Study on the removal of malachite green by manganese dioxide with different crystalline forms

doi:10.19965/j.cnki.iwt.2021-1115

Abstract

Abstract:

Three different crystalline forms of manganese dioxide（α-MnO₂， β-MnO₂ and δ-MnO₂） were prepared through hydrothermal synthesis method by controlling K⁺ concentration. It could be observed that α-MnO₂ had a linear structure， β-MnO₂ had a filamentous structure， and δ-MnO₂ had a two-dimensional layered cauliflower shape with rougher morphology and a large specific surface area. XRD analysis showed that β-MnO₂ showed many sharp and narrow peaks with good crystallinity. The characteristic peaks of XRD spectra of α-MnO₂ became wider and shorter， indicating the presence of smaller crystallites. The peaks of δ-MnO₂ was broaden and had poor crystallinity， with the smallest grains and large interplanar spacing， which was favorable to the catalytic reaction. The removal rates of malachite green（MG） by the three manganese dioxide were δ-MnO₂> β-MnO₂> α-MnO₂ in descending order， indicating that the morphological structure and characteristics of δ-MnO₂ were most favorable to removal of MG. The effects of pH and the initial mass concentration of pollutants in δ-MnO₂ system on the MG removal were investigated， and the results showed that the removal rate of MG increased with the increase of pH and decreased with the increase of initial mass concentration of MG. In addition， the adsorption behavior of δ-MnO₂on MG was in accordance with the Langmuir model and pseudo-secondary kinetic model， which belonged to monomolecular adsorption. The surface adsorption sites were uniformly distributed， and the adsorption rate was controlled by chemisorption with a theoretical adsorption capacity of 40.55 mg/g.

Key words: manganese dioxide, crystal structure, malachite green, adsorption

摘要：

采用水热合成法，通过控制K⁺浓度得到3种不同晶型的二氧化锰（α-MnO₂、β-MnO₂和δ-MnO₂）。从微观结构来看，α-MnO₂为线状结构，β-MnO₂呈丝状结构，δ-MnO₂呈二维层状花椰菜状，表面粗糙，比表面积较大。XRD晶型分析表明，β-MnO₂显示出许多尖锐的窄峰，结晶度较好；α-MnO₂的XRD谱图特征峰变宽变矮，表明存在较小的微晶；δ-MnO₂的峰型宽化，结晶度较差，晶粒最小且晶面间距大，有利于催化反应的发生。3种晶型二氧化锰对孔雀石绿（MG）的去除率由高到低依次为δ-MnO₂>β-MnO₂>α-MnO₂，表明δ-MnO₂的形貌结构与晶型特征最有利于反应的进行。探究了δ-MnO₂体系中pH及污染物初始质量浓度对MG去除效果的影响，结果表明，MG的去除率随pH的增加而增大，随MG初始质量浓度的提高而呈下降趋势。此外，δ-MnO₂对孔雀石绿的吸附行为符合Langmuir模型和伪二级动力学模型，属于单层吸附，表面吸附位点分布均匀，吸附速度受化学吸附控制，理论吸附量为40.55 mg/g。

关键词: 二氧化锰, 晶型, 孔雀石绿, 吸附

CLC Number:

X703
O647.3

Yong XIAO, Huiru HAO, Jun LI, Jin YUE, Min ZHONG, Qian ZHANG. Study on the removal of malachite green by manganese dioxide with different crystalline forms[J]. Industrial Water Treatment, 2022, 42(8): 142-148.

肖勇, 郝慧茹, 李军, 乐进, 钟敏, 张倩. 不同晶型二氧化锰去除孔雀石绿的研究[J]. 工业水处理, 2022, 42(8): 142-148.

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URL: https://www.iwt.cn/EN/10.19965/j.cnki.iwt.2021-1115

https://www.iwt.cn/EN/Y2022/V42/I8/142

Figures/Tables 9

Fig.1 Three crystal types of manganese dioxide

Fig. 2 SEM images（a~c） and XRD spectra（d） of MnO₂

Fig. 3 Removal rates of MG by different crystalline MnO₂

Fig. 4 Removal rates of MG at different pH

Table 1 Removal rates of MG at different initial mass concentrations

初始质量浓度/（mg·L^-1）	10	20	50	100	150	200	250	300
吸附量/（mg·L^-1）	8.81	17.42	29.09	34.79	37.05	38.66	39.75	40.24
去除率/%	96.38	92.62	77.43	43.82	29.47	19.33	18.12	17.58

Fig. 5 Adsorption of δ-MnO₂ on MG at different initial mass concentrations and isothermal model

Table 2 Langmuir and Freundlich isothermal model parameters

项目	Langmuir等温模型			Freundlich等温模型
项目	q _m/（mg·g^-1）	K _L/（L·mg^-1）	R ²	K _F/〔mg·g^-1·（L·mg^-1） $1 / n$ 〕	1/n	R ²
数值	40.55	0.174 8	0.998 5	11.21	0.249 9	0.908 8

Table 2 Langmuir and Freundlich isothermal model parameters

项目	Langmuir等温模型			Freundlich等温模型
项目	q _m/（mg·g^-1）	K _L/（L·mg^-1）	R ²	K _F/〔mg·g^-1·（L·mg^-1） $1 / n$ 〕	1/n	R ²
数值	40.55	0.174 8	0.998 5	11.21	0.249 9	0.908 8

Fig. 6 Kinetic curves（a） and fitted curves（b， c） of MG adsorption by δ-MnO₂

Table 3 Kinetic fitting parameters

项目	准一级动力学			准二级动力学
项目	q _e，cal/（mg·g^-1）	K ₁/min^-1	R ²	q _e，cal/（mg·g^-1）	K ₂/（g·mg^-1·min^-1）	R ²
数值	37.02	0.042 3	0.984 3	41.22	1.609×10^-3	0.992 8

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