Degradation of rhodamine B by peroxymonosulfate activated by Prussian blue analogue derivatives

doi:10.11949/0438-1157.20240371

Abstract

Abstract:

Permonosulfate (PMS) was activated by copper-iron Prussian blue derivatives (Cu _n Fe₁-PBAs) to degrade rhodamine B (RhB). The effects of the molar ratio of iron to copper, the amount of catalyst, the molar ratio of PMS to RhB, initial pH and common ions in water on RhB degradation were investigated. The results showed that Cu₂Fe₁-PBAs could effectively activate PMS to degrade RhB. RhB degradation was most favorable under alkaline conditions when RhB concentration was 20 mg/L, Cu₂Fe₁-PBAs dosage was 0.6 g/L, and PMS concentration was 0.513 g/L. $N O_{3}^{-}$ , $H C O_{3}^{-}$ and Cl^- promoted the degradation of RhB, while $S O_{4}^{2 -}$ inhibited the degradation of RhB. Sulfate radical ( $S O_{4}^{-}$ ·), hydroxyl radical (·OH), singlet oxygen (¹O₂) and superoxide radical (· $O_{2}^{-}$ ) all participated in the RhB degradation of Cu₂Fe₁-PBAs activated PMS.

Key words: Cu _n Fe₁-PBAs, peroxymonosulfate, rhodamine B, singlet oxygen, superoxide radical

摘要：

采用铜铁类普鲁士蓝衍生物（Cu _n Fe₁-PBAs）活化过一硫酸盐（PMS）降解罗丹明B（RhB），考察铁铜摩尔比、催化剂投加量、PMS与RhB的摩尔比、起始pH和水中常见离子对RhB降解的影响。结果表明：Cu₂Fe₁-PBAs可以有效活化PMS降解RhB。在RhB浓度为20 mg/L，Cu₂Fe₁-PBAs用量为0.6 g/L，PMS浓度为0.513 g/L，碱性条件时最有利于RhB降解。 $N O_{3}^{-}$ 、 $H C O_{3}^{-}$ 、Cl^-促进RhB的降解， $S O_{4}^{2 -}$ 抑制RhB的降解。硫酸根自由基（ $S O_{4}^{-}$ ·）、羟基自由基（·OH）、单线态氧（¹O₂）和超氧自由基（· $O_{2}^{-}$ ）均参与Cu₂Fe₁-PBAs活化PMS降解RhB反应过程。

关键词: 类普鲁士蓝衍生物, 过一硫酸盐, 罗丹明B, 单线态氧, 超氧自由基

CLC Number:

TQ 028.8

Guimei CHEN, Yuyun XIE, Youwei YANG, Yan GAO, Chunying WANG. Degradation of rhodamine B by peroxymonosulfate activated by Prussian blue analogue derivatives[J]. CIESC Journal, 2024, 75(10): 3804-3814.

陈贵梅, 谢雨芸, 杨有威, 高艳, 王春英. 类普鲁士蓝衍生物活化过一硫酸盐降解罗丹明B[J]. 化工学报, 2024, 75(10): 3804-3814.

Figures/Tables 15

Fig.1 Effect of molar ratio of iron to copper on degradation of RhB(reaction conditions: [Cu2Fe1-PBAs]0=400 mg/L; [PMS]0=500 mg/L; pH0=5.16; [RhB]0=20 mg/L; temperature 25℃±2℃)

Table 1 Experiment comparison for the degradation of RhB by activated peroxymonosulfate

催化剂	催化剂浓度/(mg/L)	初始浓度/(mg/L)	PMS/(mg/L)	pH	反应时间/min	去除率/%	文献
Cu₂Fe₁-PBAs	600	20.0	513	5.16	30	92.72	本文
磁性茶渣炭	213	40.0	302	5	80	98	[16]
紫外线下施氏矿物	500	4.79	307	—	45	93.7	[17]
黄铁矿	1000	20	307	5	180	99	[18]
铁酸铜	100	2.39	61	—	30	88.87	[19]
氧化铜纳米颗粒	500	50	614	7.5	60	93.38	[20]
兔粪生物炭	600	25	400	—	40	98	[21]

Fig.2 Effect of Cu2Fe1-PBAs dosage on RhB degradation (a) and the corresponding curves of pseudo-first order reaction kinetics (b) (reaction conditions: [PMS]0=513 mg/L; pH0=5.16; [RhB]0=20 mg/L; temperature 25℃±2℃)

Fig.3 Effect of PMS Dosage on RhB degradation (a) and the corresponding curves of pseudo-first order reaction kinetics (b)(reaction conditions: [Cu2Fe1-PBAs]0=600 mg/L; pH0=5.16; [RhB]0=20 mg/L; temperature 25℃±2℃)

Fig.4 Residual degradation of PMS (reaction conditions: [Cu2Fe1-PBAs]0=600 mg/L; pH0=5.16; [RhB]0=20 mg/L; temperature 25℃±2℃)

Fig.5 Catalytic effect of four cycles of catalyst (reaction conditions: [Cu2Fe1-PBAs]0=600 mg/L; [PMS]0=513 mg/L; pH0= 5.16; [RhB]0=20 mg/L; temperature 25℃±2℃)

Fig.6 Effect of initial pH on RhB degradation (reaction conditions: [Cu2Fe1-PBAs]0=600 mg/L; [PMS]0=513 mg/L; [RhB]0=20 mg/L; temperature 25℃±2℃)

Fig.7 Ultraviolet-visible spectrum of catalytic degradation of RhB system (reaction conditions: [Cu2Fe1-PBAs]0=600 mg/L; [PMS]0=513 mg/L; [RhB]0=20 mg/L; temperature 25℃±2℃)

Fig.8 Effect of co-existing anions on RhB degradation (reaction conditions: coexisting anion 5 mmol/L; [Cu2Fe1-PBAs]0=600 mg/L; [PMS]0=513 mg/L; pH0= 5.16; [RhB]0=20 mg/L; temperature 25℃±2℃)

Fig.9 Effects of different radical scavengers on RhB degradation (a); EPR spectra of TEMP (b) and DMPO [(c),(d)] (reaction conditions: [Cu2Fe1-PBAs]0=600 mg/L; [PMS]0=513 mg/L; pH0=5.16; [RhB]0=20 mg/L; temperature 25℃±2℃)

Fig.10 XRD patterns

Fig.11 SEM images

Fig.12 FTIR spectra

Fig.13 XPS spectra of Cu2Fe1-PBAs

Fig.14 Free radical production mechanism

References 40

1	秦彬, 谷晋川, 殷萍, 等. 染料废水处理技术研究进展[J]. 化工环保, 2021, 41(1): 9-18.
	Qin B, Gu J C, Yin P, et al. Research progresses on dye wastewater treatment technology[J]. Environmental Protection of Chemical Industry, 2021, 41(1): 9-18.
2	任冬梅, 于清小, 赵阳, 等. 物理法去除废水中罗丹明B研究进展[J]. 渤海大学学报(自然科学版), 2020, 41(2): 97-104.
	Ren D M, Yu Q X, Zhao Y, et al. Research progress of physical method for removing rhodamine B from wastewater[J]. Journal of Bohai University (Natural Science Edition), 2020, 41(2): 97-104.
3	王春英, 朱清江, 谷传涛, 等. 稀土Ce³⁺掺杂Bi₂WO₆光催化降解罗丹明B的研究[J]. 中国环境科学, 2015, 35(9): 2682-2689.
	Wang C Y, Zhu Q J, Gu C T, et al. Investigation of rhodamine B photocatalytic degradation by Ce³⁺ doped Bi₂WO₆ [J]. China Environmental Science, 2015, 35(9): 2682-2689.
4	赵朦, 李梅, 白毛毛, 等. 高级氧化技术在印染废水处理中的研究进展[J]. 应用化工, 2023, 52(6): 1884-1890.
	Zhao M, Li M, Bai M M, et al. Research progress of advanced oxidation technology in dyeing wastewater treatment[J]. Applied Chemical Industry, 2023, 52(6): 1884-1890.
5	谷得明, 郭昌胜, 冯启言, 等. 基于硫酸根自由基的高级氧化技术及其在环境治理中的应用[J]. 环境化学, 2018, 37(11): 2489-2508.
	Gu D M, Guo C S, Feng Q Y, et al. Sulfate radical-based advanced oxidation processes and its application in environmental remediation[J]. Environmental Chemistry, 2018, 37(11): 2489-2508.
6	李尚真, 张治宏, 易晓辉, 等. 改性猪粪制生物炭活化过硫酸盐(PS)去除罗丹明B[J]. 环境化学, 2022, 41(3): 929-939.
	Li S Z, Zhang Z H, Yi X H, et al. Removal of rhodamine B by modified pig manure made biochar-activated persulfate(PS)[J]. Environmental Chemistry, 2022, 41(3): 929-939.
7	傅晓艳, 鲍建国, 杜江坤, 等. 淀粉稳定化纳米零价铁活化过硫酸盐降解罗丹明B试验研究[J]. 安全与环境工程, 2015, 22(6): 51-56.
	Fu X Y, Bao J G, Du J K, et al. Degradation of rhodamine B by persulfate activated with starch-stabilized nZVI[J]. Safety and Environmental Engineering, 2015, 22(6): 51-56.
8	龚程. 铁钴水滑石活化过一硫酸盐降解罗丹明B的研究[D]. 长沙: 湖南大学, 2017.
	Gong C. Study on degradation of rhodamine B by iron-cobalt hydrotalcite activated persulfate[D]. Changsha: Hunan University, 2017.
9	黄艳, 邢波, 晏伟, 等. 钢渣/氮掺杂改性活性炭复合材料催化过硫酸盐降解罗丹明B[J].工业水处理, 2024(2): 147-156.
	Huang Y, Xing B, Yan W, et al. Catalytic degradation of rhodamine B by steel slag/nitrogen-doped modified activated carbon composite[J]. Industrial Water Treatment, 2024(2): 147-156.
10	张磊, 林子雨, 张文静. 紫外强化CuO活化过硫酸盐降解罗丹明B染料废水[J]. 环境科学与技术, 2020, 43(11): 82-89.
	Zhang L, Lin Z Y, Zhang W J, et al. Degradation of dyeing wastewater containing rhodamine B by CuO-activated persulfate with UV strengthening[J]. Environmental Science & Technology, 2020, 43(11): 82-89.
11	相里鹏, 崔佳丽, 张峰, 等. 磁性生物炭活化过硫酸盐去除水中罗丹明B [J]. 中国环境科学, 2023, 43(4): 1672-1687.
	Xiangli P, Cui J L, Zhang F, et al. Removal of rhodamine B from aqueous solutions by magnetic biochar activated persulfate[J]. China Environmental Science, 2023, 43(4): 1672-1687.
12	陈于梁, 成先雄, 连军峰, 等. 非均相膨润土@Fe₃O₄活化PMS降解RhB[J]. 环境科学与技术, 2021, 44(8): 75-81.
	Chen Y L, Cheng X X, Lian J F, et al. Heterogeneous bentonite@Fe₃O₄ activated persulfate to degrade rhodamine B[J]. Environmental Science & Technology, 2021, 44(8): 75-81.
13	Hou M J, Gong S Q, Ji L L, et al. Three-dimensional porous ultrathin carbon networks reinforced PBAs-derived electrocatalysts for efficient oxygen evolution[J]. Chemical Engineering Journal, 2021, 419: 129575.
14	Zhao C X, Liu B, Li X N, et al. A Co-Fe Prussian blue analogue for efficient Fenton-like catalysis: the effect of high-spin cobalt[J]. Chemical Communications, 2019, 55(50): 7151-7154.
15	Liu J Y, Li X N, Liu B, et al. Shape-controlled synthesis of metal-organic frameworks with adjustable Fenton-like catalytic activity[J]. ACS Applied Materials & Interfaces, 2018, 10(44): 38051-38056.
16	吴永娟, 马青春, 刘博. 磁性茶渣炭的简易制备及其活化过硫酸盐降解罗丹明B的性能[J]. 安徽农业大学学报, 2022, 49(6): 955-960.
	Wu Y J, Ma Q C, Liu B. Facile synthesis of magnetic biochar derived from tea residue and its activation of potassium persulfate for degradation of rhodanine B[J]. Journal of Anhui Agricultural University, 2022, 49(6): 955-960.
17	刘慧, 周佳兴, 任鹏飞, 等. 紫外光下施氏矿物活化过硫酸盐降解罗丹明B[J]. 工业水处理, 2022, 42(5): 110-116.
	Liu H, Zhou J X, Ren P F, et al. Degradation of rhodamine B by schwertmannite activated persulfate under UV light[J]. Industrial Water Treatment, 2022, 42(5): 110-116.
18	熊玲, 国晓波, 程聪, 等. 黄铁矿活化过硫酸盐降解罗丹明B[J]. 中南民族大学学报(自然科学版), 2021, 40(3): 226-230.
	Xiong L, Guo X B, Cheng C, et al. Degradation of rhodamine B by pyrite-activated persulfate[J]. Journal of South-Central University for Nationalities (Natural Science Edition), 2021, 40(3): 226-230.
19	杨珂, 唐琪, 杨晓丹, 等. 铁酸铜非均相活化过硫酸盐降解罗丹明B[J]. 中国环境科学, 2019, 39(9): 3761-3769.
	Yang K, Tang Q, Yang X D, et al. Degradation of rhodamine B by heterogeneous activation of persulfate with copper ferrate[J]. China Environmental Science, 2019, 39(9): 3761-3769.
20	Ouyang F, Liu Y J, Chen J, et al. Study on preparation of rabbit manure biochar and activation of peroxymonosulfate for rhodamine B degradation[J]. Water, 2023, 15(11): 2015.
21	Channab B E, El Ouardi M, Marrane S E, et al. Alginate@ZnCO₂O₄ for efficient peroxymonosulfate activation towards effective rhodamine B degradation: optimization using response surface methodology[J]. RSC Advances, 2023, 13(29): 20150-20163.
22	Guo Y X, Yan L G, Li X G, et al. Goethite/biochar-activated peroxymonosulfate enhances tetracycline degradation: inherent roles of radical and non-radical processes[J]. Science of the Total Environment, 2021, 783: 147102.
23	王雅洁, 龚先河. PMS/Cl^-体系中橙黄Ⅱ脱色的影响因素和机理[J]. 安全与环境工程, 2021, 28(1): 219-225, 238.
	Wang Y J, Gong X H. Effects and mechanism of decolorization of orange Ⅱ in PMS/Cl^- system[J]. Safety and Environmental Engineering, 2021, 28(1): 219-225, 238.
24	吴瑶. 水稻秸秆生物炭协同过硫酸钠降解水中苯胺和罗丹明B的效果与机制研究[D].南京: 南京农业大学, 2018.
	Wu Y. Study on the effect and mechanism of rice straw biochar combined with sodium persulfate to degrade aniline and rhodamine B in water[D]. Nangjing: Nanjing Agricultural University, 2018.
25	Chen L Q, Zhang Z H, Wang Y J, et al. Photocatalytic properties and electrochemical characteristic of a novel biomimetic oxygenase enzyme photocatalyst iron(Ⅱ) tetrahydroxymethyl tetra(1,4-dithiin) porphyrazine for the degradation of organic pollutants[J]. Journal of Molecular Catalysis A: Chemical, 2013, 372: 114-120.
26	Jiang M D, Lu J H, Ji Y F, et al. Bicarbonate-activated persulfate oxidation of acetaminophen[J]. Water Research, 2017, 116: 324-331.
27	Cao J Y, Lai L D, Lai B, et al. Degradation of tetracycline by peroxymonosulfate activated with zero-valent iron: performance, intermediates, toxicity and mechanism[J]. Chemical Engineering Journal, 2019, 364: 45-56.
28	Zhang G C, Yang X Y, Wu Z X, et al. Fe-Mn bimetallic oxide-enabled facile cleaning of microfiltration ceramic membranes for effluent organic matter fouling mitigation via activation of oxone[J]. ACS ES&T Water, 2022, 2(7): 1234-1246.
29	Santamarina J C, Klein K A, Wang Y H, et al. Specific surface: determination and relevance[J]. Canadian Geotechnical Journal, 2002, 39(1): 233-241.
30	Zhang S Q, Yang X, Liu L, et al. Adsorption behavior of selective recognition functionalized biochar to Cd(Ⅱ) in wastewater[J]. Materials, 2018, 11(2): 299.
31	任洁青, 王朝旭, 张峰, 等. 改性稻壳生物炭对水中Cd²⁺的吸附性能研究[J]. 生态与农村环境学报, 2021, 37(1): 73-79.
	Ren J Q, Wang C X, Zhang F, et al. Adsorption of Cd²⁺ from aqueous solution by modified rice husk-derived biochars[J]. Journal of Ecology and Rural Environment, 2021, 37(1): 73-79.
32	Habibi M H, Parhizkar H J. FTIR and UV-vis diffuse reflectance spectroscopy studies of the wet chemical (WC) route synthesized nano-structure CoFe₂O₄ from CoCl₂ and FeCl₃ [J]. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2014, 127: 102-106.
33	Wu Z D, Wang X M, Yao J, et al. Synthesis of polyethyleneimine modified CoFe₂O₄-loaded porous biochar for selective adsorption properties towards dyes and exploration of interaction mechanisms[J]. Separation and Purification Technology, 2021, 277: 119474.
34	Liu F, Zhou H Y, Pan Z C, et al. Degradation of sulfamethoxazole by cobalt-nickel powder composite catalyst coupled with peroxymonosulfate: performance, degradation pathways and mechanistic consideration[J]. Journal of Hazardous Materials, 2020, 400: 123322.
35	Cagnetta G, Huang J, Lu M N, et al. Defect engineered oxides for enhanced mechanochemical destruction of halogenated organic pollutants[J]. Chemosphere, 2017, 184: 879-883.
36	Yang Y W, Guo C S, Zeng Y T, et al. Peroxymonosulfate activation by CuFe-Prussian blue analogues for the degradation of bisphenol S: effect, mechanism, and pathway[J]. Chemosphere, 2023, 311: 138748.
37	Yamashita T, Hayes P. Analysis of XPS spectra of Fe²⁺ and Fe³⁺ ions in oxide materials[J]. Applied Surface Science, 2008, 254(8): 2441-2449.
38	Wang S X, Tian J Y, Wang Q, et al. Development of CuO coated ceramic hollow fiber membrane for peroxymonosulfate activation: a highly efficient singlet oxygen-dominated oxidation process for bisphenol a degradation[J]. Applied Catalysis B: Environmental, 2019, 256: 117783.
39	Guo R N, Chen Y, Nengzi L C, et al. In situ preparation of carbon-based Cu-Fe oxide nanoparticles from CuFe Prussian blue analogues for the photo-assisted heterogeneous peroxymonosulfate activation process to remove lomefloxacin[J]. Chemical Engineering Journal, 2020, 398: 125556.
40	Niu L J, Zhang G M, Xian G, et al. Tetracycline degradation by persulfate activated with magnetic γ - F e 2 O 3 / C e O 2 catalyst: performance, activation mechanism and degradation pathway[J]. Separation and Purification Technology, 2021, 259: 118156.

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