Activating Cobalt Nanoparticles via the Mott-Schottky Effect in Nitrogen-Rich Carbon Shells for Base-Free Aerobic Oxidation of Alcohols to Esters
Activating Cobalt Nanoparticles via the Mott-Schottky Effect in Nitrogen-Rich Carbon Shells for Base-Free Aerobic Oxidation of Alcohols to Esters
复制标题
通过富氮碳壳中的莫特肖特基效应激活钴纳米颗粒，用于醇无碱有氧氧化成酯
DOI：
10.1021/jacs.6b10710
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发表时间：
2017-01-18
影响因子：
15
通讯作者：
Chen, Jie-Sheng
中科院分区：
文献类型：
--
作者：
Su, Hui;Zhang, Ke-Xin;Chen, Jie-Sheng
过渡金属非均相催化剂是均相催化剂的理想替代品，但过渡金属纳米粒子活性较低，成为其应用的主要障碍。在这里，从头设计的Mott-Schottky型多相催化剂的报道，以提高过渡金属纳米催化剂的活性，通过在金属/氮掺杂的碳界面的电子转移。在g-C3 N4粉末存在下，通过简单有机分子和无机金属盐的直接缩聚反应制备了富氮碳包覆钴纳米粒子（Co@NC）Mott-Schottky催化剂。具有可控氮含量且费米能和催化活性可调的Co@NC表现出高转换频率（TOF）值（8.12 mol苯甲酸甲酯mol（-1）Co h（-1）），可直接、无碱、有氧氧化苯甲醇为苯甲酸甲酯;该TOF比文献报道的最新过渡金属基纳米催化剂高30倍。所提出的高效Mott-Schottky催化剂可以引发一系列烷基酯甚至双酯的高产率合成。
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.