Engineering spin polarization of encaging Co nanoparticles in atomic CoNx sites evoke high valent Co species for boosting organic compound oxidation

doi:10.1016/S1872-2067(25)64763-2

Abstract

Abstract:

Precise manipulation of the catalytic spin configuration and delineation of the relationship between spin related properties and oxidation pathways remain significant challenges in Fenton-like processes. Herein, encapsulated cobalt nanoparticles and cobalt-nitrogen-doped carbon moieties, endowed with confinement effects and variations in shell curvature were constructed via straightforward pyrolysis strategies, inducing alterations in magnetic anisotropy, electronic energy levels and spin polarization. The enhanced spin polarization at cobalt sites leads to a reduction in crystal field splitting energy and an increase in electronic spin density. This phenomenon facilitated electron transfer from cobalt orbitals to p_z orbitals of oxygen species within peroxymonosulfate molecules, thereby promoting the formation of high-valent cobalt species. The encapsulation effectively stabilized cobalt nanoparticles, mitigating their dissolution or deactivation during reactions, which in turn enhances stability and durability in continuous flow processes. The high-valent cobalt species within the shell exhibit increased exposure and generate localized high concentrations, thereby intensifying interactions with migrating pollutants and enabling efficient and selective oxidation of emerging compounds with elevated redox potentials. This work underscores the profound impact of confined encapsulation curvature and spin polarization characteristics of metal sites on catalytic oxidation pathways and performance, opening novel avenues for spin engineering in practical environmental catalysis.

Key words: Spin crossover, Spin polarization, Confined microstructure, Oxidation pathway modulation, Fenton-like reaction

Liang Zhang, Jialiang Rui, Yiqian Li, Zhizhi Yang, Shiro Kubuki, Junhu Wang, Bofan Zhang. Engineering spin polarization of encaging Co nanoparticles in atomic CoN_x sites evoke high valent Co species for boosting organic compound oxidation[J]. Chinese Journal of Catalysis, 2025, 77: 184-198.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64763-2

https://www.cjcatal.com/EN/Y2025/V77/I10/184

Figures/Tables 6

Fig. 1. XRD pattern (a), TEM images (b), N2 adsorption-desorption isotherms (c), and FT k3-weighted Co K-edge EXAFS and WT-EXAFS spectra (d,e) of CM-1, CoNP and references. (f) Co 2p XPS spectra of CM-1, CoNP and CM-3 catalysts. χm-T and 1/χm-T (inserted images) plots of CM-1 (g) and CoNP (h).

Fig. 2. (a) HBA degradation in various systems. (b) Corresponding first-order kinetic and normalized rate constant analysis. (c) Different organic compounds removal efficiency in CM-1 system. (d) Comparison of specific activity with previous research reported. (e) PMS decomposition performance. (f) Recycling activity of CM-1 system for HBA degradation. Influences of different ions (g) and initial pH value (h). (i) TOC removal rate and iron ions leached content in different systems. Reaction conditions: [Catalyst] = 0.15 g L-1, [PMS] = 1.0 mmol L-1, [HBA] = 200 μmol L-1, [Initial pH] = 5.1, [Anions] = 20 mg L-1.

Fig. 3. (a-c) Impacts of various quenchers on HBA degradation in CM-1 and CoNP systems. (d-f) EPR spectra of ?OH/SO4?-, 1O2 and O2?- in different reaction systems. (g) PMS decomposition in HBA and H2O quality matrixes. (h,i) PMSO consumption, PMSO2 generation and corresponding conversion rate in CM-1 and CoNP systems.

Fig. 4. (a) 1,10-phenanthroline poising experiment. XPS spectra of Co 2p (b) and N 1s (c) in used CM-1 catalyst. (d) EIS curves. (e,f) Open potential and linear sweep voltammetry measurement with subsequent addition of PMS and HBA. (g,h) In-situ Raman spectra with extension reaction time and addition of PMS and HBA. (i) First-order kinetics in CM-1 and CoNP systems towards various organics with different IP values.

Fig. 5. (a) PDOS plots of Co 3d orbital and N 2p orbital for CoNP and CM-1. (b) Differential charge distribution, Bader charge, electron transfer quantity and PMS adsorption energy of CM-1 and CoNP. Proposed Co 3d and O 2p orbital interaction (c) and electron localization function plots (d) of CoNP and CM-1. (e) Proposed mechanism of CoIV=O catalytic generation in CM-1 system.

Fig. 6. (a) The resistance performance of CM-1 towards different water matrixes. (b-d) Schematic illustration of continuous experiments and corresponding treatment performances. (e) Proposed oxidation pathway of HBA in CM-1 system. (f) The antibacterial activity of CM-1 material and possible attack behavior towards Ecoli cells.

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