Mixed hetero-/homogeneous TiO_(2)/N-hydroxyimide photocatalysis in visible-light-induced controllable benzylic oxidation by molecular oxygen  

多相/均相TiO_(2)/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

作　　者：Igor B.Krylov Elena R.Lopat'eva Irina R.Subbotina Gennady I.Nikishin Bing Yu Alexander O.Terent'ev Igor B.Krylov;Elena R.Lopateva;Irina R.Subbotina;Gennady I.Nikishin;Bing Yu;Alexander O.Terent'ev(俄罗斯科学院泽林斯基有机化学研究所,俄罗斯莫斯科;俄罗斯门捷列夫化工大学,俄罗斯莫斯科;郑州大学化学学院绿色催化中心,河南郑州)

机构地区：[1]N.D.zelinsky institute of organic chemistry of the russian academy of sciences,moscow 119991,russian federation [2]Mendeleev university of chemical technology of russia,moscow 125047,russian federation [3]Green catalysis center,college of chemistry,zhengzhou university,zhengzhou 450001,henan,china

出　　处：《Chinese Journal of Catalysis》2021年第10期1700-1711,共12页催化学报（英文）

摘　　要：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 het-ero-/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 TiO_(2)(heterogeneous UV-active photoredox catalyst).The interaction of NHPI with TiO_(2) 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/TiO_(2) ratio controls the selectivity of oxidation affording preferential formation of hydroperoxide or ketone from alkylarene.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TiO_(2)(多相紫外光活性光氧化催化剂)两种组分组成.NHPI与TiO_(2)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/TiO_(2)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：TiO_(2) Photoredox catalysis N-HYDROXYPHTHALIMIDE N-oxyl radicals Aerobic oxidation 

分 类 号：O621.251[理学—有机化学]