Ligand-Controlled Co-reduction versus Electroless Co-deposition: Synthesis of Nanodendrites with Spatially Defined Bimetallic Distributions

Abstract

The predictable synthesis of bimetallic nanostructures via co-reduction of two metal precursors is challenging due to our limited understanding of precursor ligand effects. Here, the influence of different metal-ligand environments is systematically examined in the synthesis of Pd-Pt nanostructures as a model bimetallic system. Nanodendrites with different spatially defined Pd-Pt compositions are achieved, where the local ligand environments of metal precursors dictate if temporally separated co-reduction dominates to achieve core-shell nanostructures or whether electroless co-deposition proceeds to facilitate alloyed nanostructure formation. As the properties of bimetallic nanomaterials depend on crystal ordering and composition, chemical routes to structurally defined bimetallic nanomaterials are critically needed. The approaches reported here should be applicable to other bimetallic compositions given the established reactivity of coordination complexes available for use as precursors.

Facile Synthesis of Rhodium Icosahedra with Controlled Sizes up to 12 nm

“…Because benzyla lcoholi sa na mphiphilic solvent, am ixture of oleylamine (OAm) and oleic acid (OAc) can be used as organic stabilizers and weak reducing agents insteado fP VP in the standard protocol. [33,34,38,39] As reported in literature, OAm exhibited relativelys tronger reducing power and stabilizing behavior than OAc during the synthesis of noble-metaln anocrystals. [33,38] In this case, the reduction kinetics required for the evolution of Rh twinned nanocrystals can be achieved by adjustingt he volumetric ratio of OAm to OAc (V OAm /V OAc ).…”

“…The thermal decomposition of aR hp recursorc ompound to aR hi on and then the reduction to aR h atom is governed by the denticity of ligand binding to Rh in the precursor. [33,34] As such, it makes ense to compareR hp recursors adopting different ligands. In our standardp rotocol, bidentate acetylacetonate is the ligand for Rh in precursor Rh(acac) 3 ,w hich binds more strongly than the mono-dentate ligandss uch as nitrate,h alides, and carbon monoxide.…”

Dual Metastability in Electroless Plating: Complex Inertness Enabling the Deposition of Composition‐Tunable Platinum Copper Alloy Nanostructures

“…Aside the reducer, additives and ligands can also cause interferences. For instance, while complexation represents a powerful strategy for tailoring the electrochemical reactivity, limitations arise due to the concurrent effect of ligands on all present metal ions.…”

Attachment-based growth: building architecturally defined metal nanocolloids particle by particle

“…In addition to these thermodynamic parameters, reconstruction of interface atoms upon collision to form strong metallic bonds is important. PdPt, [30][31][32][33] PdAg, 30 PdPtAg, 30 PtRh, 34 AuAg, 35 PdCu, 36 PtFe, 8 PtAg, 29 AuPd, 37 PtRu 38 ) have been synthesized by co-reduction of different metal salts coupled with growth by oriented attachment. The results showed that Ag can easily diffuse at the Pt 50 Ag 50 particle interfaces, whereas Pt does not at Pt particle interfaces (Fig.…”