Isolated iridium oxide sites on modified carbon nitride for photoreforming of plastic derivatives

Abstract

The rising concentration of plastics due to extensive disposal and inefficient recycling of plastic waste poses an imminent and critical threat to the environment and ecological systems. Photocatalytic reforming of plastic derivatives to value-added chemicals under ambient conditions proceeds at lower oxidation potential which galvanizes the hydrogen evolution. We report the synthesis of a narrow band gap NCN-functionalized O-bridged carbon nitride (MC) through condensation polymerization of hydrogen-bonded melem (M)-cyameluric acid (C) macromolecular aggregate. The MC scaffold hosts well-dispersed Ir single atom (MCIrSA) sites which catalyze oxidative photoreforming of alkali-treated polylactic acid (PLA) and polyethylene terephthalate (PET) derivatives to produce H₂ at a rate of 147.5 and 29.58 μmol g⁻¹_cat h⁻¹ under AM1.5G irradiation. Solid-state electron paramagnetic resonance (EPR) and time-resolved photoluminescence (TRPL) reveals efficient charge carrier generation and separation in MCIrSA. X-ray absorption spectroscopy (XAS) and Bader charge analysis reveal undercoordinated IrN₂O₂ SA sites pinned in C₆N₇ moieties leading to efficient hole quenching. The liquid phase EPR, in situ FTIR and density functional theory (DFT) studies validate the facile generation of •OH radicals due to the evolution of O-Ir-OH transient species with weak Ir--OH desorption energy barrier.