Acidity scales of deep eutectic solvents based on IR and NMR

• Published in: Physical chemistry chemical physics : PCCP 2022-07, Vol.24 (28), p.16973-16978
• Main Authors: Zhou, Fengyi, Shi, Ruifen, Wang, Yingxiong, Xue, Zhimin, Zhang, Baolong, Mu, Tiancheng
• Format: Article
• Language: English
• Subjects: Acetonitrile; Charge density; Infrared instruments; Measurement methods; NMR; Nuclear magnetic resonance; Solvents
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/d2cp01816k

Acidic deep eutectic solvents (ADESs) have been utilized in various applications. Clearly, it is crucial to obtain acidity information that could reveal the relationship with performance. However, appropriate methods for measuring acidity are limited. Herein, we developed two promising approaches (without additional solvents) to identify and characterize both Lewis and Brønsted acidities by applying acetonitrile as an infrared probe and trimethylphosphine oxide (TMPO) as a nuclear magnetic resonance (NMR) probe. The acetonitrile IR approach is suitable for measuring the acidity of Lewis ADESs by monitoring the peak of ν (C&z.tbd;N) around 2300 cm −1 , and the 31 P-TMPO NMR approach could identify and scale both Lewis and Brønsted acidities precisely. Moreover, a perfect linear relationship between the IR shift of ν (C&z.tbd;N) and the effective charge density of metal cations was established, which provides a better understanding of Lewis acidity. In short, this study not only offers two efficient acidity measurement methods but also provides a molecular basis for optimizing the performance of ADESs in applications. This work not only offers two methods for determining both Lewis and Brønsted acidity of DES but also provides a molecular basis for optimizing the performance of DESs in applications.