催化学报 ›› 2021, Vol. 42 ›› Issue (10): 1700-1711.DOI: 10.1016/S1872-2067(21)63831-7

• 论文 • 上一篇    下一篇

多相/均相TiO2/N-羟酰亚胺混合体系中可见光诱导分子氧可控光催化氧化苄基反应

Igor B. Krylova,b, Elena R. Lopat’evaa,b, Irina R. Subbotinaa, Gennady I. Nikishina, Bing Yuc, Alexander O. Terent’eva,b()   

  1. a俄罗斯科学院泽林斯基有机化学研究所, 莫斯科, 俄罗斯
    b俄罗斯门捷列夫化工大学, 莫斯科, 俄罗斯
    c郑州大学化学学院绿色催化中心, 河南郑州, 中国
  • 收稿日期:2020-12-19 接受日期:2021-04-14 出版日期:2021-06-20 发布日期:2021-06-20
  • 通讯作者: Alexander O. Terent’ev
  • 作者简介:*电话: +7-499-137-29-44; 传真: +7-499-135-53-28; 电子信箱:alterex@yandex.ru

Mixed hetero-/homogeneous TiO2/N-hydroxyimide photocatalysis in visible-light-induced controllable benzylic oxidation by molecular oxygen

Igor B. Krylova,b, Elena R. Lopat’evaa,b, Irina R. Subbotinaa, Gennady I. Nikishina, Bing Yuc, Alexander O. Terent’eva,b()   

  1. aN. D. Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences, Moscow 119991, Russian Federation
    bMendeleev University of Chemical Technology of Russia, Moscow 125047, Russian Federation
    cGreen Catalysis Center, College of Chemistry, Zhengzhou University, Zhengzhou 450001, Henan, China
  • Received:2020-12-19 Accepted:2021-04-14 Online:2021-06-20 Published:2021-06-20
  • Contact: Alexander O. Terent’ev

摘要:

均相催化和多相催化通常被认为是独立甚至相互对立的学科. 本文提出了一种新型的用于分子氧选择性氧化烷基苯的杂多酸/均相混合催化体系. 该催化体系由N-羟基邻苯二甲酰亚胺(NHPI, 用于自由基链式反应的均相有机催化剂)和纳米TiO2(多相紫外光活性光氧化催化剂)两种组分组成. NHPI与TiO2的协同作用使光氧化活性从紫外光转移到可见光, 并产生邻苯二甲酰亚胺-N-氧基(PINO)自由基. NHPI/PINO催化的自由基链式反应能够在没有额外光输入的情况下进行, 从而从根本上提高能源效率. 通过控制NHPI/TiO2比率优化产物选择性, 进而使烷基芳烃优先形成过氧化氢或酮.

关键词: TiO2, 光氧化还原催化, N-羟基邻苯二甲酰亚胺, N-氧自由基, 需氧氧化

Abstract:

Homogeneous and heterogeneous types of catalysis are frequently considered as separate disciplines or even opposed to each other. In the present work, a new type of mixed hetero-/homogeneous catalysis was demonstrated for the case of selective alkylarene oxidation by molecular oxygen. The proposed catalytic system consists of two widely available components: N-hydroxyphthalimide (NHPI, a homogeneous organocatalyst for free-radical chain reactions) and nanosized TiO2 (heterogeneous UV-active photoredox catalyst). The interaction of NHPI with TiO2 allows for a shift from UV to visible light photoredox activity and generation of phthalimide-N-oxyl (PINO) radicals that diffuse into the solution where NHPI/PINO-catalyzed free-radical chain reaction can proceed without the additional light input providing a fundamental increase in energy efficiency. The NHPI/TiO2 ratio controls the selectivity of oxidation affording preferential formation of hydroperoxide or ketone from alkylarene.

Key words: TiO2, Photoredox catalysis, N-hydroxyphthalimide, N-oxyl radicals, Aerobic oxidation