Aerobic Oxidation of Alcohols at Room Temperature and Atmospheric Conditions Catalyzed by Reusable Gold Nanoclusters Stabilized by the Benzene Rings of Polystyrene Derivatives

Miyamura, Hiroyuki; Matsubara, Ryosuke; Miyazaki, Y.; Kobayashi, Shū

doi:10.1002/anie.200700080

Cited by 349 publications

(171 citation statements)

References 51 publications

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“…Such polymer-incarcerated gold clusters exhibited high catalytic activity and excellent selectivity at room temperature in the aerobic oxidation of alcohols, 36,37 hydroquinones, 38 and amines 29 in organic solvents mixed with water and aerobic oxidative esterification of alcohols. 39 In the case of amine oxidation gold NPs with larger diameters (510 nm) are more active than gold clusters (23 nm).…”

Section: Gold Clusters Stabilized or Supported By Organic Compounds Imentioning

confidence: 99%

Size- and Structure-specificity in Catalysis by Gold Clusters

2014

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Although gold in bulk is poorly active as a catalyst, it exhibits surprisingly high catalytic activity when deposited as nanoparticles (NPs) on base metal oxides. The catalytic performance of supported gold NPs can be created by choosing the kind of support materials, by controlling the size of gold, and by building up strong contact of gold with the supports. Since perimeter interfaces around gold NPs act, in principle, as the active sites for oxidation and hydrogenation, gold should be smaller than 10 nm in diameter. A new area of research is clusters, which are smaller than 2 nm in diameter and less than 200 atoms. Gold clusters possess electronic structures different from those of bulk gold and at the same time provide increased fractions of edges and corners which are highly unsaturatedly coordinated sites. Accordingly, gold clusters will be blessed by unique catalytic performance, and many examples have recently been emerging. This article summarizes such examples in terms of "size-and structure-specificity," covering gas-phase free clusters, polymer-or organic-ligand-stabilized clusters in liquid phase, and clusters supported on base metal oxides, carbon materials, and organic polymers for gas-phase and liquid-phase reactions.

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Section: Gold Clusters Stabilized or Supported By Organic Compounds Imentioning

confidence: 99%

Size- and Structure-specificity in Catalysis by Gold Clusters

2014

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“…The resulting Ru@MOF-253 was examined in the oxidation of a variety of alcohols exhibiting high selectivities for ketones and aldehydes (up to 99%) under mild reaction conditions. This is remarkable, as the selective oxidation of primary alcohols to aldehydes at room temperature with heterogeneous catalysts is still rather limited and represents a challenging area in green chemistry 55 .…”

Section: Oxidation Of Alcoholsmentioning

confidence: 99%

Metal-Organic Frameworks as Selective or Chiral Oxidation Catalysts

2014

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Since the discovery of Metal Organic Frameworks (MOFs) in the early 1990, the amount of new structures has grown exponentially. A MOF typically consists of inorganic nodes that are connected by organic linkers to form crystalline, highly porous structures. MOFs have attracted a lot of attention lately, as the versatile design of such materials holds promises of interesting applications in various fields. In this review, we will focus on the use of MOFs as heterogeneous oxidation catalysts. MOFs are very promising candidates to replace homogeneous catalysts by sustainable and stable heterogeneous catalysts. The catalytic active function can be either the active metal sites of the MOF itself or can be introduced as an extra functionality in the linker, a dopant or a "ship-in-a-bottle" complex. As the pore size, pore shape and functionality of MOFs can be designed in numerous ways, shape selectivity and even chiral selectivity can be created. In this review, we will present an overview on the state of the art of the use of MOFs as a heterogeneous catalyst in liquid phase oxidation reactions.

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“…Thus, a goal of many investigations has been to increase the selectivity of the intermediate product(s), even at the expense of activity [2][3][4] . One well-studied group of systems that demonstrate this selective oxidation is the aerobic oxidation of primary alcohols to afford aldehydes, because aldehydes are important intermediates that find application in the synthesis of many pharmaceuticals, agrochemicals and perfumes 3,[5][6][7][8] . Benzyl alcohol is one of the most widely studied substrates 6,9,10 .…”

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confidence: 99%