Application of CoMn/CoFe layered double hydroxide based on metal–organic frameworks template to activate peroxymonosulfate for 2,4-dichlorophenol degradation

Abstract

Metal-organic frameworks (MOFs) have unique properties and stable structures, which have been widely used as templates/precursors to prepare well developed pore structure and high specific surface area materials. In this article, an innovative and facile method of crystal reorganization was designed by using MOFs as sacrificial templates to prepare a layered double hydroxide (LDH) nano-layer sheet structure through a pseudomorphic conversion process under alkaline conditions. The obtained CoMn-LDH and CoFe-LDH catalysts broke the ligand of MOFs and reorganized the structure on the basis of retaining a high specific surface area and a large number of pores, which had higher specific surface area and well developed pore structure compared with LDH catalysts prepared by traditional methods, and thus provide more active sites to activate peroxymonosulfate (PMS). Due to the unique framework structure of MOFs, the MOF-derived CoMn-LDH and CoFe-LDH catalysts could provide more active sites to activate PMS, and achieve a 2,4-dichlorophenol degradation of 99.3% and 99.2% within 20 minutes, respectively. In addition the two LDH catalysts displayed excellent degradation performance for bisphenol A, ciprofloxacin and 2,4-dichlorophenoxyacetic acid (2,4-D). X-ray photoelectron spectroscopy indicated that the valence state transformation of metal elements participated in PMS activation. Electron paramagnetic resonance manifested that sulfate radical () and singlet oxygen (1O2) were the main species for degrading pollutants. In addition, after the three-cycle experiment, the CoMn-LDH and CoFe-LDH catalysts also showed long-term stability with a slight activity decrease in the third cycle. The phytotoxicity assessment determined by the germination of mung beans proved that PMS activation by MOF-derived LDH catalysts can basically eliminate the phytotoxicity of a 2,4-D solution. This research not only developed high-activity LDH catalysts for PMS activation, but also expanded the environmental applications of MOF derivants.

Electronic structure modification of ultrathin MnFeOOH and integration with Ni3S2 as bifunctional electrocatalysts for improved alkaline water splitting

“…S4a †), the deconvoluted peaks at 641.0, 642.3 and 652.7, and 645.4 and 654.0 eV can be assigned to the Mn 2+ , Mn 3+ and Mn 4+ species, respectively. 38 The existence of tetravalent manganese is due to the fact that a hydroxide anion is a weak field ligand and Mn 3+ ions with a d 4 electronic configuration exist in the high spin state, which are prone to Jahn-Teller distortions and can be oxidized into tetravalent manganese. Additionally, it can be inferred that the manganese ions are mainly in the trivalent form, which should be in the form of MnOOH.…”