A new strategy to construct MOF-on-MOF derivatives for the removal of tetracycline hydrochloride from water by activation of peroxymonosulfate.

A MOF-on-MOF composite derivative material named ZIF-67@Ce-MOF-600 was designed and synthesized. The preparation of ZIF-67@Ce-MOF-600 was optimized from the aspects of the ratio of metal and ligand, heat-treatment temperature. It was demonstrated by XRD, FT-IR, SEM-EDS and TEM. The optimum conditions for the activation of PMS by ZIF-67@Ce-MOF-600 for the degradation of tetracycline (TC) were investigated by adjusting the catalyst dosage, TC, pH, peoxymonosulfate (PMS) concentration, and different kinds of water, co-existing anions and pollution. Under optimal conditions (20 mg catalysts and 50 mg PMS added) in 100 mL of tetracyclines (TC) solvent (20 mg TC/L), the removal rate could reach up to 99.2% and after five cycles was 70.5%. The EPR results indicated the presence of free radicals and non-free radical, among which free radicals intended to play a major role in the degradation process. Its possible degradation pathways and attack sites were analyzed by liquid-phase mass spectrometry and DFT analysis.

Preparation of VCo-MOF@MXene composite catalyst and study on its removal of ciprofloxacin by catalytically activating peroxymonosulfate: Construction of ternary system and superoxide radical pathway.

The synergistic effect between transition metal active centers and the generation of multiple removal pathways has a significant impact on the catalytic activation efficiency of peroxymonosulfate. In this work, a kind of composite catalyst was prepared by growing VCo-metal-organic frameworks (VCo-MOF) in-situ on the surface of Ti3C2Tx by a solvothermal method. The morphology and structure are characterized by Transmission Electron Microscope (TEM), Energy Dispersion Spectrum (EDS), Atomic Force Microscope (AFM), etc. Response surface methodology was used to optimize the experimental conditions. Only 5 mg catalyst can be used to effectively activate PMS and remove 96.14 % ciprofloxacin (CIP, 20 mg/L) within 30 min. The removal effect of catalyst on CIP in different actual water environment was explored. In addition, the fluorescence spectrum test also verified the effective removal of ciprofloxacin. V-Co-Ti ternary system provides a wealth of active sites for CIP removal. Cyclic voltammetry (CV) and lear sweep voltammetry (LSV) tests showed the existence of the electron transfer pathway. The results of density functional theory (DFT) calculation show that VCo-MOF@Ti3C2Tx has excellent adsorption and activation ability for PMS. At the same time, the hydrophilicity of the catalyst makes PMS more inclined to react with water molecules, which promotes the formation of a unique superoxide radical path.

Novel NbCo-MOF as an advanced peroxymonosulfate catalyst for organic pollutants removal: Growth, performance and mechanism study.

Multivariate metal-organic frameworks (MTV-MOFs) are expected as catalyst to apply to the advanced oxidation processes (AOPs) based on sulfate radical (SO4·-) to treat wastewater containing organic pollutants. Mixing metals de novo method was combined with stringent solvothermal conditions to synthesize macaroon-like NbCo-MOF catalyst. NbCo-MOF catalyst prepared with different atom ratios and growth time presented various morphology, structure, performance, and distinctive MTV-MOFs growth law which were confirmed by SEM, TEM, EDS, XRD, FTIR, raman spectra and UV-vis spectra. Besides, optimum peroxymonosulfate (PMS) catalytic activation conditions were studied. Furthermore, the effects of anions (Cl-, NO3-, HCO3-, and C2O42-) on NbCo-MOF catalytic activation were explored which were proved very limited. Particularly, the Co2+/Co3+ cycle combining with the Nb4+/Nb5+ cycle for PMS activation were verified by XPS. EPR and quenching experiment results indicated exists non-radical pathway (1O2), but radical pathways are dominant (SO4·- O2·-, and ·OH). Moreover, the TC removal rate exhibited no significant reduce after three times run. Furthermore, NbCo-MOF exhibited excellent decomposing ability towards methylene blue, tylosin tartrate, rhodamine B, and tetracycline with the removal rate reaching to 100%, 98.4%, 99.7%, and 99.7% in 30 min respectively and also maintained good performance in actual water environment.