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Bond Energies of Adsorbed Intermediates to Metal Surfaces: Correlation with Hydrogen–Ligand and Hydrogen–Surface Bond Energies and Electronegativities
Author(s) -
Carey Spencer J.,
Zhao Wei,
Campbell Charles T.
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201811225
Subject(s) - electronegativity , chemistry , enthalpy , hydrogen bond , bond energy , ligand (biochemistry) , adsorption , catalysis , bond order , computational chemistry , bond strength , metal , thermodynamics , bond length , molecule , organic chemistry , biochemistry , physics , receptor , adhesive , layer (electronics)
Understanding what controls the strength of bonding of adsorbed intermediates to transition‐metal surfaces is of central importance in many technologies, especially catalysis and electrocatalysis. Our recently measured bond enthalpies of −OH, −OCH 3 , −O(O)CH and −CH 3 to Pt(111) and Ni(111) surfaces are fit well (standard deviation of 7.2 kJ mol −1 ) by a predictive equation involving only known parameters (gas‐phase ligand–hydrogen bond enthalpies, bond enthalpies of adsorbed H atoms to that surface, electronegativities of the elements, and group electronegativities of the ligands). This equation is based upon Pauling's equation, with improvements introduced by Matcha, derived here following manipulations of Matcha's equation similar to (but going beyond) those introduced by Schock and Marks to explain ligand–metal bond enthalpy trends in organometallic complexes.