Seed-mediated co-reduction in a large lattice mismatch system: synthesis of Pd-Cu nanostructures.

Metal nanoparticles (NPs) are of interest for applications in catalysis, electronics, chemical sensing, and more. Their utility is dictated by their composition and physical parameters such as particle size, particle shape, and overall architecture (e.g., hollow vs. solid). Interestingly, the addition of a second metal to create bimetallic NPs adds multifunctionality, with new emergent properties common. However, synthesizing structurally defined bimetallic NPs remains a great challenge. One synthetic pathway to architecturally controlled bimetallic NPs is seed-mediated co-reduction (SMCR) in which two metal precursors are simultaneously co-reduced to deposit metal onto shape-controlled metal seeds, which direct the overgrowth. Previously demonstrated in a Au-Pd system, here SMCR is applied to a system with a larger lattice mismatch between the depositing metals: Pd and Cu (7% mismatch for Pd-Cu vs. 4% for Au-Pd). Through manipulation of precursor reduction kinetics, the morphology and bimetallic distribution of the resultant NPs can be tuned to achieve eight-branched Pd-Cu heterostructures with Cu localized at the tips of the Pd nanocubes as well as branched Pd-Cu alloyed nanostructures and polyhedra. Significantly, the symmetry of the seeds can be transferred to the final nanostructures. This study expands our understanding of SMCR as a route to structurally defined bimetallic nanostructures and the synthesis of multicomponent nanomaterials more generally.

Seeding a New Kind of Garden: Synthesis of Architecturally Defined Multimetallic Nanostructures by Seed-Mediated Co-Reduction.

Bimetallic nanoparticles display unique optical and catalytic properties that depend on crystallite size and shape, composition, and overall architecture. They may serve as multifunctional platforms as well. Unfortunately, many routes toward shape and architecturally controlled bimetallic nanocrystals yield polydisperse samples on account of the challenges associated with homogeneously nucleating a defined bimetallic phase by co-reduction methods. Developed by the Skrabalak laboratory, seed-mediated co-reduction (SMCR) involves the simultaneous co-reduction of two metal precursors to deposit metal onto shape-controlled metal nanocrystalline seeds. The central premise is that seeds will serve as preferential and structurally defined platforms for bimetallic deposition, where the shape of the seeds can be transferred to the shells. With Au-Pd as a model system, a set of design principles has been established for the bottom-up synthesis of shape-controlled bimetallic nanocrystals by SMCR. This strategy is successful at synthesizing symmetrically stellated Au-Pd nanocrystals with a variety of symmetries and core@shell Au@Au-Pd nanocrystals. Achieving nanocrystals with high morphological control via SMCR is governed by the following parameters: seed size, shape, and composition as well as the kinetics of seeded growth (through manipulation of synthetic parameters such as pH and metal precursor ratios). For example, larger seeds yield larger nanocrystals as does increasing the amount of metal deposited relative to the number of seeds. This increase in nanocrystal size leads to red-shifts in their localized surface plasmon resonance. Additionally, seed shape directs the overgrowth process during SMCR so the resultant nanocrystals adopt related symmetries. The ability to tune structure is important due to the size-, shape- and composition-dependent optical properties of bimetallic nanocrystals. Using this toolkit, the light scattering and absorption properties of Au-Pd octopods, 8-branched nanocrystals, could be tuned and were shown to be highly sensitive to changes in refractive index. The refractive index sensitivity displayed a linear correlation to the localized surface plasmon resonance initial position, where the sensitivity is greater than that of monometallic Au structures. Due to their bimetallic composition and unique architecture enabled by SMCR, Au-Pd octopods are promising refractive index based sensors. This Account summarizes the underlying principles for synthesis of bimetallic nanocrystals by SMCR, which have been established by systematic manipulation of synthetic parameters in a model Au-Pd system. These principles are anticipated to be general to other bimetallic systems, allowing for the design and synthesis of new nanocrystals with fascinating optical and catalytic properties.