Introducing structural sensitivity into adsorption–energy scaling relations by means of coordination numbers

The search for improved heterogeneous catalysts is an important but difficult task. Scaling relations between the adsorption energies of reaction intermediates greatly facilitate the computational design of catalysts. However, this methodology does not currently incorporate structure sensitivity and...

Full description

Saved in:
Bibliographic Details
Published in:Nature chemistry 2015-05, Vol.7 (5), p.403-410
Main Authors: Calle-Vallejo, Federico, Loffreda, David, Koper, Marc T. M., Sautet, Philippe
Format: Article
Language:English
Subjects:
119/118
639/638/77/887
Adsorption
Analytical Chemistry
Biochemistry
Catalysis
Chemical Sciences
Chemistry
Chemistry/Food Science
Design
Geometry
Inorganic Chemistry
or physical chemistry
Organic Chemistry
Physical Chemistry
Theoretical and
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:The search for improved heterogeneous catalysts is an important but difficult task. Scaling relations between the adsorption energies of reaction intermediates greatly facilitate the computational design of catalysts. However, this methodology does not currently incorporate structure sensitivity and hence cannot describe adequately the overall activity of realistic catalyst particles and extended surfaces with several facets, edges and apices. Here, we generalize scaling relations by examining twelve different low-index, stepped and kinked surfaces of nine transition metals. This allows us to quantify the effect of the adsorption-site geometry on these relations, ensures a full prediction of their parameters, and helps in identifying intrinsic thermodynamic restrictions to the performance of catalysts. The resulting fully predictable, structure-sensitive scaling relations are a step towards the long-sought rational design of multifaceted catalytic particles. Such a design can now target not only the chemical nature of active materials but also the actual geometry of their active sites. Scaling relations between the adsorption energies of reaction intermediates facilitate the computational design of catalysts. However, these relations are restricted to low-index surfaces and how they differ from surface to surface cannot be predicted. Structural sensitivity has now been incorporated into scaling relations by elucidating how they are affected by the coordination number of an adsorption site.
ISSN:1755-4330
1755-4349
DOI:10.1038/nchem.2226