FeNi nanoparticles cooperate with single-atom sites to drive non-radical fenton-like catalysis: Dominant singlet oxygen and electron transfer pathways for efficient wastewater purification

doi:10.1016/S1872-2067(25)64881-9

Abstract

Abstract:

Heterogeneous Fenton-like systems provide sustainable water-purification solutions; however, improving their catalytic efficiency and recyclability remains challenging. We developed a facile strategy to prepare an FeNi nanoparticle (NPs)-coupled single-atom site catalyst ((FeNi)_NPs,SAs-N-C)), which exhibits a strong synergy between FeNi NPs and monodisperse Fe/Ni active sites. This catalyst effectively activates peroxymonosulfate (PMS) at low concentrations (0.2 mmol/L), generating abundant reactive oxygen species. Under the condition of continuous flow, the optimized system achieved over 99% sulfamethazine degradation within 3000 min, with a kinetic rate constant (k = 1.5758 min^-1) that is 16, 17, and 7 times higher than those of MIL-88B(Fe), MIL-88B(Fe,Ni) and Fe_NPs,SAs-N-C, respectively. Mechanistic studies showed that PMS activation occurs via a nonradical pathway dominated by singlet oxygen (¹O₂) and direct electron transfer, enhancing the resistance to interference from inorganic anions and natural organic matter. Density functional theory calculations showed that FeNi NPs donated electrons to affect the d-orbitals in Fe single-atom sites, enhancing their interaction with PMS to produce ¹O₂ and enable electron transfer. This study presents a viable method for creating efficient NPs coupled with single-atom site catalysts for environmental clean-up.

Key words: Fenton-like, Bimetallic catalyst, Nanoparticles and single atoms, Singlet oxygen (¹O₂), Electron transfer

Bei Han, Chen Jin, Cuihong Luo, Yuntao Liu, Zhichao Dai, Yunqiang Sun, Zibao Gan, Chong-Chen Wang, Xiuwen Zheng, Zunfu Hu. FeNi nanoparticles cooperate with single-atom sites to drive non-radical fenton-like catalysis: Dominant singlet oxygen and electron transfer pathways for efficient wastewater purification[J]. Chinese Journal of Catalysis, 2026, 82: 187-200.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64881-9

https://www.cjcatal.com/EN/Y2026/V82/I3/187

Figures/Tables 6

Fig. 1. (a) Schematic of (FeNi)NPs,SAs-N-C synthesis. (b) PXRD patterns of catalysts. (c) TEM image. (d) SEM image. (e) HRTEM image. (f,g) AC-HAADF-STEM images of the (FeNi)NPs,SAs-N-C (atomic Fe and Ni species circled by red). (h) EDS mapping images of (FeNi)NPs,SAs-N-C.

Fig. 2. (a) XPS spectra of N 1s. (b) Fe K-edge XANES. (c) Ni K-edge XANES. (d) Fe K-edge FT-EXAFS spectra. (e) Ni K-edge FT-EXAFS spectra. (f) Fe K-edge EXAFS fitting curves. (g) Ni K-edge EXAFS fitting curves. (h,i) WT of (FeNi)NPs,SAs-N-C.

Fig. 3. Catalytic degradation of SMZ (a) and the corresponding reaction rate constants and removal efficiency (b) in various reaction systems. (c) Summary of experimental data for optimizing reaction conditions. (d) Effect of various anions and organics on SMZ removal by (FeNi)NPs,SAs-N-C+PMS system. (e) Effects of HA, SA and BSA on SMZ degradation in the FeNPs,SAs-N-C+PMS and (FeNi)NPs,SAs-N-C+PMS systems. (f) Cyclic experiment for the (FeNi)NPs,SAs-N-C+PMS system. (g) SMZ degradation in simulated wastewater prepared using different water environments with the (FeNi)NPs,SAs-N-C+PMS system. (h) Removal of various pollutants by the (FeNi)NPs,SAs-N-C+PMS system. (i) k values for degradation with different catalyst systems.

Fig. 4. (a) SMZ removal rate constants of various quenching systems. (b) Oxidation of trans-stilbene in the reactions of (FeNi)NPs,SAs-N-C+PMS and (c) FeNPs,SAs-N-C+PMS systems. (d) UV-vis spectra of DPBF in the MIL-88B(Fe)+PMS, MIL-88B(Fe,Ni)+PMS, FeNPs,SAs-N-C+PMS and (FeNi)NPs,SAs-N-C+PMS systems. (e) SMZ oxidation via a premixture of (FeNi)NPs,SAs-N-C and PMS at estimated time intervals. (f) ESR spectra for 1O2, ?OH, SO4?- and ?O2-. (g) Contributions of various ROS for SMZ degradation in the (FeNi)NPs,SAs-N-C+PMS and FeNPs,SAs-N-C+PMS systems.

Fig. 5. (a) Scheme of GOS with catalyst. (b) LSV of (FeNi)NPs,SAs-N-C electrodes under different conditions. (c) EIS spectra of MIL-88B(Fe), MIL-88B(Fe,Ni), FeNPs,SAs-N-C and (FeNi)NPs,SAs-N-C. (d) I-t curves. (e) Radar chart of SMZ degradation/PMS usage rate, COD and 1O2 yield of these catalysts. (f) Toxicity evaluation of intermediates. (g) Toxicity levels of the (FeNi)NPs,SAs-N-C+PMS system. Evaluation of SMZ removal using fresh (FeNi)NPs,SAs-N-C+PMS (h) and regenerated (FeNi)NPs,SAs-N-C+PMS (i) systems.

Fig. 6. (a) Front and side views of FeNPs,SAs-N-C and (FeNi)NPs,SAs-N-C. Blue, green, gray and gold spheres represent Fe, Ni, N and C atoms, respectively. (b) Eads, lO-O and Bader charges of PMS adsorbed on the FeNPs,SAs-N-C and (FeNi)NPs,SAs-N-C. Blue represent electron accumulation and yellow represent electron depletion. (c) Bader charges of FeNPs,SAs-N-C and (FeNi)NPs,SAs-N-C. Blue represent electron accumulation and yellow represent electron depletion. (d) Free energy profiles of 1O2 and FeIVNx=O in different systems. (e) PDOS of Fe atoms and N atoms and the d-band center of Fe sites in FeNPs,SAs-N-C and (FeNi)NPs,SAs-N-C. (f) Adsorption configuration and corresponding adsorption energy of FeIVN4=O on the amido gen sites (-NH2) of SMZ and FeIVN2=O on imino (-NH) sites of SMZ. (g) Schematic illustration of different attack pathways of SMZ at FeIVN4=O and FeIVN2=O sites.

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