Is single-atom catalyzed peroxymonosulfate activation better? Coupling with metal oxide may be better

doi:10.1016/S1872-2067(24)60009-4

Abstract

Abstract:

Single-atom catalysts (SACs) as a new class of peroxymonosulfate (PMS) activator are still limited by the low metal loading and activity. Here, we introduce a new strategy of interfacial coupling SACs with metal oxides to fine-tune the active single-atom sites and improve the atomic utilization efficiency. Taking Co₃O₄@Co₁/C₃N₅ as a case, the formation of heterostructures enhanced the activity of outer-sphere SACs for PMS activation, further upgrading the kinetics of diclofenac sodium degradation. The degradation rate of the composite increases by up to approximately 28.0 and 2.5 times compared to Co₃O₄and Co₁/C₃N₅, respectively. The Co₁-O (Co₃O₄) and Co-N (Co₁/C₃N₅) bonds between Co₁/C₃N₅ and Co₃O₄ make a tightly coupled interface for charge migration, which synergically optimizes the PMS adsorption configuration toward reactive species generation with lower activation energy. Co₃O₄@Co₁/C₃N₅ also exhibits excellent reusability and can be employed in broad application scenarios.

Key words: Single-atom catalyst, Metal oxide, Synergy, Peroxymonosulfate activation, Co₃O₄@Co₁/C₃N₅

Junlei Zhang, Wencong Liu, Biao Liu, Xiaoguang Duan, Zhimin Ao, Mingshan Zhu. Is single-atom catalyzed peroxymonosulfate activation better? Coupling with metal oxide may be better[J]. Chinese Journal of Catalysis, 2024, 59: 137-148.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60009-4

https://www.cjcatal.com/EN/Y2024/V59/I4/137

Figures/Tables 5

Fig. 1. (A) The development trend of heterogeneous PMS activators. (B) The DCF degradation rates in the reaction system of Co3O4, Co1/C3N5 or Co3O4@Co1/C3N5 coupled PMS.

Fig. 2. (A) The scheme of Co3O4@Co1/C3N5 preparation. (B) TEM image of Co3O4@Co1/C3N5. (C) HR-TEM image of Co3O4 in Co3O4@Co1/C3N5. (D) HADDF-STEM image of Co1/C3N5 in Co3O4@Co1/C3N5. (E) Co k edge XANES spectra of Co foil, CoO, Co3O4, Co2O3, Co1/C3N5, and Co3O4@Co1/C3N5. (F-G) high-resolution XPS of Co 2p from Co3O4@Co1/C3N5 and Co1/C3N5. The corresponding Fourier transform spectra of Co foil, CoO, Co3O4, Co2O3, Co1/C3N5, and Co3O4@Co1/C3N5 (H), and EXAFS fitting curves at K (I) and R (J) space of Co1/C3N5, respectively.

Fig. 3. The degradation curves (A), rates (B), and mineralization efficiencies (C) of DCF in the system of PMS alone, Co3O4@Co1/C3N5 alone, C3N5 coupled PMS, Co3O4 coupled PMS, Co1/C3N5 coupled PMS or Co3O4@Co1/C3N5 coupled PMS. (D) Comparison of the DCF degradation rate and TOC removal by Co3O4 plus Co1/C3N5 and Co3O4@Co1/C3N5. The degradation curves (E) and TOC removal efficiencies (F) of DCF in various waterbodies (e.g., deionized (DI) water, rain water, tap water, river water, and medical wastewater) over the reaction system of Co3O4@Co1/C3N5 coupled PMS. (G) The adsorption energy Eads of PMS adsorbed on the C3N5, Co1/C3N5, and Co3O4@Co1/C3N5 surfaces, inset showing corresponding relaxed configuration. (H) The pathway of the free radical production process. (I) The relaxed configuration of the free radical production process on the C3N5, Co1/C3N5, and Co3O4@Co1/C3N5 surfaces, where IS, TS and FS represent initial structure, transition structure and final structure of the reaction, respectively. The gray, blue, red, yellow, white, nattier blue spheres in this Fig. are C, N, O, S, H, Co atoms, respectively.

Fig. 4. Effects of scavengers on DCF degradation in the Co3O4@Co1/C3N5 (A), Co1/C3N5 (B) or Co3O4 (C) coupled PMS system. ESR spectra of TEMP-1O2 (D), DMPO-OH/SO4- (E), and DMPO-O2- (F) in the systems of PMS alone, and Co3O4, Co1/C3N5 or Co3O4@Co1/C3N5 coupled PMS, respectively. (G) The proposed mechanism of Co3O4@Co1/C3N5 to activate PMS for PPCPs degradation.

Fig. 5. (A) The degradation products and summarized possible degradation pathways of DCF in the system of Co3O4@Co1/C3N5 coupled PMS. Acute toxicity (B), developmental toxicity (C), bioaccumulation factor (D), and mutagenicity (E) of DCF and corresponding products. (F) Recycling degradation curves of DCF by reusing Co3O4@Co1/C3N5 to activate PMS. (G) XRD patterns of fresh, used, and calcined Co3O4@Co1/C3N5 samples.

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