Atomically dispersed Cu-N3 on hollow spherical carbon nitride for acetaminophen degradation: Generation of 1O2 from H2O2

Abstract

Discharge of recalcitrant pharmaceuticals into aquatic systems has caused severe impacts on public health and ecosystem. Advanced oxidation processes (AOPs) are effective for eliminating these refractory pollutants, for which single-atom catalysts (SACs) become the state-of-the-art materials owing to the maximized exposure of active metal sites. In this work, hollow spherical graphitic carbon nitride (hsCN) was fabricated to incorporate copper species to develop Fenton-like catalysts for acetaminophen (ACT) removal. Through pyrolysis of supramolecular assemblies derived from melamine-Cu complex and cyanuric acid, single atom Cu-N3 sites were anchored on hsCN by N-coordination to obtain SACu-hsCN. In virtue of the atomically dispersed Cu-N3 sites as well as the hollow structure of hsCN providing smooth channels for the interactions between single Cu atoms and reactants, the optimal 5.5SACu-hsCN removed 94.8% of ACT after 180 min of Fenton-like reactions, which was superior to that of 5.5AGCu-hsCN with aggregated Cu particles on hsCN (56.7% in 180 min). Moreover, 5.5SACu-hsCN was still active after four cycles of regeneration. The mechanism investigation demonstrated that both hydroxyl radicals (OH) and singlet oxygen (1O2) contributed to ACT degradation in 5.5SACu-hsCN/H2O2 system, in which non-radical 1O2 played the dominant role.