期刊
JOURNAL OF SUPERCRITICAL FLUIDS
卷 54, 期 1, 页码 9-15出版社
ELSEVIER
DOI: 10.1016/j.supflu.2010.03.002
关键词
Supercritical CO2; Frequency shift; Local softness; Hydrogenation
资金
- NSFC [20573104]
- CAS
- Grants-in-Aid for Scientific Research [22360327] Funding Source: KAKEN
The interactions between CO2 and carbonyl compounds at different CO2 pressures have been studied both experimentally and theoretically. In situ high-pressure FTIR on carbonyl compounds, i.e., acetaldehyde, acetone, and crotonaldehyde, in supercritical CO2 have been measured at various CO2 pressures varying from 6 to 22 MPa. In order to get insights into the mechanism, theoretical study has been conducted concerning the effect of CO2 on frequency shift of C = O in acetaldehyde, acetone, benzaldehyde, crotonaldehyde and cinnamaldehyde at different CO2 pressures. It has been shown that the experimental frequency shifts can be well simulated by the theoretical model calculations using particular structures, in which a carbonyl compound interacts with a few CO2 molecules, depending on the carbonyl compounds examined, except for acetaldehyde. The interaction energies between CO2 and those carbonyl compounds are also given. In addition, the effect of CO2 on hydrogenation of crotonaldehyde and benzaldehyde has been discussed by means of the local softness (s(+)) calculated at CO2 pressures of 0-22 MPa, which can explain the reactivity difference in the crotonaldehyde and benzaldehyde hydrogenations in supercritical CO2. (C) 2010 Elsevier B.V. All rights reserved.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据