Ammonium Bicarbonate Significantly Accelerates the Microdroplet Reactions of Amines with Carbon Dioxide

The reactions between amines and carbon dioxide (CO₂) are among the most commonly used and important carbon fixation reactions at present. Microdroplets generated by electrospray ionization (ESI) have been proved to increase the conversion ratio (R_C) of amines. In this work, we confirmed that the presence of ammonium bicarbonate (NH₄HCO₃) in ESI microdroplets significantly increased the R_C of amines. The R_C went up remarkably with the increase in the concentration of NH₄HCO₃ from 0.5 to 20 mM. The R_C of N,N-dibutyl-1,3-propanediamine (DBPA) reached 93.7% under 20 mM NH₄HCO₃, which was significantly higher than previous reports. The rise in R_C became insignificant when the concentration of NH₄HCO₃ was increased beyond 20 mM. Further investigations were made on the mechanism of the phenomenon. According to the results, it was suggested that NH₄HCO₃ decomposed into CO₂ and formed microbubbles within the microdroplets of ESI. The microbubbles acted as direct internal CO₂ sources. The conversion reactions occurred at the liquid-gas interface. The formation of CO₂ microbubbles remarkably increased the total area of the interface, thus promoting the conversion reactions. ¹³C-labeled experiments confirmed that NH₄HCO₃ acted as an internal CO₂ source. Factors that influenced the R_C of the reaction were optimized. Pure water was proved to be the optimal solvent. Lower temperature of the mass spectrometer's entrance capillary was beneficial to the stabilization of the product carbamic acids. The sample flow rate of ESI was crucial to the R_C. It determined the initial sizes of the microdroplet. Lower flow rates ensured higher R_C of amines. The present work implied that NH₄HCO₃ could be a superior medium for CO₂ capture and utilization. It might offer an alternative choice for future CO₂ conversion research studies. In addition, our study also provided evidence that NH₄HCO₃ decomposed and generated microbubbles in the droplets during ESI. Attention should be paid to this when using NH₄HCO₃ as an additive in mass spectrometry-based analysis.