{"title":"在 MnCeOx/HY 催化剂上促进金属氧化物与沸石的电子相互作用,以提高氮氧化物还原能力","authors":"Yonglong Li, Guobo Li, Hao Li, Wenming Liu, Jian Ji, Shengyong Lu, Zhenguo Li, Honggen Peng","doi":"10.1016/j.apcatb.2024.124535","DOIUrl":null,"url":null,"abstract":"The MnO-CeO metal oxides are considered as promising alternative catalysts for selective catalytic reduction with NH (NH-SCR) to remove NO due to its excellent low temperature performance. However, their strong oxidative ability can lead to NH over-oxidation, narrowing the active temperature range and reducing N selectivity. Moreover, their weak surface acidity hampers medium to high-temperature activity and alkali metal resistance. Hence, in this study, MnCeO metal oxides were coupled with HY zeolite to create MnCeO/HY, demonstrating excellent NH-SCR performance. The high dispersion of metal oxides on the zeolite surface and their close integration promoted strong electron interaction, effectively reducing oxygen vacancies and surface adsorbed oxygen concentrations. Consequently, the oxidative ability of active metal oxides was appropriately weakened, suppressing undesirable side reactions. MnCeO/HY also notably suppressed NO adsorption and nitrate formation, promoting the catalytic reaction solely through the E-R mechanism and enhancing N selectivity. The abundant strong acid sites on the zeolite surface facilitates NH adsorption at moderate to high temperatures, notably expanding the active temperature window. Furthermore, the acid sites of HY zeolite serve as sacrificial sites, preferentially reacting with alkali metals, thus exhibiting excellent resistance to alkali metal poisoning on MnCeO/HY. Combining with the DFT results, the structure-activity relationships in this study also reveal the importance of the effective synergy between acid sites and redox sites for optimal catalytic performance, offering valuable insights into the development of highly active and alkali-resistant denitrification catalysts.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":"59 1","pages":""},"PeriodicalIF":0.0000,"publicationDate":"2024-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Promoting metal oxides–zeolite electron interaction on MnCeOx/HY catalyst for boosting nitrogen oxides reduction\",\"authors\":\"Yonglong Li, Guobo Li, Hao Li, Wenming Liu, Jian Ji, Shengyong Lu, Zhenguo Li, Honggen Peng\",\"doi\":\"10.1016/j.apcatb.2024.124535\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"The MnO-CeO metal oxides are considered as promising alternative catalysts for selective catalytic reduction with NH (NH-SCR) to remove NO due to its excellent low temperature performance. However, their strong oxidative ability can lead to NH over-oxidation, narrowing the active temperature range and reducing N selectivity. Moreover, their weak surface acidity hampers medium to high-temperature activity and alkali metal resistance. Hence, in this study, MnCeO metal oxides were coupled with HY zeolite to create MnCeO/HY, demonstrating excellent NH-SCR performance. The high dispersion of metal oxides on the zeolite surface and their close integration promoted strong electron interaction, effectively reducing oxygen vacancies and surface adsorbed oxygen concentrations. Consequently, the oxidative ability of active metal oxides was appropriately weakened, suppressing undesirable side reactions. MnCeO/HY also notably suppressed NO adsorption and nitrate formation, promoting the catalytic reaction solely through the E-R mechanism and enhancing N selectivity. The abundant strong acid sites on the zeolite surface facilitates NH adsorption at moderate to high temperatures, notably expanding the active temperature window. Furthermore, the acid sites of HY zeolite serve as sacrificial sites, preferentially reacting with alkali metals, thus exhibiting excellent resistance to alkali metal poisoning on MnCeO/HY. Combining with the DFT results, the structure-activity relationships in this study also reveal the importance of the effective synergy between acid sites and redox sites for optimal catalytic performance, offering valuable insights into the development of highly active and alkali-resistant denitrification catalysts.\",\"PeriodicalId\":516528,\"journal\":{\"name\":\"Applied Catalysis B: Environment and Energy\",\"volume\":\"59 1\",\"pages\":\"\"},\"PeriodicalIF\":0.0000,\"publicationDate\":\"2024-08-26\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Applied Catalysis B: Environment and Energy\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.1016/j.apcatb.2024.124535\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Applied Catalysis B: Environment and Energy","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1016/j.apcatb.2024.124535","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
引用次数: 0
摘要
由于 MnO-CeO 金属氧化物具有出色的低温性能,因此被认为是 NH 选择性催化还原(NH-SCR)去除 NO 的理想替代催化剂。然而,它们的强氧化能力会导致 NH 过度氧化,从而缩小活性温度范围并降低 N 的选择性。此外,它们的弱表面酸性也会影响中高温活性和耐碱金属性。因此,在本研究中,将 MnCeO 金属氧化物与 HY 沸石耦合,生成了 MnCeO/HY,显示出优异的 NH-SCR 性能。金属氧化物在沸石表面的高度分散和紧密结合促进了强烈的电子相互作用,有效降低了氧空位和表面吸附氧浓度。因此,活性金属氧化物的氧化能力被适当削弱,抑制了不良的副反应。MnCeO/HY 还显著抑制了 NO 的吸附和硝酸盐的形成,促进了仅通过 E-R 机制进行的催化反应,提高了 N 的选择性。沸石表面丰富的强酸位点促进了 NH 在中高温下的吸附,显著扩大了活性温度窗口。此外,HY 沸石的酸性位点可作为牺牲位点,优先与碱金属发生反应,从而在 MnCeO/HY 上表现出优异的抗碱金属中毒能力。结合 DFT 结果,本研究中的结构-活性关系还揭示了酸性位点和氧化还原位点之间的有效协同作用对实现最佳催化性能的重要性,为开发高活性、耐碱的脱硝催化剂提供了宝贵的启示。
Promoting metal oxides–zeolite electron interaction on MnCeOx/HY catalyst for boosting nitrogen oxides reduction
The MnO-CeO metal oxides are considered as promising alternative catalysts for selective catalytic reduction with NH (NH-SCR) to remove NO due to its excellent low temperature performance. However, their strong oxidative ability can lead to NH over-oxidation, narrowing the active temperature range and reducing N selectivity. Moreover, their weak surface acidity hampers medium to high-temperature activity and alkali metal resistance. Hence, in this study, MnCeO metal oxides were coupled with HY zeolite to create MnCeO/HY, demonstrating excellent NH-SCR performance. The high dispersion of metal oxides on the zeolite surface and their close integration promoted strong electron interaction, effectively reducing oxygen vacancies and surface adsorbed oxygen concentrations. Consequently, the oxidative ability of active metal oxides was appropriately weakened, suppressing undesirable side reactions. MnCeO/HY also notably suppressed NO adsorption and nitrate formation, promoting the catalytic reaction solely through the E-R mechanism and enhancing N selectivity. The abundant strong acid sites on the zeolite surface facilitates NH adsorption at moderate to high temperatures, notably expanding the active temperature window. Furthermore, the acid sites of HY zeolite serve as sacrificial sites, preferentially reacting with alkali metals, thus exhibiting excellent resistance to alkali metal poisoning on MnCeO/HY. Combining with the DFT results, the structure-activity relationships in this study also reveal the importance of the effective synergy between acid sites and redox sites for optimal catalytic performance, offering valuable insights into the development of highly active and alkali-resistant denitrification catalysts.