{"title":"增强用于氮氧化物 NH3-SCR 的 Ce-Mn Oxide 改性 Cu-SSZ-39 催化剂的低温活性和水热稳定性","authors":"Ahui Tang, Fuzhen Yang, Ying Xin, Xiaoli Zhu, Long Yu, Shuai Liu, Dongxu Han, Junxiu Jia, Yaning Lu, Zhenguo Li, Zhaoliang Zhang","doi":"10.3390/catal14010010","DOIUrl":null,"url":null,"abstract":"Cu-SSZ-39 zeolite with an AEI structure exhibits excellent hydrothermal stability and can be a potential alternative to Cu-SSZ-13 zeolite SCR catalysts for NOx removal in diesel vehicles. However, the inferior low-temperature performance of Cu-SSZ-39 leads to substantial NOx emissions during the cold-start period, impeding its practical application. In this study, Ce-Mn oxide-modified Cu-SSZ-39 catalysts (CeMnOx/Cu-SSZ-39) and references (CeO2/Cu-SSZ-39 and MnOx/Cu-SSZ-39) were prepared by the ion-exchange of Cu ions followed by impregnation of the oxide precursors, with the aim of enhancing the NH3-SCR performance at low temperatures. The modified catalysts exhibited improved low-temperature activity and hydrothermal stability compared to the unmodified counterpart. In particular, CeMnOx/Cu-SSZ-39 showed the highest activity among the three catalysts and achieved NOx conversions above 90% within the temperature range of 180 °C to 600 °C, even after undergoing hydrothermal aging at 800 °C. Experimental results indicated that the synergistic effect between Ce and Mn in CeMnOx improves the redox properties and acidity of the catalyst due to the presence of Ce3+, Mn4+, and abundant adsorbed oxygen species, which facilitate low-temperature SCR reactions. Furthermore, the interaction of CeMnOx with Cu-SSZ-39 stabilizes the zeolite framework and hinders the agglomeration of Cu species during the hydrothermal aging process, contributing to its exceptional hydrothermal stability. The kinetics and NO oxidation experiments demonstrated that CeMnOx provides access to fast SCR reaction pathways by oxidizing NO to NO2, resulting in a significant increase in low-temperature activity. This study provides novel guidelines for the design and preparation of Cu-SSZ-39 zeolite with outstanding SCR performance over a wide temperature range.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":"38 25","pages":""},"PeriodicalIF":3.8000,"publicationDate":"2023-12-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Enhanced Low-Temperature Activity and Hydrothermal Stability of Ce-Mn Oxide-Modified Cu-SSZ-39 Catalysts for NH3-SCR of NOx\",\"authors\":\"Ahui Tang, Fuzhen Yang, Ying Xin, Xiaoli Zhu, Long Yu, Shuai Liu, Dongxu Han, Junxiu Jia, Yaning Lu, Zhenguo Li, Zhaoliang Zhang\",\"doi\":\"10.3390/catal14010010\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Cu-SSZ-39 zeolite with an AEI structure exhibits excellent hydrothermal stability and can be a potential alternative to Cu-SSZ-13 zeolite SCR catalysts for NOx removal in diesel vehicles. However, the inferior low-temperature performance of Cu-SSZ-39 leads to substantial NOx emissions during the cold-start period, impeding its practical application. In this study, Ce-Mn oxide-modified Cu-SSZ-39 catalysts (CeMnOx/Cu-SSZ-39) and references (CeO2/Cu-SSZ-39 and MnOx/Cu-SSZ-39) were prepared by the ion-exchange of Cu ions followed by impregnation of the oxide precursors, with the aim of enhancing the NH3-SCR performance at low temperatures. The modified catalysts exhibited improved low-temperature activity and hydrothermal stability compared to the unmodified counterpart. In particular, CeMnOx/Cu-SSZ-39 showed the highest activity among the three catalysts and achieved NOx conversions above 90% within the temperature range of 180 °C to 600 °C, even after undergoing hydrothermal aging at 800 °C. Experimental results indicated that the synergistic effect between Ce and Mn in CeMnOx improves the redox properties and acidity of the catalyst due to the presence of Ce3+, Mn4+, and abundant adsorbed oxygen species, which facilitate low-temperature SCR reactions. Furthermore, the interaction of CeMnOx with Cu-SSZ-39 stabilizes the zeolite framework and hinders the agglomeration of Cu species during the hydrothermal aging process, contributing to its exceptional hydrothermal stability. The kinetics and NO oxidation experiments demonstrated that CeMnOx provides access to fast SCR reaction pathways by oxidizing NO to NO2, resulting in a significant increase in low-temperature activity. This study provides novel guidelines for the design and preparation of Cu-SSZ-39 zeolite with outstanding SCR performance over a wide temperature range.\",\"PeriodicalId\":9794,\"journal\":{\"name\":\"Catalysts\",\"volume\":\"38 25\",\"pages\":\"\"},\"PeriodicalIF\":3.8000,\"publicationDate\":\"2023-12-21\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Catalysts\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.3390/catal14010010\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Catalysts","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.3390/catal14010010","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
摘要
具有 AEI 结构的 Cu-SSZ-39 沸石具有出色的水热稳定性,可以替代 Cu-SSZ-13 沸石 SCR 催化剂,用于去除柴油车中的氮氧化物。然而,Cu-SSZ-39 的低温性能较差,导致其在冷启动期间排放大量氮氧化物,阻碍了其实际应用。本研究通过离子交换铜离子,然后浸渍氧化物前驱体,制备了铈锰氧化物改性的 Cu-SSZ-39 催化剂(CeMnOx/Cu-SSZ-39)和参照物(CeO2/Cu-SSZ-39 和 MnOx/Cu-SSZ-39),旨在提高低温下的 NH3-SCR 性能。与未改性的催化剂相比,改性催化剂具有更高的低温活性和水热稳定性。其中,CeMnOx/Cu-SSZ-39 在三种催化剂中表现出最高的活性,在 180 °C 至 600 °C 的温度范围内,即使经过 800 °C 的水热老化,其氮氧化物转化率也能达到 90% 以上。实验结果表明,CeMnOx 中 Ce 和 Mn 的协同作用改善了催化剂的氧化还原特性和酸性,这是因为 Ce3+、Mn4+ 和丰富的吸附氧物种的存在促进了低温 SCR 反应的进行。此外,CeMnOx 与 Cu-SSZ-39 的相互作用稳定了沸石框架,阻碍了水热老化过程中 Cu 物种的团聚,使其具有优异的水热稳定性。动力学和 NO 氧化实验表明,CeMnOx 通过将 NO 氧化为 NO2,提供了快速 SCR 反应途径,从而显著提高了低温活性。这项研究为设计和制备在宽温度范围内具有出色 SCR 性能的 Cu-SSZ-39 沸石提供了新的指导。
Enhanced Low-Temperature Activity and Hydrothermal Stability of Ce-Mn Oxide-Modified Cu-SSZ-39 Catalysts for NH3-SCR of NOx
Cu-SSZ-39 zeolite with an AEI structure exhibits excellent hydrothermal stability and can be a potential alternative to Cu-SSZ-13 zeolite SCR catalysts for NOx removal in diesel vehicles. However, the inferior low-temperature performance of Cu-SSZ-39 leads to substantial NOx emissions during the cold-start period, impeding its practical application. In this study, Ce-Mn oxide-modified Cu-SSZ-39 catalysts (CeMnOx/Cu-SSZ-39) and references (CeO2/Cu-SSZ-39 and MnOx/Cu-SSZ-39) were prepared by the ion-exchange of Cu ions followed by impregnation of the oxide precursors, with the aim of enhancing the NH3-SCR performance at low temperatures. The modified catalysts exhibited improved low-temperature activity and hydrothermal stability compared to the unmodified counterpart. In particular, CeMnOx/Cu-SSZ-39 showed the highest activity among the three catalysts and achieved NOx conversions above 90% within the temperature range of 180 °C to 600 °C, even after undergoing hydrothermal aging at 800 °C. Experimental results indicated that the synergistic effect between Ce and Mn in CeMnOx improves the redox properties and acidity of the catalyst due to the presence of Ce3+, Mn4+, and abundant adsorbed oxygen species, which facilitate low-temperature SCR reactions. Furthermore, the interaction of CeMnOx with Cu-SSZ-39 stabilizes the zeolite framework and hinders the agglomeration of Cu species during the hydrothermal aging process, contributing to its exceptional hydrothermal stability. The kinetics and NO oxidation experiments demonstrated that CeMnOx provides access to fast SCR reaction pathways by oxidizing NO to NO2, resulting in a significant increase in low-temperature activity. This study provides novel guidelines for the design and preparation of Cu-SSZ-39 zeolite with outstanding SCR performance over a wide temperature range.
期刊介绍:
Catalysts (ISSN 2073-4344) is an international open access journal of catalysts and catalyzed reactions. Catalysts publishes reviews, regular research papers (articles) and short communications. Our aim is to encourage scientists to publish their experimental and theoretical results in as much detail as possible. Therefore, there is no restriction on the length of the papers. The full experimental details must be provided so that the results can be reproduced.