MICROSCAFS® for minocycline elimination from water and real wastewater: Porosity and TiO2 nanoparticles effect

• SiO 2 -TiO 2 MICROSCAFS® function both as photocatalysts and supports for TiO 2 nanoparticles (NP). • Immobilization of TiO 2 NP enhances minocyclinés photocatalytic degradation, also in real wastewater. • Minocycline sensitization boosts superoxide radicals’ formation and sunlight-driven photocatalysis. • Fewer and less toxic transformation products, corroborated by DFT and in-silico studies. • MICROSCAFS® ensure easy recoverability and applicability in continuous flow set-up. We developed and characterized a photocatalytic system utilizing sol–gel synthesized silica-titania microspheres (MICROSCAFS®) with varying interconnected porosities, functioning as a photocatalyst by itself, but also as a support for TiO 2 nanoparticles. This system was employed to remove the antibiotic minocycline from water, including real wastewater from a minocycline production plant, either in batch or flow photoreactor setups. We evaluated the pore size of MICROSCAFS® and found that the combination of medium-sized macropores together with the largest specific surface area (P0/HT) provided the highest adsorption capacity, achieving 13 % in the dark, attributed to the interaction between the positively charged antibiotic and the negatively charged MICROSCAFS®. Photocatalytic activity varied among samples, with P0/HT achieving the highest photodegradation of 73 % after 300 min of solar irradiation in a flow reactor. The immobilization of P25 TiO 2 nanoparticles (P0/HT+P25) optimized the removal, achieving 100 % degradation within 270 min. LC-HRMS/MS analysis identified specific by-products, which were fewer and less toxic than minocycline, and DFT and in-silico toxicity studies corroborate these findings. Scavenger tests highlighted the role of • OH, h + , and • O 2 – , with • O 2 – being the primary contributor. This photocatalyst, tested with real wastewater from a pharmaceutical industry, demonstrated effective environmental remediation without the need for expensive separation steps. Flow reactor experiments and a modeling study underscored its potential for continuous pollutant degradation in practical applications.

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Publication Details

Journal
Chemical Engineering Journal
Published
2024-12-25
DOI
https://doi.org/10.1016/j.cej.2024.158771
Citations
2
Primary Topic
Nanomaterials for catalytic reactions
Type
article
Field-Weighted Citation Impact
0.50

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article

MICROSCAFS® for minocycline elimination from water and real wastewater: Porosity and TiO2 nanoparticles effect

B. Barrocas, Sofia Moreira Fernandes, Mário Vale, M. Conceição Oliveira et al.
2 citations
Chemical Engineering Journal
Nanomaterials for catalytic reactions
0.50
article

MICROSCAFS® for minocycline elimination from water and real wastewater: Porosity and TiO2 nanoparticles effect

B. Barrocas, Sofia Moreira Fernandes, Mário Vale, M. Conceição Oliveira, Abeer Al Mohtar, Ana Clara Azola Marques
article en
2 citations

Abstract

• SiO 2 -TiO 2 MICROSCAFS® function both as photocatalysts and supports for TiO 2 nanoparticles (NP). • Immobilization of TiO 2 NP enhances minocyclinés photocatalytic degradation, also in real wastewater. • Minocycline sensitization boosts superoxide radicals’ formation and sunlight-driven photocatalysis. • Fewer and less toxic transformation products, corroborated by DFT and in-silico studies. • MICROSCAFS® ensure easy recoverability and applicability in continuous flow set-up. We developed and characterized a photocatalytic system utilizing sol–gel synthesized silica-titania microspheres (MICROSCAFS®) with varying interconnected porosities, functioning as a photocatalyst by itself, but also as a support for TiO 2 nanoparticles. This system was employed to remove the antibiotic minocycline from water, including real wastewater from a minocycline production plant, either in batch or flow photoreactor setups. We evaluated the pore size of MICROSCAFS® and found that the combination of medium-sized macropores together with the largest specific surface area (P0/HT) provided the highest adsorption capacity, achieving 13 % in the dark, attributed to the interaction between the positively charged antibiotic and the negatively charged MICROSCAFS®. Photocatalytic activity varied among samples, with P0/HT achieving the highest photodegradation of 73 % after 300 min of solar irradiation in a flow reactor. The immobilization of P25 TiO 2 nanoparticles (P0/HT+P25) optimized the removal, achieving 100 % degradation within 270 min. LC-HRMS/MS analysis identified specific by-products, which were fewer and less toxic than minocycline, and DFT and in-silico toxicity studies corroborate these findings. Scavenger tests highlighted the role of • OH, h + , and • O 2 – , with • O 2 – being the primary contributor. This photocatalyst, tested with real wastewater from a pharmaceutical industry, demonstrated effective environmental remediation without the need for expensive separation steps. Flow reactor experiments and a modeling study underscored its potential for continuous pollutant degradation in practical applications.

Chemical Engineering JournalVol. 504
University of Lisbon (PT), Research Center for Natural Resources, Environment and Society (PT), Instituto de Biologia Experimental e Tecnológica (PT)
Fundação para a Ciência e a Tecnologia
Clean water and sanitation
Openalex Percentile: Top 37%
Nanomaterials for catalytic reactions
0.50
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