复合仿生催化体系的构建与高效有氧氧化芳基烷烃

doi:10.11944/j.issn.1000-0518.2017.09.170191

摘要/Abstract

摘要：

直接活化氧气氧化碳氢化合物是件挑战性的研究工作。根据生物酶很容易在温和条件下实现上述反应,以Keggin-型杂多酸[CuPW₁₁O₃₉]^5-(简写为CuPW₁₁)与金属-有机框架材料HKUST-1形成的复合材料CuPW₁₁@HKUST-1为催化剂,以N-羟基邻苯二甲酰亚胺为助催化剂,构建模拟酶催化氧化反应体系。其中,CuPW₁₁@HKUST-1中的杂多酸作为氧化还原中心,N-羟基邻苯二甲酰亚胺作为电子供体。该复合模拟酶催化体系在催化活化氧气氧化芳基烷烃的反应中表现出了类似生物酶催化的性质,具有反应条件温和、转化率高、转化数高和选择性高等特点,其中产物产率与转化数分别高达99%和17700,为实现在温和条件下高效活化氧气氧化惰性有机物分子提供了一条切实可行的路线。

关键词: 仿生催化, 金属-有机框架材料, 杂多酸, 协同催化

Abstract:

It is a challenge to oxidize inert hydrocarbons with molecular oxygen, which can be easily realized by enzymes under mild conditions. Inspired by the catalytic mechanism of enzymes, we used the composite material CuPW₁₁@HKUST-1, consisting of encapsulated Keggin-type polyoxometalate [CuPW₁₁O₃₉]^5-(abbreviated as CuPW₁₁) in the pore space of metal-organic framework HKUST-1, as a redox catalyst, and N-hydroxyphthalimide(NHPI) as a co-catalyst, for the biomimetic aerobic oxidation of arylalkanes under mild conditions. The biomimetic system exhibits enzyme-like features of high efficiency and high selectivity in the aerobic oxidation of arylalkanes by imitating the structural features, active sites and catalytic mechanism of enzymes, in which up to 99% yield and 17700 turnover number(TON) have been realized in the aerobic oxidation reaction. This work offers a feasible pathway for highly efficient aerobic oxidation of inert organic molecules under mild conditions.

Key words: biomimetic catalysis, metal-organic frameworks, polyoxometalates, synergistic catalysis

徐可睿, 钟志铭, 徐惠东, 王璇, 赵敏, 吴传德. 复合仿生催化体系的构建与高效有氧氧化芳基烷烃[J]. 应用化学, 2017, 34(9): 1079-1085.

XU Kerui, ZHONG Zhiming, XU Huidong, WANG Xuan, ZHAO Min, WU Chuande. Highly Efficient Aerobic Oxidation of Arylalkanes with a Biomimetic Catalyst Platform[J]. Chinese Journal of Applied Chemistry, 2017, 34(9): 1079-1085.

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