摘要
Mass spectrometry was used to observe the reactions between Y−Co heteronuclear metal carbide cluster anions Y1-3CoC1,2− and N2 at room temperature. Y2CoC1,2− can produce Co ejection products, in which Y2CoC− also has N2 association products; YCoC2− and Y3CoC− only generate N2 association products, while YCoC− and Y3CoC2− are inert to N2. Detailed reaction pathways were obtained through density functional theory calculations, which reasonably explain the experimental phenomena. Co is superior to Y as the electrophilic reaction site in the clusters and is the preferential initial adsorption site for N2. Some crucial steps were identified, including N−N dissociation, CC−N formation, C−CN dissociation, and C−N formation. The energy barriers of these steps are closely related to the coordination mode of N/N2 and C/C2 in clusters. Two indicators, the N−N bond length and the Mayer bond order, were utilized to describe the activation degree of the N−N bond. Analyses on the density of states and the frontier molecular orbitals reveal the electronic structures of key intermediates for N−N dissociation. The reaction mechanisms of N2 activation on Y−Co carbide clusters obtained may lay a preliminary foundation for the further development of catalysts for nitrogen reduction reaction (NRR).
源语言 | 英语 |
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文章编号 | e202300978 |
期刊 | ChemCatChem |
卷 | 16 |
期 | 7 |
DOI | |
出版状态 | 已出版 - 8 4月 2024 |