TY - JOUR
T1 - Activation of persulfate on fluorinated carbon
T2 - Role of semi-ionic C-F in inducing mechanism transition from radical to electron-transfer nonradical pathway
AU - Ye, Feng
AU - Su, Yinmei
AU - Li, Ruipeng
AU - Sun, Wei
AU - Pu, Mengjie
AU - Yang, Cao
AU - Yang, Wenchao
AU - Huang, Haiming
AU - Zhang, Qichun
AU - Wong, Jonathan W.C.
N1 - Funding Information:
This study was financially supported by the GuangDong Basic and Applied Basic Research Foundation (No. 2019A1515110649; 2020A1515110271; 2019A1515110244), the Guangdong Province Universities and Colleges Pearl River Scholar Funded Scheme (2017), the Research Team in Dongguan University of Technology (No. TDYB2019013).
Publisher Copyright:
© 2023 Elsevier B.V. All rights reserved.
PY - 2023/11/15
Y1 - 2023/11/15
N2 - Carbon-driven nonradical persulfate activation exhibits compelling advantages due to its good reactivity in complex aquatic surroundings. However, uncertainties still exist in the construction of nonradical-oriented activation systems and the role of positively charged carbon is ambiguous because of intricate carbon structure. In this regard, this study found that F-doping strategy not only improved the catalytic activity of carbon material, but also switched free radical persulfate (PS)-activated process into the electron-transfer-based nonradical process. The CF-1.0 achieved the promising performance in degrading bisphenol A (BPA) with a removal rate of 99.5% within 60 min, where the percentage of electron transfer contribution was up to 73.27%. Based on the Bader charge analysis in density functional theory (DFT) calculation, the “electron-loss” induced catalytic mechanism was proposed. Stimulated by the incorporation of F atom that can create the electron-deficient carbon layer, the electron-rich BPA tended to transfer electrons to carbon-activated persulfate complex (C-S2O82-*), in an effort to balance the electron loss in the carbonaceous matrix, thereby realizing the oxidative degradation of pollutant. Quantitative structure-activity relationships (QSARs) indicated that semi-ionic C-F, C-OH, and structural defects could function as electron transfer channel, SO4•−/• OH, and 1O2 formation sites, respectively. In addition, the catalytic behaviors towards periodate (PI) were also investigated in detail. Overall, this research develops nonradical reaction-targeted fluorinated carbocatalyst for persulfate activation and deepens the understanding of positively charged carbon in electron-transfer regime.
AB - Carbon-driven nonradical persulfate activation exhibits compelling advantages due to its good reactivity in complex aquatic surroundings. However, uncertainties still exist in the construction of nonradical-oriented activation systems and the role of positively charged carbon is ambiguous because of intricate carbon structure. In this regard, this study found that F-doping strategy not only improved the catalytic activity of carbon material, but also switched free radical persulfate (PS)-activated process into the electron-transfer-based nonradical process. The CF-1.0 achieved the promising performance in degrading bisphenol A (BPA) with a removal rate of 99.5% within 60 min, where the percentage of electron transfer contribution was up to 73.27%. Based on the Bader charge analysis in density functional theory (DFT) calculation, the “electron-loss” induced catalytic mechanism was proposed. Stimulated by the incorporation of F atom that can create the electron-deficient carbon layer, the electron-rich BPA tended to transfer electrons to carbon-activated persulfate complex (C-S2O82-*), in an effort to balance the electron loss in the carbonaceous matrix, thereby realizing the oxidative degradation of pollutant. Quantitative structure-activity relationships (QSARs) indicated that semi-ionic C-F, C-OH, and structural defects could function as electron transfer channel, SO4•−/• OH, and 1O2 formation sites, respectively. In addition, the catalytic behaviors towards periodate (PI) were also investigated in detail. Overall, this research develops nonradical reaction-targeted fluorinated carbocatalyst for persulfate activation and deepens the understanding of positively charged carbon in electron-transfer regime.
KW - Electron transfer
KW - Fluorinated carbon
KW - Persulfate
KW - Positively charged carbon
KW - Semi-ionic C-F
UR - http://www.scopus.com/inward/record.url?scp=85162891464&partnerID=8YFLogxK
U2 - 10.1016/j.apcatb.2023.122992
DO - 10.1016/j.apcatb.2023.122992
M3 - Journal article
AN - SCOPUS:85162891464
SN - 0926-3373
VL - 337
JO - Applied Catalysis B: Environmental
JF - Applied Catalysis B: Environmental
M1 - 122992
ER -