Switching of selectivity from benzaldehyde to benzoic acid using MIL-100(V) as a heterogeneous catalyst in aerobic oxidation of benzyl alcohol
CATALYSIS SCIENCE & TECHNOLOGY, cilt.14, ss.6524-6536, 2024 (SCI-Expanded, Scopus)
- Yayın Türü: Makale / Tam Makale
- Cilt numarası: 14
- Basım Tarihi: 2024
- Doi Numarası: 10.1039/d4cy00832d
- Dergi Adı: CATALYSIS SCIENCE & TECHNOLOGY
- Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Chemical Abstracts Core, Compendex, INSPEC, Metadex
- Sayfa Sayıları: ss.6524-6536
- Hacettepe Üniversitesi Adresli: Evet
Özet
A vanadium-centered metal organic framework [MIL-100(V)] was synthesized as a heterogeneous catalyst allowing the selectivity to be switched from almost quantitative formation of benzaldehyde (Bz-CHO) to quantitative formation of benzoic acid (Bz-COOH) by changing only the temperature in the aerobic oxidation of benzyl alcohol (Bz-OH). The aerobic oxidation of Bz-OH was performed using molecular oxygen or air in the temperature range of 60-120 degrees C. A Bz-CHO formation yield of 98.1% was obtained with quantitative Bz-OH conversion at 80 degrees C. When the oxidation temperature was set to 100 degrees C, a Bz-COOH formation yield of 100% was achieved with quantitative Bz-OH conversion. The suitability of a serial reaction mechanism including Bz-CHO formation from Bz-OH and Bz-COOH formation from Bz-CHO as the first and second stage reactions, respectively was investigated for the aerobic oxidation process. The apparent first-order rate constants determined for first and second stage reactions demonstrated that the first-stage reaction was faster with respect to the second one. The proposed kinetic model allowed the calculation of apparent activation energies for Bz-CHO formation from Bz-OH and Bz-COOH formation from Bz-CHO as 77.3 and 149.2 kJ mol-1, respectively. The presence of hydroxyl (