Palladium/Alginate/Poly(NIPAM) Beads with Thermally Tunable Hydrophobic–Hydrophilic Domains for Nitroarene Reduction Reactions in Aqueous Media


ÖZTÜRK B. Ö., Yildiz A. M., Sari B. S., Kucuk B. N., Inci F.

Organic Process Research and Development, cilt.30, sa.6, ss.1634-1641, 2026 (SCI-Expanded, Scopus)

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 30 Sayı: 6
  • Basım Tarihi: 2026
  • Doi Numarası: 10.1021/acs.oprd.6c00065
  • Dergi Adı: Organic Process Research and Development
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Chemical Abstracts Core, Compendex
  • Sayfa Sayıları: ss.1634-1641
  • Anahtar Kelimeler: 4-nitrophenol, alginate, hydrogenation, palladium, thermoresponsive polymers
  • Hacettepe Üniversitesi Adresli: Evet

Özet

This study introduces a thermoresponsive hybrid hydrogel catalyst that integrates a poly(N-isopropylacrylamide) (poly(NIPAM)) core, palladium catalytic centers, and a biobased alginate shell to enable efficient aqueous-phase reduction of nitroarene derivatives. Core–shell alginate gel beads were successfully fabricated above the lower critical solution temperature (LCST) of poly(NIPAM), yielding a structurally robust and hierarchically organized catalytic architecture. Upon thermal activation at 50 °C, the poly(NIPAM) core undergoes a reversible phase transition that generates hydrophobic domains in situ, markedly enhancing the partitioning and diffusion of hydrophobic reactants toward the embedded catalytic sites in an otherwise aqueous environment. Catalytic activity was assessed using 4-nitrophenol as a model substrate, achieving a high turnover number of 9100 and a turnover frequency of 27,324 h–1 at 50 °C. Moreover, the catalyst demonstrates broad substrate tolerance across both hydrophilic and hydrophobic nitroarene derivatives, while maintaining excellent physical integrity and reusability for at least five catalytic cycles. Collectively, these results underscore the significance of coupling thermoresponsive polymer physics with renewable biopolymer scaffolds to create adaptive, robust, and eco-friendly catalytic systems, offering a general strategy for sustainable catalysis under green reaction conditions.