Geng Lijun, Jia Yuhan, Zhang Hanyu, Cui Chaonan, Luo Zhixun
Beijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P. R. China.
School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing, 100049, P. R. China.
Chemphyschem. 2022 Sep 5;23(17):e202200288. doi: 10.1002/cphc.202200288. Epub 2022 Jun 29.
We have performed a study on the accommodation of nitrogen doping toward superatomic states of transition metal clusters. By reacting cobalt clusters with N in the presence of plasma radiation, a large number of odd-nitrogen clusters were observed, typically Co N (m=1-5) and Co N (m=1-6) series, showing N≡N bond cleavage in the mild plasma atmosphere. Interestingly, the Co N , Co N , and Co N clusters exhibit prominent mass abundances. First-principles calculation results elucidate the stability of the diverse cobalt nitride clusters and find unique stability of Co N with a swallow-kite structure of which four coordinated N molecules causes a significantly enlarged HOMO-LUMO gap, while the single N atom doping gives rise to superatomic states of 1S 1P ||1D . We reveal an efficient dinitrogen activation strategy by reacting multiple N molecules with cobalt clusters under a plasma atmosphere.
我们对氮掺杂向过渡金属簇超原子态的适配性进行了一项研究。通过在等离子体辐射存在下使钴簇与氮反应，观察到大量奇数氮簇，典型的是CoₘNₙ（m = 1 - 5）和CoₘNₙ（m = 1 - 6）系列，表明在温和的等离子体气氛中N≡N键发生了断裂。有趣的是，Co₃N₄、Co₄N₅和Co₅N₆簇表现出显著的质量丰度。第一性原理计算结果阐明了各种氮化钴簇的稳定性，并发现具有燕尾风筝结构的Co₄N₅具有独特的稳定性，其中四个配位的N分子导致显著扩大的HOMO - LUMO能隙，而单个N原子掺杂则产生1S²1P⁶||1D¹⁰的超原子态。我们揭示了一种在等离子体气氛下通过使多个N分子与钴簇反应的高效双氮活化策略。
