Cyclic penta-twinned noble metal nanocrystals exhibit promising properties due to their unique geometric and electronic structures. However, the controlled synthesis of cyclic penta-twinned nanostructures, especially of noble metals with a high cohesive energy (e.g., Rh), is very difficult, and the corresponding growth mechanism is not fully understood. Herein, we report a facile one-pot hydrothermal approach for the synthesis of cyclic penta-twinned Rh icosahedral nanocrystals. It was found that apart from regulating the surface free energy by changing the concentration or category of the capping agents, the solvent might influence the adsorption ability of the surfactant on the Rh crystal surface, which results in a change in the surface free energy and thus allows the formation of Rh cyclic penta-twinned nanostructures. In addition, due to their unique electronic and geometric structures, the Rh icosahedral nanocrystals exhibit superior catalytic activity and stability for the electrooxidation of ethanol as compared to single-crystal Rh tetrahedral nanocrystals and commercial Rh black.

Rh is an important catalyst that is widely used in a variety of organic reactions. In recent years, many efforts have focused on improving its catalytic efficiency by fabricating catalyst nanoparticles with controlled size and morphology. However, the frequently employed synthesis route using organic compounds either as the reaction medium or capping agent often results in residual molecules on the catalyst surface, which in turn drastically diminishes the catalytic performance. Herein, we report a facile, aqueous, surfactant-free synthesis of a novel Rh flowerlike structure obtained via hydrothermal reduction of Rh(acac)₃ by formaldehyde. The unique Rh nanoflowers were constructed from ultrathin nanosheets, whose basal surfaces comprised {111} facets with an average thickness of ~1.1 nm. The specific surface area measured by CO stripping was 79.3 m²·g^-1, which was much larger than that of commercial Rh black. More importantly, the Rh nanoflower catalyst exhibited excellent catalytic performance in the catalytic hydrogenation of phenol and cyclohexene, in contrast to the commercial Rh black and polyvinyl pyrrolidone (PVP)-capped Rh nanosheets exposed by similar {111} basal surfaces.

Researchers appear to have neglected a special form of crystallites, pentagonal cyclic twinning, in which an obvious two-dimensional lattice expansion exists leading to novel physical–chemical properties associated with the changes in geometric and electronic structures. Using the storage and release of hydrogen in Pd nanocrystals as a probe, we have found that icosahedral pentagonal cyclic twinned Pd nanocrystals had distinct hydrogen storage properties, due to the two-dimensional lattice expansions, quite different from those of the octahedral single crystalline counterpart. In addition, the two-dimensional lattice expansion in pentagonal cyclic twinned Pd nanocrystals causes a change in electronic structure, which results in novel catalytic properties involving in situ formation of PdH_x pentagonal cyclic twinned nanocrystals.

Rational synthesis of bimetallic alloy nanocrystals (NCs) is still a great challenge. Especially, spatially uniform alloy NCs are very difficult to achieve because of the different reduction rates of the individual alloy components. Herein we propose a facile wet chemical synthetic strategy to prepare uniform bimetallic alloy NCs with tunable composition by controlling the growth of alloy NCs under diffusion controlled conditions. Using this strategy, we successfully synthesized trisoctahedral (TOH) Au–Pd alloy NCs enclosed by {hhl} high-index facets with uniform spatial distributions and different compositions. Significantly, using our strategy, the composition of the as-prepared Au–Pd alloy NCs is identical to the ratio of the two metal precursors in the reaction solution over a wide range. Investigation of the composition-dependent electrochemical behavior of the as-prepared TOH Au–Pd alloy NCs showed that the TOH Au–Pd alloy NCs containing 14.1 atom% Pd exhibited the best activity.

Platinum (Pt) is an outstanding catalyst for many important industrial products. Because of its high cost and scarce reserves, it is very important to improve the performance of Pt catalysts. As the metal nanocrystals (NCs) with high-index surfaces usually show very good catalytic activity because of their high density of atomic steps and kinks, the preparation of Pt NCs with high-index facets has become a very important and hot research topic recently. In this article, we report a facile synthesis of high-yield Pt NCs with a series of {hkk} high-index facets including {211} and {411} via a solvothermal method using Pt(II) acetylacetonate as the Pt source, 1-octylamine as the solvent and capping agent, and formaldehyde as an additional surface structure regulator. Multipod Pt NCs with dominant {211} side surfaces were produced without formaldehyde, while concave Pt NCs with dominant {411} surfaces formed under the influence of formaldehyde. By analyzing the products by IR spectroscopy, we found the presence of CO on the surface of concave Pt NCs with {411} surfaces prepared from the solution containing formaldehyde. It was concluded that amine mainly stabilized the monoatomic step edges, resulting in the {211} exposed surface; with addition of formaldehyde, it decomposed into CO, leading to the formation of {411} surfaces by the additional adsorption of the CO on the {100} terraces. In addition, it was found that the as-prepared Pt NCs with high-index {211} and {411} surfaces exhibited much better catalytic activity in the electro-oxidation of ethanol than a commercial Pt/C catalyst or Pt nanocubes with low-index {100} surfaces, and the catalytic activities of Pt crystal facets decreased in the sequence {411} > {211} > {100}.

Hexagram shaped gold particles and their analogues enclosed by high index facets with kinks have been successfully synthesized by reducing HAuCl₄ with ascorbic acid (AA) in the presence of poly(diallyldimethylammonium chloride) at room temperature. By using electron microscopy, the surfaces of the hexagram shaped Au particle were found to be {541} planes, which contain high-density steps and kinks. In addition, it was found that hexagonal shield-like and other kind of particles present in the product were analogues of the hexagram shaped Au particles structure, in that they had the same surface structure. In order to confirm the surface structure of all the prepared particles, surface structure sensitive underpotential deposition of Pb was carried out, and the cyclic voltammetric profile was in accordance with the proposed {541} surface. Finally, structure–property relationships of the Au hexagrams were experimentally analyzed by employing the electrocatalytic oxidation of AA as a probe reaction. The electrocatalytic reactions of gold cubes with low-index {100} facets and gold trioctahedra with {221} facets were studied as references. The experimental results showed that the hexagram shaped Au particles and their analogues with exposed {541} facets have the highest catalytic activity among the three kinds of gold particles, owing to the high density of kink atoms. This study should motivate us to further explore methods for the preparation of other well-defined polyhedral metal nanocrystals enclosed by high index surfaces.