B→Co electron donation programs Lewis-basic sites in cobalt boride for selective inner-sphere peroxymonosulfate activation

doi:10.1016/S1872-2067(26)65238-2

Abstract

Abstract:

Peroxymonosulfate (PMS)-based advanced oxidation processes are promising for contaminant removal but are often limited by nonselective radical pathways. Here we show that selective PMS activation can be achieved by regulating Lewis acid-base interactions in cobalt boride (Co_xB). Electron donation from boron to cobalt modifies the electronic structure of surface Co sites, generating Lewis-basic centers that interact strongly with electrophilic oxygen atoms in PMS. This interaction promotes inner-sphere electron transfer and favors selective ¹O₂ generation while suppressing radical-mediated reactions. Under optimized conditions, the Co_xB/PMS system removes 99.0% of oxytetracycline within 20 min, delivering a kinetic constant of 0.309 min^-1 and a molar degradation rate of 14.48 min^-1·mol·L^-1, outperforming representative cobalt oxides. The catalyst also shows strong stability, retaining 97.6% activity after 15 cycles and sustaining > 99% removal efficiency in continuous-flow operation for 30 h (1.8 L throughput). X-ray photoelectron spectroscopy measurements reveal reversible Co valence modulation during PMS activation, whereas density functional theory calculations indicate stronger PMS adsorption and a lower potential-determining barrier on Co_xB relative to Co₃O₄. Together, these results identify Lewis-basic Co sites as key centers for selective non-radical PMS activation and provide a strategy for designing efficient boride-based oxidation catalysts.

Key words: Lewis acid-base coupling, Cobalt boride, Peroxymonosulfate activation, Non-radical pathway, Emerging contaminant degradation

Haoran Wei, Wei Zhao, Junlei Zhang, Guojia Yu, Fang Yang, Xiaobing Wang, Wuwan Xiong, Shijie Li. B→Co electron donation programs Lewis-basic sites in cobalt boride for selective inner-sphere peroxymonosulfate activation[J]. Chinese Journal of Catalysis, 2027, 92: 428-441.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65238-2

https://www.cjcatal.com/EN/Y2027/V92/I1/428

Figures/Tables 7

Scheme 1. Hypothesis for selective non-radical PMS activation on programmed CoxB.

Fig. 1. (a) Degradation performance (pseudo-first-order rate constant, k1) for OTC removal using PMS activated by CoxB, Co3O4, and Co2O3. Cycling stability under identical conditions for CoxB (15 cycles) (b), Co3O4 (4 cycles) (c), and Co2O3 (4 cycles) (d). (e) Activity decline percent comparison after repeated use. (f) Benchmarking of CoxB against representative cobalt-based PMS activators (details and references in Table S1). (g) Catalytic degradation of MB, MO and OTC with fitted pseudo-first-order rate constants (k1). (h) Catalytic degradation of AF, CTC, LOF, RhB, TC, DOX and OTC with corresponding pseudo-second-order rate constants (k2). Reaction conditions: OTC 40 mg·L-1; catalyst 15 mg; deionized water 20 mL; PMS 0.7 g·L-1; 20 °C; pH = 6.4; MB, MO, AF, CTC, LOF, RhB, TC, and DOX 40 mg·L-1.

Fig. 2. (a) OTC degradation by CoxB/PMS in different water matrices (rainwater, river water, tap water). (b) Effect of initial pH. (c) Effect of humic acid (HA). (d) Influence of coexisting anions (NO3-, CO32-, HPO42-, Cl-, HCO3-). (e) Continuous-flow OTC degradation and photo of the apparatus (catalyst 30 mg; OTC 10 mg·L-1; PMS 0.7 g·L-1; flow 1 mL·min-1; Room temperature).

Fig. 3. HR-XPS spectra of Co 2p3/2 and the corresponding average Co valence state during successive catalytic cycles. (a-c) CoxB samples (fresh, after 1 cycle [CoxB-1], and after 15 cycles [CoxB-15]). (d-f) Co3O4 samples (fresh, after 1 cycle [Co3O4-1], and after 4 cycles [Co3O4-4]). Evolution of the average Co valence state for CoxB (g) and Co3O4 (h).

Fig. 4. (a) Optimized adsorption configurations and adsorption energies (Eads) of PMS on CoxB and Co3O4 surfaces through S-O and O-H binding modes. (b) Differential charge density maps comparing electron transfer in PMS activation: significant electron accumulation (yellow)/depletion (cyan) on CoxB versus minimal redistribution on Co3O4. Calculated Gibbs free energy diagrams for PMS activation on CoxB (c) and Co3O4 (d). Proposed PMS activation pathways favoring singlet-oxygen-associated non-radical oxidation on CoxB (e) and radical oxidation on Co3O4 (f).

Fig. 5. (a) Apparent relative importance of ROS-related pathways estimated from concentration-dependent inhibition experiments. (b) Quenching efficiencies of specific scavengers in the CoxB/PMS system for OTC degradation: L-histidine (1O2), TEMPO (•O2), ethanol (•OH and •SO4-), and tert-butanol (•OH). (c) Dissolved oxygen experiment evaluating its role in degradation. (d) TEMP-trapped EPR spectra for singlet oxygen (1O2). (e) Methanol-based DMPO EPR spectra for superoxide radicals (•O2-). (f) Aqueous DMPO EPR spectra for hydroxyl radicals (•OH). (g) Schematic illustration of reactive species generation pathways over CoxB vs. Co3O4.

Fig. 6. (a) Proposed PMS-mediated degradation pathways of OTC. (b) Predicted toxicity profiles of the resulting transformation products.

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