Activating peroxymonosulfate with MOF-derived NiO-NiCo2O4/titanium membrane for water treatment: A non-radical dominated oxidation mechanism

Abstract

Traditional peroxymonosulfate (PMS) catalytic membranes dominated by radical pathways often face interference from complex components in water bodies. Herein, we employed a controlled electro-deposition technique to coat a Ni-Co metal–organic framework (MOF) precursor onto titanium hollow fiber membrane (THFM), followed by high-temperature calcination to synthesize a MOF-derived NiO-NiCo2O4/THFM (M−NNCO−THFM) PMS catalytic membrane. Then, the M−NNCO−THFM filtration integrated with PMS activation (MFPA process) for water treatment. Experimental results demonstrated that the M−NNCO−THFM MFPA process successfully achieved complete phenol (PE) removal via a non-radical-dominated degradation pathway, involving singlet oxygen (1O2) and electron transfer, while exhibiting wide pH adaptability and exceptional stability in complex water matrices. Mechanism analysis revealed that the electron transfer process was significantly enhanced by the MOF-derived heterojunction structure, which increased the flat-band potential from 0.39 eV to 0.56 eV, thereby facilitating efficient electron transfer for PE removal. The non-radical 1O2 pathway was primarily due to the cycling of metal valence states (Ni2+/Co3+), leading to the reduction of Co2+ and its reaction with PMS, resulting in the generation of reactive species. Furthermore, electrochemical measurements indicated that the M−NNCO−THFM exhibited lower charge transfer resistance and enhanced charge transfer efficiency compared to non-MOF-derived NNCO-THFM, corresponding to the superior catalytic performance and electrochemically active surface area of M−NNCO−THFM.