Homogeneous Carbon Dot-Anchored Fe(III) Catalysts with Self-Regulated Proton Transfer for Recyclable Fenton Chemistry

Ting Zhang; Zhelun Pan; Jianying Wang; Xufang Qian; Hiromi Yamashita; Zhenfeng Bian; Yixin Zhao

doi:10.1021/jacsau.2c00644

Homogeneous Carbon Dot-Anchored Fe(III) Catalysts with Self-Regulated Proton Transfer for Recyclable Fenton Chemistry

JACS Au. 2023 Jan 17;3(2):516-525. doi: 10.1021/jacsau.2c00644. eCollection 2023 Feb 27.

Authors

Ting Zhang¹, Zhelun Pan¹, Jianying Wang¹, Xufang Qian¹, Hiromi Yamashita², Zhenfeng Bian³, Yixin Zhao¹

Affiliations

¹ School of Environmental Science and Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai200240, China.
² Division of Materials and Manufacturing Science, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita565-0871, Osaka, Japan.
³ The Education Ministry Key Lab. of Resource Chemistry, Shanghai Key Laboratory of Rare Earth Functional Materials, Shanghai Normal University, 100 Guilin Road, Shanghai200234, China.

Abstract

Fenton chemistry has been widely studied in a broad range from geochemistry, chemical oxidation to tumor chemodynamic therapy. It was well established that Fe³⁺/H₂O₂ resulted in a sluggish initial rate or even inactivity. Herein, we report the homogeneous carbon dot-anchored Fe(III) catalysts (CD-COOFe^III) wherein CD-COOFe^III active center activates H₂O₂ to produce hydroxyl radicals (^•OH) reaching 105 times larger than that of the Fe³⁺/H₂O₂ system. The key is the ^•OH flux produced from the O-O bond reductive cleavage boosting by the high electron-transfer rate constants of CD defects and its self-regulated proton-transfer behavior probed by operando ATR-FTIR spectroscopy in D₂O and kinetic isotope effects, respectively. Organic molecules interact with CD-COOFe^III via hydrogen bonds, promoting the electron-transfer rate constants during the redox reaction of CD defects. The antibiotics removal efficiency in the CD-COOFe^III/H₂O₂ system is at least 51 times large than the Fe³⁺/H₂O₂ system under equivalent conditions. Our findings provide a new pathway for traditional Fenton chemistry.