TY - JOUR
T1 - First-Principles Investigation of Surface pKa and the Behavior of Acids at Aqueous-Metal Interfaces
AU - Karimadom, Basil Raju
AU - Meyerstein, Dan
AU - Mizrahi, Amir
AU - Kornweitz, Haya
N1 - Publisher Copyright:
© 2024 The Authors. Published by American Chemical Society.
PY - 2024/12/19
Y1 - 2024/12/19
N2 - Several computational methods were reported for the accurate determination of pKa values in a solvent medium, but the research on surfaces and interfaces is limited. This study reports a new method for accurately determining the surface pKa (*pKa) of acids on surfaces. The *pKa is defined as the function of the adsorption energies of neutral acids and their deprotonated form. In the suggested method, the estimated proton solvation-free energy value is not required, a fact that increases the accuracy of the results. The *pKa values of various organic and inorganic acids on the (111) surfaces of Ag, Au, and Pt were evaluated. The results are validated with available experimental results on various surface coverage ratios. The results point out that weak acids adsorbed on the metal-aqueous interface are orders of magnitude stronger acids than those in homogeneous solutions. The shift of the pKas is largest on platinum. These results are of major importance in electrochemistry and heterogeneous catalysis.
AB - Several computational methods were reported for the accurate determination of pKa values in a solvent medium, but the research on surfaces and interfaces is limited. This study reports a new method for accurately determining the surface pKa (*pKa) of acids on surfaces. The *pKa is defined as the function of the adsorption energies of neutral acids and their deprotonated form. In the suggested method, the estimated proton solvation-free energy value is not required, a fact that increases the accuracy of the results. The *pKa values of various organic and inorganic acids on the (111) surfaces of Ag, Au, and Pt were evaluated. The results are validated with available experimental results on various surface coverage ratios. The results point out that weak acids adsorbed on the metal-aqueous interface are orders of magnitude stronger acids than those in homogeneous solutions. The shift of the pKas is largest on platinum. These results are of major importance in electrochemistry and heterogeneous catalysis.
UR - http://www.scopus.com/inward/record.url?scp=85212542866&partnerID=8YFLogxK
U2 - 10.1021/acs.jpcc.4c06554
DO - 10.1021/acs.jpcc.4c06554
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AN - SCOPUS:85212542866
SN - 1932-7447
VL - 128
SP - 21572
EP - 21580
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
IS - 50
ER -