Periodic mesoporous organosilicas containing naphthalenediimides as organic sensitizers for sulfadiazine photodegradation

Abstract

In this work, periodic mesoporous organosilicas (PMO) functionalized with the organic sentisizer naphthalenediimide (NDI) were employed as heterogeneous catalysts for the photodegradation of the antibiotic sulfadiazine (SDZ), taken as a model for contaminants of emerging concern (CECs). The catalysts, designated as PMONDI, were prepared by surfactant-directed co-condensation of the precursor N,N'-bis(3-triethoxysilylpropyl)- 1,4,5,8-naphthalenediimide with tetraethoxysilane. The synthesized PMONDI were characterized using transmission electron microscopy, nitrogen adsorption isotherms and small and large angle x-ray scattering. The performance of PMONDI catalysts in the photodegradation of SDZ was compared to that of TiO₂ nanoparticles impregnated into SBA-15 mesoporous silica (TiO₂/SBA-15), under irradiation with a Hg lamp with a bandpass filter of 320-500 nm. Under optimal conditions, PMONDI degraded 100% of the SDZ in 45 min, while the total degradation of SDZ was achieved only after 150 min with TiO₂/SBA-15. PMONDI also performed better than TiO₂/SBA-15 in reuse tests. The mechanism of photodegradation with PMONDI involves the formation of excited triplet states of NDI (³NDI*) upon irradiation, which can then react with molecular oxygen to form reactive oxygen species, which degrade SDZ. Analysis of the SDZ degradation products indicated two main pathways: (1) hydroxylation of the aniline ring and (2) SO₂ extrusion and rearrangement, followed by oxidation of the aniline ring to nitrobenzene. In conclusion, the great potential of the PMONDI materials as photocatalysts for CECs degradation was demonstrated in this work, encouraging further research on these materials for the degradation of pollutants.

Keywords: Contaminants of Emerging Concern; Heterogeneous Photocatalysis; Naphthalenediimides; Periodic Mesoporous Organosilicas; Sulfadiazine.