Glucose-mediated independent pyrolysis strategy optimises the pore structure of MOF-derived carbon catalysts to promote the conversion of HMF to FDCA

Abstract

2,5-Furanedicarboxylic acid (FDCA) is a key platform chemical that can be sustainably produced via the catalytic selective oxidation of biomass-derived 5-hydroxymethylfurfural (HMF). Utilizing metal-organic framework (MOF)-derived carbon-based catalysts has proven to be an effective strategy for this production. In this study, we incorporated glucose-modified catalytic pore structures into copper-based MOFs to modulate the pore architecture of MOF-derived carbon catalysts. This approach operates independently of MOF synthesis, simultaneously supplementing the pore structure during pyrolysis of the MOF skeleton. Glucose acts as a sacrificial structural component during pyrolysis, synergistically regulating carbonization behaviour and pore structure evolution, thereby markedly enhancing mass transport properties and improving the accessibility of active sites. Glucose-induced co-construction of specific pore structures in the Cu-based MOF framework was critical for tuning catalyst activity. Under optimized conditions, the optimal catalyst achieved 100% HMF conversion and 94.7% FDCA selectivity. Notably, this catalyst exhibited a six-fold enhancement in FDCA selectivity at ambient air compared to catalysts without glucose modification, while maintaining a stable FDCA yield of 50% over 11 cycles without significant deterioration. This work underscores the importance of mesoporous structures and chemical properties in catalyst design, thereby advancing the fundamental understanding of organic transformation reactions.