A Unique Fe–N4 Coordination System Enabling Transformation of Oxygen into Superoxide for Photocatalytic C-H Activation with High Efficiency and Selectivity

Xiao，Xudong1; Ruan，Zhoushilin2; Li，Qi1; Zhang，Liping3; Meng，Huiyuan4; Zhang，Qun2; Bao，Hongliang5; Jiang，Baojiang1; Zhou，Jing5; Guo，Chuanyu1; Wang，Xiaolei1; Fu，Honggang1

2022

10.1002/adma.202200612

ADVANCED MATERIALS   影响因子和分区

0935-9648

1521-4095

Selective oxidation of C-H bonds is one of the most important reactions in organic synthesis. However, activation of the α-C-H bond of ethylbenzene by use of photocatalysis-generated superoxide anions (O) remains a challenge. Herein, the formation of individual Fe atoms on polymeric carbon nitride (CN), that activates O to create O for facilitating the reaction of ethylbenzene to form acetophenone, is demonstrated. By utilizing density functional theory and materials characterization techniques, it is shown that individual Fe atoms are coordinated to four N atoms of CN and the resultant low-spin Fe–N system (te) is not only a great adsorption site for oxygen molecules, but also allows for fast transfer of electrons generated in the CN framework to adsorbed O, producing O. The oxidation reaction of ethylbenzene triggered by O ions turns out to have a high conversion rate of 99% as well as an acetophenone selectivity of 99%, which can be ascribed to a novel reaction pathway that is different from the conventional route involving hydroxyl radicals and the production of phenethyl alcohol. Furthermore, it possesses great potential for other C-H activation reactions besides ethylbenzene oxidation.

carbon nitride charge transfer selective oxidation single atoms visible-light photocatalysis

SCI ; EI

英语

NI论文

其他

WOS:000804999200001

20222312190457

Activation analysis ; Atoms ; Carbon nitride ; Chemical activation ; Density functional theory ; Ethylbenzene ; Ketones ; Oxidation ; Photocatalysis

Light/Optics:741.1 ; Chemical Reactions:802.2 ; Chemical Products Generally:804 ; Organic Compounds:804.1 ; Probability Theory:922.1 ; Atomic and Molecular Physics:931.3 ; Quantum Theory; Quantum Mechanics:931.4

MATERIALS SCIENCE

2-s2.0-85131158718

Scopus

1.Key Laboratory of Functional Inorganic Material Chemistry,Ministry of Education of the People's Republic of China,Heilongjiang University,Harbin,Heilongjiang,150080,China
2.Hefei National Laboratory for Physical Sciences at the Microscale,Department of Chemical Physics,Synergetic Innovation Center of Quantum Information and Quantum Physics,University of Science and Technology of China,Hefei,Anhui,230026,China
3.Department of Mechanical and Energy Engineering,Southern University of Science and Technology,Shenzhen,Guangdong,518055,China
4.School of Safety Engineering,Heilongjiang University of Science and Technology,Harbin,Heilongjiang,150022,China
5.Shanghai Institute of Applied Physics,Chinese Academy of Sciences,Shanghai,201800,China

Xiao，Xudong,Ruan，Zhoushilin,Li，Qi,等. A Unique Fe–N4 Coordination System Enabling Transformation of Oxygen into Superoxide for Photocatalytic C-H Activation with High Efficiency and Selectivity[J]. ADVANCED MATERIALS,2022,34.

Xiao，Xudong.,Ruan，Zhoushilin.,Li，Qi.,Zhang，Liping.,Meng，Huiyuan.,...&Fu，Honggang.(2022).A Unique Fe–N4 Coordination System Enabling Transformation of Oxygen into Superoxide for Photocatalytic C-H Activation with High Efficiency and Selectivity.ADVANCED MATERIALS,34.

Xiao，Xudong,et al."A Unique Fe–N4 Coordination System Enabling Transformation of Oxygen into Superoxide for Photocatalytic C-H Activation with High Efficiency and Selectivity".ADVANCED MATERIALS 34(2022).