水热法合成二氧化锰及其对染料的脱色性能研究

doi:10.19964/j.issn.1006-4990.2021-0019

摘要/Abstract

摘要：

采用水热法以十二烷基苯磺酸钠为模板合成二氧化锰,并研究水热温度对二氧化锰的结构和染料脱色性能的影响,以及样品投加量和染料溶液的pH对二氧化锰染料脱色性能的影响。结果表明:当水热温度为110 ℃时,得到2~8 μm球状γ-二氧化锰,对亚甲基蓝（MB）和罗丹明B（RhB）的脱色效果最好。当其投加量为6 g/L时,分别对50 mg/L的MB和RhB脱色率达到86.95%和76.07%。强酸和强碱条件下其对MB的脱色率有明显的提升,二氧化锰对MB的吸附过程符合Langmuir和Freundlich等温模型;强酸条件下其对RhB的脱色率有明显的提升,对RhB的吸附过程符合Freundlich等温模型。二氧化锰样品可循环使用,循环吸附3次后对MB和RhB的吸附量分别减少1.08 mg/g和2.66 mg/g。

关键词: 水热法, 二氧化锰, 脱色, 亚甲基蓝, 罗丹明B

Abstract:

MnO₂ was synthesized by hydrothermal method using sodium dodecyl benzene sulfonate as templates.The effect of hydrothermal temperature on the structure of MnO₂ and decolorization properties of dyes and the effect of product dosage and pH of dye solution on decolorization performance of dyes by MnO₂ were studied.The results showed that when the hydro-thermal temperature was 110 ℃,2~8 μm spherical γ-MnO₂ were obtained,which had the best decolorization rate on methylene blue（MB） and Rhodamine B（RhB）.When the adding amount of MnO₂ was 6 g/L,the decolorization rates of 50 mg/L MB and RhB reached 86.95% and 76.07%,respectively.The addition of strong acid and strong alkali had a significant increase in the decolorization rate of MB.The adsorption process of MnO₂ on MB was conformed to the Langmuir and Freundlich isothermal model.The addition of strong acid had a significant increase in the decolorization rate of RhB.The adsorption pro-cess of MnO₂ on RhB conformed to the Freundlich isothermal model.The product was recyclable,and the adsorption amount of MB and RhB only decreased with 1.08 mg/g and 2.66 mg/g after three cyclic adsorption,respectively.

Key words: hydrothermal method, manganese dioxide, decolorization, methylene blue, rhodamine B

中图分类号:

TQ137.12

朱丹琛,李名洁,陈彰旭,林倩. 水热法合成二氧化锰及其对染料的脱色性能研究[J]. 无机盐工业, 2021, 53(11): 60-65.

ZHU Danchen,LI Mingjie,CHEN Zhangxu,LIN Qian. Study on hydrothermal synthesis of MnO₂ and its decolorization performance on dyes[J]. Inorganic Chemicals Industry, 2021, 53(11): 60-65.

图/表 14

图1

图2

图3

图4

图5

图6

图7

图8

表1

表2

表3

图9

图10

图11

参考文献 29

[1]	HE Y, JIANG D B, CHEN J, et al. Synjournal of MnO₂ nanosheets on montmorillonite for oxidative degradation and adsorption of methy-lene blue[J]. Journal of Colloid and Interface Science, 2018, 510:207-220.
[2]	SHAKOOR S, NASAR A. Removal of methylene blue dye from arti-fıcially contaminated water using citrus limetta peel waste as a very low cost adsorbent[J]. Journal of the Taiwan Institute of Chemical Engineers, 2016, 66:154-163.
[3]	MA J P, CHEN L, WU Z, et al. Pyroelectric Pb(Zr_0.52Ti_0.48)O₃ polariz-ed ceramic with strong pyro-driven catalysis for dye wastewater de-composition[J]. Ceramics International, 2019, 45(9):11934-11938.
[4]	LIU Y N, QU R X, LI X Y, et al. A bifunctional β-MnO₂ mesh for expeditious and ambient degradation of dyes in activation of perox-ymonosulfate(PMS) and simultaneous oil removal from water[J]. Journal of Colloid and Interface Science, 2020, 579:412-424.
[5]	AN Y Y, ZHENG H L, ZHENG X Y, et al. Use of a floating adsor-bent to remove dyes from water:A novel efficient surface separation method[J]. Journal of Hazardous Materials, 2019, 375:138-148.
[6]	王建芳, 王君, 杨和平, 等. Fe₃O₄/δ-MnO₂纳米片的制备及其对亚甲基蓝的吸附研究[J]. 无机盐工业, 2019, 51(10):93-96.
[7]	胡月, 李盼, 吕宏凌, 等. 纳米MnO₂/羧甲基纤维素复合膜制备及光催化降解罗丹明B性能研究[J]. 化工新型材料, 2019, 47(11):167-170,174.
[8]	王春雨, 侯永江, 刘璇, 等. 不同晶型二氧化锰催化臭氧化降解亚甲基蓝废水[J]. 环境工程学报, 2017, 11(2):908-914.
[9]	JIANG S B, YU T F, XIA R, et al. Realization of super high adsorp-tion capability of 2D δ-MnO₂/GO through intra-particle diffusion[J]. Materials Chemistry and Physics, 2019, 232:374-381.
[10]	PARGOLETTI E, PIFFERI V, LUIGI F, et al. A detailed investiga-tion of MnO₂ nanorods to be grown onto activated carbon.High efficiency towards aqueous methyl orange adsorption/degrada-tion[J]. Applied Surface Science, 2019, 472:118-126.
[11]	YANG H, LI C, ZHANG J. Determining roles of in-situ measured surface potentials of phase controlled synthesized MnO₂ nanostruc-tures for superficial adsorption[J]. Applied Surface Science, 2020, 513.Doi. org/10.1016/j.apsusc.2020.145752.
[12]	孙宏, 张泽, 宋坤. 纳米层状二氧化锰去除水中罗丹明B的效能研究[J]. 印染助剂, 2016, 33(3):38-40.
[13]	朱丹琛, 肖伽励, 杨丽丽, 等. 水热合成MnO₂及其染料吸附性能的构效关系研究[J]. 化工进展, 2019, 38(8):3774-3781.
[14]	蔡冬鸣, 李圭白. 天然粉末二氧化锰处理染料废水的试验研究[J]. 中国给水排水, 2007, 23(7):62-65.
[15]	ZHAO B H, RAN R, XU X D, et al. Phase structures,morphologies,and NO catalytic oxidation activities of single-phase MnO₂ catalysts[J]. Applied Catalysis A:General, 2016, 514:24-34.
[16]	ZHAO Z W, GENG C, YANG C, et al. A novel flake-ball-like ma-gnetic Fe₃O₄/γ-MnO₂ meso-porous nano-composite:Adsorption of fluorinion and effect of water chemistry[J]. Chemosphere, 2018, 209:173-181.
[17]	DUAN Y P, PANG H F, ZHANG Y H, et al. Morphology-controlled synjournal and microwave absorption properties of β-MnO₂ micro-ncube with rectangular pyramid[J]. Materials Characterization, 2016, 112:206-212.
[18]	ZHANG Y G, CHEN L Y, ZHENG Z, et al. A redox-hydrothermal route to β-MnO₂ hollow octahedra[J]. Solid State Sciences, 2009, 11(7):1265-1269.
[19]	陈丽雅, 程高, 刘冠良, 等. 三维海胆状二氧化锰微球对电催化氧还原反应的晶型效应[J]. 无机化学学报, 2020, 36(3):458-466.
[20]	靳福娅, 余林, 蓝邦, 等. 水热法制备二氧化锰及在过氧化氢传感器中的应[J]. 化工进展, 2017, 36(9):3380-3387.
[21]	SHARMA G, DIONYSIOU D D, SHARMA S, et al. Highly efficient Sr/Ce/activated carbon bimetallic nanocomposite for photoinduced degradation of Rhodamine B[J]. Catalysis Today, 2019, 335:437-451.
[22]	WANG Y R, ZHANG X F, HE X, et al. In situ synjournal of MnO₂ coated cellulose nanofibers hybrid for effective removal of methy-lene blue[J]. Carbohydrate Polymers, 2014, 110:302-308.
[23]	SHAYESTEH H, ASHRAFI A, RAHBAR-KELISHAMI A. Evalua-tion of Fe₃O₄@MnO₂ core-shell magnetic nanoparticles as an adsor-bent for decolorization of methylene blue dye in contaminated wa-ter:Synjournal and characterization,kinetic,equilibrium,and ther-modynamic studies[J]. Journal of Molecular Structure, 2017, 1149:199-205.
[24]	赵颖, 王仁国, 曾武, 等. 纳米二氧化锰的制备及其对亚甲基蓝的吸附研究[J]. 水处理技术, 2012, 38(1):55-58.
[25]	YAMAGUCHI S, MINBUTA S, MATSUI K. Rhodamine B adsorp-tion on anodic porous alumina in sodium dodecyl sulfate solutio-ns[J]. Colloids and Surfaces A, 2018, 555:209-216.
[26]	RACHNAA K, AGRWALB A, SINGH N B. Preparation and charac-terization of zinc ferrite-polyaniline nanocomposite for removal of rhodamine B dye from aqueous solution[J]. Environmental Nano-technology,Monitoring & Management, 2018(9):154-163.
[27]	ZHAO Y J, ZHU L, LI W H, et al. Insights into enhanced adsorptive removal of Rhodamine B by different chemically modifıed garlic peels:Comparison,kinetics,isotherms,thermodynamics and me-chanism[J]. Journal of Molecular Liquids, 2019, 293.Doi: org/10.1016/j.molliq.2019.111516.
[28]	陈丽群, 张红杰, 朱荣耀, 等. 木质素/Fenton污泥基磁性活性炭对亚甲基蓝和苯酚吸附特性的研究[J]. 中国造纸, 2020, 39(5):23-28.
[29]	段贤扬, 何梦奇, 徐继红, 等. CTS-G-PAA/ATP水凝胶制备及对染料的吸附性能[J]. 功能材料, 2020, 51(2):2203-2208.

温度/ ℃	Langmuir等温模型			Freundlich等温模型
温度/ ℃	K_L/ （L·mg^-1）	Q_m/ （mg·g^-1）	R²	K_F	1/n	R²
25	0.039 2	63.572 8	0.998 3	5.004 0	0.454 5	0.908 1
35	0.022 3	79.302 1	0.989 3	4.054 3	0.513 01	0.965 0
45	0.012 3	116.009 3	0.957 9	3.707 7	0.565 51	0.986 8

温度/ ℃	Langmuir等温模型			Freundlich等温模型
温度/ ℃	K_L/ （L·mg^-1）	Q_m/ （mg·g^-1）	R²	K_F	1/n	R²
25	0.050 4	32.894 7	0.822 2	2.500 7	0.605 2	0.943 9
35	0.072 4	24.330 9	0.959 2	2.566 6	0.541 7	0.964 7
45	0.022 5	51.020 4	0.722 5	1.510 9	0.767 8	0.972 3

循环次数	MB吸附量/（mg·g^-1）	RhB吸附量/（mg·g^-1）
0	17.16	15.58
1	16.38	15.13
2	16.31	13.77
3	16.08	12.92

首页

全国无机盐信息中心

中国化工学会

无机酸碱盐专业委员会