Molecular Mechanism for Converting Carbon Dioxide Surrounding Water Microdroplets Containing 1,2,3-Triazole to Formic Acid

Abstract

Spraying water microdroplets containing 1,2,3-triazole (Tz) has been found to effectively convert gas-phase carbon dioxide (CO 2 ), but not predissolved CO 2 , into formic acid (FA). Herein, we elucidate the reaction mechanism at the molecular level through quantum chemistry calculations and ab initio molecular dynamics (AIMD) simulations. Computations suggest a multistep reaction mechanism that initiates from the adsorption of CO 2 by Tz to form a CO 2 -Tz complex (named reactant complex (RC)). Then, the RC either is reduced by electrons that were generated at the air−liquid interface of the water microdroplet and then undergoes intramolecular proton transfer (PT) or switches the reduction and PT steps to form a [HCO 2 -(Tz-H)] − complex (named PC − ). Subsequently, PC − undergoes reduction and the C−N bond dissociates to generate COOH − and [Tz-H] − (m/z = 69). COOH − easily converts to HCOOH and is captured at m/z = 45 in mass spectroscopy. Notably, the intramolecular PT step can be significantly lowered by the oriented electric field at the interface and a water-bridge mechanism. The mechanism is further confirmed by testing multiple azoles. The AIMD simulations reveal a novel proton transfer mechanism where water serves as a transporter and is shown to play an important role dynamically. Moreover, the transient •COOH captured by the experiment is proposed to be partly formed by the reaction with H•, pointing again to the importance of the air−water interface. This work provides valuable insight into the important mechanistic, kinetic, and dynamic features of converting gas-phase CO 2 to valuable products by azoles or amines dissolved in water microdroplets.

Deciphering the Microdroplet Acceleration Factors of Aza-Michael Addition Reactions

“…Nevertheless, our quantum chemistry calculation using the SMD solvent model and the limited number of explicit solvent molecules does not account for the dynamical process in the real air–liquid interface, which could be important for proton transfer. Such information can be gained by performing molecular dynamics simulations. − …”