Focusing on the competing pathways of methanol oxidation on platinum and platinum/gold bimetallic catalysts, we explore a novel density functional theory (DFT)‐based approach to the study of reactions on catalyst surfaces. Traditionally, DFT has been used to compute binding energies of products and intermediates as proxies for catalytic activity, and to compute full reaction pathways and their activation energy barriers. Merging the computational simplicity and intuitive clarity of binding energy calculations with the site sensitivity of transition state calculations, we construct maps of the binding energies of relevant atoms and molecules at all sites on a surface. We show that knowledge of the arrangement of strong and weak binding sites on a surface is powerful in rationalizing the ease with which a reaction step proceeds on a given local motif of surface atoms. We highlight the prospects and challenges of this approach toward catalyst screening and prediction.
Tailoring the molecular components of hybrid organic-inorganic materials enables precise control over their electronic properties. Designing electrically conductive coordination materials, e.g. metal-organic frameworks (MOFs), has relied on single-metal nodes because the metal-oxo clusters present in the vast majority of MOFs are not suitable for elec- trical conduction due to their localized electron orbitals. Therefore, the development of metal-cluster nodes with delocal- ized bonding would greatly expand the structural and electrochemical tunability of conductive materials. Whereas the cuboidal [Fe4S4] cluster is a ubiquitous cofactor for electron transport in biological systems, few electrically conductive artificial materials employ the [Fe4S4] cluster as a building unit due to the lack of suitable bridging linkers. In this work, we bridge the [Fe4S4] clusters with ditopic N-heterocyclic carbene (NHC) linkers through charge-delocalized Fe-C bonds that enhance electronic communication between the clusters. [Fe4S4Cl2(ditopic NHC)] exhibits a high electrical conductivity of 1 mS cm−1 at 25 oC, surpassing the conductivity of related but less covalent materials. These results highlight that synthetic control over individual bonds is critical to the design of long-range behavior in semiconductors.
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