Top Organomet Chem (2020) 66: 207–242
https://doi.org/10.1007/3418_2020_46
# Springer Nature Switzerland AG 2020
Published online: 21 July 2020
Nanoparticle Catalysts in Flow Systems
Hiroyuki Miyamura and Shū Kobayashi
Contents
1 Introduction: Nanoparticles as Heterogeneous Catalysts in Flow “Fine” Synthesis . . . . . . . 208
2 Metal Nanoparticle Catalysts Immobilized in Microchannels and Microreactors . . . . . . . . . 211
2.1 Polymer-Incarcerated Palladium Nanoparticles Immobilized in Microchannels
for Hydrogenation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211
2.2 Polysilane-Supported Palladium Nanoparticles Immobilized in Microchannels
for Hydrogenation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212
2.3 Gold Nanoparticles Immobilized in a Capillary for Aerobic Oxidation . . . . . . . . . . . . . 214
2.4 Polymeric Palladium Nanoparticle Membrane-Installed Microflow Devices
for Hydrodehalogenation . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . .. . . . . . . . . 215
3 Continuous-Flow Reactions Using Metal Nanoparticles Packed in Columns (Fixed-Bed
Reactors) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
3.1 Continuous-Flow Hydrogenation Using Polysilane-Supported Palladium Catalysts 219
3.2 Poly(dimethyl)silane-Supported Palladium Nanoparticles for Continuous-Flow
Hydrogenation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
3.3 Reductive Amination Through Hydrogenation Using Metal Nanoparticle Catalysts
Under Continuous-Flow Conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
3.4 Hydrogenation of Arenes and Heteroarenes Using Metal Nanoparticle Catalysts
Under Continuous-Flow Conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
3.5 Aerobic Oxidation of Alcohols Under Continuous-Flow Conditions Using Metal
Nanoparticle Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
3.6 Control of Selectivity in Heterogeneous Gold Catalysis Under Flow Conditions . . 237
4 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
Abstract By taking advantage of the high catalytic activity and high turnover
frequency (TOF) of heterogeneous metal nanoparticle catalysts, continuous-flow
systems, in which introduced reactants are converted into the desired product in
high yield, can be realized. These continuous-flow reactors possess high compatibility with sequential continuous-flow systems, which enable multistep flow
H. Miyamura and S. Kobayashi (*)
Department of Chemistry, Graduate School of Science, The University of Tokyo, Tokyo, Japan
e-mail: shu_kobayashi@chem.s.u-tokyo.ac.jp