多级结构α-MoO3空心微球的构筑及其对有机染料的吸附性能

doi:10.15541/jim20180132

无机材料学报 ›› 2019, Vol. 34 ›› Issue (2): 193-200.DOI: 10.15541/jim20180132 CSTR: 32189.14.10.15541/jim20180132

多级结构α-MoO₃空心微球的构筑及其对有机染料的吸附性能

隋丽丽¹,王润¹,赵丹²,申书昌¹,孙立¹,徐英明²,程晓丽²,霍丽华²

1. 齐齐哈尔大学化学与化学工程学院, 齐齐哈尔 161006;
2. 黑龙江大学化学化工与材料学院功能无机材料化学教育部重点实验室, 哈尔滨150080

收稿日期:2018-03-30 修回日期:2018-06-05 出版日期:2019-02-20 网络出版日期:2019-01-24
作者简介:隋丽丽(1980-),女,副教授. E-mail: sui_leelee@126.com
基金资助:
国家自然科学基金(21771060, 51802167);黑龙江省青年科学基金(QC2018015);黑龙江省教育厅资助项目(135109206, 135209221);黑龙江省普通本科高等学校青年人才培养计划(UNPYSCT-2016088)

Construction of Hierarchical α-MoO₃ Hollow Microspheres and Its High Adsorption Performance towards Organic Dyes

SUI Li-Li¹, WANG Run¹, ZHAO Dan², SHEN Shu-Chang¹, SUN Li¹, XU Ying-Ming², CHENG Xiao-Li², HUO Li-Hua²

1. School of Chemistry and Chemical Engineering, Qiqihar University, Qiqihar 161006, China;
2. Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education, School of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, China

Received:2018-03-30 Revised:2018-06-05 Published:2019-02-20 Online:2019-01-24
About author:SUI Li-Li. E-mail: sui_leelee@126.com
Supported by:
National Natural Science Foundation of China (21771060, 51802167);Youth Science Foundation of Heilongjiang Province (QC2018015);Heilongjiang Educational Department (135109206, 135209221);University Nursing Program for Young Scholars with Creative Talents in Heilongjiang Province (UNPYSCT-2016088)

摘要/Abstract

摘要：

具有多级结构的半导体金属氧化物, 其特有的立体空间结构使材料具有超高活性, 在吸附领域具有应用潜力。研究采用简单的一步溶剂热法制备了空心球状的MoO₂前驱体, 400 ℃热处理后得到多级结构α-MoO₃空心微球。空心球的直径为600~800 nm, 由宽度约70 nm的纳米棒构筑而成。该球状α-MoO₃纳米材料对亚甲基蓝(MB)染料具有优良的吸附性能。当α-MoO₃吸附剂用量为0.5 g/L、MB染料浓度为20 mg/L、吸附时间为5 min时, 移除率可达到73.40%。吸附60 min时, 吸附达到平衡, 此后移除率为97.53%~99.65%。该吸附动力学过程符合拟二级动力学模型, 吸附等温线符合 Langmuir 模型拟合, 最大吸附量为 1543.2 mg/g。α-MoO₃微球由于多级且中空的纳米结构, 对MB染料具有用量少、吸附速率快和吸附完全等特点。该材料可以用于吸附废水中其他有机染料。

关键词: 多级结构, α-MoO₃空心球;, 溶剂热法, 亚甲基蓝, 吸附性能

Abstract:

Hierarchical semiconducting metal oxide is highly active due to its special stereostructure, which is potential adsorbent for dye contaminants. Precursors of MoO₂ hollow spheres were successfully synthesized via a simple and one-step solvothermal method. And hierarchical α-MoO₃ hollow microspheres were obtained after subsequent calcination at 400 ℃. Diameters of the α-MoO₃ microspheres were about 600-800 nm which were assembled by nanorods with a width of 70 nm. The as-obtained α-MoO₃ nanomaterials presented excellent adsorption performance for methylene blue (MB). MB removal percentage attained 73.40% in the first 5 min when the concentration of α-MoO₃ absorbent was 0.5 g/L in MB solution at the concentration of 20 mg/L. The equilibrium was established after adsorption for 60 min, and the removal percentages stabilized in the range of 97.53%-99.65%. Their adsorption kinetics was well fitted to a pseudo-second-order model. The adsorption isotherm conformed to Langmuir isotherm model, and the maximum uptake capacity was 1543.2 mg/g. The α-MoO₃ microspheres are cost-effective, fast and complete for MB removal owing to its hierarchical and hollow nanostructures, which also can be employed for adsorption of other organic dyes in waste water.

Key words: hierarchical structure, α-MoO₃ hollow microsphere;, solvothermal method, methylene blue, adsorption performance

中图分类号:

TB321

隋丽丽,王润,赵丹,申书昌,孙立,徐英明,程晓丽,霍丽华. 多级结构α-MoO₃空心微球的构筑及其对有机染料的吸附性能[J]. 无机材料学报, 2019, 34(2): 193-200.

SUI Li-Li, WANG Run, ZHAO Dan, SHEN Shu-Chang, SUN Li, XU Ying-Ming, CHENG Xiao-Li, HUO Li-Hua. Construction of Hierarchical α-MoO₃ Hollow Microspheres and Its High Adsorption Performance towards Organic Dyes[J]. Journal of Inorganic Materials, 2019, 34(2): 193-200.

图/表 12

图1 前驱体(a)和400 ℃煅烧2 h后产物(b)的XRD图谱

Fig. 1 XRD patterns of the precursor (a) and the product calcined at 400 ℃ in air for 2 h (b)

图2 前驱体在400 ℃空气中煅烧2 h后产物的FT-IR谱图

Fig. 2 FT-IR spectrum of the product calcined at 400 ℃ in air for 2 h

图3 前驱体微球(a)~(b)和α-MoO3微球(c)的SEM照片

Fig. 3 Typical SEM images of precursor (a, b) and α-MoO3 microspheres (c)

图4 α-MoO3空心微球的TEM照片(a)~(b), HRTEM照片(c)和SAED照片((c)中插图)

Fig. 4 Typical TEM (a, b), HRTEM (c) images and SAED pattern (inset in (c)) of α-MoO3 hollow microspheres

图5 α-MoO3空心微球的的N2脱附-吸附等温曲线及其孔径分布图(插图)

Fig. 5 Nitrogen adsorption-desorption isotherms and pore size distribution plot (inset) of α-MoO3 hollow microspheres

图6 吸附剂用量(a)和MB染料浓度(b)对α-MoO3微球吸附性能影响曲线, 不同吸附时间α-MoO3微球对MB染料的紫外-可见光谱图(c)和移除率曲线(d)

Fig. 6 Effect of adsorbent dosage (a) and concentration of MB (b) on the adsorption performances of α-MoO3 hollow microspheres, UV-Vis spectra (c) and removal percentage curves (d) of α-MoO3 to MB for different contact times

图7 α-MoO3空心球对不同浓度MB吸附过程的拟一级动力学方程(a)和拟二级动力学方程(b)拟合曲线

Fig. 7 Pseudo-first-order (a) and pseudo-second-order (b) sorption kinetics for different concentrations of MB onto α-MoO3 hollow microspheres

表1 α-MoO3空心微球对MB的吸附动力学参数

Table 1 Kinetic parameters for adsorption of MB on the samples of α-MoO3 hollow microspheres

C₀/(mg·L^-1)	q_e._exp/(mg·g^-1)	Pseudo-second-order			Pseudo-first-order
C₀/(mg·L^-1)	q_e._exp/(mg·g^-1)	q_e._cal/(mg·g^-1)	k₂/(×10^-3, g·mg^-1·min^-1)	R²	q_e._cal/(mg·g^-1)	k₁/(×10^-3, min^-1)	R²
10	19.97	20.83	4.10	0.9996	6.98	10.13	0.6385
20	39.86	40.16	10.90	0.9999	5.34	20.45	0.8994
30	58.16	59.85	0.63	0.9907	44.67	13.04	0.9456
40	65.22	65.10	0.82	0.9903	36.89	9.30	0.9308

图8 α-MoO3空心微球吸附MB的Langmuir (a)和Freundlich (b)吸附等温线

Fig. 8 Langmuir (a) and Freundlich (b) adsorption isotherm curves for adsorption of MB by α-MoO3 hollow microspheres

表2 α-MoO3空心微球对MB的吸附热力学参数

Table 2 Adsorption isotherm parameters of α-MoO3 hollow microspheres to MB

Adsorption	Langmuir model				Freundlich model
Adsorption	q_m/(mg·g^-1)	K_L/(L·mg^-1)	R_L	R²	K_F/(L·g^-1)	n	R²
MB	1543.2	1.19	0.0014	0.9978	724.44	1.82	0.9035

表3 不同金属氧化物吸附剂材料对MB染料的最大吸附容量比较

Table 3 Comparison of the maximum adsorption capacities for MB on adsorbents of different metal oxides

Adsorbent	Maximum adsorption capacity, q_m/(mg·g^-1)	Ref.
Hierarchical α-MoO₃ hollow microspheres	1543.2	This work
WO₃ nanotube	75.0	[26]
WO₃ nanorods	73.0	[27]
WO₃ hollow spheres	138.9	[28]
Hierarchical WO₃ hydrates	274.3	[8]
SiO₂ nanoparticles	679.9	[29]
Fe₃O₄@Ag/SiO₂ nanospheres	128.5	[30]

图9 不同pH条件下α-MoO3空心微球表面Zeta电位图

Fig. 9 Zeta potential of α-MoO3 hollow microspheres at different pH

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多级结构α-MoO₃空心微球的构筑及其对有机染料的吸附性能

Construction of Hierarchical α-MoO₃ Hollow Microspheres and Its High Adsorption Performance towards Organic Dyes

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