Novel Fenton-like Catalyst HKUST-1(Cu)/MoS2-3-C with Non-Equilibrium-State Surface for Selective Degradation of Phenolic Contaminants: Synergistic Effects of σ-Cu-Ligand and ≡Mo–OOSO3− Complex

Abstract

Novel Fenton-like catalyst HKUST-1(Cu)/MoS2-3-C with a non-equilibrium-state surface was constructed for selective degradation of phenolic contaminants. Electron-polarized distribution facilitated the formation of σ-Cu-ligand between electron-poor Cu centre and phenolic compounds, which not only enhanced radicals generation but also accelerated the Cu(I)/Cu(II) redox. Meanwhile, ≡Mo–OOSO3− complexes formed by the electron-rich Mo centre and peroxymonosulfate (PMS), could directly oxidize phenolic contaminants with the generation of SO4•−. The radical quenching experiments and EPR tests indicated that both SO4•− and •OH played a dominant role in the reaction. Additionally, O2 could be reduced to O2•− by OVs and subsequently converted into 1O2 over the Mo centre. DFT calculation, FT-IR, and in situ Raman spectra analysis results demonstrated that phenolic compounds and PMS were respectively adsorbed by electron-poor Cu centre and electron-rich Mo centre, favouring the electrons transfer from phenolic contaminants to Mo centre for PMS activation. With synergistic effects of σ-Cu-ligand and ≡Mo–OOSO3− complexes, HKUST-1(Cu)/MoS2-3-C achieved a high degradation rate of phenolic contaminants and utilization efficiency of PMS.