以过硫酸钾和乙酸锰为原料,采用固相法制备了氧化锰八面体分子筛(OMS-2PS),采用X射线衍射仪(XRD),傅里叶变换红外光谱仪(FT-IR),X射线光电子能谱仪(XPS)等手段对OMS-2PS进行表征,考察了OMS-2PS活化过硫酸盐(PS)降解有机污染物的性能,研究了催化剂投加量,PS浓度和初始pH值等反应条件对目标污染物去除效果的影响,探究了OMS-2PS活化PS的作用机制.结果表明,采用固相法成功制备出OMS-2PS,且呈纳米棒状结构.OMS-2PS可有效活化PS降解水中有机污染物,当酸性橙7(AO7)浓度为50mg/L,催化剂投加量为1.0g/L,PS浓度为2.0mmol/L时,60min内AO7的去除率和矿化率分别为97.4%和50.1%.离子共存实验结果表明,Cl−,NO3−和CO32−对AO7的去除具有显著的抑制作用,而HA对AO7的去除几乎没有影响.自由基淬灭实验和电子顺磁共振(EPR)分析结果表明,OMS-2PS/PS体系中主要活性物种为·OH和SO4•−,且其中·OH对AO7的去除起主导作用.XPS分析结果表明,OMS-2PS表面的Mn (Ⅳ)和晶格氧是活化PS的主要活性位点.结合实验结果,分析OMS-2PS活化PS的机制可能是PS先通过OMS-2PS表面-OH和OMS-2PS结合,进而PS与OMS-2PS表面的活性位点反应产生活性物种.此外,将OMS-2PS/PS体系用于不同水体及其他有机污染物(双酚A,萘,四环素)的降解,也展现出良好的降解效果,表明该体系在环境污染治理领域具有广阔的应用前景.
Abstract
In the present study, Manganese oxide octahedral molecular sieve (OMS-2PS) was synthesized using K2S2O8 and (CH3COO)2Mn·4H2O via a solid-phase method. The physicochemical properties of OMS-2PS were analyzed via X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS). The performance of persulfate activation by OMS-2PS for degrading organic contaminants was examined. This study also investigated the effect of various parameters, including dosage of OMS-2PS, PS concentration, and initial pH, on AO7 removal efficiency. Moreover, the mechanism of PS activation by OMS-2PS was explored. The results showed OMS-2PS was successfully synthesized via a solid-phase method, which exhibits a nanorod structure. OMS-2PS could activate PS to degrade organic contaminants. The use of 50mg/L AO7, 1.0g/L OMS-2PS, and 2.0mmol/L PS led to the AO7 removal and mineralization rates of 97.4% and 50.1%, respectively. Ion coexistence experiments demonstrated that AO7 removal was considerably inhibited by Cl−, NO3−, and CO32−, while HA had almost no effect on it. The free radical quenching experiments and electron paramagnetic resonance (EPR) analysis indicated ·OH and SO4•−were the primary active oxygen species in the OMS-2PS/PS system, and ·OH played the dominant role in the AO7 degradation. XPS analysis revealed Mn(IV) and lattice oxygen on the surface of OMS-2PS were the main active sites for PS activation. Based on experiment results, a potential activation mechanism of PS by OMS-2PS was proposed that PS combined with OMS-2PS through the hydroxyl groups on the surface of OMS-2PS, and then PS reacted with the active sites on the surface of OMS-2PS to produce active oxygen species. In addition, The OMS-2PS/PS system effectively removed AO7 from different water bodies, and also degraded efficiently other pollutants including bisphenol A, naphthalene, and tetracycline, indicating that the OMS-2PS/PS system have a bright application prospect in environmental pollution control.
关键词
OMS-2 /
催化活化 /
过硫酸盐 /
有机污染物
Key words
catalytic activation /
OMS-2 /
organic contaminants /
persulfate
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基金
国家重点研发计划基金资助项目(2023YFC3709700);福建省科技计划引导性项目基金资助项目(2022Y0073)
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