钐对SmxMn0.3−xTi催化剂NH3选择性催化还原NOx过程中N2选择性的影响

张生杨; 张柏林; 邬博宇; 刘波; 张深根

doi:10.1007/s12613-021-2348-5

Volume 30 Issue 4

Apr. 2023

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文章导航 > 矿物冶金与材料学报（英文） > 2023 > 30(4): 642-652

Shengyang Zhang, Bolin Zhang, Boyu Wu, Bo Liu, and Shengen Zhang, Effect of samarium on the N₂ selectivity of Sm_xMn_0.3−xTi catalysts during selective catalytic reduction of NO_x with NH₃, Int. J. Miner. Metall. Mater., 30(2023), No. 4, pp. 642-652. https://doi.org/10.1007/s12613-021-2348-5

Cite this article as:

Shengyang Zhang, Bolin Zhang, Boyu Wu, Bo Liu, and Shengen Zhang, Effect of samarium on the N2 selectivity of SmxMn0.3−xTi catalysts during selective catalytic reduction of NOx with NH3, Int. J. Miner. Metall. Mater., 30(2023), No. 4, pp. 642-652. https://doi.org/10.1007/s12613-021-2348-5

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研究论文

钐对Sm_xMn_0.3−xTi催化剂NH₃选择性催化还原NO_x过程中N₂选择性的影响

1)
北京科技大学新材料技术研究院，北京 100083，中国
2)
北京科技大学顺德创新学院，佛山 528399，中国

通讯作者:
张柏林 E-mail: zhangbolin@ustb.edu.cn

张深根 E-mail: zhangshengen@mater.ustb.edu.cn

文章亮点

(1) Sm_0.15Mn_0.15Ti催化剂在180‒300℃下，NO转化率达到100%，N₂选择性达到87%以上。

(2) 掺杂Sm降低了Sm_0.15Mn_0.15Ti催化剂的氧化还原性能，有效提高了N₂选择性。

(3) 掺杂Sm增加了催化剂的比表面积、表面吸附氧、酸强度和总酸量。

(4) Sm_0.15Mn_0.15Ti催化剂在100‒300°C下，NH₃-SCR反应主要遵循Eley–Rideal机制。

中文摘要

本文研究了Sm对Mn基催化剂NH₃选择性催化还原NO的改善作用。采用共沉淀法制备了一系列Sm_xMn_0.3−xTi催化剂(x = 0, 0.1, 0.15, 0.2和0.3)。活性测试表明，Sm_0.15Mn_0.15Ti催化剂在180‒300°C条件下，NO转化率达100%，N₂选择性达87%以上。表征结果表明，Mn基催化剂中添加Sm，抑制了TiO₂和Mn₂O₃相的结晶，提高了比表面积和酸性，其中Sm改性催化剂的比表面积从152.2增加至241.7 m²·g⁻¹。这些作用有利于提高催化活性。X射线光电子能谱(XPS)结果表明，Sm_0.15Mn_0.15Ti的Sm³⁺/Sm和O_β/O的相对原子比分别为76.77at%和44.11at%，添加Sm增加了表面吸附氧(O_β)，降低了Mn⁴⁺的表面浓度；程序升温还原H₂(H₂-TPR)结果表明，Sm_0.15Mn_0.15Ti催化剂还原温度提高，H₂消耗量降低至0.3 mmol⋅g⁻¹。Sm的引入降低了催化剂Mn⁴⁺表面浓度，使得该催化剂氧化还原性能降低，进一步抑制NH₃氧化和非选择性催化还原反应生成N₂O，从而提高了催化剂的N₂选择性。原位漫反射红外傅立叶变换光谱(DRIFTs)表明，Sm_0.15Mn_0.15Ti催化剂的NH₃-SCR反应主要遵循Eley‒Rideal机制。Sm掺杂增加了Sm_0.15Mn_0.15Ti催化剂的表面吸附氧(O_β)，降低了氧化还原性能，提高了Sm_0.15Mn_0.15Ti催化剂的NO转化率和N₂选择性。

关键词:

Research Article

Effect of samarium on the N₂ selectivity of Sm_xMn_0.3−xTi catalysts during selective catalytic reduction of NO_x with NH₃

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Abstract

Abstract

This work aims to study the improvement effect of Sm on Mn-based catalysts for selective catalytic reduction (SCR) of NO with NH₃. A series of Sm_xMn_0.3−xTi catalysts (x = 0, 0.1, 0.15, 0.2, and 0.3) were prepared by co-precipitation. Activity tests indicated that the Sm_0.15Mn_0.15Ti catalyst showed superior performances, with a NO conversion of 100% and N₂ selectivity above 87% at 180–300°C. The characterizations showed that Sm doping suppressed the crystallization of TiO₂ and Mn₂O₃ phases and increased the specific surface area and acidity. In particular, the surface area increased from 152.2 m²·g⁻¹ for Mn_0.3Ti to 241.7 m²·g⁻¹ for Sm_0.15Mn_0.15Ti. These effects contributed to the high catalytic activity. The X-ray photoelectron spectroscopy (XPS) results indicated that the relative atomic ratios of Sm³⁺/Sm and O_β/O of Sm_0.15Mn_0.15Ti were 76.77at% and 44.11at%, respectively. The presence of Sm contributed to an increase in surface-absorbed oxygen (O_β) and a decrease in Mn⁴⁺ surface concentration, which improved the catalytic activity. In the results of hydrogen temperature-programmed reduction (H₂-TPR), the presence of Sm induced a higher reduction temperature and lower H₂ consumption (0.3 mmol·g⁻¹) for the Sm_0.15Mn_0.15Ti catalyst compared to the Mn_0.3Ti catalyst. The decrease in Mn⁴⁺ weakened the redox property of the catalysts and increased the N₂ selectivity by suppressing N₂O formation from NH₃ oxidation and the nonselective catalytic reduction reaction. The in situ diffuse reflectance infrared Fourier transform spectra (DRIFTs) revealed that NH₃-SCR of NO over the Sm_0.15Mn_0.15Ti catalyst mainly followed the Eley–Rideal mechanism. Sm doping increased surface-absorbed oxygen and weakened the redox property to improve the NO conversion and N₂ selectivity of the Sm_0.15Mn_0.15Ti catalyst.
- manganese oxides;
- nitric oxide;
- nitrous oxide;
- samarium;
- selective catalytic reduction;
- nitrogen selectivity

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钐对Sm_xMn_0.3−xTi催化剂NH₃选择性催化还原NO_x过程中N₂选择性的影响

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中文摘要

Effect of samarium on the N₂ selectivity of Sm_xMn_0.3−xTi catalysts during selective catalytic reduction of NO_x with NH₃

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