Top Organomet Chem (2020) 66: 49–76
DOI: 10.1007/3418_2020_40
# Springer Nature Switzerland AG 2020
Published online: 31 July 2020
Metal Nanoparticles for Redox Reactions
Koichiro Jitsukawa and Takato Mitsudome
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
2 Metal NP-Catalyzed Selective Reductions Using H 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
2.1 Design of Core–Shell NPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
2.2 Nitrogen or Sulfur Modification of Metal NP Surface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
3 Metal NP-Catalyzed Selective Oxidations Using O 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
3.1 Aerobic Oxidation of Alcohols Using Pd NPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
3.2 Bimetallic NP-Catalyzed Alcohol Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
3.3 Base Metal NP-Catalyzed Alcohol Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
3.4 Wacker-Type Oxidation Using Pd NPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
4 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
Abstract Reduction and oxidation reactions (redox reactions) are fundamental and
important transformation of chemicals in both laboratory and industrial chemistries.
With regard to atom economy and the environmental demands, an ultimate goal of
these reactions is to employ molecular hydrogen (H 2 ) or molecular oxygen (O 2 ).
High-performance heterogeneous catalysts with high activity, selectivity, recoverability, and reusability are ideal for the development of green sustainable processes
using H 2 or O 2 . Moreover, the heterogeneous catalyst systems are the promising
approach to solve the disadvantage of homogeneous ones, such as short lifetimes
(low stability), risk of contaminating products with metals (low recoverability),
tedious workups for reuse (low reusability), and so on. For the design of highperformance heterogeneous catalysts under liquid-phase redox reactions, metal
nanoparticles (NPs) is the most promising strategy because of their unusual properties compared to bulk metal. This review provides an overview of metal NP
heterogeneous catalysts developed for redox reactions using H 2 or O 2 . The stateof-the-art metal NP catalysts show higher activity and selectivity for the
K. Jitsukawa (*) and T. Mitsudome
Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka
University, Toyonaka, Osaka, Japan
e-mail: jitkk@cheng.es.osaka-u.ac.jp
DOI: 10.1007/3418_2020_40
# Springer Nature Switzerland AG 2020
Published online: 31 July 2020
Metal Nanoparticles for Redox Reactions
Koichiro Jitsukawa and Takato Mitsudome
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
2 Metal NP-Catalyzed Selective Reductions Using H 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
2.1 Design of Core–Shell NPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
2.2 Nitrogen or Sulfur Modification of Metal NP Surface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
3 Metal NP-Catalyzed Selective Oxidations Using O 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
3.1 Aerobic Oxidation of Alcohols Using Pd NPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
3.2 Bimetallic NP-Catalyzed Alcohol Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
3.3 Base Metal NP-Catalyzed Alcohol Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
3.4 Wacker-Type Oxidation Using Pd NPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
4 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
Abstract Reduction and oxidation reactions (redox reactions) are fundamental and
important transformation of chemicals in both laboratory and industrial chemistries.
With regard to atom economy and the environmental demands, an ultimate goal of
these reactions is to employ molecular hydrogen (H 2 ) or molecular oxygen (O 2 ).
High-performance heterogeneous catalysts with high activity, selectivity, recoverability, and reusability are ideal for the development of green sustainable processes
using H 2 or O 2 . Moreover, the heterogeneous catalyst systems are the promising
approach to solve the disadvantage of homogeneous ones, such as short lifetimes
(low stability), risk of contaminating products with metals (low recoverability),
tedious workups for reuse (low reusability), and so on. For the design of highperformance heterogeneous catalysts under liquid-phase redox reactions, metal
nanoparticles (NPs) is the most promising strategy because of their unusual properties compared to bulk metal. This review provides an overview of metal NP
heterogeneous catalysts developed for redox reactions using H 2 or O 2 . The stateof-the-art metal NP catalysts show higher activity and selectivity for the
K. Jitsukawa (*) and T. Mitsudome
Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka
University, Toyonaka, Osaka, Japan
e-mail: jitkk@cheng.es.osaka-u.ac.jp