Aerobic Oxidation of 5-Hydroxymethylfurfural (HMF) in Aqueous Medium over Fe-Doped-Poly(heptazine imide) Photocatalysts: Unveiling the Bad Role of Hydroxyl Radical Generation on the Catalytic Performance

5-hydroxymethylfurfural (HMF) oxidation in aqueous media using visible photocatalysis is a green and sustainable route for the valorization of lignocellulosic biomass derivatives. Several semiconductors have already been applied for this purpose; however, the use of Poly(heptazine imides), which has high crystallinity and a special cation exchange property that allows the replacement of the cation held between the layers of C 3 N 4 structure by transition metal ions (TM), remains scarce. In this study, PHI(Na) was synthesized using a melamine/NaCl method and used as precursor to prepare metal (Fe, Co, Ni, or Cu)-doped PHI catalysts. The catalysts were tested for selective oxidation of HMF to 2,5-diformylfuran (DFF) in water and O 2 atmosphere under blue LED radiation. The catalytic results revealed that the 0.1 wt% PHI(Fe) catalyst is the most efficient photocatalyst while higher Fe loading (1 and 2 wt%) favors the formation of Fe 3+ clusters, which are responsible for the drop in HMF oxidation. Moreover, the 0.1 wt% PHI(Fe) photocatalyst has strong oxidative power due to its efficiency in H 2 O 2 production, thus boosting the generation of nonselective hydroxyl radicals ( ● OH) via different pathways that can destroy HMF. We found that using 50 mM, the highest DFF production rate (393 μmol·h −1 ·g −1 ) was obtained in an aqueous medium under visible light radiation.