Dependency of solvation effects on metal identity in surface reactions

Solvent interactions with adsorbed moieties involved in surface reactions are often believed to be similar for different metal surfaces. However, solvents alter the electronic structures of surface atoms, which in turn affects their interaction with adsorbed moieties. To reveal the importance of met...

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Bibliographic Details
Published in:Communications chemistry 2020-12, Vol.3 (1), p.187-10, Article 187
Main Authors: Zare, Mehdi, Saleheen, Mohammad, Kundu, Subrata Kumar, Heyden, Andreas
Format: Article
Language:English
Subjects:
639/4077/909/4053/906
639/638/563/606
639/638/77/887
biofuels
Catalysis
Charge transfer
Chemistry
Chemistry and Materials Science
Chemistry/Food Science
computational chemistry
Copper
Dependence
Ductile-brittle transition
Ethylene glycol
Gold
heterogeneous catalysis
Hydrogen bonds
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Metal surfaces
Metals
Nickel
Palladium
Platinum
Potential energy
Quantum mechanics
Silver
Solvation
Solvents
Surface reactions
Transition metals
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Summary:Solvent interactions with adsorbed moieties involved in surface reactions are often believed to be similar for different metal surfaces. However, solvents alter the electronic structures of surface atoms, which in turn affects their interaction with adsorbed moieties. To reveal the importance of metal identity on aqueous solvent effects in heterogeneous catalysis, we studied solvent effects on the activation free energies of the O–H and C–H bond cleavages of ethylene glycol over the (111) facet of six transition metals (Ni, Pd, Pt, Cu, Ag, Au) using an explicit solvation approach based on a hybrid quantum mechanical/molecular mechanical (QM/MM) description of the potential energy surface. A significant metal dependence on aqueous solvation effects was observed that suggests solvation effects must be studied in detail for every reaction system. The main reason for this dependence could be traced back to a different amount of charge-transfer between the adsorbed moieties and metals in the reactant and transition states for the different metal surfaces. Solvents play a central role in catalytic reactions, but predicting specific solvation effects in heterogeneous systems remains a challenge. Here, a hybrid quantum mechanical/molecular mechanical method is used to elucidate solvation effects on O–H and C–H bond cleavage in ethylene glycol over the (111) facet of six transition metals.
ISSN:2399-3669
2399-3669
DOI:10.1038/s42004-020-00428-4