Tandem cooperative catalysis over a Zr-MOF for the synthesis of hydroxyurethanes under solvent-free conditions

Ghosh A., Bhattacharjee S., Chongdar S., Sen T., Banerjee S., Das A. K., ...Daha Fazla

Applied Catalysis A: General, cilt.704, 2025 (SCI-Expanded, Scopus)

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 704
  • Basım Tarihi: 2025
  • Doi Numarası: 10.1016/j.apcata.2025.120397
  • Dergi Adı: Applied Catalysis A: General
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Chemical Abstracts Core, Chimica, Compendex
  • Anahtar Kelimeler: Metal-organic framework, Hydroxyurethanes, Tandem aminolysis, Solvent-free catalysis, CO2 fixation
  • Atatürk Üniversitesi Adresli: Hayır

Özet

Carbon sequestration via CO2 fixation into value added chemicals is of great importance for the sustainable future of the world. Hydroxyurethane derivatives are very demanding chemical intermediate for the polymer and adhesive industries, which can be synthesized by a tandem sustainable route involving the fixing CO2 on epoxides to cyclic carbonates followed by ring opening through aminolysis. In this work, we have synthesized a crystalline tritopic Zr-based metal-organic framework (MOF) having secondary building unit (SBU) as [Zr6(µ3-O)4(µ3-OH)4(OH)6(TPA-COOH)2] (TPA = triphenylamine), which we coined as Zr-TPA-MOF. This MOF was prepared through a sustainable microwave assisted synthesis route within 45 min. at 120 °C. Zr-TPA-MOF exhibited plate like morphology and possesses a good specific surface area of 312 m2g−1. Zr-TPA-MOF material displayed good reversible CO2 uptakes at different temperatures (1.4 mmol at 273 K and 1.0 mmol at 298 K). We have also analyzed the thermodynamics of CO2 affinity on Zr-TPA-MOF thoroughly. So, this property has been explored further, where Zr-TPA-MOF is used as a heterogeneous catalyst for the CO2 fixation reaction to form hydroxyurethanes over different epoxides via tandem aminolysis. Here, we have enlightened a broader context of CO2 fixation using nontoxic, cost effective Zr-MOF as a promising catalyst in isocyanate-free synthesis of hydroxyurethane derivatives.