Chemical Industry and Engineering Progress ›› 2019, Vol. 38 ›› Issue (08): 3774-3781.DOI: 10.16085/j.issn.1000-6613.2018-2018

• Materials science and technology • Previous Articles     Next Articles

Hydrothermal synthesis of MnO2 and the structure-activity relationship of its adsorption of dye

Danchen ZHU1,2(),Jiali XIAO1,3,Lili YANG1,Minglian FU1,2   

  1. 1. College of Environmental and Biological Engineering, Putian University, Putian 351100, Fujian, China
    2. Fujian Key Laboratory of Ecology-Toxicological Effects & Control for Emerging Contaminants, Putian 351100, Fujian, China
    3. M China, Shanghai 200336, China
  • Received:2018-10-12 Online:2019-08-05 Published:2019-08-05
  • Contact: Danchen ZHU

水热合成MnO2及其染料吸附性能的构效关系

朱丹琛1,2(),肖伽励1,3,杨丽丽1,傅明连1,2   

  1. 1. 莆田学院环境与生物工程学院,福建 莆田 351100
    2. 福建省新型污染物生态毒理效应与控制重点实验室,福建 莆田 351100
    3. M中国有限公司,上海 200336
  • 通讯作者: 朱丹琛
  • 作者简介:朱丹琛(1987—),女,硕士研究生,实验师,主要从事无机材料化学的研究。E-mail:ptuzdc@163.com
  • 基金资助:
    福建省自然科学基金(2015J01644);福建省教育厅A类项目(JAT160431);莆田学院育苗基金(2015060);莆田学院校级项目(2016015);福建省大学生创新创业训练计划(201711498034)

Abstract:

MnSO4 and (NH4)2S2O8 were used as the raw materials for the hydrothermal synthesis of MnO2, which is an inexpensive, low toxic and effective adsorbent. The structure, morphology and adsorption performance of the obtained MnO2 were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM) and adsorption experiments, respectively. Moreover, the structure-active relationship was studied. The results showed that burr spherical MnO2 with three different crystal phases (α, β and γ), β-MnO2 with spheroidic and needle-like morphologies could be prepared by changing the hydrothermal temperature and hydrothermal time. Among them, the adsorption capacity of burr spherical γ-MnO2 on methylene blue (MB) could reach 19.33mg/g. The burr spherical like γ-MnO2 was synthesized at hydrothermal temperature of 80℃ and hydrothermal time of 12h. Burr spherical MnO2 can be obtained under either of the following situation: ① when the hydrothermal time is 12h, and the hydrothermal temperatures are between 50℃ and 110℃. ② hydrothermal temperature is 80℃ with various hydrothermal time(4h, 8h, 24h). The adsorption of MB is influenced by the crystal phase and morphology of MnO2. The adsorption performance of burr spherical MnO2 with various crystal phases is in the order of β<α<γ. Moreover, the adsorption performance of β-MnO2 with different morphologies is in the order of needle-like2. The adsorption performance of burr spherical γ-MnO2 on MB was improved by changing the pH of MB solution from 10.00 to 1.00. The adsorption process was accompanied by chemical reaction, and can be described by the Langmuir isothermal model. The result provides a basis for the study of the mechanism and the structure-activity relationship of MnO2 for adsorbing dye.

Key words: manganese dioxide, adsorption property, methylene blue, morphology, crystal phase, structure-active relationship

摘要:

以MnSO4和(NH4)2S2O8为反应原料,采用水热法制备廉价低毒的MnO2吸附剂。借助X射线粉末衍射(XRD)、扫描电镜(SEM)和静态吸附实验,探究材料的结构、形貌、吸附性能以及构效关系。结果表明,通过改变水热温度、反应时间,可以得到毛刺球状α、β、γ三种晶型MnO2以及类球状和针状β-MnO2。其中水热温度80℃、反应12h时得到的毛刺球状γ-MnO2吸附亚甲基蓝(MB)效果最好,达到19.33mg/g。当水热温度在50~110℃反应12h以及水热温度为80℃反应4h、8h、24h,所得到的产品的形貌均为毛刺球状。晶型和形貌对MnO2吸附MB能力均有影响。不同晶型的MnO2毛刺球对MB吸附性能的影响为β<α<γ;不同形貌的β-MnO2却对吸附效果影响较大,为针状<类球状<毛刺球形。随着MB溶液的pH从10.00减少到1.00时,毛刺球状γ-MnO2对MB的吸附量呈上升趋势,吸附过程还伴随着化学反应,且吸附的过程符合Langmuir等温模型。本文将为MnO2吸附染料的机制和构效关系研究提供依据。

关键词: 二氧化锰, 吸附能力, 亚甲基蓝, 形貌, 晶型, 构效关系

CLC Number: 

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