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.
Authors
- B. Barrocas (ORCID: https://orcid.org/0000-0002-2720-1908)
- Sofia Moreira Fernandes (ORCID: https://orcid.org/0000-0003-0878-7189)
- Mário Vale (ORCID: https://orcid.org/0000-0002-7986-9651)
- M. Conceição Oliveira (ORCID: https://orcid.org/0000-0002-3068-4920)
- Abeer Al Mohtar (ORCID: https://orcid.org/0000-0002-9212-1269)
- Ana Clara Azola Marques (ORCID: https://orcid.org/0000-0002-2947-1186)
Institutions
- University of Lisbon (PT)
- Research Center for Natural Resources, Environment and Society (PT)
- Instituto de Biologia Experimental e Tecnológica (PT)
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
Funders
- Fundação para a Ciência e a Tecnologia