Acta Physico-Chimica Sinica ›› 2018, Vol. 34 ›› Issue (8): 904-911.doi: 10.3866/PKU.WHXB201712281

Special Issue: 绿色化学

• ARTICLE • Previous Articles     Next Articles

Investigation on the Thermal Stability of Deep Eutectic Solvents

Wenjun CHEN1,Zhimin XUE2,*(),Jinfang WANG1,Jingyun JIANG1,Xinhui ZHAO1,Tiancheng MU1,*()   

  1. 1 Department of Chemistry, Renmin University of China, Beijing 100872, P. R. China
    2 College of Materials Science and Technology, Beijing Forestry University, Beijing 100083, P. R. China
  • Received:2017-12-12 Accepted:2017-12-26 Published:2018-04-03
  • Contact: Zhimin XUE,Tiancheng MU E-mail:zmxue@bjfu.edu.cn;tcmu@ruc.edu.cn
  • Supported by:
    The project was supported by the National Natural Science Foundation of China(21773307);The project was supported by the National Natural Science Foundation of China(21503016)

Abstract:

In recent years, deep eutectic solvents (DESs) have attracted considerable attention. They have been applied in many fields such as dissolution and separation, electrochemistry, materials preparation, reaction, and catalysis. The DESs are generally formed by the hydrogen bonding interactions between hydrogen-bond donors (HBDs) and acceptors (HBAs). Knowledge of the thermal stability of DESs is very important for their application at high temperatures. However, there have been relatively few studies on the thermal stability of DESs. Herein, a systematic investigation on the thermal stability of 40 DESs was carried out using thermal gravimetric analysis (TGA), and the onset decomposition temperatures (Tonset) of these solvents were obtained. The most important conclusion drawn from this work is that the thermal behavior of DESs is quite different from that of ionic liquids. The anions or cations of ionic liquids decompose first, followed by the decomposition of the opposite ion at elevated temperatures. On the other hand, the DESs generally first decompose to HBDs and HBAs at high temperatures through the weakening of the hydrogen bond interactions. Subsequently, the HBDs with relatively low boiling points or poor stabilities undergo volatilization or decomposition; the HBAs also undergo volatilization or decomposition but at a higher temperature. For example, the most commonly used HBA choline chloride (ChCl) begins to decompose at around 250 ℃. The hydrogen bond plays an important role in the thermal stability of DESs. It hinders the "escape" of molecules and requires greater energy to break than pure HBAs and HBDs, which causes the Tonset of DESs to shift to higher temperatures. Note that the thermal stability of HBDs has a crucial effect on the Tonset of DESs. The HBDs would decompose or volatilize first during TGA because of their relatively poor thermal stability or lower boiling points. The more stable the HBDs are, the greater would be the Tonset values of the corresponding DESs. Further, the effects of anions on HBAs, molar ratio of HBAs to HBDs, and heating rate in fast scan TGA have been discussed. As the heating rate increased, the TGA curves of DESs shifted to higher temperatures gradually, and the temperature hysteretic effect became prominent when the rate reached 10 ℃?min?1. From an industrial application point of view, there is an overestimation of the onset decomposition temperatures of DESs by Tonset, so the long-term stability of DESs was investigated at the end of the study. This study could help understand the thermal behavior of DESs (progressive decomposition) and provide guidance for designing DESs with appropriate thermal stability for practical applications.

Key words: Deep eutectic solvents, Choline chloride, TGA, Thermal stability, Hydrogen bond

MSC2000: 

  • O642