Acta Chimica Sinica ›› 2022, Vol. 80 ›› Issue (9): 1238-1249.DOI: 10.6023/A22050227 Previous Articles     Next Articles



李小娟, 叶梓瑜, 谢书涵, 王永净, 王永好, 吕源财, 林春香*()   

  1. 福州大学 环境与安全工程学院 福州 350108
  • 投稿日期:2022-05-16 发布日期:2022-08-11
  • 通讯作者: 林春香
  • 基金资助:
    国家自然科学基金(51908132); 福建省自然科学基金(2022J01108); 福建省自然科学基金(2020J01506); 福建省自然科学基金(2020Y0016)

Study on Performance and Mechanism of Phenol Degradation through Peroxymonosulfate Activation by Nitrogen/Chlorine Co-doped Porous Carbon Materials

Xiaojuan Li, Ziyu Ye, Shuhan Xie, Yongjing Wang, Yonghao Wang, Yuancai Lv, Chunxiang Lin()   

  1. College of Environment & Safety Engineering, Fuzhou University, Fuzhou 350108, China
  • Received:2022-05-16 Published:2022-08-11
  • Contact: Chunxiang Lin
  • Supported by:
    National Natural Science Foundation of China(51908132); Natural Science Foundation of Fujian Province, China(2022J01108); Natural Science Foundation of Fujian Province, China(2020J01506); Natural Science Foundation of Fujian Province, China(2020Y0016)

Heteroatomic co-doped carbon materials have broad application prospect in the field of persulfate-based advanced oxidation processes. In this paper, nitrogen and chlorine co-doped ZIF-8 derived porous carbon materials (NClC) were synthesized by a two-step pyrolysis method, as follows: 1.5 g ZIF-8 was transferred to a quartz boat, calcined for 6 h at 800 ℃ with a heating rate of 5 ℃/min in a N2 atmosphere, and cool naturally to room temperature; the black carbon material obtained was further treated with 0.5 mol/L HCl for 24 h to remove the residual Zn and then dried in a 60 ℃ oven to acquire N-doped porous carbon (NC); subsequently, 1.2 g NH4Cl was uniformly dissolved in 20 mL ultrapure water, and 0.15 g of the synthesized NC was added; after stirring and reaction for 5 h, the mixture was placed in a 60 ℃ oven to dry overnight; the dried sample was ground to a uniform powder and then calcined for 2 h at 700, 800, 900 or 1000 ℃ in a N2 atmosphere to obtain NClCX, in which the “X” represents the secondary calcination temperature (℃). Additionally, NC900 was obtained by calcination of NC at 900 ℃ in the same way without any modification. The composition and structure of all carbon materials were characterized by field emission scanning electron microscope (FESEM), transmission electron microscope (TEM), X-ray diffraction (XRD), Raman, BET and X-ray photoelectron spectroscopy (XPS). Phenol was employed as a targeted contaminant to explore the performance of NClCX on PMS activation, and the results showed NClC900 exhibited excellent catalytic performance with 97.7% of phenol and 72.4% of total organic carbon (TOC) removal in 30 min. NClC900/PMS system presented excellent acid-base tolerance and anti-interference ability, which can effectively remove phenol over a broad pH range (pH=3~9) or under the interference of various anions (NO3-, Cl-, H2PO4-, HCO3-) and humic acid (HA). Moreover, the NClC900/PMS system performed outstanding feasibility in the removal of dyes, antibiotics, phenols, pesticide and purification of actual contaminated water samples. Cyclic experiments showed that NClC900 had good stability and could remove 72.1% of phenol after repeated use for 4 times. Quenching experiments, electron paramagnetic resonance and electrochemical analysis indicated that 1O2 and surface-bound SO4•- were the main active species for phenol degradation, and the graphite N, C—Cl of NClC900 were the key active sites for generating of 1O2 and surface-bound SO4•-.

Key words: peroxymonosulfate, metal-organic frameworks, co-doped, surface-bound radical, singlet oxygen