Molecular Engineering toward Pyrrolic N‐Rich M‐N4 (M = Cr, Mn, Fe, Co, Cu) Single‐Atom Sites for Enhanced Heterogeneous Fenton‐Like Reaction. (14th January 2021)

• Record Type: Journal Article
• Authors: Chen, Feng; Wu, Xi‐Lin; Shi, Chenyang; Lin, Hongjun; Chen, Jianrong; Shi, Yanpeng; Wang, Shaobin; Duan, Xiaoguang
• Is Part Of: Advanced functional materials. Volume 31:Number 13(2021)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2021-01-14
• Subjects: carbon nitride -- Fenton‐like reaction -- molecular engineering -- photocatalysis -- single‐atom catalysis; Materials -- Periodicals; Chemical vapor deposition -- Periodicals; 620.11
• DOI: 10.1002/adfm.202007877
• Languages: English
• ISSNs: 1616-301X

Abstract

Abstract: 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‐C3 N4 (PN‐g‐C3 N4 ) 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‐C3 N4, SA‐Cr/PN‐g‐C3 N4 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)‐N4 sites with the metalloporphyrin‐like structure are more reactive than the doped Cr(II) sites in the g‐C3 N4 matrix, which act as the peroxidase‐mimicking nanozyme for efficient and homolytic cleavage of peroxide OO in H2 O2 . 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. Abstract : Synergistic catalysis induced by transition metal single‐atom sites coordinated onto pyrrolic N‐rich graphitic carbon nitride leads to an outstanding performance toward the photocatalytic Fenton‐like reaction with outstanding cyclic stability and a wide effective pH range.