脂肪酸在CoPc/MWCNT上脱碳制烯烃:活性位点和反应机理

IF 5.3 3区 工程技术 Q2 ENERGY & FUELS
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*, 
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引用次数: 0

摘要

生物质衍生脂肪酸的脱碳为高价值长链烯烃提供了一条绿色和可持续的途径。氮掺杂碳负载钴(Co-NC)催化剂由于其优异的催化活性和成本效益,已成为脂肪酸脱羰化的有希望的候选者。然而,确定活性位点和阐明反应机制仍然是一个重大挑战。为了解决这些问题,我们通过在多壁碳纳米管(MWCNTs)上浸渍钴酞菁,然后进行热解,开发了富含Co单原子的催化剂(CoPc/MWCNT及其热解衍生物CoPc/MWCNT- x)。这些催化剂表现出较高的硬脂酸脱碳活性,将十六烯的产率从12.9%提高到47.4%,烯烃与烷烃的比值高达4.3。综合表征和对照实验表明,Co单原子位点是活性位点,而共存的Co/CoO纳米颗粒的活性可以忽略不计,没有协同效应。原位漂移显示羰基在Co单原子上的吸附,DFT计算证实了通过C-O键裂解产生定向烯烃。本研究建立了高性能脱碳催化剂的简易合成策略,明确了关键的单原子活性位点,同时对脂肪酸转化机制有了深入的了解。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Decarbonylation of Fatty Acids to Alkenes over CoPc/MWCNT: Active Sites and Reaction Mechanism

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.

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来源期刊
Energy & Fuels
Energy & Fuels 工程技术-工程:化工
CiteScore
9.20
自引率
13.20%
发文量
1101
审稿时长
2.1 months
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.
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