Influence of an electrified interface on the entropy and energy of solvation of methanol oxidation intermediates on platinum(111) under explicit solvation

Abstract

Liquid water and electric fields play significant roles in phenomena occurring at catalytic and electrocatalytic interfaces; however, how their interplay influences interfacial energetics remains uncertain. Electric fields control the orientations...

Differences in solvation thermodynamics of oxygenates at Pt/Al2O3 perimeter versus Pt(111) terrace sites

“…We find the calculated partial charges have a maximum 0.2 meV/K influence on the calculated entropies of solvation. At 300 K, this results in a 0.07 eV uncertainty in the free energy of solvation, which is within the standard error due to the method 54 as well as the configurational variability caused by thermal disorder in the liquid structure. 55 , 56 Further, we find that variation of partial charges in the adsorbates is not systematic and hence not due to small particle size effects (see the model validation sections below).…”

“… is calculated from two separate MD simulations, following our previous publications 40 , 54 : where is the average energy of interaction between the H 2 O molecules and the adsorbate over an NVT trajectory, and is the Helmholtz free energy of solvation of the adsorbate, calculated using the method of free energy perturbation (FEP) in MD. Values used to compute are provided in Table S12 .…”

“…The comparison shown in Table S5 reflects similar free energy values, in the case of Δ E int DFT (eV) the difference is within the uncertainty of ±0.10 eV as in our prior publications. 54 For this reason, this small cell is considered sufficient to capture the trend between TΔS int MD and ΔE int DFT ; and the trend for the larger number of Pt(111) adsorbates was made with this DFT efficient smaller cell. Hence, the small cell was used to obtain the enthalpy and entropy results presented in the main text, and the large cell was used to explain the trends in the discussion section.…”

“…On our previous studies, 40 , 54 in the calculation of the solvation free energy and entropy with MD, the Platinum atoms were included in the scaling of the FEP calculation, accounting for the Coulombic component in the solvation, due to charge redistribution in the Platinum atoms. A comparison of the solvation entropy calculated with the previous studies 40 , 54 scheme, including both the adsorbate and the Platinum Coulombic component (Scaling: Ads(LJ + Coul)+Pt(Coul)) and the method employed in the main text, only scaling the adsorbate (Scaling: Ads(LJ + Coul)) is provided in Table S11 . The inclusion of this component in most of the cases had a minor effect in the solvation entropy, with the exception of COH and CHOH, because they presented high cluster charges; the charge transfer effect is diluted with larger Platinum particles.…”

Enhanced CO2 Reactive Capture and Conversion Using Aminothiolate Ligand–Metal Interface

“…Due to the electrostatic attraction, the alkali cations become close to the electrode surface. Therefore, there will be a negative electric field effect on altering the energetics (adsorption, reaction, and activation barriers) of the reactions involving polarized intermediates, such as adsorbed CO 2 , CO dimer, and the post C–C coupling species. − Such an electric field effect induced by the cations at the solid/liquid interface will be our future direction.…”