Carbon dioxide (CO2) chemical absorption and regeneration was investigated in two diamino carboxylate protic ionic liquids (PILs), dimethylethylenediamine formate (DMEDAH formate) and dimethylpropylenediamine acetate (DMPDAH acetate), using novel calorimetric techniques. The PILs under study have previously been shown to possess a CO2 absorption capacity similar to the industrial standard, 30% aqueous MEA, while requiring much lower temperatures to release the captured CO2. We show that this is in part due to the fact that the PILs exhibit enthalpies of CO2 desorption as low as 40 kJ mol(-1), significantly lower than the 85 kJ mol(-1) required for 30% aqueous MEA. Computational and spectroscopic analyses were used to probe the mechanism of CO2 capture, which was found to proceed via the formation of carbamate moieties on the primary amine of both DMEDAH and DMPDAH. Evidence was also found that weakly acidic counter-ions such as formate and acetate provide, unexpectedly, an additional proton acceptor site in the traditional carbamate mechanism, revealing opportunities to increase CO2 uptake capacity in the future through careful design of the anion and cation used in the PIL capture agent.
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http://dx.doi.org/10.1039/c5cp05200a | DOI Listing |
J Phys Chem B
January 2025
Department of Applied Chemistry, Graduate School of Science and Engineering, Doshisha University, Kyotanabe, Kyoyo 610-0321, Japan.
Excited-state proton transfer (ESPT) reactions of 5-cyano-2-naphthol (5CN2) and 5,8-dicyano-2-naphthol (DCN2) were investigated in protic ionic liquids (PILs) composed of quaternary ammonium (NH) ( = 2, 4, or 8) and hexanoate (CHCOO) using time-resolved fluorescence spectroscopy. The effects of the number of alkyl carbons in the cation and the basicity of the anion on the reaction yield and dynamics were examined. In a series of [NH][CHCOO], fluorescence from the hydrogen-bonding complex (AHBX) of a proton-dissociated form (RO) with a solvent acid in the electronic excited state was observed between the fluorescence bands of an acidic form (ROH) and an anionic form (RO) as in the case of [NH][CFCOO] (Fujii et al.
View Article and Find Full Text PDFJ Phys Chem B
January 2025
Department of Chemistry, J. C. Bose University of Science and Technology, YMCA, Faridabad 121006, India.
Binary ionic melts formed by a protic ionic liquid (PIL) 1,2,4-triazolium methanesulfonate ([TAZ][MS]) dissolved in methanesulfonic acid are studied as non-stoichiometric electrolytes. The composition-driven structure-property relationship of methanesulfonic acid is explored at varying molar fraction ratios from 0/100 to 10/90, 20/80, and 30/70 by the addition of 1,2,4-triazolium methanesulfonate [TAZ][MS] IL. To unveil molecular characteristics of these mixtures of [TAZ][MS] PIL and CHSOH, we performed classical molecular dynamics simulations at varying temperatures from 293 to 303, 363, and 423 K.
View Article and Find Full Text PDFJ Phys Chem B
January 2025
Collaborative Innovation Center of Chemical Science and Engineering, Tianjin University, Tianjin 300072, China.
As a predictive tool, quantum chemical calculations can be used to design protic ionic liquids (PILs) and predict the result. By adding anionic negative potential sites, two dual-functional PILs diethylenetriamine-barbituric acid [CHN][CHNO] and diethylenetriamine-ethylenolactonium [CHN][CHNO] were designed. The simulation results indicated that multisite absorption of anions and cations resulted in an expected absorption ratio exceeding 3:1 (mol CO:mol ILs).
View Article and Find Full Text PDFMaterials (Basel)
December 2024
Hunan Provincial Key Laboratory of Chemical Power Sources, College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China.
This study presents the synthesis of a transparent, flexible gel polymer electrolyte (GPE) based on the protic ionic liquid BMImHSO and on polyvinyl alcohol (PVA) through solution casting and electrochemical evaluation in a 2.5 V symmetrical C/C electrical double-layer solid-state capacitor (EDLC). The freestanding GPE film exhibits high thermal stability (>300 °C), wide electrochemical windows (>2.
View Article and Find Full Text PDFChemistryOpen
January 2025
Energy engineering, Division of Energy Science, Luleå, University of Technology, 97187, Luleå, Sweden.
We report the synthesis of two pyridinium-based room temperature protic ionic liquids (PILs), pyridinium bisulfate, [HPyr][HSO] and pyridinium sulphate, [HPyr][SO] and investigation of the kinetics of their water sorption behaviour and its influence on their density, ionic conductivity, and potential windows. The PILs were synthesized by the reaction of pyridine base with an acid, HSO, under solventless conditions, and confirmed by FTIR spectroscopy and 1H NMR spectra. The appearance vibration bands in the 3095-3252 cm range for -NH stretching in the FTIR spectra and a peak at a chemical shift of 8.
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