# Oxidative Ring-Opening of Dimethylfuran in Zeolitic Imidazolate Frameworks through Computational Design

## TL;DR

Researchers used computational methods to study how ZIF-8 and modified ZIF materials affect the selective oxidation of DMF into enediones.

## Contribution

A computational protocol combining configurational search and DFT modeling was used to understand and improve the selectivity of ZIF-based catalysts for DMF oxidation.

## Key findings

- ZIF-8 suppresses overoxidation of enedione compared to the blank reaction.
- Vinyl-substituted ZIF shows the highest selectivity for DMF oxidation.
- Pore accessibility and linker geometry in ZIFs influence reaction selectivity.

## Abstract

Furans are versatile
feedstocks for producing valuable
chemicals
and fuels, with 2,5-dimethylfuran (DMF) particularly standing out
for its potential in oxidative ring-opening reactions, yielding enediones.
The zeolitic imidazolate framework ZIF-8 has shown promise as a mediator
to achieve high selectivity, although a precise mechanistic understanding
of how this heterogeneous system works is unclear. Here, we employ
a computational protocol, combining a configurational search with
force fields (GFN-FF) with a refinement at the periodic density functional
theory (DFT) level, to model the oxidation of DMF with H2O2 and explicit MeOH solvent in the absence and presence
of ZIF-8. In line with experimental observations, our results reveal
that ZIF-8 suppresses overoxidation of the enedione cf. to results for the blank reaction. We further substituted the methyl
group of ZIF-8 with other groups and tested the resulting materials
in the above-mentioned reaction. We observe that vinyl-substituted
ZIF emerges as the most selective material, while ZIF-H (SALEM-2)
offers poor selectivity when compared with the blank reaction. A featurization
study, correlating energy barriers and structural features, reveals
how pore accessibility and linker geometry influence the selectivity.
Our findings seek to deepen the understanding of molecular interactions
in ZIFs and guide the rational design of MOFs for biomass conversion.