Controllable synthesis of copper-organic frameworks via ligand adjustment for enhanced photo-Fenton-like catalysis

The efficient heterogeneous photo-Fenton-like catalysts based on two secondary ligand-induced Cu(II) metal–organic frameworks (Cu-MOF-1 and Cu-MOF-2) were constructed for the first time and investigated for the degradation of multiple antibiotics. Herein, two novel Cu-MOFs were prepared using mixed ligands by a facile hydrothermal method. The one-dimensional (1D) nanotube-like structure could be obtained by using V-shaped, long and rigid 4,4′-bis(3-pyridylformamide)diphenylether (3-padpe) ligand in Cu-MOF-1, while polynuclear Cu cluster could be prepared more easily by using short and small isonicotinic acid (HIA) ligand in Cu-MOF-2. Their photocatalytic performances were measured by degradation of multiple antibiotics in Fenton-like system. Comparatively, Cu-MOF-2 exhibited superior photo-Fenton-like performance under visible light irradiation. The outstanding catalytic performance of Cu-MOF-2 was ascribed to the tetranuclear Cu cluster configuration and excellent ability of photoinduced charge transfer and hole separation thus improved the photo-Fenton activity. In addition, Cu-MOF-2 showed high photo-Fenton activity in wide pH working range 3–10 and maintained wonderful stability after five cyclic experiments. The degradation intermediates and pathways were deeply studied. The main active species h+, O2− and OH worked together in photo-Fenton-like system and possible degradation mechanism was proposed. This study provided a new approach to design the Cu-based MOFs Fenton-like catalysts.