钾改性Mn/Ce0.65Zr0.35O2催化剂催化氧化甲苯

doi:10.3866/PKU.WHXB201905047

摘要/Abstract

摘要：

碱金属作为助剂，能够调变催化剂的电子和结构性能，从而改善催化剂的活性。本工作中，我们研究了碱金属K的添加对MnO_x/Ce_0.65Zr_0.35O₂催化剂氧化甲苯的性能影响。结果表明，掺杂碱金属K可以明显提高催化剂的催化活性；当K与Mn的摩尔比为0.2时，催化剂Mn/Ce_0.65Zr_0.35O₂-K-0.2表现出最好的活性。在体积空速为12000 h⁻¹时，其完全转化温度T₉₀为242 ℃。同时采用X射线粉末衍射、紫外/可见拉曼、程序升温还原与吸脱附、光电子能谱及红外原位等表征技术研究K的添加对催化剂MnO_x/Ce_0.65Zr_0.35O₂性能影响。结果表明，适量K的添加可以提高催化剂的氧化还原性能，增加催化剂表面缺陷位并提高晶格氧的移动性，同时增加了催化剂表面活性氧物种浓度，从而提高催化剂催化氧化甲苯的能力。

关键词: 甲苯, 催化氧化, 钾, 铈锆固溶体, 锰氧化物

Abstract:

Volatile organic compounds (VOCs) are both harmful to human health and the environment; however, catalytic combustion offers a promising method for VOC purification because of its high efficiency without secondary pollution. Although manganese-based catalysts have been well studied for VOC catalytic oxidation, their catalytic activity at low temperature must be improved. Alkali metals as promoters have the potential to modulate the electronic and structural properties of the catalysts, improving their catalytic activity. Herein, a Ce_0.65Zr_0.35O₂ support was prepared by co-precipitation and MnO_x/Ce_0.65Zr_0.35O₂ catalysts were obtained through the incipient-wetness impregnation method. The catalytic properties of K-modified MnO_x/Ce_0.65Zr_0.35O₂ for toluene oxidation with different molar ratios of K/Mn were investigated. In addition, the catalysts were characterized by XRD, UV/visible Raman, Hydrogen temperature program reduction (H₂-TPR), Oxygen temperature programmed desorption (O₂-TPD), X-ray photoelectron spectroscopy (XPS) and in situ diffuse reflectance FTIR spectroscopy (DRIFTS) experiments. The results showed that alkali metal doping with K significantly improved the catalytic activity. In particular, when the molar ratio of K/Mn was 0.2, the monolith catalyst Mn/Ce_0.65Zr_0.35O₂-K-0.2 exhibited the best performance with the lowest complete conversion temperature T₉₀ of 242 ℃ at a GHSV of 12000 h⁻¹. The XRD results suggested that MnO_x was uniformly distributed on the surface of the catalyst and that Mn⁴⁺ partially reduced to Mn³⁺ on the addition of K. The Raman spectrum demonstrated that with increasing K content, both the β- and α-MnO₂ phases coexisted on the Mn/Ce_0.65Zr_0.35O₂-K-0.2 catalyst, increasing the number of surface defect sites. The H₂-TPR experiment results confirmed that Mn/Ce_0.65Zr_0.35O₂-K-0.2 exhibited the lowest reduction temperature and good reducibility. From the O₂-TPD experiments, it was clear that Mn/Ce_0.65Zr_0.35O₂-K-0.2 contained the most surface adsorbed oxygen species and excellent lattice oxygen mobility, which benefitted the toluene oxidation activity. In addition, the XPS results suggested that the content of surface adsorbed oxygen species of the Mn/Ce_0.65Zr_0.35O₂-K-0.2 catalyst was the highest among all the tested samples. In addition, toluene-TPSR in N₂ as measured by in situ DRIFTs analysis demonstrated that available lattice oxygen was present in the Mn/Ce_0.65Zr_0.35O₂-K-0.2 catalyst. Therefore, the Mn/Ce_0.65Zr_0.35O₂-K-0.2 catalyst exhibited the best redox properties and oxygen mobility of the prepared samples and showed excellent activity toward toluene oxidation. Therefore, it was concluded that the addition of an appropriate amount of K improved the redox performance of the catalyst and increased the number of surface defect sites and mobility of the lattice oxygen of the catalyst as well as the concentration of the surface active oxygen species, thereby significantly improving catalytic ability.

Key words: Toluene, Catalytic oxidation, Potassium, Ce_0.65Zr_0.35O₂, Manganese oxide

赖潇潇, 冯洁, 周晓英, 侯忠燕, 林涛, 陈耀强. 钾改性Mn/Ce_0.65Zr_0.35O₂催化剂催化氧化甲苯[J]. 物理化学学报, 2020, 36(8), 1905047. doi: 10.3866/PKU.WHXB201905047

Xiaoxiao Lai, Jie Feng, Xiaoying Zhou, Zhongyan Hou, Tao Lin, Yaoqiang Chen. Catalytic Oxidation of Toluene Over Potassium Modified Mn/Ce_0.65Zr_0.35O₂ Catalyst[J]. Acta Physico-Chimica Sinica 2020, 36(8), 1905047. doi: 10.3866/PKU.WHXB201905047

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201905047

https://www.whxb.pku.edu.cn/CN/Y2020/V36/I8/1905047

图/表 14

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Catalyst	S_BET/(m²·g⁻¹)	Pore volume/(cm³·g⁻¹)	Pore size/nm	Major reduction temperature/℃	Total hydrogen consumption/(μmol·g⁻¹ catalyst) ± 0.2
Mn/CZ	77	0.27	6.5	332, 453	2023.6
Mn/CZ-K-0.05	72	0.26	7.0	334, 439	1903.9
Mn/CZ-K-0.2	73	0.27	7.1	329, 403	1869.6
Mn/CZ-K-0.5	60	0.24	7.6	352, 403	1672.1
CZ	86	0.33	5.9	500–650	720.6

Sample	T_d/℃	The amount of oxygen desorption/ (μmol∙g⁻¹ catalyst) ± 0.1 (T < 400 ℃)
Mn/CZ	123	226.3
Mn/CZ-K-0.05	127	240.2
Mn/CZ-K-0.2	118	262.4
Mn/CZ-K-0.5	125	215.0

Sample	Ce³⁺/Ce_total (%)	Mn⁴⁺	Mn³⁺	Mn²⁺	Mn³⁺/Mn⁴⁺	O_sur/O_total (%)
Mn/CZ	14.72	37.93	34.68	27.39	0.91	32.58
Mn/CZ-K-0.05	15.68	32.20	43.74	24.06	1.36	37.21
Mn/CZ-K-0.2	14.78	26.60	48.75	24.66	1.83	43.39
Mn/CZ-K-0.5	15.21	21.32	53.63	25.05	2.51	37.80
CZ	16.21	–	–	–	–	27.30

Sample	T₅₀ (℃)	T₉₀ (℃)
Mn/CZ	245	265
Mn/CZ-K-0.05	234	256
Mn/CZ-K-0.2	228	242
Mn/CZ-K-0.5	247	277
CZ	257	360

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钾改性Mn/Ce_0.65Zr_0.35O₂催化剂催化氧化甲苯

Catalytic Oxidation of Toluene Over Potassium Modified Mn/Ce_0.65Zr_0.35O₂ Catalyst

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