Thermal Stability of Au Rhombic Dodecahedral Nanocrystals Can Be Greatly Enhanced by Coating Their Surface with an Ultrathin Shell of Pt.

Rhombic dodecahedral nanocrystals have been considered particularly difficult to synthesize because they are enclosed by {110}, a low-index facet with the greatest surface energy. Recently, we demonstrated the use of seed-mediated growth for the facile and robust synthesis of Au rhombic dodecahedral nanocrystals (AuRD). While the unique shape and surface structure of AuRD are desirable for potential applications in plasmonics and catalysis, respectively, their high surface energy makes them highly susceptible to thermal degradation. Here we demonstrate that it is feasible to greatly improve the thermal stability with some sacrifice to the plasmonic properties of the original AuRD by coating their surface with an ultrathin shell made of Pt. Our in situ electron microscopy analysis indicates that the ultrathin Pt coating can increase the thermal stability from 60 up to 450 °C, a trend that is also supported by the results from a computational study.

Twin Proliferation and Prolongation under Kinetic Control: Pd-Au Janus Icosahedra versus Pd@Au Core-Shell Starfishes.

Heterogeneous bimetallic nanocrystals featuring explicit spatial configurations and abundant twin defects can simultaneously enable geometric and ligand effects to enhance catalytic and photonic applications. Herein, we report two growth patterns of Au atoms on penta-twinned Pd decahedra, involving twin proliferation to generate asymmetric Pd-Au Janus icosahedra and twin elongation to produce anisotropic Pd@Au core-shell starfishes, respectively. Mechanistic analysis indicates that the injection rate determines the lower-limit number (nlow) of Au(III) ions in the steady state and thus controls the growth pattern. When nlow ≤ 5.5, the kinetic rate is slow enough to initiate asymmetrical one-side growth but fast enough to outpace surface diffusion; Au tetrahedral subunits are successively proliferated along the axial ⟨110⟩ direction of Pd decahedra to form Pd-Au Janus icosahedra. Composed of five Pd and 15 Au tetrahedral subunits, such a heterogeneous icosahedron supports high (2.2 GPa) tensile strain and high strain difference up to +21.9%. In contrast, when nlow > 5.5, the fast reduction kinetics promotes symmetric growth with inadequate surface diffusion. As such, Au atoms are laterally deposited along five high-indexed ⟨211⟩ ridges of Pd decahedra to generate concave Pd@Au core-shell starfishes with tunable sizes (28-40 nm), twin elongation ratios (33.82-162.08%), and lattice expansion ratios (8.82-20.10%).

Phase-Controlled Synthesis of Ru Nanocrystals via Template-Directed Growth: Surface Energy versus Bulk Energy.

Despite the successful control of crystal phase using template-directed growth, much remains unknown about the underlying mechanisms. Here, we demonstrate that the crystal phase taken by the deposited metal depends on the lateral size of face-centered cubic (fcc)-Pd nanoplate templates with 12 nm plates giving fcc-Ru while 18-26 nm plates result in hexagonal closed-packed (hcp)-Ru. Although Ru overlayers with a metastable fcc- (high in bulk energy) or stable hcp-phase (low in bulk energy) can be epitaxially deposited on the basal planes, the lattice mismatch will lead to jagged hcp- (high in surface energy) and smooth fcc-facets (low in surface energy), respectively, on the side faces. As the proportion of basal and side faces on the nanoplates varies with lateral size, the crystal phase will change depending on the relative contributions from the surface and bulk energies. The Pd@fcc-Ru outperforms the Pd@hcp-Ru nanoplates toward ethylene glycol and glycerol oxidation reactions.

Rh@Au Core-Shell Nanocrystals with the Core in Tensile Strain and the Shell in Compressive Strain.

Bimetallic nanocrystals provide a versatile platform for utilizing the desired characteristics of two different elements within one particle. Core-shell nanocrystals, in particular, have found widespread use in catalysis by providing an ability to leverage the strains arising from the lattice mismatch between the core and the shell. However, large (>5%) lattice mismatch tends to result in nonepitaxial growth and lattice defects in an effort to release the strain. Herein, we report the epitaxial growth of Au on Rh cubic seeds under mild reaction conditions to generate Rh@Au truncated octahedra featuring a lattice mismatch of 7.2%. Key to the success was the use of small (4.5 nm) Rh cubes as seeds, which could homogeneously distribute the tensile strain arising from the epitaxial growth of a conformal, compressively strained Au shell. Further, delicate tuning of kinetic parameters through the introduction of NaOH and KBr into the synthesis allowed for a unique nucleation pattern that led to centrally located cores and a narrow size distribution for the product. A thorough investigation of the various possible highly strained morphologies was conducted to gain a full understanding of the system.

Silver Nanocubes: From Serendipity to Mechanistic Understanding, Rational Synthesis, and Niche Applications.

Silver has long been interwoven into human history, and its uses have evolved from currency and jewelry to medicine, information technology, catalysis, and electronics. Within the last century, the development of nanomaterials has further solidified the importance of this element. Despite this long history, there was essentially no mechanistic understanding or experimental control of silver nanocrystal synthesis until about two decades ago. Here we aim to provide an account of the history and development of the colloidal synthesis of silver nanocubes, as well as some of their major applications. We begin with a description of the first accidental synthesis of silver nanocubes that spurred subsequent investigations into each of the individual components of the protocol, revealing piece by piece parts of the mechanistic puzzle. This is followed by a discussion of the various obstacles inherent to the original method alongside mechanistic details developed to optimize the synthetic protocol. Finally, we discuss a range of applications enabled by the plasmonic and catalytic properties of silver nanocubes, including localized surface plasmon resonance, surface-enhanced Raman scattering, metamaterials, and ethylene epoxidation, as well as further derivatization and development of size, shape, composition, and related properties.

Facile Synthesis of Palladium-Based Nanocrystals with Different Crystal Phases and a Comparison of Their Catalytic Properties.

A relatively unexplored aspect of noble-metal nanomaterials is polymorphism, or their ability to crystallize in different crystal phases. Here, a method is reported for the facile synthesis of Ru@Pd core-shell nanocrystals featuring polymorphism, with the core made of hexagonally close-packed (hcp)-Ru while the Pd shell takes either an hcp or face-centered cubic (fcc) phase. The polymorphism shows a dependence on the shell thickness, with shells thinner than ≈1.4 nm taking the hcp phase whereas the thicker ones revert to fcc. The injection rate provides an experimental knob for controlling the phase, with one-shot and drop-wise injection of the Pd precursor corresponding to fcc-Pd and hcp-Pd shells, respectively. When these nanocrystals are tested as catalysts toward formic acid oxidation, the Ru@Pdhcp nanocrystals outperform Ru@Pdfcc in terms of both specific activity and peak potential. Density functional theory calculations are also performed to elucidate the origin of this performance enhancement.