高分散还原态Pt基催化剂的制备及其NO氧化的催化性能

doi:10.3866/PKU.WHXB202005009

物理化学学报 >> 2022, Vol. 38 >> Issue (4): 2005009.doi: 10.3866/PKU.WHXB202005009

高分散还原态Pt基催化剂的制备及其NO氧化的催化性能

丁心湄¹, 梁艳丽², 张海龙³, 赵明¹^,*(), 王健礼¹^,*(), 陈耀强¹

¹ 四川大学化学学院，绿色化学与技术教育部重点实验室，成都 610064
² 四川大学高分子材料工程国家重点实验室，成都 610064
³ 厦门大学化学与化学工程学院化学系，福建厦门 361005

收稿日期:2020-05-05 录用日期:2020-06-16 发布日期:2020-06-19
通讯作者: 赵明,王健礼 E-mail:zhaoming@scu.edu.cn;wangjianli@scu.edu.cn
基金资助:
国家自然科学基金(21972098)

Preparation of Reduced Pt-Based Catalysts with High Dispersion and Their Catalytic Performances for NO Oxidation

Xinmei Ding¹, Yanli Liang², Hailong Zhang³, Ming Zhao¹^,*(), Jianli Wang¹^,*(), Yaoqiang Chen¹

¹ Key Laboratory of Green Chemistry & Technology of the Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, China
² State Key Laboratory of Polymer Materials Engineering of China (Sichuan University), Polymer Research Institute of Sichuan University, Chengdu 610064, China
³ Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian Province, China

Received:2020-05-05 Accepted:2020-06-16 Published:2020-06-19
Contact: Ming Zhao,Jianli Wang E-mail:zhaoming@scu.edu.cn;wangjianli@scu.edu.cn
About author:Email: wangjianli@scu.edu.cn (J.W.); Tel./Fax: +86-28-85418451 (J.W.)
Email: zhaoming@scu.edu.cn (M.Z.)
Supported by:
the National Natural Science Foundation of China(21972098)

摘要/Abstract

摘要：

Pt⁰被认为是NO氧化的活性物种，而催化剂的制备方法对活性物种的含量起着决定性作用。本文采用非惰性气氛保护的改性醇还原-浸渍法(MARI)合成了高分散高Pt⁰含量的1% (w, 质量分数) Pt/SiO₂-Al₂O₃催化剂(MA-Pt/SA)。X射线粉末衍射(XRD)、CO-漫反射傅里叶变换红外吸收光谱(CO-DRIFTS)和透射电镜(TEM)表征证实在550 ℃焙烧3 h后催化剂的Pt颗粒仅有3.8 nm。同时，X射线光电子能谱(XPS)和H₂-程序升温还原(H₂-TPR)结果表明催化剂具有高Pt⁰含量(60.3%)。模拟柴油车尾气气氛进行活性测试，并与传统浸渍法制备的1% (w) Pt/SiO₂-Al₂O₃催化剂(C-Pt/SA)对比，结果显示MA-Pt/SA具有优异的催化氧化性能，其NO最大转化率高达74%，比C-Pt/SA的NO转化率高了23%。经670 ℃高温老化15 h后，老化的MA-Pt/SA的NO转化率仍然高达69%。此外NO + O₂共吸附原位漫反射傅里叶变换红外吸收光谱(in situ DRIFTS of NO + O₂ co-adsorption)表明高的Pt分散度和高Pt⁰含量能够促进中间物种桥式硝酸盐的生成及分解，进而导致了优异的NO氧化活性。最后，利用同样方法将Pt的负载量降低至0.5% (w)制备催化剂，NO转化率仍达64%。这种制备方法能够获得低贵金属高性能的Pt基催化剂。

关键词: 柴油车氧化催化剂, 改性的醇还原-浸渍法, NO氧化, 高性能Pt基催化剂, 低Pt含量

Abstract:

Pt-based catalysts are widely used in diesel oxidation catalyst (DOC) units, primarily to oxidize the harmful HC, CO, and NO emissions. Notably, NO₂ produced from NO oxidation is beneficial for low-temperature activity in NH₃-SCR and promotes soot oxidation in diesel particulate filters (DPF). Thus, the conversion of NO is an important parameter for determining the performance of DOCs. Considering the increasingly stringent emission regulations and the economic effectiveness, preparation of low-cost and highly active Pt-based catalysts is indispensable. Generally, the Pt⁰ content is crucial as it is an active component of DOCs. Small Pt size is beneficial for improving the catalytic activity. In this study, we applied a modified alcohol reduction-impregnation (MARI) method to synthesize highly active 1% (w, mass fraction) Pt/SiO₂-Al₂O₃ (denoted as MA-Pt/SA) catalyst. Meanwhile, using the conventional impregnation method, we prepared the Pt/SiO₂-Al₂O₃ catalyst with the same Pt loading (denoted as C-Pt/SA) as a reference sample. X-ray photoelectron spectroscopy (XPS) and hydrogen temperature program reduction (H₂-TPR) analyses proved that the MARI method could produce Pt catalysts with higher Pt⁰ content. Pt⁰ content in MA-Pt/SA was ~60.3% while that in C-Pt/SA was only ~23.1%. X-ray diffraction (XRD), CO-diffuse reflectance infrared Fourier transform spectroscopy (CO-DRIFTS), and transmission electron microscopy (TEM) characterization confirmed that the Pt particle size is much smaller over MA-Pt/SA as compared to that over C-Pt/SA. Performance evaluation of MA-Pt/SA and C-Pt/SA was conducted in a simulated diesel atmosphere. The results showed that the maximum NO conversion into NO₂ over MA-Pt/SA is 74% and 68% in the absence and presence of H₂O, respectively, which were much higher than those over C-Pt/SA (42% and 51% NO conversion with and without H₂O, respectively). Furthermore, the temperature for 30% NO conversion over MA-Pt/SA (218 ℃) markedly decreased as compared to that over C-Pt/SA (248 ℃), indicating the excellent low temperature activity. After the aging treatment with reaction gas at high temperatures, aged MA-Pt/SA maintained 69% NO conversion while aged C-Pt/SA showed only 41% NO conversion. In addition, in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) of NO + O₂ co-adsorption suggested that higher Pt dispersion and higher Pt⁰ content over MA-Pt/SA could facilitate the formation of bridging nitrates as intermediate species in NO oxidation at lower temperatures and could also facilitate their rapid decomposition (or desorption) at higher temperatures, thus imparting a high catalytic activity. Furthermore, a decrease in the Pt loading to 0.5% (w) resulted in a maximum NO conversion of 64% via the MARI method, suggesting a higher catalytic activity compared to that of C-Pt/SA with 1% (w) Pt loading. This work provides a method to prepare highly active Pt-based catalysts with low noble loading.

Key words: DOC, Modified alcohol reduction-impregnation method, NO oxidation, High-performing Pt catalyst, Low Pt loading

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丁心湄, 梁艳丽, 张海龙, 赵明, 王健礼, 陈耀强. 高分散还原态Pt基催化剂的制备及其NO氧化的催化性能[J]. 物理化学学报, 2022, 38(4), 2005009. doi: 10.3866/PKU.WHXB202005009

Xinmei Ding, Yanli Liang, Hailong Zhang, Ming Zhao, Jianli Wang, Yaoqiang Chen. Preparation of Reduced Pt-Based Catalysts with High Dispersion and Their Catalytic Performances for NO Oxidation[J]. Acta Phys. -Chim. Sin. 2022, 38(4), 2005009. doi: 10.3866/PKU.WHXB202005009

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202005009

https://www.whxb.pku.edu.cn/CN/Y2022/V38/I4/2005009

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Sample	Relative area ratio (%)
Sample	Pt⁰	Pt²⁺	Pt⁴⁺
C-Pt/SA-f	23.1	41.9	35.0
MA-Pt/SA-f	60.3	17.8	21.9

Catalyst	Pt size (nm)	Pt dispersion^c (%)	T₅₀/T₉₀ (℃)		NO Max conversion (%)	Temperature (℃) ^d	TOF (s^-1)
Catalyst	Pt size (nm)	Pt dispersion^c (%)	CO	HC	NO Max conversion (%)	Temperature (℃) ^d	TOF (s^-1)
C-Pt/SA-f	27.5^a/7.8 ^b	14.5	221/236	229/237	51	248	0.06^e
MA-Pt/SA-f	8.2^a/3.8 ^b	29.6	197/209	208/212	74	218	0.22^e
C-Pt/SA-a	34.1^a/9.2 ^b	12.3	233/248	245/253	41	278	0.03^f
MA-Pt/SA-a	9.5^a/5.1 ^b	22.0	204/217	215/222	69	226	0.21^f

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高分散还原态Pt基催化剂的制备及其NO氧化的催化性能

Preparation of Reduced Pt-Based Catalysts with High Dispersion and Their Catalytic Performances for NO Oxidation

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