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氮掺杂碳上的锌-氮位点用于C(CO)-C键的有氧氧化裂解和酯化反应。

Zn-N sites on N-doped carbon for aerobic oxidative cleavage and esterification of C(CO)-C bonds.

作者信息

Xie Chao, Lin Longfei, Huang Liang, Wang Zixin, Jiang Zhiwei, Zhang Zehui, Han Buxing

机构信息

Key Laboratory of Catalysis and Energy Materials Chemistry of Ministry of Education & Hubei Key Laboratory of Catalysis and Materials Science, South-Central University for Nationalities, Wuhan, China.

Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Colloid, Interface and Chemical Thermodynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing, China.

出版信息

Nat Commun. 2021 Aug 10;12(1):4823. doi: 10.1038/s41467-021-25118-0.

Abstract

Selective cleavage of C-C bonds is very important in organic chemistry, but remains challenging because of their inert chemical nature. Herein, we report that Zn/NC-X catalysts, in which Zn coordinate with N species on microporous N-doped carbon (NC) and X denotes the pyrolysis temperature, can effectively catalyze aerobic oxidative cleavage of C(CO)-C bonds and quantitatively convert acetophenone to methyl benzoate with a yield of 99% at 100 °C. The Zn/NC-950 can be applied for a wide scope of acetophenone derivatives as well as more challenging alkyl ketones. Detail mechanistic investigations reveal that the catalytic performance of Zn/NC-950 can be attributed to the coordination between Zn and N species to change the electronic state of the metal, synergetic effect of the Zn single sites with their surrounding N atoms, as well as the microporous structure with the high surface area and structural defects of the NC.

摘要

碳-碳键的选择性断裂在有机化学中非常重要,但由于其化学性质惰性,仍然具有挑战性。在此,我们报道了Zn/NC-X催化剂,其中Zn与微孔氮掺杂碳(NC)上的氮物种配位,X表示热解温度,该催化剂能有效催化C(CO)-C键的有氧氧化断裂,并在100°C下将苯乙酮定量转化为苯甲酸甲酯,产率为99%。Zn/NC-950可应用于广泛的苯乙酮衍生物以及更具挑战性的烷基酮。详细的机理研究表明,Zn/NC-950的催化性能可归因于Zn与氮物种之间的配位作用改变了金属的电子状态、Zn单原子位点与其周围N原子的协同效应,以及NC的高比表面积和结构缺陷的微孔结构。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0b67/8355145/61ce469e879f/41467_2021_25118_Fig1_HTML.jpg

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