Synergistic Alloy and Support Effects in Covalent Organic Framework-Stabilized AuPd Catalysts for Aerobic 5-Hydroxymethylfurfural Oxidation to 2,5-Furandicarboxylic Acid

Catalytically converting 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) underpins renewable, bio -based plastics, yet designing metal-efficient catalysts remains challenging. Here, we combine alloy and support effects by anchoring AuPd alloy nanoparticles on 2D covalent organic frameworks (COFs). Rationalizing alloy composition and COF functionality yielded Au 67 Pd 33 /TTATP, which converted HMF → FDCA in water using atmospheric O 2 mild conditions, delivering >99% FDCA yield, stable reusability, a turnover number (TON) of ∼100 at HMF/metal = 100, increasing to 518 at 600 (86.4% yield). High performance stems from alloy-support synergy that (i) partitions function (Au: HMF dehydrogenation; Pd: O 2 activation) and (ii) matches adsorption-desorption (TTATP enriches HMF yet releases FDCA; alloy surfaces moderate HMF binding and avoid the strong FDCA adsorption of Pd alone), thereby enhancing metal atom efficiency. Graphical AuPd alloy nanoparticles were anchored on 2D covalent organic frameworks (COFs) to integrate alloy-support synergistic effects. The catalyst Au 67 Pd 33 /TTATP achieved >99% FDCA yield with the high metal utilization efficiency under mild conditions, owing to the synergy effect optimized reactant/product adsorption-desorption.