(630h) Understanding and Manipulating the Solvent Microenvironment for Selective, Catalytic Amination of Renewable Oxygenates
AIChE Annual Meeting
2021
2021 Annual Meeting
Catalysis and Reaction Engineering Division
Catalysis in Liquid Media II
Thursday, November 11, 2021 - 5:36pm to 5:54pm
We performed Density Functional Theory (DFT) calculations using VASP 5.4.4. Electron-core interactions were treated using the Projector Augmented Wave method (PAW), while exchange-correlation effects were accounted for using the PBE-D3 functional. The energy cut-off was set to 420 eV. A 444 slab was used to model the Ru(0001) surface. We performed condensed phase simulations using the iSMS method1.
Under all reaction conditions, we exclusively observe 3A-THF as the main product. We predict a limited overall TOF (Table 1) at moderate temperatures in all reaction environments. Only at elevated temperatures, we observe an appreciable activity. The high apparent activation barrier can be explained by both a high intrinsic activation barrier and a relatively crowded Ru surface. Implicit solvation models predict only a limited impact of a condensed-phase environment on the TOF; however, Ru is well-known to exhibit a significant increase in activity for aqueous phase reduction reactions.2 To overcome the limitations of implicit solvation models, we developed a neural network potential for the water-ruthenium inaction that can be used together with free energy perturbation calculations to predict solvation effects on free energies of the most critical steps in the reaction network of the reductive amination of 3HBL.
References.
(1) Faheem, M.; Suthirakun, S.; Heyden, A. J. Phys. Chem. C 2012, 116 (42), 22458â22462.
(2) Michel, C.; Gallezot, P. ACS Catal. 2015, 5 (7), 4130â4132.