Bond Energies of Adsorbed Intermediates to Metal Surfaces: Correlation with Hydrogen–Ligand and Hydrogen–Surface Bond Energies and Electronegativities

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, −OCH3, −O(O)CH and −CH3 to Pt(111) and Ni(111) surfaces a...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2018-12, Vol.57 (51), p.16877-16881
Main Authors: Carey, Spencer J., Zhao, Wei, Campbell, Charles T.
Format: Article
Language:English
Subjects:
adsorption energies
Bonding strength
calorimetry
Catalysis
Electronegativity
Enthalpy
Hydrogen
Hydrogen bonds
Intermediates
Ligands
Metal surfaces
Metals
Organometallic complexes
Pauling's equation
surfaces
transition metals
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Summary: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, −OCH3, −O(O)CH and −CH3 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. Putting a number on it: An equation is derived based on Pauling's equation and is shown to accurately estimate the bond enthalpies of small molecular fragments to transition‐metal surfaces.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201811225