Poly(N-Heterocyclic Carbene)-Capped Alloy and Core-Shell AuAg Bimetallic Nanoparticles.

N-Heterocyclic carbene (NHC)-stabilized metal nanoparticles (NPs) have recently attracted considerable attention. While most efforts in the field have been devoted to the development of NHC-tethered monometallic NPs and enhancing their stabilities under various conditions, their bimetallic counterparts are rare in the literature. Herein, we demonstrate that the covalent immobilization of Au and Ag atoms on polymerized NHCs is a powerful method to access bimetallic AuAg NPs. In addition, we show that while AuAg alloy NPs are often obtained via this method, the use of bimetallic polymeric substrates with lower Ag content, relative to Au, results in the formation of core-shell NPs with Au core and Ag shell. Application of these nanomaterials for oxygen reduction reaction is demonstrated with all materials exhibiting electrocatalytic activity. This work demonstrates for the first time that while bimetallic poly(NHC-metal)s are viable substrates to access NHC-stabilized bimetallic NPs, careful adjustment of metal content in the polymeric substrates can finetune the microstructure of the resulting NPs, i.e. alloy vs. core-shell.

Ultrathin Atomic Layer Deposited Al2O3 Overcoat Stabilizes Al2O3-Pt/Ni-Foam Hydrogenation Catalysts.

Galvanic exchange seeds the growth of Pt nanostructures on the Ni foam monolith. Subsequent atomic layer deposition of ultrathin Al2O3 followed by annealing under air affords supported Pt catalysts with ultralow loading (0.020 ppm). In addition to the expected enhancement of the stability of the Pt particles on the surface, the ∼2 nm Al2O3 overcoat appears to also play a crucial role in the overall structural integrity of the NiOx nanoplates that grow on the Ni foam surface as a result of the preparative route. The resulting material is physically robust toward repeated handling and showcases retention of catalytic activity over 10 standard catalyst recycling trials, standing in marked contrast to the uncoated samples. Catalyst activity was tested via the hydrogenation of various functionalized styrenes at low temperatures and low hydrogen pressure in ethanol as a solvent, with a TOF as high as 9.5 × 106 h-1 for unfunctionalized styrene. Notably, the catalysts show excellent tolerance toward F, Cl, and Br substituents and no hydrogenation of the aromatic ring.