Zhang Qingnan, Qu Hui, Chen Mohua, Zhou Mingfei
Collaborative Innovation Center of Chemistry for Energy Materials, Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials, Fudan University , Shanghai 200433, China.
J Phys Chem A. 2016 Jan 28;120(3):425-32. doi: 10.1021/acs.jpca.5b11809. Epub 2016 Jan 14.
The reactions of carbon dioxide with scandium monoxide molecules and scandium atoms are investigated using matrix isolation infrared spectroscopy in solid neon. The species formed are identified by the effects of isotopic substitution on their infrared spectra as well as density functional calculations. The results show that the ground state ScO molecule reacts with carbon dioxide to form the carbonate complex ScCO3 spontaneously on annealing. The ground state Sc atom reacts with two carbon dioxide molecules to give the carbonate carbonyl complex OCScCO3 via the previously reported OScCO insertion intermediate on annealing. The observation of these spontaneous reactions is consistent with theoretical predictions that both the Sc + 2CO2 → OCScCO3 and ScO + CO2 → ScCO3 reactions are thermodynamically exothermic and are kinetically facile, requiring little or no activation energy.
在固体氖中使用基质隔离红外光谱法研究了二氧化碳与一氧化钪分子和钪原子的反应。通过同位素取代对其红外光谱的影响以及密度泛函计算来识别所形成的物种。结果表明，基态ScO分子与二氧化碳反应，在退火时自发形成碳酸盐配合物ScCO₃。基态Sc原子与两个二氧化碳分子反应，在退火时通过先前报道的OScCO插入中间体生成碳酸盐羰基配合物OCScCO₃。这些自发反应的观察结果与理论预测一致，即Sc + 2CO₂ → OCScCO₃和ScO + CO₂ → ScCO₃反应在热力学上都是放热的，并且在动力学上很容易进行，几乎不需要或不需要活化能。
