不同形貌ɛ-MnO2催化剂的制备及其催化燃烧甲苯性能

doi:10.16085/j.issn.1000-6613.2020-2037

化工进展 ›› 2021, Vol. 40 ›› Issue (10): 5547-5553.DOI: 10.16085/j.issn.1000-6613.2020-2037

不同形貌ɛ-MnO₂催化剂的制备及其催化燃烧甲苯性能

余伟雄¹(), 程高¹^,², 崔晓娥¹, 曾小红¹, 蓝邦²^,⁴, 李永峰¹^,², 张灿仰³, 孙明¹^,², 余林¹^,²()

^1.广东工业大学轻工化工学院，广东广州 510006
^2.广东工业大学广州市清洁交通能源化学重点实验室，广东广州 510006
^3.广东中投环保股份有限公司，广东广州 510700
^4.嘉应学院化学与环境学院，广东梅州 514015

收稿日期:2020-10-10 修回日期:2021-01-20 出版日期:2021-10-10 发布日期:2021-10-25
通讯作者: 余林
作者简介:余伟雄（1994—），男，硕士研究生，研究方向为环境催化。E-mail：yuweixiong0828@163.com。
基金资助:
国家自然科学基金(21576054);广东省科技创新战略专项资金(2018A030310563);2019年度广东省普通高校青年创新人才类项目(2019KQNCX142)

Preparation of ɛ-MnO₂ with different morphologies and their catalytic combustion of toluene

YU Weixiong¹(), CHENG Gao¹^,², CUI Xiao’e¹, ZENG Xiaohong¹, LAN Bang²^,⁴, LI Yongfeng¹^,², ZHANG Canyang³, SUN Ming¹^,², YU Lin¹^,²()

^1.School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, Guangdong, China
^2.Guangzhou Key Laboratory of Clean Transportation Energy Chemistry, Guangdong University of Technology, Guangzhou 510006, Guangdong, China
^3.Guangdong ZhongTou Environmental Protection Co. , Ltd. , Guangzhou 510700, Guangdong, China
^4.School of Chemistry and Environment, Jiaying University, Meizhou 514015, Guangdong, China

Received:2020-10-10 Revised:2021-01-20 Online:2021-10-10 Published:2021-10-25
Contact: YU Lin

摘要/Abstract

摘要：

采用三种不同的制备方法合成出具有不同形貌的?-MnO₂颗粒，分别为球状?-MnO₂、卵状?-MnO₂和块状?-MnO₂，并考察了这三种不同形貌?-MnO₂颗粒的催化燃烧甲苯性能。借助扫描电镜（SEM）、X射线衍射（XRD）、X射线光电子能谱（XPS）、H₂-程序升温还原（H₂-TPR）和N₂吸附-脱附等表征手段对其物化性质进行分析。结果表明，不同形貌的?-MnO₂的甲苯催化燃烧性能具有明显的差异，其活性顺序为球状?-MnO₂>块状?-MnO₂>卵状?-MnO₂。其中，球状?-MnO₂具有最优异的甲苯催化燃烧性能，这与其较大的比表面积、较高的Mn³⁺含量和较好的可还原性相关。此外，经过连续60h的稳定性测试，球状?-MnO₂仍保持良好的催化活性。

关键词: 二氧化锰, 形貌, 纳米材料, 催化剂, 氧化

Abstract:

?-MnO₂with different morphologies, including sphere, ellipsoid and cube were prepared by three methods and their catalytic activities were investigated by catalytic combustion of toluene. The physicochemical properties of the ?-MnO₂catalysts were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), N₂ adsorption-desorption, X-ray photoelectron spectrum (XPS), and H₂-programmed temperature reduction (H₂-TPR). The results showed that the catalytic activity of ?-MnO₂depended strongly on the morphology, following the sequence of sphere > cube > ellipsoid. The superior catalytic activity of sphere-like ?-MnO₂was due to its larger surface area, higher content of Mn³⁺ and better reducibility. Moreover, the sphere-like ?-MnO₂ still kept good catalytic activity after a 60h long-term test.

Key words: manganese dioxide, morphology, nanomaterials, catalyst, oxidation

中图分类号:

O643

余伟雄, 程高, 崔晓娥, 曾小红, 蓝邦, 李永峰, 张灿仰, 孙明, 余林. 不同形貌ɛ-MnO₂催化剂的制备及其催化燃烧甲苯性能[J]. 化工进展, 2021, 40(10): 5547-5553.

YU Weixiong, CHENG Gao, CUI Xiao’e, ZENG Xiaohong, LAN Bang, LI Yongfeng, ZHANG Canyang, SUN Ming, YU Lin. Preparation of ɛ-MnO₂ with different morphologies and their catalytic combustion of toluene[J]. Chemical Industry and Engineering Progress, 2021, 40(10): 5547-5553.

图/表 9

图1 三种不同形貌的MnO2样品的XRD谱图

图2 三种不同形貌的?-MnO2样品的SEM图

图3 三种不同形貌?-MnO2样品的N2吸附脱附曲线和孔径分布

图4 三种不同形貌的?-MnO2样品的甲苯催化燃烧性能

图5 不同空速下球状?-MnO2样品甲苯催化燃烧性能

图6 球状?-MnO2样品甲苯催化燃烧稳定性

表1 三种不同形貌?-MnO2样品的比表面积、平均孔径、H2-TPR还原峰、Mn3+/Mn4+、T50和T90

样品	比表面积/m²·g^-1	平均孔径/nm	H₂-TPR还原峰/℃	表面元素摩尔比（Mn³⁺/Mn⁴⁺）	催化燃烧甲苯活性
样品	比表面积/m²·g^-1	平均孔径/nm	H₂-TPR还原峰/℃	表面元素摩尔比（Mn³⁺/Mn⁴⁺）	T₅₀/℃	T₉₀/℃
卵状?-MnO₂	79.66	7.46	259	1.18	203	209
块状?-MnO₂	88.51	7.87	237	1.68	193	199
球状?-MnO₂	137.19	6.15	229	1.79	191	194

图7 三种不同形貌?-MnO2样品Mn 2p3/2的XPS图

图8 三种不同形貌?-MnO2样品的H2-TPR图

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不同形貌ɛ-MnO₂催化剂的制备及其催化燃烧甲苯性能

Preparation of ɛ-MnO₂ with different morphologies and their catalytic combustion of toluene

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