Dissociative Adsorption of N2 onto Size-Selected Tin+ and TinO+ (n ≦ 16) toward Nitrogen Fixation
Dissociative Adsorption of N2 onto Size-Selected Tin+ and TinO+ (n ≦ 16) toward Nitrogen Fixation
复制标题
N2 解离吸附到尺寸选定的 Tin+ 和 TinO+ (n ≤ 16) 上以实现固氮
DOI：
10.1021/acs.jpca.1c03106
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发表时间：
2021
期刊：
影响因子：
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通讯作者：
Hideho Odaka
中科院分区：
文献类型：
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作者：
Masahiko Ichihashi;Tetsu Hanmura;Hideho Odaka
用串联质谱仪研究了钛簇离子及其氧化物在低碰撞能量0.5 eV下与分子氮的反应性。该簇可以吸附二氮并释放钛原子以消耗获得的多余能量。这说明n2的吸附能大到足以破坏钛团簇。而较小的团簇反应活性相对较低，测量的反应截面随着团簇尺寸的增大而增大，在较大的团簇上达到了Langevin截面的近三分之一。密度泛函理论计算表明，反应是放热进行的，分子氮是离解吸附在簇上的。结果表明，钛团簇的最高已占据分子轨道的能级对n2活化具有决定性的重要作用。
The reactivity of titanium cluster ions and their oxides with molecular dinitrogen was examined using a tandem-type mass spectrometer at a low collision energy of 0.5 eV. The clusters can adsorb dinitrogen and release a titanium atom to consume the obtained excess energy. This indicates that N2adsorption energy is large enough to break the titanium cluster. While the smaller clusters have relatively low reactivity, the measured reaction cross section increases with the cluster size and reaches nearly one-third of the Langevin cross section at the larger clusters. Density functional theory calculations indicate that the reaction proceeds exothermically and that molecular dinitrogen adsorbs on the clusters dissociatively. It is suggested that the energy levels of the highest occupied molecular orbitals of the titanium clusters are decisively important for N2activation.