Metal Nanoparticles for Redox Reactions
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
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Metal Nanoparticles for Redox Reactions Koichiro Jitsukawa and Takato Mitsudome
Contents 1 Introduction 2 Metal NP-Catalyzed Selective Reductions Using H2 2.1 Design of Core–Shell NPs 2.2 Nitrogen or Sulfur Modification of Metal NP Surface 3 Metal NP-Catalyzed Selective Oxidations Using O2 3.1 Aerobic Oxidation of Alcohols Using Pd NPs 3.2 Bimetallic NP-Catalyzed Alcohol Oxidation 3.3 Base Metal NP-Catalyzed Alcohol Oxidation 3.4 Wacker-Type Oxidation Using Pd NPs 4 Summary References
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 (H2) or molecular oxygen (O2). High-performance heterogeneous catalysts with high activity, selectivity, recoverability, and reusability are ideal for the development of green sustainable processes using H2 or O2. 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 H2 or O2. 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: [email protected]
K. Jitsukawa and T. Mitsudome
chemoselective hydrogenations of carbonyl, nitro, and alkynyl compounds while retaining C¼C bonds, and the aerobic oxidation of alcohols and the Wacker type oxidation of alkenes, which overcome the limitations of the conventional catalyst systems. This improved catalytic performance is due to significant advances in the precise fabrication of nanoscale metals, which has made it possible to explore novel catalysis and design metal active centers. Keywords Catalyst · Hydrogenation · Metal · Nanoparticle · Oxidation
1 Introduction Reduction and oxidation reactions (redox reactions) are fundamental and important transformations in both laboratory and industrial chemistries. In conventional redox reaction systems, metal hydrides, such as NaBH4 and LiAlH4, or heavy metal salts, such as permanganate and dichromate, have been employed as reducing or oxidizing agents. As these stoichiometric reagents have serious drawbacks, including high costs, toxicity, and producing large amounts of waste, the development of promising catalytic systems to replace these stoichiometric reactions has attracted much attention. With regard to atom economy and
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