Chapter 4
MNP Catalysis in Ionic Liquids
Muhammad I. Qadir, Nathália M. Simon, David Rivillo, and Jairton Dupont
Abstract Ionic liquids (ILs) are the green, versatile and alternative fluids in the
fabrication of soluble ‘surface-clean’ nanoparticles (NPs) that act not only as stabilising agents but also as templates to generate NPs of desired size. Ligand-free NPs
in ILs can be prepared either by hydrogen-driven chemical methods, i.e., by the
simple hydrogenation/decomposition of zero-valent metal complexes or by a physical
method (magnetron sputtering). ILs can be used as liquid supports for NPs, providing
an encapsulation-like environment for the catalytically active species that may allow
the modulation of the stability of the catalyst and the miscibility of the substrates and
products at the active catalytic centre. In this chapter, the hydrogen-involved nanocatalytic reactions (hydrogenation, hydroformylation, Fischer-Tropsch synthesis) in
ILs will be summarised.
Keywords Ionic liquids · Nanoparticles · Catalysis · Hydrogenation ·
Hydroformylation · CO 2 hydrogenation
4.1 Introduction
Room temperature ionic liquids (RTILs) are molten salts that consist entirely of
ions. They have noteworthy properties, such as negligible vapour pressure, high
chemical and thermal stability, a wide electrochemical window, non-flammability,
melting points below 100 °C, high ionic conductivity, acceptable biocompatibility,
good capability of dissolving various organic/inorganic materials, high boiling
points and stability [1–5]. The very first molten salt, ethylammonium nitrate, was
prepared in 1914 with a low melting point of 12 °C. Alkylimidazolium aluminate IL
(EMIm.AlCl 4 ), which was prepared by mixing 1-ethyl-2-methylimidazolium chloride with aluminium chloride, has a melting point below −88 °C [6]. In 1990,
organochloroaluminate IL (BMIm.AlCl 4) was used as a solvent for the dimerisation of propene to hexene isomers at −15 °C catalysed by nickel complexes. But,
M. I. Qadir · N. M. Simon · D. Rivillo · J. Dupont (B)
Institute of Chemistry, Universidade Federal do Rio Grande do Sul, UFRGS, Av. Bento
Gonçalves, 9500, Porto Alegre, RS 91501-970, Brazil
e-mail: jairton.dupont@ufrgs.br
© 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_4
107
MNP Catalysis in Ionic Liquids
Muhammad I. Qadir, Nathália M. Simon, David Rivillo, and Jairton Dupont
Abstract Ionic liquids (ILs) are the green, versatile and alternative fluids in the
fabrication of soluble ‘surface-clean’ nanoparticles (NPs) that act not only as stabilising agents but also as templates to generate NPs of desired size. Ligand-free NPs
in ILs can be prepared either by hydrogen-driven chemical methods, i.e., by the
simple hydrogenation/decomposition of zero-valent metal complexes or by a physical
method (magnetron sputtering). ILs can be used as liquid supports for NPs, providing
an encapsulation-like environment for the catalytically active species that may allow
the modulation of the stability of the catalyst and the miscibility of the substrates and
products at the active catalytic centre. In this chapter, the hydrogen-involved nanocatalytic reactions (hydrogenation, hydroformylation, Fischer-Tropsch synthesis) in
ILs will be summarised.
Keywords Ionic liquids · Nanoparticles · Catalysis · Hydrogenation ·
Hydroformylation · CO 2 hydrogenation
4.1 Introduction
Room temperature ionic liquids (RTILs) are molten salts that consist entirely of
ions. They have noteworthy properties, such as negligible vapour pressure, high
chemical and thermal stability, a wide electrochemical window, non-flammability,
melting points below 100 °C, high ionic conductivity, acceptable biocompatibility,
good capability of dissolving various organic/inorganic materials, high boiling
points and stability [1–5]. The very first molten salt, ethylammonium nitrate, was
prepared in 1914 with a low melting point of 12 °C. Alkylimidazolium aluminate IL
(EMIm.AlCl 4 ), which was prepared by mixing 1-ethyl-2-methylimidazolium chloride with aluminium chloride, has a melting point below −88 °C [6]. In 1990,
organochloroaluminate IL (BMIm.AlCl 4) was used as a solvent for the dimerisation of propene to hexene isomers at −15 °C catalysed by nickel complexes. But,
M. I. Qadir · N. M. Simon · D. Rivillo · J. Dupont (B)
Institute of Chemistry, Universidade Federal do Rio Grande do Sul, UFRGS, Av. Bento
Gonçalves, 9500, Porto Alegre, RS 91501-970, Brazil
e-mail: jairton.dupont@ufrgs.br
© 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_4
107