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分子氧选择性醇氧化的协同催化作用

Cooperative Catalysis for Selective Alcohol Oxidation with Molecular Oxygen.

作者信息

Slot Thierry K, Eisenberg David, van Noordenne Dylan, Jungbacker Peter, Rothenberg Gadi

机构信息

Van 't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH, Amsterdam, The Netherlands.

出版信息

Chemistry. 2016 Aug 22;22(35):12307-11. doi: 10.1002/chem.201602964. Epub 2016 Jul 27.

Abstract

The activation of dioxygen for selective oxidation of organic molecules is a major catalytic challenge. Inspired by the activity of nitrogen-doped carbons in electrocatalytic oxygen reduction, we combined such a carbon with metal-oxide catalysts to yield cooperative catalysts. These simple materials boost the catalytic oxidation of several alcohols, using molecular oxygen at atmospheric pressure and low temperature (80 °C). Cobalt and copper oxide demonstrate the highest activities. The high activity and selectivity of these catalysts arises from the cooperative action of their components, as proven by various control experiments and spectroscopic techniques. We propose that the reaction should not be viewed as occurring at an 'active site', but rather at an 'active doughnut'-the volume surrounding the base of a carbon-supported metal-oxide particle.

摘要

双原子氧用于有机分子的选择性氧化的活化是一个重大的催化挑战。受氮掺杂碳在电催化氧还原中活性的启发,我们将这种碳与金属氧化物催化剂相结合,以制备协同催化剂。这些简单的材料在常压和低温(80°C)下使用分子氧促进了几种醇的催化氧化。氧化钴和氧化铜表现出最高的活性。各种对照实验和光谱技术证明,这些催化剂的高活性和选择性源于其组分的协同作用。我们认为,该反应不应被视为在“活性位点”发生,而应是在“活性圆环”发生——即碳负载金属氧化物颗粒底部周围的体积区域。

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