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

doi:10.11949/0438-1157.20220344

Abstract

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

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

CLC Number:

TQ 032.4

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.

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.

Figures/Tables 13

Fig.1 Activity evaluation equipment

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

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

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

Fig.4 SEM images of MnO2-X

Fig.5 XPS spectra of the MnO2-X catalysts

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

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

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

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

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

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

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

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

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

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