{"title":"揭示Al2O3@Cu-Ce核壳纳米纤维催化剂对羰基硫化物低温水解的卓越催化性能","authors":"Xin Song, Lina Sun, Panting Gao, Rongji Cui, Weiliang Han, Xiaosheng Huang, Zhicheng Tang","doi":"10.1002/ece2.70011","DOIUrl":null,"url":null,"abstract":"<p>Carbonyl sulfide represents a significant organic sulfur impurity in furnace gas, and its removal can enhance the economic value of furnace gas. In this study, a series of Al-based core–shell nanofiber catalysts were synthesized and employed for the catalytic hydrolysis of COS. The Al<sub>2</sub>O<sub>3</sub>@Cu-Ce catalyst demonstrated a 100% COS conversion efficiency at a gas hourly space velocity of 15 000 h<sup>−1</sup> at 70°C. The interaction of Cu and Ce can enhance their dispersion and facilitate the formation of micropores. The formation of Cu<sub>2</sub>Al<sub>4</sub>O<sub>7</sub> and CeAlO<sub>3</sub> resulted in a reduction in the number of micropores and effective active components on the catalyst surface. The primary catalytic roles were played by Cu<sup>2+</sup> and Ce<sup>3+</sup>. The high content of adsorbed state oxygen O<sub>β</sub> and suitable water resistance resulted in enhanced hydrolysis performance. The Al<sub>2</sub>O<sub>3</sub> shell layer is capable of effectively protecting the Cu and Ce components from being covered and consumed, thereby prolonging the lifetime of the catalyst. The addition of Cu resulted in alterations to both the weakly and moderately basic sites, whereas the addition of Ce primarily affected the weakly basic sites. The formation of Cu-O-Ce increased the percentage of CuO in the Cu fraction, thereby enhancing the COS removal performance. There is a competitive adsorption relationship between COS and H<sub>2</sub>S on the CuO (002) surface. COS, H<sub>2</sub>O, and H<sub>2</sub>S compete for adsorption on the O<sub>v</sub>-CeO<sub>2</sub> (111) surface. O<sub>v</sub>-CeO<sub>2</sub> (111) promotes the dissociation of H<sub>2</sub>O and the generation of -SH groups. The hydrolysis process of COS occurs in steps on CuO (002) and O<sub>v</sub>-CeO<sub>2</sub> (111).</p>","PeriodicalId":100387,"journal":{"name":"EcoEnergy","volume":"3 3","pages":""},"PeriodicalIF":0.0000,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ece2.70011","citationCount":"0","resultStr":"{\"title\":\"Unveiling the Remarkable Catalytic Performance of Al2O3@Cu-Ce Core–Shell Nanofiber Catalyst for Carbonyl Sulfide Hydrolysis at Low Temperature\",\"authors\":\"Xin Song, Lina Sun, Panting Gao, Rongji Cui, Weiliang Han, Xiaosheng Huang, Zhicheng Tang\",\"doi\":\"10.1002/ece2.70011\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Carbonyl sulfide represents a significant organic sulfur impurity in furnace gas, and its removal can enhance the economic value of furnace gas. In this study, a series of Al-based core–shell nanofiber catalysts were synthesized and employed for the catalytic hydrolysis of COS. The Al<sub>2</sub>O<sub>3</sub>@Cu-Ce catalyst demonstrated a 100% COS conversion efficiency at a gas hourly space velocity of 15 000 h<sup>−1</sup> at 70°C. The interaction of Cu and Ce can enhance their dispersion and facilitate the formation of micropores. The formation of Cu<sub>2</sub>Al<sub>4</sub>O<sub>7</sub> and CeAlO<sub>3</sub> resulted in a reduction in the number of micropores and effective active components on the catalyst surface. The primary catalytic roles were played by Cu<sup>2+</sup> and Ce<sup>3+</sup>. The high content of adsorbed state oxygen O<sub>β</sub> and suitable water resistance resulted in enhanced hydrolysis performance. The Al<sub>2</sub>O<sub>3</sub> shell layer is capable of effectively protecting the Cu and Ce components from being covered and consumed, thereby prolonging the lifetime of the catalyst. The addition of Cu resulted in alterations to both the weakly and moderately basic sites, whereas the addition of Ce primarily affected the weakly basic sites. The formation of Cu-O-Ce increased the percentage of CuO in the Cu fraction, thereby enhancing the COS removal performance. There is a competitive adsorption relationship between COS and H<sub>2</sub>S on the CuO (002) surface. COS, H<sub>2</sub>O, and H<sub>2</sub>S compete for adsorption on the O<sub>v</sub>-CeO<sub>2</sub> (111) surface. O<sub>v</sub>-CeO<sub>2</sub> (111) promotes the dissociation of H<sub>2</sub>O and the generation of -SH groups. The hydrolysis process of COS occurs in steps on CuO (002) and O<sub>v</sub>-CeO<sub>2</sub> (111).</p>\",\"PeriodicalId\":100387,\"journal\":{\"name\":\"EcoEnergy\",\"volume\":\"3 3\",\"pages\":\"\"},\"PeriodicalIF\":0.0000,\"publicationDate\":\"2025-07-08\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ece2.70011\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"EcoEnergy\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/ece2.70011\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"EcoEnergy","FirstCategoryId":"1085","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/ece2.70011","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
羰基硫化物是炉气中重要的有机硫杂质,去除羰基硫化物可以提高炉气的经济价值。本研究合成了一系列al基核壳纳米纤维催化剂,并将其用于催化水解COS。Al2O3@Cu-Ce催化剂在70°C下,气体每小时空速为15,000 h−1时,其COS转化效率为100%。Cu和Ce的相互作用增强了它们的分散性,促进了微孔的形成。Cu2Al4O7和CeAlO3的形成导致催化剂表面微孔数量减少,有效活性成分减少。Cu2+和Ce3+起主要催化作用。高含量的吸附态氧Oβ和适宜的耐水性提高了水解性能。Al2O3壳层能够有效地保护Cu和Ce组分不被覆盖和消耗,从而延长催化剂的使用寿命。Cu的加入对弱碱性位点和中碱性位点都有影响,而Ce的加入主要影响弱碱性位点。Cu- o - ce的形成提高了Cu组分中CuO的百分比,从而提高了COS的去除性能。COS和H2S在CuO(002)表面存在竞争吸附关系。COS、H2O和H2S在Ov-CeO2(111)表面竞争吸附。Ov-CeO2(111)促进H2O的解离和-SH基团的生成。COS的水解过程在CuO(002)和Ov-CeO2(111)上分步进行。
Unveiling the Remarkable Catalytic Performance of Al2O3@Cu-Ce Core–Shell Nanofiber Catalyst for Carbonyl Sulfide Hydrolysis at Low Temperature
Carbonyl sulfide represents a significant organic sulfur impurity in furnace gas, and its removal can enhance the economic value of furnace gas. In this study, a series of Al-based core–shell nanofiber catalysts were synthesized and employed for the catalytic hydrolysis of COS. The Al2O3@Cu-Ce catalyst demonstrated a 100% COS conversion efficiency at a gas hourly space velocity of 15 000 h−1 at 70°C. The interaction of Cu and Ce can enhance their dispersion and facilitate the formation of micropores. The formation of Cu2Al4O7 and CeAlO3 resulted in a reduction in the number of micropores and effective active components on the catalyst surface. The primary catalytic roles were played by Cu2+ and Ce3+. The high content of adsorbed state oxygen Oβ and suitable water resistance resulted in enhanced hydrolysis performance. The Al2O3 shell layer is capable of effectively protecting the Cu and Ce components from being covered and consumed, thereby prolonging the lifetime of the catalyst. The addition of Cu resulted in alterations to both the weakly and moderately basic sites, whereas the addition of Ce primarily affected the weakly basic sites. The formation of Cu-O-Ce increased the percentage of CuO in the Cu fraction, thereby enhancing the COS removal performance. There is a competitive adsorption relationship between COS and H2S on the CuO (002) surface. COS, H2O, and H2S compete for adsorption on the Ov-CeO2 (111) surface. Ov-CeO2 (111) promotes the dissociation of H2O and the generation of -SH groups. The hydrolysis process of COS occurs in steps on CuO (002) and Ov-CeO2 (111).