Quantitative correlation of Fe(III) electronic structure regulation in peroxymonosulfate activation via atomic cobalt doping AgFeO2

doi:10.1016/S1872-2067(25)64784-X

Abstract

Abstract:

The influence of electronic structure on the performance of catalysts for peroxymonosulfate (PMS) activation remains ambiguous. In this study, the 3d electron configuration of Fe(III) in AgFeO₂ was atomically regulated using cobalt doping. The amount of PMS adsorbed and the catalytic performance were positively correlated with the total effective magnetic moment and the ratios of high-spin Fe(III) and e_g filling within the catalysts. These 3d electron regulations favor PMS adsorption and electron transfer owing to the lower PMS adsorption energy, increased electronic states near the Fermi level, and reduced dz² orbital occupancy. Benefiting from fine tailoring of the electron configuration, the AgFe_0.80Co_0.20O₂ catalyst exhibited outstanding catalytic PMS activation and favorable application potential, achieving efficient pharmaceutical wastewater treatment and more than 80% ofloxacin removal after 72 h of continuous-flow operation. Notably, this study offers a comprehensive understanding for the influence mechanism of electronic structure regulation on PMS activation, providing design guidance for the development of efficient heterogeneous Fenton-like catalytic systems.

Key words: 3d electron configuration, Heterogeneous catalysis, Peroxymonosulfate activation, Electron transfer, AgFeO₂

Chen Xu, Di Song, Xinggang Liu, Fang Deng, Yongcai Zhang, Mingshan Zhu, Xijun Liu, Jianping Zou, Xubiao Luo. Quantitative correlation of Fe(III) electronic structure regulation in peroxymonosulfate activation via atomic cobalt doping AgFeO₂[J]. Chinese Journal of Catalysis, 2025, 77: 87-98.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64784-X

https://www.cjcatal.com/EN/Y2025/V77/I10/87

Figures/Tables 9

Fig. 1. (a) Eads and S-O bond lengths of the adsorbed PMS molecules on AgFeO2 and AgFe0.80Co0.20O2 surface. (b) DOS diagrams of AgFeO2 and AgFe0.80Co0.20O2. (c) PDOS for Fe-3d orbitals in AgFeO2 and AgFe0.80Co0.20O2. (d) PDOS of the Fe eg orbital in AgFeO2 and AgFe0.80Co0.20O2. (e) Schematic sketch of the spin-state-dependent PMS activation process.

Fig. 2. SEM (a), TEM (b) and HRTEM (c) images of AgFe0.80Co0.20O2. (d) EDS mappings of AgFe0.80Co0.20O2.

Fig. 3. XRD patterns (a) and FT-IR spectra (b) of AgFeO2 and AgFe1-xCoxO2. Ag 3d (c), Fe 2p (d), O 1s (e), and Co 2p (f) XPS spectra of AgFeO2 and AgFe0.80Co0.20O2.

Fig. 4. (a) Fe K-edge normalized XANES spectra. (b) FT-EXAFS spectra of AgFeO2, AgFe0.80Co0.20O2 and standard samples. (c) The FT-EXAFS K-space fitting curve of AgFeO2. (d) The FT-EXAFS K-space fitting curve of AgFe1-xCoxO2. (e) EPR spectra of AgFeO2 and AgFe0.80Co0.20O2. (f) Temperature-dependent magnetic susceptibilities of different catalysts. (g) The quantitative changes of μeff,Fe, high spin state, low spin state and eg filling for AgFe1-xCoxO2 with different Co-doping amount. (h) Schematic illustration of strong interaction and eg occupancy of FeOh and CoOh in AgFe0.80Co0.20O2.

Fig. 5. (a) OFL removal efficiency in different AgFe1-xCoxO2/PMS systems. (b) The kobs change with different Co-doping ratio. (c) The TOC removal ratio of OFL solution in AgFe1-xCoxO2/PMS systems with different Co-doping amount. (d) The quantitative correlation of kobs with high spin and low-spin proportion, eg filling and μeff,Fe.

Fig. 6. (a) Quenching experiment of reactive species in AgFe0.80Co0.20O2/PMS. (b) EPR spectra of DMPO-O2?? in AgFeO2/PMS and AgFe0.80Co0.20O2/PMS system. (c) PMS adsorption and consumption in AgFe1-xCoxO2/PMS. (d) Quantitative correlation of PMS adsorption with high spin and low-spin proportion, eg filling and μeff,Fe. (e) Correlation between lnkobs and PMS adsorption quantity. Catalysts: 1 g L-1, C[PMS]: 0.5 mmol L-1, C[MeOH]: 100 mmol L-1, C[BQ] = C[DMSO]: 1 mmol L-1, C[NaN3] = C[IPA] = C[KI]: 10 mmol L-1, C0[OFL]: 15 mg L-1, initial solution pH = 7.0, and T = 25 ± 2 °C.

Fig. 7. (a) I-t curves. (b) LSV curves obtained under different conditions. (c) EIS Nyquist plots in different systems. (d) CV curves of AgFeO2 and AgFe0.80Co0.20O2.

Fig. 8. (a) Influence of various anions on OFL degradation in the AgFe0.80Co0.20O2/PMS system. (b) OFL removal efficiency in different actual water samples. Catalysts: 1 g L-1, C0[OFL]: 15 mg L-1, C[PMS]: 0.5 mmol L-1, and T = 25 ± 2 °C. (c) Consecutive use of AgFe0.80Co0.20O2. (d) Fe 2p XPS spectrum of the recovered AgFe0.80Co0.20O2.

Fig. 9. (a) COD and TOC removal of actual pharmaceutical wastewater by the AgFe0.80Co0.20O2/PMS system. (b) Enhanced biodegradability of pharmaceutical wastewater by the AgFe0.80Co0.20O2/PMS system. (c) The photo of continuous flow reactor. (d) OFL removal by catalyst packed column. catalyst loading = 0.1 g, C0[OFL]: 10 mg L-1, C[PMS]: 0.5 mmol L-1, flow rate = 14 mL h-1).

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Quantitative correlation of Fe(III) electronic structure regulation in peroxymonosulfate activation via atomic cobalt doping AgFeO₂

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