一步法合成α-MnO2/β-MnO2催化剂及其对甲苯催化氧化的性能研究

doi:10.11949/0438-1157.20220344

化工学报 ›› 2022, Vol. 73 ›› Issue (8): 3615-3624.DOI: 10.11949/0438-1157.20220344

• 催化、动力学与反应器 • 上一篇下一篇

一步法合成α-MnO₂/β-MnO₂催化剂及其对甲苯催化氧化的性能研究

李治东¹(), 万佳琪², 刘莹², 唐艺溪², 刘威², 宋忠贤³, 张学军¹()

^1.沈阳化工大学环境与安全工程学院，辽宁沈阳 110142
^2.沈阳化工大学理学院，辽宁沈阳 110142
^3.河南城建学院市政与环境工程学院，河南平顶山 467041

收稿日期:2022-03-07 修回日期:2022-05-10 出版日期:2022-08-05 发布日期:2022-09-06
通讯作者: 张学军
作者简介:李治东（1995—），男，硕士研究生，857227848@qq.com
基金资助:
国家自然科学基金项目(21872096);辽宁省教育厅基本科研项目(LZ2019002)

α-MnO₂/β-MnO₂ catalysts synthesized by one-pot method and their catalytic performance for the oxidation of toluene

Zhidong LI¹(), Jiaqi WAN², Ying LIU², Yixi TANG², Wei LIU², Zhongxian SONG³, Xuejun ZHANG¹()

^1.College of Environmental and Safety Engineering, Shenyang University of Chemical Technology, Shenyang 110142, Liaoning, China
^2.College of Science, Shenyang University of Chemical Technology, Shenyang 110142, Liaoning, China
^3.College of Municipal and Environmental Engineering, Henan University of Urban Construction, Pingdingshan 467041, Henan, China

Received:2022-03-07 Revised:2022-05-10 Online:2022-08-05 Published:2022-09-06
Contact: Xuejun ZHANG

摘要/Abstract

摘要：

采用水热法在不同pH条件下制备了一系列MnO₂基催化剂，通过XRD、SEM、N₂吸脱附等手段对其进行了表征，并评价了它们对甲苯催化氧化反应的催化活性。表征结果表明，不同的pH本质上改变了s反应溶液的初始H⁺浓度，从而影响了所得样品的结晶环境，并赋予它们不同的晶相。甲苯的催化氧化评价结果表明，催化剂的催化性能与α-MnO₂的含量密切相关。当pH=11时所得到的MnO₂-11催化剂，具有最大的比表面积和最多的缺陷结构，使其具有最佳的催化活性（T₅₀=245℃和T₉₀=256℃）和优异的循环稳定性。

关键词: MnO₂催化剂, 催化燃烧, 挥发性有机化合物

Abstract:

A series of MnO₂ catalysts were prepared via a hydrothermal method at different pH, characterized by XRD, SEM, N₂-adsorption XPS and H₂-TPR, and tested in the total oxidation of toluene. Different pH essentially changes the initial H⁺ concentration of the reaction solution during the synthesis process of different samples, which dramatically affects the crystallization environment of the obtained samples and gives them different crystal phase. The catalytic activity of the as-prepared MnO₂ catalysts was evaluated by the catalytic oxidation of toluene, and the result illustrates that the catalytic performance of the catalysts is linearly dependent on the content of α-MnO₂. When pH=11, the obtained MnO₂-11 catalyst has the largest surface area and the most defect structure, which makes it have the best catalytic activity (T₅₀= 245℃ and T₉₀= 256℃) and excellent cycling stability.

Key words: MnO₂ catalyst, catalytic combustion, volatile organic compounds

中图分类号:

TQ 032.4

李治东, 万佳琪, 刘莹, 唐艺溪, 刘威, 宋忠贤, 张学军. 一步法合成α-MnO₂/β-MnO₂催化剂及其对甲苯催化氧化的性能研究[J]. 化工学报, 2022, 73(8): 3615-3624.

Zhidong LI, Jiaqi WAN, Ying LIU, Yixi TANG, Wei LIU, Zhongxian SONG, Xuejun ZHANG. α-MnO₂/β-MnO₂ catalysts synthesized by one-pot method and their catalytic performance for the oxidation of toluene[J]. CIESC Journal, 2022, 73(8): 3615-3624.

图/表 13

图1 活性评价装置

Fig.1 Activity evaluation equipment

图2 MnO2-X样品的 XRD谱图

Fig.2 Powder XRD patterns of the MnO2-X catalysts

图3 MnO2-X样品的N2吸附-解吸等温线和孔径分布

Fig.3 Nitrogen adsorption-desorption isotherms and corresponding pore size distribution curves of the MnO2-X catalysts

表1 不同样品的比表面积、平均孔径、孔容积、晶粒尺寸

Table 1 BET surface areas， average pore sizes， pore volume， crystallite sizes of samples

样品	比表面积 /(m²/g)	平均孔径/ nm	孔容积/(cm³/g)	晶粒尺寸/nm
MnO₂-12	58.5	27.1	0.3	37
MnO₂-11	66.6	20.6	0.3	39
MnO₂-9	20.8	26.8	0.1	67
MnO₂-5	18.1	26.8	0.1	65
MnO₂-1	62.5	24.2	0.3	15

图4 MnO2-X的SEM图

Fig.4 SEM images of MnO2-X

图5 MnO2-X 样品的XPS谱图

Fig.5 XPS spectra of the MnO2-X catalysts

表2 MnO2-X样品的 XPS结果

Table 2 The XPS data of the MnO2-X samples

样品	Mn³⁺/Mn⁴⁺	O_ads/O_latt
MnO₂-12	1.23	0.179
MnO₂-11	1.43	0.299
MnO₂-9	1.21	0.167
MnO₂-5	1.06	0.155
MnO₂-1	1.34	0.204

图6 MnO2-X 样品的H2-TPD谱图

Fig.6 H2-TPR profiles of the MnO2-X catalysts

图7 MnO2-X 样品的O2-TPD谱图

Fig.7 O2-TPD profiles of the MnO2-X catalysts

图8 MnO2-X催化剂的甲苯转化率和CO2选择性

Fig.8 Toluene conversion and CO2 yield over different of the MnO2-X catalysts

图9 MnO2-11样品的稳定性及耐水性测试和四次循环测试结果

Fig.9 Stability and water resistance tests and four-cycle test performance of the MnO2-11 catalysts

图10 催化剂的甲苯催化燃烧的Arrhenius图

Fig.10 Arrhenius plots of the as-synthesized catalysts for the catalytic combustion of toluene

图11 MnO2-X 样品的甲苯完全转化温度与XPS结果的关系

Fig.11 Relationship between toluene complete conversion temperature of MnO2-X samples and XPS results

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一步法合成α-MnO₂/β-MnO₂催化剂及其对甲苯催化氧化的性能研究

α-MnO₂/β-MnO₂ catalysts synthesized by one-pot method and their catalytic performance for the oxidation of toluene

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