Hirabayashi Shinichi, Ichihashi Masahiko
East Tokyo Laboratory , Genesis Research Institute, Inc. , 717-86 Futamata , Ichikawa , Chiba 272-0001 , Japan.
Cluster Research Laboratory, Toyota Technological Institute: in East Tokyo Laboratory , Genesis Research Institute, Inc. , 717-86 Futamata , Ichikawa , Chiba 272-0001 , Japan.
J Phys Chem A. 2018 May 31;122(21):4801-4807. doi: 10.1021/acs.jpca.8b03017. Epub 2018 May 21.
Reactions of copper oxide cluster cations, Cu O ( n = 3-7; m ≤ 5), with ammonia, NH, are studied at near thermal energies using a guided ion beam tandem mass spectrometer. The single-collision reactions of specific clusters such as CuO, CuO, CuO, CuO, and CuO give rise to the release of HO after NH adsorption efficiently and result in the formation of Cu O NH. These Cu O clusters commonly have Cu average oxidation numbers of 1.0-1.4. On the other hand, the formation of Cu O H, i.e., the release of HNO, is dominantly observed for CuO with a higher Cu oxidation number. Density functional theory calculations are performed for the reaction CuO + NH → CuONH + HO as a typical example of HO release. The calculations show that this reaction occurs almost thermoneutrally, consistent with the experimental observation. Further, our experimental studies indicate that the multiple-collision reactions of CuO and CuO with NH lead to the production of Cu and CuO, respectively. This suggests that the desirable NH oxidation to N and HO proceeds on these clusters.
使用导向离子束串联质谱仪在接近热能的条件下研究了氧化铜团簇阳离子Cu₂Oₙ（n = 3 - 7；m ≤ 5）与氨（NH₃）的反应。特定团簇如Cu₂O₃、Cu₂O₄、Cu₂O₅、Cu₂O₆和Cu₂O₇的单碰撞反应在NH₃吸附后能有效地释放出H₂O，并导致形成Cu₂OₙNH₃。这些Cu₂Oₙ团簇的Cu平均氧化数通常为1.0 - 1.4。另一方面，对于具有较高Cu氧化数的Cu₂O₇，主要观察到Cu₂O₇H₂的形成，即释放出HNO₂。以Cu₂O₅ + NH₃ → Cu₂O₅NH₃ + H₂O反应为例，进行了密度泛函理论计算，作为H₂O释放的典型例子。计算表明该反应几乎是热中性的，与实验观察结果一致。此外，我们的实验研究表明，Cu₂O₅和Cu₂O₆与NH₃的多碰撞反应分别导致生成Cu和Cu₂O。这表明在这些团簇上发生了将NH₃理想地氧化为N₂和H₂O的反应。
