, the nanotechnology, although this is not a novelty for humanity.
The book written by the philosopher and medical doctor Francisci Antonii in 1618,
Aurea–Auro Potabile, is considered as the first book on colloidal Au. The reputation
of soluble Au until the Middle Ages was to disclose fabulous curative powers for
various diseases, such as heart and venereal problems, dysentery, epilepsy and tumors
and for diagnosis of syphilis. Also, this book includes considerable information on
the formation of colloidal Au solutions and their medical uses, including successful
practical cases (Fig. 1.1), whereas the extraction of Au started in the 5th millennium
J. Oliver–Meseguer · A. Leyva–Pérez (B)
Instituto de Tecnología Química (UPV–CSIC), Universitat Politècnica de València–Consejo
Superior de Investigaciones Científicas, Avda. de Los Naranjos s/n, 46022 València, Spain
e-mail: anleyva@itq.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_1
1