A systematic study of heterogeneous Buchwald-Hartwig amination using shape-controlled Pd nanocrystals with distinctly different surface facets is presented.

Polyoxometalates (POMs), as inorganic ligands, can endow metal nanocrystals (NCs) with unique reactivities on account of their characteristic redox properties. In the present work, we present a facile POM-mediated one-pot aqueous synthesis method for the production of single-crystalline Pd NCs with controlled shapes and sizes. The POMs could function as both reducing and stabilizing agents in the formation of NCs, and thus gave a fine control over the nucleation and growth kinetics of NCs. The prepared POM-stabilized Pd NCs exhibited excellent catalytic activity and stability for electrocatalytic (formic acid oxidation) and catalytic (Suzuki coupling) reactions compared to Pd NCs prepared without the POMs. This shows that the POMs play a pivotal role in determining the catalytic performance, as well as the growth, of NCs. We envision that the present approach can offer a convenient way to develop efficient NC-based catalyst systems.

We report a systematic study on the correlation of the modified electronic structure of nanocrystal catalysts with the adsorption properties of the substrate and the resultant catalytic activity by using Baeyer–Villiger oxidation catalyzed by composition‐controlled Pt‐based nanocubes (NCs) as a model heterogeneous catalysis reaction. The incorporation of 3d transition metals into Pt to form PtM (M=Zn, Co, and Ni) alloy NCs allowed fine‐tuning of the electronic structure of Pt. PtM NCs with a higher‐lying d band center exhibited higher catalytic performance owing to the enhanced initial activation of the carbonyl group of the substrate. This work emphasizes the importance of fine‐tuning the electronic structure of heterogeneous catalysts to advance their catalytic function.