In the limit of very dilute alloying—the so-called “single-atom-alloy” (SAA) regime—certain bimetallic systems exhibit weak mixing between constituent metal wavefunctions, resulting in sharp, single-atom-like electronic states localized on the dilute component of the alloy. This work shows that when these sharp states are appropriately positioned relative to given molecular orbitals, selective hybridization is enhanced, in accordance with intuitive principles of molecular orbital theory. We demonstrate the phenomenon for activation pathways of crotonaldehyde, a model <i>α</i>,<i>β</i>-unsaturated aldehyde relevant to a wide range of chemical manufacturing. This analysis suggests new possible mechanisms of selectivity control for heterogeneous catalysts.

Steering selectivity with free-atom-like d-states in single-atom-alloy catalysts

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ACS Fall 2022

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