Selectivity Control in the Oxidative Ring-Opening of Dimethylfuran Mediated by Zeolitic-Imidazolate Framework‑8 Nanoparticles

• Published in: ACS sustainable chemistry & engineering Vol. 9; no. 24; pp. 8090 - 8096
• Main Authors: Franco, Ana, Negi, Arvind, Luque, Rafael, Carrillo-Carrión, Carolina
• Format: Journal Article
• Language: English
• Published: American Chemical Society 21.06.2021
• Subjects: selectivity; nanoscale MOF; ring-opening; zeolitic-imidazolate framework-8 (ZIF-8); metal−organic framework (MOF); furans
• ISSN: 2168-0485; 2168-0485
• DOI: 10.1021/acssuschemeng.1c00708

The conversion of biomass-derived furans to synthetically valuable chemicals is highly desirable but it remains a formidable challenge with regard to product selectivity, particularly in oxidative reactions. For example, the oxidative ring-opening of 2,5-dimethylfuran (DMF) using hydrogen peroxide as the oxidant proceeds in a nonselective manner, resulting in a multicomponent mixture along with the target compound (3-hexene-2,5-dione). In this work, we address the selectivity issue with a simple and efficient approach using zeolitic-imidazolate framework-8 nanoparticles (ZIF-8 NPs) as selectivity mediators on the base of their unique ordered structure. A quantitative conversion of DMF with 85% of selectivity to the target 3-hexene-2,5-dione (in comparison to 27% selectivity in the blank reaction) was achieved in the presence of ZIF-8 NPs, and importantly, under mild conditions (60 °C, and methanol as solvent). Furthermore, computational studies based on the chemisorption models of ZIF-8 demonstrated a plausible explanation of the observed selectivity. This work may pave the way toward the development of alternative and cost-effective strategies to improve product selectivity in biomass conversion with a view of green and sustainable developments in the chemical industry.