Abstract
Adsorption of organics in the aqueous phase is an area which is experimentally difficult to measure, while computational techniques require extensive configurational sampling of the solvent and adsorbate. This is exceedingly computationally demanding, which excludes its routine use. If implicit solvent could be applied instead, this would dramatically reduce the computational cost as configurational sampling of solvent is not needed. Here, using statistical thermodynamic arguments and DFT calculations with implicit solvent models, we show that semiquantitative values for the free energy and entropy change of adsorption in the aqueous phase (δGadssolvand δSadssolv) for small organics can be calculated, for a range of coverages. We parametrize the soft sphere based solute dielectric cavity to an approximated free energy of solvation for a single Pt atom at the (111) facet, forming upper and lower bounds based on the entropy of water at the aqueous metal interface (δGsolv(Pt) = -4.35 to -7.18 kJ mol-1). This captures the decrease in δGadssolvcompared to the free energy of adsorption in the vacuum phase (δGadsvac), while solvent models with electron density based cavities fail to do so. For a range of oxygenated aromatics, the adsorption energetics using horizontal gas phase geometries significantly overestimate δGadssolvcompared to experiment by ∼100 kJ mol-1, but they agree with ab initio MD simulations using similar geometries. This suggests oxygenated aromatic compounds adsorb perpendicular to the metallic surface, while the δGadssolvfor vertical geometries of furfural and cyclohexanol agree to within 20 kJ mol-1of experimental studies. The proposed techniques provide an inexpensive toolset for validation and prediction of adsorption energetics on solvated metallic surfaces, which could be further validated by the future availability of more experimental measurements for the aqueous entropy/free energy of adsorption.
Original language | English |
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Pages (from-to) | 1849-1861 |
Number of pages | 13 |
Journal | Journal of Chemical Theory and Computation |
Volume | 18 |
Issue number | 3 |
DOIs | |
State | Published - Mar 8 2022 |
Externally published | Yes |
Funding
V.-A.G., M.-T.N., and R.R. were supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (BES), Chemical Sciences, Geosciences, and Biosciences Division. Computer resources were provided by Research Computing at Pacific Northwest National Laboratory (PNNL) and the National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility operated under Contract No. DE-AC02-05CH11231. PNNL is operated by Battelle for the U.S. Department of Energy under Contract No. DE-AC05-76RL01830. G.A.B. acknowledges support for his Ph.D. funding equally from EPSRC and BES. The authors acknowledge the use of the IRIDIS High Performance Computing Facility (IRIDIS 5) and associated support services at the University of Southampton in the completion of this work. We are grateful to the U.K. Materials and Molecular Modeling Hub (Young HPC) for computational resources, which is partially funded by EPSRC (EPSRC Grant No. EP/T022213/1), and to the UKCP consortium for access to the ARCHER2 supercomputer (EPSRC Grant No. EP/P022030/1).