The hydrogenation of alkenes is among the important technological reactions catalyzed by supported metals, finding application in the pharmaceutical, agrochemical, and commodity chemical industries. Palladium on carbon is a very common and efficient catalyst for this type of reaction. Considering the cost of Pd, a logical step is to optimize its dispersion on the support. The maximum dispersion that can be achieved involves the use of single atom catalysts (SAC). Given that H2 dissociation can be rate limiting in Pd-SAC since the Pd atoms are electro-deficient, strategy to engineer the minimal catalytic ensemble that will activate H2 would represent substantial progress toward highly efficient Pd/C hydrogenation catalysts.Here, we show through a combined experimental-theoretical study that a cooperative catalysis exists between Pd-SAC and Pd-nanoparticles (NP) deposited on carbon for various terpene hydrogenation. By using DFT calculations, we demonstate that Pd-NP dissociate easily dihydrogen, and H-spillover provides Pd-H species on the Pd-SAC. The Pd-H-SAC formed are much more active than Pd- H-NP for the hydrogenation of C=C double bonds (see Figure). Experimentally it is also shown that tuning the SAC/NP ratio in such catalysts allow reaching extremely high catalytic activity. We believe that these results can allow major advances in supported catalysis. Indeed, while such a cooperative effect may already occur in (many) existing catalysts, it has never been recognized as such, or exploited to improve the catalytic performances.

Theoretical insights on cooperative catalysis between palladium single atoms and nanoparticles in Pd/C catalyzed alkene hydrogenation

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.