Formic acid stability in different solvents by DFT calculations

Author(s)

Alvim, Raphael da Silva ; Bresciani, Antonio Esio ; Alves, Rita Maria Brito

• Document type: Journal article
• Source: Journal of Molecular Modeling; v. 30, n. 3, p. 12-pg., 2024-03-01.

Abstract

Context New technologies have been developed toward the use of green energies. The production of formic acid (FA) from carbon dioxide (CO2) hydrogenation with H-2 is a sustainable process for H-2 storage. However, the FA adduct stabilization is thermodynamically dependent on the type of solvent and thermodynamic conditions. The results suggest a wide range of dielectric permittivity values between the dimethyl sulfoxide (DMSO) and water solvents to stabilize the FA in the absence of base. The thermodynamics analysis and the infrared and charge density difference results show that the formation of the FA complex with H2O is temperature dependent and has a major influence on aqueous solvents compared to the FA adduct with amine, in good agreement with the experiment. In these conditions, the stability thermodynamic of the FA molecule may be favorable at non-organic solvents and dielectric permittivity values closer to water. Therefore, a mixture of aqueous solvents with possible ionic composition could be used to increase the thermodynamic stability of H-2 storage in CO2 conversion processes. Methods Using the Quantum ESPRESSO package, density functional theory (DFT) calculations were performed with periodic boundary conditions, and the electronic wave functions were expanded in plane waves. For the exchange-correlation functional, we use the vdW-DF functional with the inclusion of van der Waals (vdW) forces. Electron-ion interactions are treated by the projector augmented wave (PAW) method with pseudopotentials available in the PSlibrary repository. The wave functions and the electronic densities were expanded employing accurate cut-off energies of 6.80x10(2) and 5.44x10(3) eV, respectively. The electronic density was computed from the wave functions calculated at the Gamma-point in the first Brillouin-zone. Each structural optimization was minimized according to the Broyden-Fletcher-Goldfarb-Shanno (BFGS) algorithm, with force and energy convergence criteria of 25 meVx & Aring;(-1) and 1.36 meV, respectively. The electrostatic solvation effects were performed by the Environ package with the Self-Consistent Continuum Solvation (SCCS) approach. (AU)

• FAPESP's process: 14/50279-4 - Brasil Research Centre for Gas Innovation
• Grantee: Julio Romano Meneghini
• Support Opportunities: Research Grants - Research Centers in Engineering Program
• FAPESP's process: 20/15230-5 - Research Centre for Greenhouse Gas Innovation - RCG2I
• Grantee: Julio Romano Meneghini
• Support Opportunities: Research Grants - Research Centers in Engineering Program