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

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.

A novel copper oxide/titanium membrane integrated with peroxymonosulfate activation for efficient phenolic pollutants degradation.

Herein, a novel CuO catalyst functionalized Ti-based catalytic membrane (FCTM) was prepared via the regulated electro-deposition technique followed with low-temperature calcination. The morphology of CuO catalyst and oxygen vacancy (OV) content can be controlled by adjusting the preparation conditions, under optimal condition (400 °C, electrolyte as sulfuric acid), the fern-shaped CuO catalyst was formed and the OV content was up to its highest level. Under the optimal treatment condition, the 4-chlorophenol (4-CP) removal of the membrane filtration combined with peroxymonosulfate (PMS) activation (MFPA) process was up to 98.2% (TOC removal of 88.2%). Mechanism studying showed that the enhanced performance in this system was mainly due to the increased production of singlet oxygen (1O2) via the co-effect of fern-shaped CuO (increased specific surface area) and its fine-tuned OV (precursor of 1O2), which not only synergistically enhanced adsorption ability but also offered more active sites for PMS activation. Theoretical calculations showed that the OV-rich CuO displayed high adsorption energy for PMS molecule, leading to the change in OO and OH bond (tend to 1O2) of the PMS molecule. Finally, the possible three degradation pathways of 4-CP were formed by the electrophilic attacking of 1O2.

Confining peroxymonosulfate activation in carbon nanotube intercalated nitrogen doped reduced graphene oxide membrane for enhanced water treatment: The role of nanoconfinement effect.

Coupling membrane filtration with peroxymonosulfate (PMS) activation is promising to overcome the selectivity-permeability trade-off in membrane-based water treatment. However, the PMS catalytic efficiency of membrane still needs improvement to offset the insufficient reaction time during filtration process. Herein, an oxidized carbon nanotube intercalated nitrogen doped reduced graphene oxide (NRGO-OCNT) membrane with PMS activation function was firstly designed and prepared, which confined PMS activation in membrane interlayer for enhanced water treatment. The influence of confinement scale on membrane performance was studied through changing the OCNT intercalation ratio. Under the optimal confinement condition, the NRGO-OCNT membrane filtration integrated with PMS activation (MFPA) could realize 100% 4-chlorophenol removal at a high permeate flux of 290.2 L m-2 h-1 bar-1 (retention time of only 0.36 s), whose performance was 2.8, 1.7 and 5.0 times higher than that of filtration alone, NRGO MFPA (excessive confinement) and NRGO-OCNT powder-based batch reaction (no confinement), respectively. Moreover, NRGO-OCNT MFPA preferentially removed smaller-sized organics which easily entered and diffused in confined interlayer. The outstanding performance of NRGO-OCNT MFPA was owing to the nanoconfinement effect in appropriate confined interspacing, where the mass transfer rate of reactants was greatly boosted for enhanced generation of SO4- and OH towards pollutant.

Peroxymonosulfate activation through ferromagnetic bimetallic spinel sulfide composite (Fe3O4/NiCo2S4) for organic pollutant degradation.

Spinel sulfides are a good candidate as heterogeneous catalysts for wastewater treatment through peroxymonosulfate (PMS) activation. In this paper, magnetic Fe3O4/NiCo2S4 composite was successfully synthesized by hydrothermal method. Catalyst screening displayed that the composite catalyst with a Fe3O4:NiCo2S4 molar ratio of 1:3 (i.e.,0.33-Fe3O4/NiCo2S4) is the most optimal. The results showed that 0.33-Fe3O4/NiCo2S4 composite catalyst had superior catalytic activity, achieving 99.8%,65.1% and 40.7% of RhB, COD and TOC removals within 30 min with 180 m g/L PMS and 75 mg/L catalyst. We proposed a potential catalytic mechanism of PMS activation by Fe3O4/NiCo2S4 in two aspects. On the one hand, sulfur species such as S2- and S22- enhance the Co3+/Co2+, Ni3+/Ni2+ and Fe3+/Fe2+ cycles on Fe3O4/NiCo2S4 surface. On the other hand, there is the synergistic effect of Co3+/Co2+, Ni3+/Ni2+ and Fe3+/Fe2+ cycles in activating PMS. Overall, owing to its excellent catalytic activity, reusability, and easy recovery, Fe3O4/NiCo2S4 is a potentially useful catalyst for remediation of contaminated water.

Enhanced peroxymonosulfate activation on dual active sites of N vacancy modified g-C3N4 under visible-light assistance and its selective removal of organic pollutants.

Constructing highly efficient metal-free material towards peroxymonosulfate (PMS) activation under photocatalytic assistance is a promising strategy for water decontamination. Herein, N vacancy modified g-C3N4 nanotube (VCN) was prepared to build a novel photo-assisted PMS activation system (PPAS), in which the unique electronic structure created by N vacancy could favor the PMS activation on VCN under visible-light irradiation. The role of N vacancy in PPAS was firstly studied through tuning its content in VCN. The results showed that the N vacancy greatly improved PMS activation on VCN PPAS towards organic pollutants removal. The VCN PPAS with moderate N vacancy modification performed best, whose kinetic constant for Rhodamine B degradation was 9.6 and 2.6 times higher than that of VCN/PMS system and pristine g-C3N4 PPAS, respectively. Moreover, the VCN PPAS performed well in wide pH range (3-12) and real water background. Selective removal of different organic pollutants was found on VCN PPAS, owing to the different interaction between pollutant and the catalyst surface with surface-bound radicals. The O2- and OH were major oxidants for pollutant removal in VCN PPAS, which were produced on dual active sites of VCN via two pathways: The N vacancy enhanced PMS adsorption and trapped photogenerated electrons for PMS reduction into OH, while the electron-deficient C atoms created by N loss promoted the PMS oxidation into O2-.