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Molecular Engineering toward Pyrrolic N‐Rich M‐N 4 (M = Cr, Mn, Fe, Co, Cu) Single‐Atom Sites for Enhanced Heterogeneous Fenton‐Like Reaction
Author(s) -
Chen Feng,
Wu XiLin,
Shi Chenyang,
Lin Hongjun,
Chen Jianrong,
Shi Yanpeng,
Wang Shaobin,
Duan Xiaoguang
Publication year - 2021
Publication title -
advanced functional materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 6.069
H-Index - 322
eISSN - 1616-3028
pISSN - 1616-301X
DOI - 10.1002/adfm.202007877
Subject(s) - catalysis , materials science , bisphenol a , photocatalysis , photochemistry , chemistry , organic chemistry , epoxy , composite material
Heterogeneous Fenton‐like reactions (HFLR) are promising alternative strategies to address the inherent limitations of the classic Fenton systems. Herein, a facile and scale‐up approach for the synthesis of transition metal single‐atom sites (SA‐TM, TM = Cr, Mn, Fe, Co, Cu) coordinated onto pyrrolic N‐rich g‐C 3 N 4 (PN‐g‐C 3 N 4 ) scaffold is developed. The regulated pyrrolic N‐rich SA‐TM catalytic sites exhibit excellent performances for HFLR. As a model of SA‐TM/PN‐g‐C 3 N 4 , SA‐Cr/PN‐g‐C 3 N 4 is efficient for the catalytic oxidation of bisphenol A via HFLR under visible light with outstanding cyclic stability and wide effective pH range (3.0–11.0). The synergy of photocatalysis and single‐atom catalysis leads to accelerated production and separation of charge carriers as well as the cycling of Cr 3+ /Cr 2+ couple, consequently boosting the performance in HFLR. Theoretical calculations indicate that the Cr(II)‐N 4 sites with the metalloporphyrin‐like structure are more reactive than the doped Cr(II) sites in the g‐C 3 N 4 matrix, which act as the peroxidase‐mimicking nanozyme for efficient and homolytic cleavage of peroxide OO in H 2 O 2 . This study expands the family of the iron‐free Fenton‐like systems and provides new strategies to the rational design and precise regulation of on‐demand multifunctional single‐atom catalysts for advanced water remediation.