Canyang Zhang, Guangtong Hai, Chao Chen, Yin Liang, Wei Zhao, Bolong Li*, Jianghao Wang, Zhenyu Zhang*, Huiping Ji, Kaige Wang, Reinout Meijboom and Jie Fu*,
{"title":"脂肪酸在CoPc/MWCNT上脱碳制烯烃:活性位点和反应机理","authors":"Canyang Zhang, Guangtong Hai, Chao Chen, Yin Liang, Wei Zhao, Bolong Li*, Jianghao Wang, Zhenyu Zhang*, Huiping Ji, Kaige Wang, Reinout Meijboom and Jie Fu*, ","doi":"10.1021/acs.energyfuels.5c03046","DOIUrl":null,"url":null,"abstract":"<p >The decarbonylation of biomass-derived fatty acids offers a green and sustainable route to high-value long-chain alkenes. Nitrogen-doped carbon-supported cobalt (Co-NC) catalysts have emerged as promising candidates for fatty acid decarbonylation, attributed to their exceptional catalytic activity and cost-effectiveness. However, identifying the active sites and elucidating the reaction mechanism remain significant challenges. To address these issues, we developed Co single-atom-rich catalysts (CoPc/MWCNT and pyrolyzed derivatives CoPc/MWCNT-X) via the impregnation of cobalt phthalocyanine onto multiwalled carbon nanotubes (MWCNTs), followed by pyrolysis. These catalysts exhibited a high stearic acid decarbonylation activity, increasing the heptadecene yield from 12.9 to 47.4%, with an alkene-to-alkane ratio of up to 4.3. Comprehensive characterization and control experiments conclusively demonstrated that Co single-atom sites serve as the active sites, while coexisting Co/CoO nanoparticles showed negligible activity and no synergistic effects. <i>In situ</i> DRIFTS revealed carbonyl group adsorption on Co single atoms, with DFT calculations confirming directional alkene production via C–O bond cleavage. This work establishes a facile synthetic strategy for high-performance decarbonylation catalysts and unambiguously identifies the critical single-atom active sites while enabling a profound understanding of fatty acid conversion mechanisms.</p>","PeriodicalId":35,"journal":{"name":"Energy & Fuels","volume":"39 32","pages":"15320–15329"},"PeriodicalIF":5.3000,"publicationDate":"2025-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Decarbonylation of Fatty Acids to Alkenes over CoPc/MWCNT: Active Sites and Reaction Mechanism\",\"authors\":\"Canyang Zhang, Guangtong Hai, Chao Chen, Yin Liang, Wei Zhao, Bolong Li*, Jianghao Wang, Zhenyu Zhang*, Huiping Ji, Kaige Wang, Reinout Meijboom and Jie Fu*, \",\"doi\":\"10.1021/acs.energyfuels.5c03046\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >The decarbonylation of biomass-derived fatty acids offers a green and sustainable route to high-value long-chain alkenes. Nitrogen-doped carbon-supported cobalt (Co-NC) catalysts have emerged as promising candidates for fatty acid decarbonylation, attributed to their exceptional catalytic activity and cost-effectiveness. However, identifying the active sites and elucidating the reaction mechanism remain significant challenges. To address these issues, we developed Co single-atom-rich catalysts (CoPc/MWCNT and pyrolyzed derivatives CoPc/MWCNT-X) via the impregnation of cobalt phthalocyanine onto multiwalled carbon nanotubes (MWCNTs), followed by pyrolysis. These catalysts exhibited a high stearic acid decarbonylation activity, increasing the heptadecene yield from 12.9 to 47.4%, with an alkene-to-alkane ratio of up to 4.3. Comprehensive characterization and control experiments conclusively demonstrated that Co single-atom sites serve as the active sites, while coexisting Co/CoO nanoparticles showed negligible activity and no synergistic effects. <i>In situ</i> DRIFTS revealed carbonyl group adsorption on Co single atoms, with DFT calculations confirming directional alkene production via C–O bond cleavage. This work establishes a facile synthetic strategy for high-performance decarbonylation catalysts and unambiguously identifies the critical single-atom active sites while enabling a profound understanding of fatty acid conversion mechanisms.</p>\",\"PeriodicalId\":35,\"journal\":{\"name\":\"Energy & Fuels\",\"volume\":\"39 32\",\"pages\":\"15320–15329\"},\"PeriodicalIF\":5.3000,\"publicationDate\":\"2025-07-31\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Energy & Fuels\",\"FirstCategoryId\":\"5\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.energyfuels.5c03046\",\"RegionNum\":3,\"RegionCategory\":\"工程技术\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"ENERGY & FUELS\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Energy & Fuels","FirstCategoryId":"5","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.energyfuels.5c03046","RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"ENERGY & FUELS","Score":null,"Total":0}
Decarbonylation of Fatty Acids to Alkenes over CoPc/MWCNT: Active Sites and Reaction Mechanism
The decarbonylation of biomass-derived fatty acids offers a green and sustainable route to high-value long-chain alkenes. Nitrogen-doped carbon-supported cobalt (Co-NC) catalysts have emerged as promising candidates for fatty acid decarbonylation, attributed to their exceptional catalytic activity and cost-effectiveness. However, identifying the active sites and elucidating the reaction mechanism remain significant challenges. To address these issues, we developed Co single-atom-rich catalysts (CoPc/MWCNT and pyrolyzed derivatives CoPc/MWCNT-X) via the impregnation of cobalt phthalocyanine onto multiwalled carbon nanotubes (MWCNTs), followed by pyrolysis. These catalysts exhibited a high stearic acid decarbonylation activity, increasing the heptadecene yield from 12.9 to 47.4%, with an alkene-to-alkane ratio of up to 4.3. Comprehensive characterization and control experiments conclusively demonstrated that Co single-atom sites serve as the active sites, while coexisting Co/CoO nanoparticles showed negligible activity and no synergistic effects. In situ DRIFTS revealed carbonyl group adsorption on Co single atoms, with DFT calculations confirming directional alkene production via C–O bond cleavage. This work establishes a facile synthetic strategy for high-performance decarbonylation catalysts and unambiguously identifies the critical single-atom active sites while enabling a profound understanding of fatty acid conversion mechanisms.
期刊介绍:
Energy & Fuels publishes reports of research in the technical area defined by the intersection of the disciplines of chemistry and chemical engineering and the application domain of non-nuclear energy and fuels. This includes research directed at the formation of, exploration for, and production of fossil fuels and biomass; the properties and structure or molecular composition of both raw fuels and refined products; the chemistry involved in the processing and utilization of fuels; fuel cells and their applications; and the analytical and instrumental techniques used in investigations of the foregoing areas.