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Ligands on Nanoparticles – Combining the Benefits of Homogeneous and Heterogeneous Catalysis


A considerable benefit of supported metal nanoparticles (NPs) over homogeneous catalysts is their handling in terms of catalyst recovering and performing continuous processes. However, homogeneous catalysts exhibit significant advantages regarding selectivity control. Especially, chemo- and stereo-selectivity, which are fundamental challenges in heterogeneous catalysis, can be achieved with homogeneous catalysts by application of tailored ligands that guide the reaction through specific interactions with the reactant.

Recently, it has been demonstrated that the use of ligands is not restricted to homogenous catalysis. We demonstrated that chemo- and even stereoselectivity can be achieved with supported NPs when using ligands.[1,2] Thereby the ligands do not act as spectators but they interact with the reactant. This can lead to enhanced activities and allow for the unique molecular control over selectivity known from homogeneous catalysis. We developed a model that describes the origin of stereoselectivity on a molecular level and by application of general guiding principles from asymmetric homogeneous catalysis we were able to raise enantiomeric excesses above 80 %, the limit for industrial relevance.[3] These results highlight the possibility to transfer fundamental principles from homogeneous to heterogeneous catalysis by ligand functionalization and the enormous potential arising from this idea for the development of novel highly active and selective catalysts.


References

(1) Schrader, I.; Warneke, J.; Backenköhler, J.; Kunz, S. J. Am. Chem. Soc. 2015, 137, 905.

(2) Schrader, I.; Neumann, S.; Himstedt, R.; Zana, A.; Warneke, J.; Kunz, S. Chem. Commun. 2015, 51, 16221.

(3) Schrader, I.; Neumann, S.; Sulce, A.; Schmidt, F.; Azov, A.; Kunz, S. 2017, under revision.

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