Waite Simone L, Li Hua, Page Alister J
School of Environmental & Life Sciences , The University of Newcastle , Callaghan , New South Wales 2308 , Australia.
J Phys Chem B. 2018 Apr 19;122(15):4336-4344. doi: 10.1021/acs.jpcb.8b01508. Epub 2018 Apr 5.
Deep eutectic solvents (DESs) are promising candidates as alternate media for industrial gas sequestration processes, such as denitrification via NO adsorption. Here, quantum chemical methods are employed to characterize the NO solvation structure and adsorption mechanism in choline chloride DES with urea, methylurea, and thiourea hydrogen bond donors. Our results show that the solvation structure of NO in bulk choline chloride DES is determined by the type of the hydrogen bond donor present. Changing the structure of the hydrogen bond donor not only changes its NO coordination mechanism but also changes that between NO and the choline and chloride ions in the DES. By using an energy decomposition analysis scheme, we show that the principle forces stabilizing NO in these DES are dispersion and polarization interactions and, consequently, that NO adsorption is most favorable in the choline chloride-thiourea DES. These results highlight a potential route for the optimization of choline chloride DES for denitrification, by modulating the hydrogen bond donor structure.
深共熔溶剂（DESs）作为工业气体封存过程的替代介质，如通过NO吸附进行反硝化，是很有前途的候选物。在此，采用量子化学方法来表征在含有尿素、甲基脲和硫脲氢键供体的氯化胆碱DES中NO的溶剂化结构和吸附机制。我们的结果表明，本体氯化胆碱DES中NO的溶剂化结构由存在的氢键供体类型决定。改变氢键供体的结构不仅会改变其与NO的配位机制，还会改变DES中NO与胆碱和氯离子之间的配位机制。通过使用能量分解分析方案，我们表明在这些DES中稳定NO的主要作用力是色散和极化相互作用，因此，NO在氯化胆碱 - 硫脲DES中的吸附最为有利。这些结果突出了通过调节氢键供体结构来优化用于反硝化的氯化胆碱DES的潜在途径。
