Preparation of Mn3O4 catalyst by redox method and study on its catalytic oxidation performance and mechanism of toluene

doi:10.11949/0438-1157.20230196

Abstract

Abstract:

The Mn₃O₄ catalyst was synthesized by controlling the calcination temperature and atmosphere based on the redox method for the preparation of α-MnO₂. Their catalytic performance was systematically investigated. The results showed that Mn₃O₄ has greater catalytic properties than that of MnO₂, its conversion rate was kept above 90% for 100 h at 230℃. In situ infrared and other series of characterization results show that compared with MnO₂, Mn₃O₄ has appropriate redox ability, higher lattice oxygen activity, more surface adsorbed oxygen and stronger toluene adsorption ability, which promotes the benzoic acid species on the surface of the catalyst and rapid conversion, thereby improving its toluene catalytic performance. This work can serve as a guide for the development of manganese-based catalysts and their mechanism for toluene catalytic oxidation performance enhancement.

Key words: Mn₃O₄ catalyst, catalytic oxidation, toluene, in situ infrared

摘要：

在氧化还原法制备α-MnO₂的基础上，通过控制焙烧温度和气氛制备了Mn₃O₄催化剂，系统考察了其甲苯催化性能。结果显示，Mn₃O₄催化性能优于MnO₂，并且在230℃下保持转化率90%以上稳定运行100 h。原位红外等表征结果表明，与MnO₂相比，Mn₃O₄具有适当的氧化还原能力、更高的晶格氧活性、更多的表面吸附氧和更强的甲苯吸附能力，促使催化剂表面苯甲酸物种的快速转化，进而提高其甲苯催化性能。本研究可为锰基催化剂的制备及其甲苯催化氧化性能提升机理研究提供参考。

关键词: Mn₃O₄催化剂, 催化氧化, 甲苯, 原位红外

CLC Number:

TQ 032.4

Chen WANG, Xiufeng SHI, Xianfeng WU, Fangjia WEI, Haohong ZHANG, Yin CHE, Xu WU. Preparation of Mn₃O₄ catalyst by redox method and study on its catalytic oxidation performance and mechanism of toluene[J]. CIESC Journal, 2023, 74(6): 2447-2457.

王辰, 史秀锋, 武鲜凤, 魏方佳, 张昊虹, 车寅, 吴旭. 氧化还原法制备Mn₃O₄催化剂及其甲苯催化氧化性能与机理研究[J]. 化工学报, 2023, 74(6): 2447-2457.

Figures/Tables 17

Fig.1 Catalyst evaluation equipment

Fig.2 Toluene conversion and CO2 selectivity on MnO2 and Mn3O4 catalyst

Fig.3 Stability and water resistance test of Mn3O4 （reaction temperature is 230℃）

Fig.4 Toluene catalytic activity of Mn3O4 at different space velocity

Fig.5 Reaction rate constant of MnO2 and Mn3O4 for the catalytic oxidation of toluene

Fig.6 XRD patterns of MnO2 and Mn3O4

Table 1 Textural parameters and reaction rate constant k of MnO2 and Mn3O4

Catalysts

S_BET/

(cm²/g)

P_V/

(cm³/g)

APD/

Average grain size/nm

MnO₂

Mn₃O₄

Fig.7 N2 adsorption-desorption isotherms of MnO2 and Mn3O4 and BJH pore size distribution of MnO2 and Mn3O4

Fig.8 SEM and TEM images of MnO2 and Mn3O4

Fig.9 H2-TPR profiles of MnO2 and Mn3O4

Fig.10 O2-TPD profiles of MnO2 and Mn3O4

Fig.11 Toluene-TPD profiles of MnO2 and Mn3O4

Fig.12 Mn 2p and O 1s XPS spectra of MnO2 and Mn3O4

Table 2 Surface elemental analysis of MnO2 and Mn3O4 determined by XPS analysis

Catalyst	O			Mn
Catalyst	O_ads/%	O_lat/%	O_ads/O_lat	Mn²⁺/%	Mn³⁺/%	Mn⁴⁺/%
Mn₃O₄	37	63	0.59	39	35	26
MnO₂	34	66	0.52	28	41	31

Fig.13 In situ DRIFTS spectra of adsorption process of the toluene and toluene-air reaction process of MnO2

Fig.14 In situ DRIFTS spectra of adsorption process of the toluene and toluene-air reaction process of Mn3O4

Fig.15 In situ DRIFTS spectra of surface adsorbed species for comparison of toluene adsorption and reaction process of MnO2 and Mn3O4

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Preparation of Mn₃O₄ catalyst by redox method and study on its catalytic oxidation performance and mechanism of toluene

氧化还原法制备Mn₃O₄催化剂及其甲苯催化氧化性能与机理研究

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