Mikalai A. Artsiusheuski, Jiawei Guo, Ambarish R. Kulkarni*, Jeroen A. van Bokhoven* and Vitaly L. Sushkevich*,
{"title":"铜(I)丝光沸石上短链烷烃低温非氧化脱氢的化学环反应","authors":"Mikalai A. Artsiusheuski, Jiawei Guo, Ambarish R. Kulkarni*, Jeroen A. van Bokhoven* and Vitaly L. Sushkevich*, ","doi":"10.1021/jacs.5c0422910.1021/jacs.5c04229","DOIUrl":null,"url":null,"abstract":"<p >We report selective low-temperature non-oxidative dehydrogenation of ethane and propane to ethylene and propylene via chemical looping using copper(I)-containing mordenite as active material. Combining Cu K-edge X-ray absorption spectroscopy, in situ infrared spectroscopy (FTIR), H/D kinetic isotope effect measurements, and density functional theory calculations, we show that the active sites for the dehydrogenation reaction are copper(I) cations hosted in zeolite framework, and the rate-limiting step is activation of the first C–H bond of alkane. The stoichiometric reaction between the gas-phase alkane and copper(I) cationic site results in the formation of a stable copper(I)-alkene π-complex and gaseous hydrogen. Complete saturation of copper(I) sites with alkenes can be attained at 573 K with a selectivity close to 100%. The strong binding of alkenes to copper(I) sites promotes the dehydrogenation reaction, enabling the yield of alkene more than 100 times greater than the gas-phase thermodynamic limit. Copper(I)-alkene complexes can be decomposed in a separate step by contact with water at near-ambient temperature, releasing alkenes into the gas phase, and the material can be regenerated without detectable loss of activity.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"147 18","pages":"15880–15889 15880–15889"},"PeriodicalIF":15.6000,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Low-Temperature Nonoxidative Dehydrogenation of Short-Chain Alkanes over Copper(I) Mordenite via Chemical Looping\",\"authors\":\"Mikalai A. Artsiusheuski, Jiawei Guo, Ambarish R. Kulkarni*, Jeroen A. van Bokhoven* and Vitaly L. Sushkevich*, \",\"doi\":\"10.1021/jacs.5c0422910.1021/jacs.5c04229\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >We report selective low-temperature non-oxidative dehydrogenation of ethane and propane to ethylene and propylene via chemical looping using copper(I)-containing mordenite as active material. Combining Cu K-edge X-ray absorption spectroscopy, in situ infrared spectroscopy (FTIR), H/D kinetic isotope effect measurements, and density functional theory calculations, we show that the active sites for the dehydrogenation reaction are copper(I) cations hosted in zeolite framework, and the rate-limiting step is activation of the first C–H bond of alkane. The stoichiometric reaction between the gas-phase alkane and copper(I) cationic site results in the formation of a stable copper(I)-alkene π-complex and gaseous hydrogen. Complete saturation of copper(I) sites with alkenes can be attained at 573 K with a selectivity close to 100%. The strong binding of alkenes to copper(I) sites promotes the dehydrogenation reaction, enabling the yield of alkene more than 100 times greater than the gas-phase thermodynamic limit. Copper(I)-alkene complexes can be decomposed in a separate step by contact with water at near-ambient temperature, releasing alkenes into the gas phase, and the material can be regenerated without detectable loss of activity.</p>\",\"PeriodicalId\":49,\"journal\":{\"name\":\"Journal of the American Chemical Society\",\"volume\":\"147 18\",\"pages\":\"15880–15889 15880–15889\"},\"PeriodicalIF\":15.6000,\"publicationDate\":\"2025-04-24\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of the American Chemical Society\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/jacs.5c04229\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of the American Chemical Society","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/jacs.5c04229","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Low-Temperature Nonoxidative Dehydrogenation of Short-Chain Alkanes over Copper(I) Mordenite via Chemical Looping
We report selective low-temperature non-oxidative dehydrogenation of ethane and propane to ethylene and propylene via chemical looping using copper(I)-containing mordenite as active material. Combining Cu K-edge X-ray absorption spectroscopy, in situ infrared spectroscopy (FTIR), H/D kinetic isotope effect measurements, and density functional theory calculations, we show that the active sites for the dehydrogenation reaction are copper(I) cations hosted in zeolite framework, and the rate-limiting step is activation of the first C–H bond of alkane. The stoichiometric reaction between the gas-phase alkane and copper(I) cationic site results in the formation of a stable copper(I)-alkene π-complex and gaseous hydrogen. Complete saturation of copper(I) sites with alkenes can be attained at 573 K with a selectivity close to 100%. The strong binding of alkenes to copper(I) sites promotes the dehydrogenation reaction, enabling the yield of alkene more than 100 times greater than the gas-phase thermodynamic limit. Copper(I)-alkene complexes can be decomposed in a separate step by contact with water at near-ambient temperature, releasing alkenes into the gas phase, and the material can be regenerated without detectable loss of activity.
期刊介绍:
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