哈尔滨工业大学CEJ:不同表面羟基和氧空位对过氧化单硫酸盐活化的协同作用机制，实现持久的水净化

第一作者：Shuyu Wang

通讯作者：闫鹏魏 助理教授/讲师

通讯单位：哈尔滨工业大学环境学院

DOI:10.1016/j.cej.2024.158259

Fig. 1. Schematic illustration of synthesis procedure for α-FeOOH and α-Fe1.6Ni0.4O3H (a). Characterization of α-FeOOH, α-Fe1.6Ni0.4O3H and α-Fe2O3. XRD patterns (b), FTIR spectra (c), TEM spectra (d), Raman spectra (e), ESR spectra (f), XPS spectra of O 1s (g) of the catalysts.

Fig. 2. Degradation of clothianidin (a) and the quasi-first-order kinetic constant of CLO degradation and PMS decomposition (b), cycling tests of catalysts (c), removal of various pollutants (d), the effect of water matrices on CLO degradation (e). Condition: catalyst dose = 200 mg/L, [PMS]0 = 100 mg/L, [CLO]0 = [ATZ]0 = [2,4-D]0 = [DTZ]0 = [IHL]0 = 1 mg/L, pH = 7.0, T = 23 ℃.

Fig. 3. ESR spectra of DMPO-OH and DMPO-SO4 (a), DMPO-O2- (b) and TEMPO (c) in PMS alone and α-Fe1.6Ni0.4O3H/PMS system. Quenching tests (d). Degradation kinetics of NB and BA by α-Fe1.6Ni0.4O3H/PMS system (e); the effect of catalyst and PMS dose on the relative steady-state concentration of ⋅OH and SO4⋅- (f) and the linear relation between them (g); the distribution of different surface hydroxyl species of α-Fe1.6Ni0.4O3H as a function of pH (h); the effect of pH on the relative steady-state concentration of ⋅OH and SO4⋅- (i). Condition: catalyst dose = 200 mg/L, [PMS]0 = 100 mg/L, [TBA]0 = [EtOH]0 = [CF]0 = 326 mM, pH = 7.0, T = 23 ℃.

Fig. 4. In situ ATR-FTIR spectra in D2O of α-Fe1.6Ni0.4O3H/PMS system (a) and that with H2PO4- (b), the effect of H2PO4- on CLO degradation (c), in situ ATR-FTIR spectra (d) and Raman spectra (e) of oxidation systems in H2O, infrared spectra of adsorbed pyridine of α-Fe2O3 and α-Fe1.6Ni0.4O3H (f); FTIR spectra (g) and ESR spectra (h), contact angle spectra (i), the surface hydroxyls concentration (j) and in-situ ATR spectra (k) of catalysts synthesized in 60 °C-600 °C, and degradation rate of CLO and PMS utilization efficiency in constructed systems (l).

Fig. 5. Energy profiles of the surface-complex process of PMS on catalysts (a); the molecular weak interaction between H2O (Ⅰ) or PMS (Ⅱ) and α-Fe1.6Ni0.4O3H (b); the PMS adsorption energy and HOMO energy of catalysts (containing the electron density difference of PMS adsorption) (c); PDOS spectra of α-Fe1.6Ni0.4O3H and PMS adsorption on α-Fe1.6Ni0.4O3H (d); the d-band center of catalysts before and after reaction (e); temperature-dependent inverse susceptibilities fitted by the Curie-Weiss law over α-Fe2O3 and α-Fe1.6Ni0.4O3H (C is the Curie constant) (f); energy profiles of SO4⋅- formation from PMS activation by catalysts (g); XPS spectra of Fe 2p of α-Fe1.6Ni0.4O3H before and after use (h); ESR spectra of fresh and used α-Fe1.6Ni0.4O3H (i), schematic illustration of reaction pathway and mechanism (j).

Fig. 6. Schematic illustration of the synthesis process and photograph of the α-Fe1.6Ni0.4O3H/PVDF catalytic membrane (a), SEM and EDS mapping of the α-Fe1.6Ni0.4O3H/PVDF catalytic membrane (b), the set-up for membrane filtration system (c, d), removal rate of CLO (e) and UV254 (f) in raw and filtered water by different system, three-dimensional excitation-emission matrix (3D-EEM) patterns of DOM in raw water and filtered water before and after PVDF membrane and α-Fe1.6Ni0.4O3H/PMS/PVDF treatment (g). (I: aromatic proteins-tyrosine, II: aromatic proteins-tryptophan, III: fulvic acid substances, IV: soluble microbial metabolic by-products, and V: humic-like substances).