4.7 Article

Non-radical oxidation by N,S,P co-doped biochar for persulfate activation: Different roles of exogenous P/S doping, and electron transfer path

Journal

JOURNAL OF CLEANER PRODUCTION
Volume 374, Issue -, Pages -

Publisher

ELSEVIER SCI LTD
DOI: 10.1016/j.jclepro.2022.133995

Keywords

Biochar; Heteroatom co -doping; Non -radical; Electron transfer

Funding

  1. National Key Research and Development Program of China [2021YFC1910400]
  2. Hunan Natural Science Foundation of Hunan Province [2022JJ40085]
  3. Changsha Natural Science Foundation [kq2202169]
  4. China Postdoctoral Science Foundation [BX2021097, 2021M701149, 2021T140192, 2021M690054]
  5. National Natural Science Foundation of China [51521006, 52100142]
  6. Training Program for Excellent Young Innovators of Changsha [kq1802022]

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This study focuses on the catalytic performance of biochar in the persulfate-based oxidation process. It found that exogenous S doping had a negative effect on removal efficiency, while exogenous P doping had a positive effect. The electrochemical characterization revealed that NSC-P-bio improved catalytic performance by increasing surface catalytic sites and enhancing electronic conductivity.
Despite many studies on single doping (especially N, S) to improve the catalytic performance of biochar in persulfate-based oxidation process (PS-AOP), the investigations of co-doping with multiple heteroatoms for biochar are relatively few. Herein, choosing shrimp shell biochar (NSC-bio, natural N,S co-doped) as research object with exogenous P/S doping, N,S co-doped and N,S,P co-doped biochars were prepared and applied in PS-AOP, respectively. Exogenous S doping (NSC-S-bio) showed a negative effect with the decreased removal effi-ciency from 88.7% to 45.7%. Quantitative structure-activity relationships analysis showed that, the decreased kobs (0.0692-0.0171 min -1) of NSC-S-bio was linearly related to the decreased Qe (229.0-158.7 mg/g), where the increased electrostatic repulsion during the key catalytic zone by S doping was the key factor. As for NSC-P-bio, a positive effect could be observed (98.9% removal). The increased kobs (0.0692-0.1299 min -1) showed high linear fitting toward P content and specific surface area (449.4-971.6 m2/g) but low fitting degree toward Qe. Further electrochemical characterization revealed that, the increased surface catalytic sites and enhanced electronic conductivity endowed NSC-P-bio improved catalytic performance, which achieved rapid activation of PDS via non-radical electron transfer path and showed selectively toward substrate with electron-donating groups. This study provides new insight for the construction of efficient co-doped biochar catalysts in PS-AOP.

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