Architecture and active motif engineering of N-CoS2@C yolk-shell nanoreactor for boosted tetracycline removal via peroxymonosulfate activation: Performance, mechanism and destruction pathways

Abstract

Rational construction of yolk-shell architecture with regulated binding configuration is crucially important but challengeable for antibiotic degradation via peroxymonosulfate (PMS) activation. In this study, we report the utilization of yolk-shell hollow architecture consisted of nitrogen-doped cobalt pyrite integrated carbon spheres (N-CoS₂@C) as PMS activator to boost tetracycline hydrochloride (TCH) degradation. The creation of yolk-shell hollow structure and nitrogen-regulated active site engineering of CoS₂ endow the resulted N-CoS₂@C nanoreactor with high activity for PMS activating toward TCH degradation. Intriguingly, the N-CoS₂@C nanoreactor exhibits an optimal degradation performance with a rate constant of 0.194 min^-1 toward TCH via PMS activation. The ¹O₂ and SO₄^•- species are demonstrated as the dominant active substances for TCH degradation through quenching experiments and electron spin resonance characterization. The possible degradation mechanism, intermediates and degradation pathways for TCH removal over the N-CoS₂@C/PMS nanoreactor are unveiled. Graphitic N, sp²-hybrid carbon, oxygenated group (C-OH) and Co species are verified as the possible catalytic sites of N-CoS₂@C for PMS activation toward TCH removal. This study offers a unique strategy to engineer sulfides as highly efficient and promising PMS activators for antibiotic degradation.

Keywords: Cobalt pyrite; Singlet oxygen; Sulfate radical; Tetracycline hydrochloride; Yolk-shell hollow spheres.