氧缺陷位MoO3-  x 的制备及其吸附性能研究

doi:10.11949/0438-1157.20190648

摘要/Abstract

摘要：

纺织印染废水中的有机污染物如亚甲基蓝的高效吸附净化是环境领域的重要研究课题，三氧化钼独特的片层结构极具吸附应用潜力。通过微波一步法制备了不同氧空穴浓度的氧化钼，具有不同的表面电荷分布，利用氧空穴氧化钼表面所带负电荷选择性高效吸附阳离子偶氮染料亚甲基蓝。揭示了氧空穴浓度与吸附性能之间的关系，发现氧空穴浓度越高则氧化钼吸附速率越快；吸附过程符合Langmuir等温线模型和准二级动力学模型，表明该吸附过程属于单分子层吸附，并分析了其吸附机理。氧空穴氧化钼(MoO_3- _x )为金属氧化物在染料吸附领域的发展和应用提供一定的基础数据和理论基础。

关键词: 三氧化钼, 氧空穴, 动力学, 吸附, 亚甲基蓝

Abstract:

The high-efficiency adsorption purification of organic pollutants such as methylene blue in textile printing and dyeing wastewater is an important research topic in the environmental field. The unique lamellar structure of molybdenum oxides has great potential for adsorption application. Molybdenum oxides with different oxygen vacancies concentration were prepared by one-step microwave assisted hydrothermal method. The prepared molybdenum oxides with different negative surface charge distribution were applied to the efficient selective adsorption of organic pollutant cationic azo dye methylene blue. The relationship between oxygen vacancies concentration and adsorption performance was explored. It is found that molybdenum oxide with oxygen vacancies concentration is relative to its adsorption rate. The adsorption process conforms to Langmuir isotherm model and pseudo second order kinetic model, indicating that the adsorption process belongs to monomolecular adsorption. Therefore, it provides a potential for the development and application of metal oxides in the field of dye adsorption.

Key words: molybdenum oxide, oxygen vacancies, kinetics, adsorption, methylene blue

中图分类号:

X 506

李姜无忌,朱巧影,陈立芳,成洪业,漆志文. 氧缺陷位MoO_3- _x 的制备及其吸附性能研究[J]. 化工学报, 2019, 70(10): 3956-3966.

Wuji LIJIANG,Qiaoying ZHU,Lifang CHEN,Hongye CHENG,Zhiwen QI. Preparation of oxygen defect vacancies MoO_3- _x and its adsorption properties[J]. CIESC Journal, 2019, 70(10): 3956-3966.

图/表 13

图1 MoO3- x 和MoO3的XRD谱图(a)；放大的MoO3- x 和MoO3的XRD谱图中(020)、(040)和(060)晶面衍射峰(b)

Fig.1 XRD patterns (a) and selected XRD pattern of (020), (040) and (060) diffraction peaks (b) of MoO3- x and MoO3

图2 氧化钼在空气以及氮气氛围下进行的热重分析TGA

Fig.2 TGA analysis of MoO3- x in air and argon atmosphere

表1 氧化钼样品的氧空穴浓度

Table 1 Oxygen vacancy concentration of MoO3– x characterized by thermogravimetric analysis

Sample	Mass decrease/%	Oxygen vacancy concentration
MoO₃	0	MoO₃
MoO_3- _x -120-150	0.314	MoO_2.97
MoO_3- _x -150-45	0.634	MoO_2.94
MoO_3- _x -180-10	1.293	MoO_2.88
MoO_3- _x -180-20	1.266	MoO_2.89

图3 氧化钼样品的XPS能谱图

Fig.3 XPS spectra of Mo 3d (a) and O 1s (b) for different MoO3- x samples

图4 MoO3- x 和MoO3吸附剂吸附MB的紫外可见光全谱图

Fig.4 UV-Vis adsorption spectra of MB over MoO3- x and MoO3

图5 MoO3- x 对不同种染料污染物的吸附性能

Fig.5 Adsorption performance of organic pollutants over MoO3- x

图6 不同氧空穴浓度的氧化钼对MB 的吸附性能

Fig.6 Adsorption performance of molybdenum oxide with different oxygen vacancies concentrations

表 2 不同吸附剂对MB的吸附能力对比

Table 2 Summary of adsorption capacity of various materials for MB

Absorbent sample	Q _max/(mg·g^-1)	Ref.
graphene	153.8	[34]
Fe-MOF	187	[35]
activated carbon	207	[36]
biomassed bamboo	606	[37]
Fe(Ⅲ)/Cr(Ⅲ) hydroxide	22.8	[38]
zeolite	53.1	[39]
clay	300	[40]
MoO₃	629	this work
MoO_3- _x	758	this work

图7 (a) 25℃下不同含氧空穴的MoO3- x 对MB的吸附等温线；(b) MoO3- x 吸附MB的Langmuir吸附等温线模型拟合曲线；(c) MoO3- x 吸附MB的Freundlich吸附等温线模型拟合曲线

Fig.7 (a) Adsorption isotherm of MoO3- x with different oxygen vacancies concentration to MB under 25℃, (b) Langmuir isothermal equations of MoO3- x to MB, (c) Freundlich isothermal equations of MoO3- x to MB

表3 MoO3- x 和MoO3吸附MB的Langmuir和Freundlich模型参数

Table 3 Adsorption isothermal equation parameters of MoO3- x and MoO3 to MB

Adsorbent	Langmuir isotherm
Adsorbent	q _m/(mg·g^-1)	R _L	R ²	1/n	K _F/((mg·g^-1)(L·mg^-1)^1/ ⁿ )	R ²
MoO_3- _x	748	0.042	0.978	0.24	134.3	0.844
MoO_3- _x -180-20	739	0.096	0.993	2.36	126.8	0.568
MoO_3- _x -150-45	721	0.356	0.976	4.56	263.4	0.497
MoO_3- _x -120-150	704	0.569	0.965	8.21	85.55	0.368
MoO₃	629	0.875	0.998	13	0.7658	0.426

图8 25°C下MoO3- x 对MB吸附过程吸附量随时间的变化

Fig.8 Variations of MoO3- x adsorption capacity to MB with time at 25°C

图9 25℃下MoO3- x 对MB吸附过程的动力学方程拟合图

Fig.9 Fitting models kinetics equations of MoO3- x to MB under 25℃

表4 25℃下动力学方程参数

Table 4 Kinetics equation parameters under 25℃

Adsorbent	Pseudo-first-order model			Pseudo-second-order model
Adsorbent	k ₁/(g·mg^-1·h^-1)	q _e,cal/(mg·g^-1)	R ²	k ₂/(g·mg^-1·min^-1)	q _e,cal/(mg·g^-1)	R ²
MoO_3- _x	0.536	6.9×10¹⁴	0.2882	0.040	762	0.99973
MoO₃	1.822×10-4	7.12×1022	0.3554	0.00252	785	0.99628

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