02063naa a2200241 a 450000100080000000500110000800800410001902200140006002400510007410000250012524501340015026000090028430000090029352013260030265300240162870000210165270000150167370000220168870000190171070000200172970000160174977300560176521785802025-09-05       2025    bl uuuu     u00u1 u    #d  a1385-89477 ahttps://doi.org/10.1016/j.cej.2025.1663062DOI1 aGABRIEL FILHO, J. B.  aVisible light-driven selective C–C cleavage of glycerol into formic acid using Ni-poly(heptazine) imide.h[electronic resource]  c2025  a9 p.  aGlycerol is a biomass platform molecule derived from the biodiesel process that has the potential to be converted into value-added compounds, such as formic acid (FA). This C1 molecule can be produced through oxidative C–C cleavage pathways. However, many systems employed (Fenton and even heterogeneous photocatalysis) lack selectivity and tend to overoxidize glycerol. In this sense, highly crystalline poly(heptazine)imides, PHI, have been synthesized using a NaCl-based precursor (Na-PHI) exchanged with 2 wt% transition metals (Fe, Co, Ni, and Cu). The photocatalytic performance was tuned by cation exchange due to metal nature. The selective conversion of glycerol into formic acid was optimal for Ni-PHI, 50.6 % of conversion and 73.7 % of selectivity, after 20 h of reaction excited by a blue light LED (457 nm) in air. Further photocatalytic investigations showed that molecular oxygen is essential for C–C cleavage and that glycolic acid (GA, byproduct) is also transformed into formic acid over time. Mechanistic studies performed by EPR showed that Ni-PHI activates the C–H bonds of glycerol and glycolic acid by photogenerated holes and hydroxyl radicals. The latter is generated by a mild Fenton-like mechanism that occurs between the in situ generated H₂O₂ and Ni+/Ni2+ species of photocatalyst.  aGlycerol conversion1 aNOLETO, L. F. G.1 aIGA, G. D.1 aGONÇALVES, F. S.1 aCARDOSO, D. R.1 aTEIXEIRA, I. F.1 aRIBEIRO, C.  tChemical Engineering Journalgv. 521, 166306, 2025.