Activating Cobalt Nanoparticles via the Mott–Schottky Effect in Nitrogen-Rich Carbon Shells for Base-Free Aerobic Oxidation of Alcohols to Esters

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• 作者：Hui SuKe-Xin Zhang ; Bing Zhang ; Hong-Hui Wang ; Qiu-Ying Yu ; Xin-Hao Li ; Markus Antonietti ; Jie-Sheng Chen
• 刊名：Journal of the American Chemical Society
• 出版年：2017
• 出版时间：January 18, 2017
• 年：2017
• 卷：139
• 期：2
• 页码：811-818
• 全文大小：551K
• ISSN：1520-5126

文摘

Heterogeneous catalysts of inexpensive and reusable transition-metal are attractive alternatives to homogeneous catalysts; the relatively low activity of transition-metal nanoparticles has become the main hurdle for their practical applications. Here, the de novo design of a Mott–Schottky-type heterogeneous catalyst is reported to boost the activity of a transition-metal nanocatalyst through electron transfer at the metal/nitrogen-doped carbon interface. The Mott–Schottky catalyst of nitrogen-rich carbon-coated cobalt nanoparticles (Co@NC) was prepared through direct polycondensation of simple organic molecules and inorganic metal salts in the presence of g-C₃N₄ powder. The Co@NC with controllable nitrogen content and thus tunable Fermi energy and catalytic activity exhibited a high turnover frequency (TOF) value (8.12 mol methyl benzoate mol^–1 Co h^–1) for the direct, base-free, aerobic oxidation of benzyl alcohols to methyl benzoate; this TOF is 30-fold higher than those of the state-of-the-art transition-metal-based nanocatalysts reported in the literature. The presented efficient Mott–Schottky catalyst can trigger the synthesis of a series of alkyl esters and even diesters in high yields.