Nonoxidative alkane dehydrogenations is a promising route to produce olefins, commonly used as building blocks in the chemical industry. Metal oxides, including γ-Al2O3 and ß-Ga2O3, are attractive dehydrogenation catalysts due...

Heterogeneous catalysts are the key components in industrial chemical transformations. Metal oxides are particularly appealing as catalysts owing to their inherent Lewis acid–base properties that facilitate the activation of chemically inert paraffinic C–H bonds. Computational chemistry provides a rich mechanistic understanding of catalyst functionality through the calculation of accurate thermodynamic and kinetic data that cannot be experimentally accessible. Using these data, one can relate the energy needed for elementary reaction steps with properties of the catalyst, paving the way for computational catalyst discovery. At the heart of this process is the development of structure–activity relationships (SARs) that facilitate the rapid prediction of promising catalytic materials for energy intense industrial transformations, guiding experimentation. In this review article, we highlight SARs on oxides for chemical reactions of high industrial relevance including (i) methane activation and conversion, (ii) alkane dehydrogenation, and (iii) alcohol dehydration. We also discuss current limitations and challenges on SARs and propose future steps to advance catalyst discovery.

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We quantified the impact of support interactions on the binding and interaction energies of CO and O adsorbed on Pt 13 nanoclusters supported on amorphous silica surfaces through the use of density functional theory calculations. We used an accurate model for amorphous silica having two different surface silanol concentrations, corresponding to low (200 °C) and high (715 °C) surface pretreatment temperatures. We compared CO and O adsorbed on supported and freestanding Pt 13 clusters. We found that Pt 13 is highly susceptible to both support-and adsorbate-induced reconstruction, depending on the relaxed structure of the Pt 13 cluster on the surface. Structure relaxation effects dominate over electronic effects of the support. We considered an ensemble of 50 different systems by varying the placement of the Pt 13 cluster on the surfaces and by exploring a range of different binding sites for CO and O on the Pt 13 cluster. In select cases, binding energy differences between supported and freestanding Pt 13 are as large as 2 eV. However, the mean absolute error between supported and freestanding clusters over all systems we studied is only a few tenths of an eV. Coverage effects on coadsorption of CO and O are significantly different on supported clusters compared with the Pt(111) surface. Our results can be used for predicting when support interactions may be important for any reaction catalyzed by small metal nanoclusters.