Title Modelling of photocatalytic degradation of pharmaceuticals in water by multi-faceted approach Title (croatian) Modeliranje fotokatalitičke razgradnje farmaceutika u vodi višestranim pristupom Author Antonija Tomić Mentor Ana Lončarić Božić (mentor)Committee member Hrvoje Kušić (predsjednik povjerenstva)Committee member Marin Kovačić (član povjerenstva)Committee member Davor Ljubas (član povjerenstva)Granter University of Zagreb Defense date and country 2023-01-10, Croatia Scientific / art field, TECHNICAL SCIENCES Universal decimal classificationUDC ) 66 - Chemical technology. Chemical and related industries 615 - Pharmacology. Therapeutics. Toxicology Abstract Pharmaceuticals, as one of the largest groups of contaminants of emerging concern (CECs), pose a threat to the environment and human health. Advanced Oxidation Processes (AOPs) have proven to be effective in the degradation of persistent, toxic, and non-biodegradable pollutants in water. Heterogeneous photocatalytic processes are multiparameter systems pertaining to AOPs based on in-situ generated radical, with overall effectiveness influenced by the different process parameters. Predicting the behaviour of photocatalytic AOPs by means of mathematical simulations is crucial not only for scale-up and process optimization, but also for controlling undesirable environmental effects such as the formation of by products with a higher toxicity than the parent compound. In this work, a multi-faceted approach was applied to develop a simulation model for the photocatalytic process for the degradation and mineralisation of pharmaceutical ibuprofen by UV-A/TiO2 P25. The mathematical – mechanistic model of heterogeneous photocatalysis includes a set of differential equations and takes into account the configuration of the photocatalytic reactor, the irradiation emission, the scattering of irradiation, the process parameters, the reaction kinetics and the degradation mechanism. The developed model was verified by experimental results obtained at different photocatalyst loadings. Coumarin and 1,4-benzoquinone were used as chemical probes to confirm the generation of hydroxyl and superoxide radicals and to fine-tune the chemical reactions in the model. To increase the robustness of the developed model, a variety of organic compounds whose structural features influence important mechanisms in photocatalytic treatment, such as adsorption on the TiO2 P25 surface and the prevalence of degradation by hydroxyl and superoxide radicals, were investigated using quantitative-structure activity/property relationship (QSA/PR) modelling. Adsorption was first investigated by a combined experimental/statistical approach using response surface method (RSM), which yielded a quadratic polynomial equation (QPE) describing adsorption for each organic compound studied. The coefficients of the QPE were related to structural features employing QSA/PR. The degradation of organic compounds by the UV-A/TiO2 P25 process in the presence of coumarin and 1,4-benzoquinone was studied, common radical scavengers for hydroxyl and superoxide radicals were investigated and coefficients were determined based on the kinetics obtained, that diversified the prevalence of oxidation or reduction mechanisms in the degradation of organic compounds. The determined coefficients were correlated with structural features of the investigated organic compounds by QSA/PR modelling. The simulation model developed by the proposed multi-faceted approach achieved good agreement between the predicted and experimental data. The QSA/PR modelling combined with RSM methodology accurately predicted the adsorption of organic compounds with complex molecular structure. The QSA/PR technique also successfully captured relevant structural features that determine degradation kinetics, so it can be used to increase the robustness of mathematical – mechanistic models which ensures their simulation capability for a wide range of organic structures.
Abstract (croatian) Farmaceutici, kao jedna od najvećih skupina onečišćivala koji izazivaju zabrinutost (eng. contaminants of emerging concern, CECs), predstavljaju prijetnju za okoliš i ljudsko zdravlje. Napredni oksidacijski procesi (eng. advanced oxidation processes, AOPs) su se pokazali učinkovitim u razgradnji postojanih, toksičnih i biološki nerazgradivih onečišćenja u vodi. Heterogeni fotokatalitički procesi kao dio AOP-a su višeparametarski sustavi, koji se temelje na in-situ generiranju radikala, pri čemu na ukupnu učinkovitost utječu različiti parametri procesa. Predviđanje ponašanja fotokatalitičkih AOP-a primjenom matematičkih simulacija važno je ne samo za uvećanje i optimizaciju procesa, nego i za kontrolu nepoželjnih učinaka na okoliš kao što su stvaranje toksičnijih nusprodukata u odnosu na primarni spoj. U ovom radu primijenjen je višestrani pristup za razvoj simulacijskog modela fotokatalitičke razgradnje i mineralizacije farmaceutika ibuprofena UV-A/TiO2 P25 procesom. Razvijeni matematičko – mehanistički model za heterogenu fotokatalizu sastoji se od seta diferencijalnih jednadžbi koje uključuju konfiguraciju fotokatalitičkog reaktora, emisiju zračenja, raspršenje zračenja, parametre procesa, kinetiku reakcije te mehanizam razgradnje. Razvijeni model verificiran je eksperimentalnim rezultatima dobivenih pri različitim koncentracijama fotokatalizatora. Kumarin i 1,4-benzokinon primijenjeni su u svrhu potvrde generiranja hidroksilnih i superoksidnih radikala te za fino podešavanja kemijskih reakcija na koje utječu u razvijenom modelu. Kako bi se povećala robusnost razvijenog modela istraženi su utjecaji strukturnih značajki različitih organskih spojeva na važne mehanizme fotokatalitičkog procesa, ponajprije na adsorpciju onečišćivala na površini TiO2 P25 te relativni doprinos razgradnji hidroksilnim i superoksidnim radikalima, primjenom kvantitativnog odnosa aktivnosti/svojstava strukture (eng. quantitative structure activity/property, QSA/PR) modeliranja. Adsorpcija je ispitana objedinjenim eksperimentalno/statističkim pristupom korištenjem metode odzivnih površina (eng. response surface methodology, RSM), a rezultat su kvadratne polinomne jednadžbe (eng. quadratic polynomial equation, QPE) koje opisuju adsorpciju za svaki pojedini ispitivani organski spoj. Koeficijenti iz QPE jednadžbi korelirani su sa strukturnim značajkama organskih spojeva primjenom QSA/PR modeliranja. Razgradnjom odabranih organskih spojeva UV-A/TiO2 P25 procesom u prisutnosti kumarina i 1,4-benzokinona, hvatača hidroksilnih i superoksidnih radikala, dobiveni su kinetički modeli te su određeni koeficijenti iz kojih je razvidan doprinos oksidacijskih i redukcijskih mehanizama prilikom razgradnje organskih spojeva. Dobiveni koeficijenti su zatim uspješno korelirani sa strukturnim značajkama ispitivanih organskih spojeva primjenom QSA/PR modeliranja. Simulacijski model, razvijen predloženim višestranim pristupom, ukazuje na dobro slaganje predviđenih i eksperimentalnih podataka. QSA/PR modeliranje kombinirano s RSM metodologijom točno predviđa adsorpciju organskih spojeva složenih molekulskih struktura. QSA/PR metodologija je uspješno ukazala na relevantne strukturne značajke koje određuju kinetiku razgradnje te se može primijeniti za uvećanje robusnosti matematičko – mehanističkog modela, što osigurava sposobnost simulacije modela za širok raspon organskih spojeva.
Keywords
adsorption
advanced oxidation processes
heterogenous photocatalysis
mathematical – mechanistic modelling
pharmaceuticals
RSM
TiO2 P25
QSA/PR
Keywords (croatian)
adsorpcija
napredni oksidacijski procesi
heterogena fotokataliza
matematičko – mehanističko modeliranje
farmaceutici
RSM
TiO2 P25
QSA/PR
Language english URN:NBN urn:nbn:hr:149:221286 Promotion 2023 Project Number: IP-2018-01-1982 Project Number: IP-2014-09-7992 Study programme Title: Chemical Engineering and Applied Chemistry - Doctoral course Type of resource Text Extent 155 str. ; 30 cm File origin Born digital Access conditions Open access Terms of use Created on 2023-03-21 12:20:23
