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

doi:10.11949/0438-1157.20230196

摘要/Abstract

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

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

中图分类号:

TQ 032.4

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.

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.

图/表 17

图1 催化剂评价装置

Fig.1 Catalyst evaluation equipment

图2 MnO2和Mn3O4催化剂上甲苯转化率和CO2选择性

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

图3 Mn3O4催化剂的稳定性测试和抗水性测试（反应温度为230℃）

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

图4 不同空速下Mn3O4催化剂的甲苯转化率

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

图5 MnO2和Mn3O4催化剂上甲苯催化氧化的反应速率常数

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

图6 MnO2和Mn3O4的XRD谱图

Fig.6 XRD patterns of MnO2 and Mn3O4

表1 MnO2和Mn3O4的结构参数和反应速率常数k

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

图7 MnO2和Mn3O4的N2吸脱附等温线和BJH孔径分布

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

图8 MnO2和Mn3O4的SEM和TEM图

Fig.8 SEM and TEM images of MnO2 and Mn3O4

图9 MnO2 和Mn3O4的H2-TPR图

Fig.9 H2-TPR profiles of MnO2 and Mn3O4

图10 MnO2 和Mn3O4的O2-TPD图

Fig.10 O2-TPD profiles of MnO2 and Mn3O4

图11 MnO2 和Mn3O4的Toluene-TPD图

Fig.11 Toluene-TPD profiles of MnO2 and Mn3O4

图12 MnO2 和Mn3O4的Mn 2p和O 1s XPS谱图

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

表2 MnO2 和Mn3O4由XPS分析测定的表面元素分析

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

图13 MnO2催化剂甲苯吸附过程和甲苯-氧气反应过程的表面吸附物种原位DRIFTS谱图

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

图14 Mn3O4催化剂甲苯吸附过程和甲苯-氧气反应过程的表面吸附物种原位DRIFTS谱图

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

图15 MnO2和Mn3O4催化剂甲苯吸附和反应过程状态对比的表面吸附物种原位DRIFTS谱图

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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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

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

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