Efficient decolorization of azo organics by singlet oxygen from activating PMS with octahedral structured FMN-700
ZHONG Qing1, YE Xiao-zhen2, ZENG Jing2, CAI Lan-yan2, WANG Yong-quan2, HONG Jun-ming1
1. College of Chemical Engineering, Huaqiao University, Fujian Province Engineering Research Center of Industrial Wastewater Biochemical Treatment, Xiamen 361021, China; 2. Xiamen Tobacco Industrial Company Limited, Xiamen 361021, China
Abstract：A catalytic material containing iron and manganese nitride (FMN-700) was prepared by high-temperature calcination using nitrogen-doped Prussian blue analogue (PBA) as a precursor for the rapid degradation of azo organic compounds by activated peroxymonosulfate (PMS). The catalysts were characterized by scanning electron microscopy (SEM), X-ray powder diffractometer (XRD) and Fourier transform infrared spectroscopy (FTIR), which demonstrated that FMN-700 has a layered stacked ortho-octahedral structure and contains Fe-Mn-nitride. The effects of catalyst dosage, PMS concentration and initial pH on the catalytic degradation of azo organics were investigated. The results showed that 99.5% decolorization of RBK5 at 10mg/L could be achieved within 60min at an initial pH of 7, a catalyst dosing of 0.2g/L and a PMS concentration of 2mmol/L. The quenching experiments and Electron Paramagnetic Resonance (EPR) indicated that 1O2 was the main active substance in the degradation system. X-ray photoelectron spectroscopy (XPS) showed that the Fe(III)/Fe(II) and Mn(III)/Mn(II) ratios increased and the pyridine N content decreased before and after the reaction. This process can induce the production of 1O2. The significant increase of fluorescence intensity of 3D-EEM spectrum showed that the azo bond with fluorescence quenching effect was broken during the degradation process and azo organic compounds were successfully decolorized and degraded.
钟晴, 叶校圳, 曾静, 蔡蓝燕, 王永全, 洪俊明. 八面体FMN-700活化过硫酸盐产生1O2降解偶氮有机物[J]. 中国环境科学, 2023, 43(12): 6374-6385.
ZHONG Qing, YE Xiao-zhen, ZENG Jing, CAI Lan-yan, WANG Yong-quan, HONG Jun-ming. Efficient decolorization of azo organics by singlet oxygen from activating PMS with octahedral structured FMN-700. CHINA ENVIRONMENTAL SCIENCECE, 2023, 43(12): 6374-6385.
[1] Zhang H C, Zhang K Q, Gao M, et al. Degradation efficiency of the azo dye acid orange 2 and microbial community characteristics in a rotating algal biofilm reactor[J]. Journal of Water Process Engineering, 2022,50(12):103233. [2] Chung K T. Azo dyes and human health: A review[J]. Journal of Environmental Science and Health Part C Environmental Carcinogenesis & Ecotoxicology Reviews, 2016,34(1-4):233-261. [3] Mansour H B, Ayed-Ajmi Y, Mosrati R, et al. Acid violet 7and its biodegradation products induce chromosome aberrations, lipid peroxidation, and cholinesterase inhibition in mouse bone marrow[J]. Environmental Science and Pollution Research, 2010,45(9):1670-1677. [4] Qiu Z M, He Y B, Liu X C, et al. Catalytic oxidation of the dye wastewater with hydrogen peroxide[J]. Chemical Engineering and Processing: Process Intensification, 2005,44(9):1013-17. [5] Zümriye Aksua, B S E, Gnül Dnmezb. Methylene Blue biosorption by Rhizopus arrhizus: Effect of SDS (sodium dodecylsulfate) surfactant on biosorption properties[J]. Chemical Engineering Journal, 2010, 158(3):474-481. [6] Ruiz-Fernández M, Alexandre-Franco M, Fernández-González C, et al. Development of activated carbon from vine shoots by physical and chemical activation methods. Some insight into activation mechanisms[J]. Adsorption, 2011,17(3):621-629. [7] Ali H. Biodegradation of Synthetic Dyes-A Review[J]. Water, Air, & Soil Pollution, 2010,213(1/4):251-273. [8] Xue Y, Zhuang M, Xu J, et al. Modulating surface properties of Mn-Fe nanocube-like catalyst to activate peroxymonosulfate for effective benzalkonium chloride degradation[J]. Chemical Engineering Journal, 2023,462(4):142077. [9] Zhu Z, Zhang Q, Xu M, et al. Highly active heterogeneous FeCo metallic oxides for peroxymonosulfate activation: The mechanism of oxygen vacancy enhancement[J]. Journal of Environmental Chemical Engineering, 2023,11(1):109071. [10] Rastogi A, Al-Abed S R, Dionysiou D D. Sulfate radical-based ferrous-peroxymonosulfate oxidative system for PCBs degradation in aqueous and sediment systems[J]. Applied Catalysis B Environmental, 2009,85(3/4):171-179. [11] Ty A, Sf B, Yang L C, et al. Fe-N/C single-atom catalysts with high density of Fe-Nx sites toward peroxymonosulfate activation for high-efficient oxidation of bisphenol A: Electron-transfer mechanism[J]. Chemical Engineering Journal, 2021,419(9):129590. [12] Wang Z, Qiu W, Pang S Y. Aqueous Iron (IV)-Oxo Complex: An emerging powerful reactive oxidant formed by Iron (II)-based advanced oxidation processes for oxidative water treatment[J]. Environmental Science & Technology, 2022,56(3):1492-1509. [13] Zong Y, Shao Y, Zeng Y, et al. Enhanced oxidation of organic contaminants by Iron(II)-Activated Periodate: The significance of high-valent Iron-Oxo species[J]. Environmental Science & Technology, 2021,55(11):7634-7642. [14] Tong X, Ma S, Qi Y, et al. Synthesis of FeCo alloy encapsulated nitrogen-doped graphitized carbon: High catalytic activation and low metal ion leaching in microwave assisted Fenton reaction[J]. Journal of the Taiwan Institute of Chemical Engineers, 2020,108:64-70. [15] Ma C Y, Guo Y J, Zhang D F, et al. Metal-nitrogen-carbon catalysts for peroxymonosulfate activation to degrade aquatic organic contaminants: Rational design, size-effect description, applications and mechanisms[J]. Chemical Engineering Journal, 2023,454(2): 140216. [16] Li J, Zhao S, Zhang L, et al. Cobalt single atoms embedded in nitrogen-doped graphene for selective oxidation of benzyl alcohol by activated peroxymonosulfate[J]. Small, 2021,17(1):2004579. [17] Liu X Y, Wang L J, Qian F, et al. Ferric nitrate/dopamine/melamine- derived nitrogen doped carbon material as the activator of peroxymonosulfate to degrade sulfamethoxazole[J]. Separation and Purification Technology, 2022,281:119844. [18] Ye J, Wang Y, Li Z, et al. 2D confinement freestanding graphene oxide composite membranes with enriched oxygen vacancies for enhanced organic contaminants removal via peroxymonosulfate activation[J]. Journal of Hazardous Materials, 2021,417:126028. [19] Nguyen H T, Lee J, Kwon E, et al. Bamboo-like N-doped carbon nanotube-confined cobalt as an efficient and robust catalyst for activating monopersulfate to degrade bisphenol A[J]. Chemosphere, 2021,279:130569. [20] Gao Y, Wu T, Yang C, et al. Activity trends and mechanisms in peroxymonosulfate assisted catalytic production of singlet oxygen over atomic metal-N-C catalysts[J]. Angewandte Chemie International Edition, 2021,60(1):22513-22521. [21] Luo R, Li M, Wang C, et al. Singlet oxygen-dominated non-radical oxidation process for efficient degradation of bisphenol A under high salinity condition[J]. Water Research, 2019,148(1):416-424. [22] Zhang L S, Jiang X H, Zhong Z A, et al. Carbon nitride supported high-loading Fe single-atom catalyst for activation of peroxymonosulfate to generate 1O2with 100% selectivity[J]. Angewandte Chemie International Edition, 2021,60(8):21751-21755. [23] Yue W, Lin Y, Yang C, et al. Calcination temperature regulates non- radical pathways of peroxymonosulfate activation via carbon catalysts doped by iron and nitrogen[J]. Chemical Engineering Journal, 2023,451(1):138468. [24] Pang H, Zhang Y, Cheng T, et al. Uniform manganese hexacyanoferrate hydrate nanocubes featuring superior performance for low-cost supercapacitors and nonenzymatic electrochemical sensors[J]. Nanoscale, 2015,7(38):16012-16019. [25] Ellis D, Eckhoff M, Neff V D. Electrochromism in the mixed-Valence hexacyanides.1Voltammetric and spectral studies of the oxidation and reduction of thin films of Prussian blue[J]. Journal of Physical Chemistry, 1981,85(9):1225-1231. [26] Tang W S, Su Y, Li Q, et al. Superparamagnetic magnesium ferrite nanoadsorbent for effective arsenic (III, V) removal and easy magnetic separation[J]. Water Research, 2013,47(7):3624-3634. [27] Paul D R. Graphitic carbon nitride: a sustainable photocatalyst for organic pollutant degradation and antibacterial applications[J]. Environmental Science and Pollution Research, 2021,28(4):3888-3896. [28] Zhu J N, Zhu X Q, Cheng F F, et al. Preparing copper doped carbon nitride from melamine templated crystalline copper chloride for Fenton-like catalysis[J]. Applied Catalysis B: Environmental, 2019, 256(5):117830. [29] Xiao T D, Zhang Y D, Strutt P R, et al. Synthesis of FexN/BN magnetic nanocomposite via chemical processing[J]. Nanostructured Materials, 1993,2(3):285-294. [30] Li J H, He L Z, Jiang J B, et al. Facile syntheses of bimetallic Prussian blue analogues (KxM[Fe(CN)6]·nH2O, M=Ni, Co, and Mn) for electrochemical determination of toxic 2-nitrophenol[J]. Electrochimica Acta, 2020,353(9):136579. [31] 佘月城,董正玉,吴丽颖,等.MnFe2O4活化过一硫酸盐降解废水中LAS[J]. 中国环境科学, 2019,39(8):3323-3331. She Y C, Dong Z Y, Wu L Y, et al. Degradation of LAS in wastewater by peroxymonosulfate activated by MnFe2O4[J]. China Environmental Science, 2019,39(8):3323-3331. [32] 董正玉,吴丽颖,王霁,等.新型Fe3O4@α-MnO2活化过一硫酸盐降解水中偶氮染料[J]. 中国环境科学, 2018,38(8):3003-3010. Dong Z Y, Wu L Y, Wang J, et al. Novel Fe2O4@α-MnO2 activated peroxymonosulfate degradation of azo dyes in aqueous solution[J]. China Environment Science, 2018,38(8):3003-3010. [33] 徐铭骏,郭兆春,李立,等.纳米片状Mn2O3@α-Fe3O4活化过碳酸盐降解偶氮染料[J]. 化工进展, 2022,41(2):1043-1053. Xu M J, Guo Z C, Li L, et al. Degradation of azo dyes by sodium percarbonate activated with nanosheet Mn2O3@α-Fe3O4[J]. Chemical Industry and Engineering Progress, 2022,41(2):1043-1053. [34] 王磊,成先雄,连军锋,等.尖晶石型c-CuFe2O4催化过硫酸盐降解偶氮染料[J]. 精细化工, 2021,38(10):2117-2124. Wang L, Cheng X X, Lian J F, et al. Degradation of azo dye by catalyzed persulfate with spinel c-CuFe2O4[J]. Fine Chemicals, 2021,38(10):2117-2124. [35] Xqc A, Fei X A, Zwl A, et al. CuFe2O4 supported on montmorillonite to activate peroxymonosulfate for efficient ofloxacin degradation[J]. Journal of Water Process Engineering, 2021,44:102359. [36] Zhang Y, Yang T, Li R, et al. Efficient degradation of ibuprofen by Co/Fe@CNFs catalyst in the presence of peroxymonosulfate and persulfate: Characterization, performance, and mechanism comparison[J]. Journal of the Taiwan Institute of Chemical Engineers, 2022, 131(2):104161. [37] He Y Z, Wang Z W, Wang H, et al. Confinement of ZIF-derived copper-cobalt-zinc oxides in carbon framework for degradation of organic pollutants[J]. Journal of Hazardous Materials, 2022,440(10): 129811. [38] Wang Y Q, Li K, Shang M Y, et al. A novel partially carbonized Fe3O4@PANI-p catalyst for tetracycline degradation via peroxymonosulfate activation[J]. Chemical Engineering Journal, 2023, 451(1):138655. [39] Xq A, Sy A, MD A, et al. Attenuation of BPA degradation by SO4in a system of peroxymonosulfate coupled with Mn/Fe MOF-templated catalysts and its synergism with Cl- and bicarbonate[J]. Chemical Engineering Journal, 2019,372:605-615. [40] Shang Y, Chen C, Zhang P, et al. Removal of sulfamethoxazole from water via activation of persulfate by Fe3C@NCNTs including mechanism of radical and nonradical process[J]. Chemical Engineering Journal, 2019,375(11):122004. [41] Sun Y N, Sui Z Y, Li X, et al. Nitrogen-doped porous carbons derived from polypyrrole-based aerogels for gas uptake and supercapacitors[J]. ACS Applied Nano Materials, 2018,1(2):609-16. [42] Rastogi A, Al-Abed S R, Dionysiou D D. Sulfate radical-based ferrous-peroxymonosulfate oxidative system for PCBs degradation in aqueous and sediment systems[J]. Applied Catalysis B Environmental, 2009,85(3/4):171-179. [43] Liu S, Zhang Z, Huang F, et al. Carbonized polyaniline activated peroxymonosulfate (PMS) for phenol degradation: Role of PMS adsorption and singlet oxygen generation[J]. Applied Catalysis B Environmental, 2021,286(6):119921. [44] Luo R, Li M, Wang C, et al. Singlet oxygen-dominated non-radical oxidation process for efficient degradation of bisphenol A under high salinity condition[J]. Water Research, 2019,148(1):416-424. [45] 赖波,廉雨,庞翠翠,等.典型的偶氮与非偶氮染料的荧光特征[J]. 光学学报, 2011,31(5):257-261. Lai B, Lian Y, Pang C C, et al. Fluorescence characteristics of typic azo and non-azo dyes[J]. Acta Optica Sinica, 2011,31(5):257-261.
