In situ photochemical formation of defect-related fluorescent ZrO<sub>2</sub> nanoparticles in solution and within UV-cured EA/TPGDA coatings


Akman O., ÖZÇELİK KAZANCIOĞLU E., ARSU N.

JOURNAL OF MACROMOLECULAR SCIENCE PART A-PURE AND APPLIED CHEMISTRY, cilt.62, sa.12, ss.1348-1358, 2025 (SCI-Expanded, Scopus) identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 62 Sayı: 12
  • Basım Tarihi: 2025
  • Doi Numarası: 10.1080/10601325.2025.2589362
  • Dergi Adı: JOURNAL OF MACROMOLECULAR SCIENCE PART A-PURE AND APPLIED CHEMISTRY
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Chemical Abstracts Core, Chimica, Compendex
  • Sayfa Sayıları: ss.1348-1358
  • Anahtar Kelimeler: epoxy acrylate/TPGDA, fluorescence emission, fluorescent t-ZrO2 nanoparticles, In situ photochemical synthesis
  • Yıldız Teknik Üniversitesi Adresli: Evet

Özet

In this study, in situ photochemical synthesis of tetragonal-ZrO2 nanoparticles (t-ZrO2 NPs) was performed both in N,N-dimethyl formamide/water solution and within an epoxy diacrylate/tripropylene glycol diacrylate polymer matrix. The photoreduction of ZrCl4 to t-ZrO2 NPs was conducted, and upon UV irradiation, ZrCl4 undergoes photochemical decomposition facilitated by radicals generated from Irgacure 2959. These radicals promote Zr-Cl bond cleavage followed by hydrolysis and oxidation, leading to the formation of Zr-O-Zr linkages and, ultimately, ZrO2 NPs. The formation of ZrO2 NPs was confirmed by the appearance of a defect-related absorption band in the UV-Vis spectrum, accompanied by enhanced fluorescence emission arising from oxygen vacancies and Zr-3+ centers. Thermogravimetric analysis was used to determine the thermal properties, and photopolymerization kinetics were studied using photo-differential scanning calorimetry, and the rate of polymerization and double bond conversions (DBC%) were calculated. Among all samples, the formulation containing 4 wt% ZrCl4 (A4) showed the highest polymerization efficiency, with a DBC of 81%. Crystallographic properties and surface morphology were evaluated by X-ray diffraction and FE-SEM analysis, respectively. Formulation A2 resulted in the most hydrophilic surface. Efficient photocatalytic degradation of methylene blue dye was achieved with 98% degradation in a solution containing t-ZrO2 NPs.