Synthesis Of Noble Metal Nanocrystals Research Articles

Effects of Ligands on Synthesis and Surface‐Engineering of Noble Metal Nanocrystals for Electrocatalysis

AbstractNoble metal nanocrystals are a family of important catalysts for a broad range of processes (especially electrocatalytic ones), which are usually obtained as a hybrid each containing a metallic core and a ligand shell. It is well recognized that the ligand plays a critical role in regulating the crystal growth into different shapes and maintaining the colloidal stability of the nanocrystals. Recently, more effects of the ligand were revealed in controlling both the synthesis and the surface property of noble metal nanocrystals, which could be maneuvered to achieve distinctive catalytic properties. In this review, we present a summary of the roles of the ligand based on typical results from the literature. The review begins with a discussion on the roles of the ligand in the controlled synthesis of noble metal nanocrystals, including the shape control, the reduction potential control for suppressing self‐nucleation and galvanic replacement reaction, and the electroless plating effect for noble metal/non‐noble metal co‐reduction. The following section includes a discussion of the effects of the ligand on the surface property of noble metal nanocrystals, including the ensemble size engineering, the ligand‐metal electron transfer, and the local microenvironment construction, toward designable electrocatalytic properties. At the end, we provide our perspectives on the future research of ligand engineering as an advanced technique for tailoring electrocatalytic properties of noble metal nanocrystals.

Shape-Controlled Photochemical Synthesis of Noble Metal Nanocrystals Based on Reduced Graphene Oxide.

The fabrication of supported noble metal nanocrystals (NCs) with well-controlled morphologies have been attracted considerable interests due to their merits in a wide variety of applications. Photodeposition is a facile and effective method to load metals over semiconductors in a simple slurry reactor under irradiation. By optimizing the photodeposition process, the size, chemical states, and the geometrical distribution of metal NCs have been successfully tuned. However, metal NCs with well-controlled shapes through the photodeposition process have not been reported until now. Here, we report our important advances in the controlled photodeposition process to load regular noble metal NCs. Reduced graphene oxide (rGO) is introduced as a reservoir for the fast transfer of photoelectrons to avoid the fast accumulation of photogenerated electrons on the noble metals which makes the growth process uncontrollable. Meanwhile, rGO also provides stable surface for the controlled nucleation and oriented growth. Noble metal NCs with regular morphologies are then evenly deposited on rGO. This strategy has been demonstrated feasible for different precious metals (Pd, Au, and Pt) and semiconductors (TiO2, ZnO, ZrO2, CeO2, and g-C3N4). In the prototype application of electrochemical hydrogen evolution reaction, regular Pd NCs with enclosed {111} facets showed much better performance compared with that of irregular Pd NCs.

Silver‐Alkylamine Complex Mediated Single Micelle toward Synthesis of Sub‐8 nm Silver Nanocrystals

AbstractSmall size and narrow distribution are the key factors to improve performances of metal nanocrystals due to nanosize effect. Here, a silver‐alkylamine complex–mediated single micelle, a one‐pot approach, for controlled synthesis of monodisperse silver nanocrystals, in which oleylamine molecules play key roles serving both as complex agent and as micellar coalescence blocker is reported. After the synthesis, monodisperse products can be directly collected through subsequent single‐step separation as the particle size is finely adjusted during the synthesis. Dual‐soluble silver oleylamine complex is prepared through liquid phase complexing and is used as oil‐soluble precursor in single reverse micelle. The as‐synthesized silver nanocrystals are very uniform with a controlled size of 6.00 ± 0.29 or 8.0 ± 0.40 nm and a narrow size distribution with a standard deviation (σ) of ≈5.0%. The protocol offers a general platform for fast synthesis of noble metal nanocrystals with rationally designed size and structure.

Size and Shape Controlled Synthesis of Pd Nanocrystals

Abstract Palladium (Pd) has attracted substantial academic interest due to its remarkable properties and extensive applications in many industrial processes and commercial devices. The development of Pd nanocrystals (NCs) would contribute to reduce overall precious metal loadings, and allow the efficient utilization of energy at lower economic costs. Furthermore, some of the important properties of Pd NCs can be substantially enhanced by rational designing and tight controlling of both size and shape. In this review, we have summarized the state-of-the-art research progress in the shape and size-controlled synthesis of noble-metal Pd NCs, which is based on the wet-chemical synthesis. Pd NCs have been categorized into five types: (1) single-crystalline Pd nano-polyhedra with well-defined low-index facets (e.g. {100}, {111} and {110}); (2) single-crystalline Pd nano polyhedra with well-defined high-index facets, such as Pd tetrahexahedra with {hk0} facets; (3) Pd NCs with cyclic penta-twinned structure, including icosahedra and decahedra; (4) monodisperse spherical Pd nanoparticles; (5) typical anisotropic Pd NCs, such as nanoframes, nanoplate, nanorods/wires. The synthetic approach and growth mechanisms of these types of Pd NCs are highlighted. The key factors that control the structures, including shapes (surface structures), twin structures, single-crystal nanostructures, and sizes are carefully elucidated. We also introduce the detailed characterization tools for analysis of Pd NCs with a specific type. The challenges faced and perspectives on this promising field are also briefly discussed. We believe that the detailed studies on the growth mechanisms of NCs provide a powerful guideline to the rational design and synthesis of noble-metal NCs with enhanced properties. Graphical Abstract:

Chirality-Controlled Syntheses of Double-Helical Au Nanowires.

The selective large-scale syntheses of noble metal nanocrystals with complex shapes using wet-chemical approaches remain exciting challenges. Here we report the chirality-controllable syntheses of double-helical Au nanowires (NWs) using chiral soft-templates composed of two organogelators with their own active functions; one organogelator serves to introduce helicity into the template and the other acts as a capping agent to control the Au shape. One-dimensional twisted-nanoribbon templates are prepared simply by mixing the two organogelators in water containing a small amount of toluene, followed by the addition of LiCl; template chirality is controlled through the selection of the handedness of the helicity-inducing organogelator. Double-helical Au NWs synthesized on these chiral templates have the same helical structure as the template because the Au NWs grow along both edges of the twisted nanoribbons with right- or left-handed helicities. Dispersions of the right- and left-handed double-helical Au NWs exhibit opposite CD signals.

Surfactant dependent evolution of Au-Pd alloy nanocrystals from trisoctahedron to excavated rhombic dodecahedron and multipod: a matter of crystal growth kinetics

In wet chemical syntheses of noble metal nanocrystals, surfactants play crucial roles in regulating their morphology. To date, more attention has been paid to the effect of the surfactant on the surface energy of crystal facets, while less attention has been paid to its effect on the growth kinetics. In this paper, using the growth of Au-Pd alloy nanocrystals as an example, we demonstrate that different concentration of surfactant hexadecyltrimethyl ammonium chloride (CTAC) may cause the different packing density of CTA+ bilayers on different sites (face, edge or vertex) of crystallite surface, which would change the crystal growth kinetics and result in preferential crystal growth along the edge or vertex of crystallites. The unique shape evolution from trisoctahedron to excavated rhombic dodecahedron and multipod structure for Au-Pd alloy nanocrystals was successfully achieved by simply adjusting the concentration of CTAC. These results help to understand the effect of surfactants on the shape evolution of nanocrystals and open up avenues to the rational synthesis of nanocrystals with the thermodynamically unfavorable morphologies.

Template Synthesis of Noble Metal Nanocrystals with Unusual Crystal Structures and Their Catalytic Applications.

Noble metal nanocrystals own high chemical stability, unique plasmonic and distinctive catalytic properties, making them outstanding in many applications. However, their practical applications are limited by their high cost and scarcity on the earth. One promising strategy to solve these problems is to boost their catalytic performance in order to reduce their usage amount. To realize this target, great research efforts have been devoted to the size-, composition-, shape- and/or architecture-controlled syntheses of noble metal nanocrystals during the past two decades. Impressively, recent experimental studies have revealed that the crystal structure of noble metal nanocrystals can also significantly affect their physicochemical properties, such as optical, magnetic, catalytic, mechanical, electrical and electronic properties. Therefore, besides the well-established size, composition, shape, and architecture control, the rise of crystal structure-controlled synthesis of noble metal nanocrystals will open up new opportunities to further improve their functional properties, and thus promote their potential applications in energy conversion, catalysis, biosensing, information storage, surface enhanced Raman scattering, waveguide, near-infrared photothermal therapy, controlled release, bioimaging, biomedicine, and so on. In this Account, we review the recent research progress on the crystal structure control of noble metal nanocrystals with a template synthetic approach and their crystal structure-dependent catalytic properties. We first describe the template synthetic methods, such as epitaxial growth and galvanic replacement reaction methods, in which a presynthesized noble metal nanocrystal with either new or common crystal structure is used as the template to direct the growth of unusual crystal structures of other noble metals. Significantly, the template synthetic strategy described here provides an efficient, simple and straightforward way to synthesize unusual crystal structures of noble metal nanocrystals, which might not be easily synthesized by commonly used chemical synthesis. To be specific, by using the epitaxial growth method, a series of noble metal nanocrystals with unusual crystal structures has been obtained, such as hexagonal close-packed Ag, 4H Ag, Pd, Pt, Ir, Rh, Os, and Ru, and face-centered cubic Ru nanostructures. Meanwhile, the galvanic replacement reaction method offers an efficient way to synthesize noble metal alloy nanocrystals with unusual crystal structures, such as 4H PdAg, PtAg, and PtPdAg nanostructures. We then briefly introduce the stability of noble metal nanocrystals with unusual crystal structures. After that, we demonstrate the catalytic applications of the resultant noble metal nanocrystals with unusual crystal structures toward different chemical reactions like hydrogen evolution reaction, hydrogen oxidation reaction and organic reactions. The relationship between crystal structures of noble metal nanocrystals and their catalytic performances is discussed. Finally, we summarize the whole paper, and address the current challenges and future opportunities for the template synthesis of noble metal nanocrystals with unusual crystal structures. We expect that this Account will promote the crystal structure-controlled synthesis of noble metal nanocrystals, which can provide a new way to further improve their advanced functional properties toward their practical applications.

ChemInform Abstract: Noble‐Metal Nanocrystals with Controlled Facets for Electrocatalysis

AbstractReview: 145 refs.

ChemInform Abstract: Shape‐Controlled Synthesis of Au—Pd Bimetallic Nanocrystals for Catalytic Applications

AbstractReview: 111 refs.

Noble-Metal Nanocrystals with Controlled Facets for Electrocatalysis.

Noble-metal nanocrystals (NCs) show excellent catalytic performance for many important electrocatalysis reactions. The crystallographic properties of the facets by which the NCs are bound, closely associated with the shape of the NCs, have a profound influence on the electrocatalytic function of the NCs. To develop an efficient strategy for the synthesis of NCs with controlled facets as well as compositions, understanding of the growth mechanism of the NCs and their interaction with the chemical species involved in NC synthesis is quite important. Furthermore, understanding the facet-dependent catalytic properties of noble-metal NCs and the corresponding mechanisms for various electrocatalysis reactions will allow for the rational design of robust electrocatalysts. In this review, we summarize recently developed synthesis strategies for the preparation of mono- and bimetallic noble-metal NCs by classifying them by the type of facets through which they are enclosed and discuss the electrocatalytic applications of noble-metal NCs with controlled facets, especially for reactions associated with fuel-cell applications, such as the oxygen reduction reaction and fuel (methanol, ethanol, and formic acid) oxidation reactions.

Large-Scale Synthesis of Metal Nanocrystals in Aqueous Suspensions

Fundamental studies and practical use of metal nanoparticles (NPs) frequently depend on the ability to reproducibly synthesize large quantities of shape-specific NPs. For this reason, facile synthetic procedures are desired that will lead to large quantities of uniformly sized metal NPs exhibiting specific shapes. Here, we report a general approach to the large-scale synthesis of noble metal nanocrystals having well-defined shapes and a narrow size distribution. This method utilizes seed-mediated NP growth in aqueous suspensions of cationic surfactants and metal salts. It leads to a ∼60-fold increase in NP volumetric production capacity, compared to the most widely used solution-based synthetic methods. In addition, it uses up to 100 times less cationic surfactant than conventional solution-based methods. The applicability of the method is demonstrated in the synthesis of Pd nanocubes, rhombic dodecahedra, and polyhedrons with low index facets; branched Pd nanocrystals; alloy Pt/Pd nanocubes; Ag nanocubes...

High‐Indexed Pt3Fe Nanocatalysts and Their Enhanced Catalytic Performance in Dual Organic Reactions

AbstractThe synthesis of noble metal nanocrystals terminated with high‐index facets has received increasing attention due to the remarkable improvement in their catalytic performance. Introducing a transition metal to noble metals (bimetallic nanocrystals) could result in a reduced cost and potentially improve properties. Keeping in mind both of these advantages, we have developed a new synthetic approach to fabricate size‐controlled Pt3Fe concave nanocubes using a high‐temperature organic solution system containing oleylamine and oleic acid. It further demonstrates that the particle size and concavity could be controlled by a number of parameters such as the ratio of oleylamine and oleic acid, the physicochemical properties of the metal carbonyl, the metal valence in the precursor, and the ratio of metal precursors. Catalytic tests show that the high‐index‐surface‐terminated ≈12 nm Pt3Fe concave nanocubes exhibit superior performance in both the hydrogenation of styrene and reduction of 4‐nitrophenol in comparison with their counterparts.

Seed-mediated growth of noble metal nanocrystals: crystal growth and shape control

Controlled synthesis of noble metal nanocrystals has received enormous attention due to the ability of tailoring the properties of nanocrystals by tuning their shape, size, and composition. The seed-mediated growth method is one of the most reliable and versatile methods to control the shapes of noble metal nanocrystals. This feature article highlights recent strategies regarding shape-controlled synthesis of noble metal nanocrystals by the seed-mediated growth method, with the aim of introducing new strategies and offering new mechanistic insights into nanocrystal shape evolution. Critical parameters affecting the nucleation and growth of noble metal NCs are systemically introduced and analyzed. New developments of extended seed-mediated growth methods were also introduced. Finally, the perspectives of future research on the seed-mediated growth method are also discussed.

Surfactant‐Concentration‐Dependent Shape Evolution of Au–Pd Alloy Nanocrystals from Rhombic Dodecahedron to Trisoctahedron and Hexoctahedron

The surface structure-controlled synthesis of noble metal nanocrystals (NCs) bounded by high-index facets has become a hot research topic due to their potential to significantly improve catalytic performance. This study reports the preparation of monodisperse Au-Pd alloy NCs with systematic shape evolution from rhombic dodecahedral (RD) to trisoctahedral (TOH), and hexoctahedral (HOH) structures by varying the concentration of surfactant in the surfactant-mediated synthesis. The as-prepared three kinds of alloy NCs possess almost the same size and composition as each other. It is suggested that the surfactant containing long-chain octadecyltrimethyl ammonium (OTA(+)) ions plays a key role in the formation of high index facets, and the crystal growth kinetics may also have an effect on the formation of different nanocrystal morphologies. In addition, the catalytic activities of these NCs are evaluated by structure-sensitive reactions, including ethanol electro-oxidation and the catalytic reduction of 4-nitrophenol (4-NPh). These three types of Au-Pd alloy NCs exhibit different catalytic selectivities towards these two reactions. The catalytic activities toward electro-oxidation of ethanol are in the order of HOH > RD > TOH, which follows the order of their corresponding surface energies. However, the activities toward catalytic reduction of 4-NPh are in the order of RD > TOH > HOH, which should be related to the local structure of the surfaces.

Progresses on syntheses of the noble-metal nanocrystals with exposed high-index facets

Due to the presence of high-density atoms on the steps and kinks, the noble-metal nanocrystals with high-index facets usually perform superb phisical/chemical properites and have important applications in catalysis and electrochemistry etc. In recent years, the syntheses of noble-metal nanocrystals with high-index facets has become a hot research topic, and important progresses have been proceeded. This review summarized achivements about the syntheses of noble-metal nanocrystals with high-index facets exposed. We specially focused on the systhetic methods from the aspects of electrochemical method, capping agent method, under-potential- deposition of foreign metal atoms, kinetic control, oxdative etching and growth, and templated method.

Synthesis of Nanocrystals with Variable High-Index Pd Facets through the Controlled Heteroepitaxial Growth of Trisoctahedral Au Templates

The shape-controlled synthesis of noble metal nanocrystals (NCs) bounded by high-index facets is a current research interest because the products have the potential of significantly improving the catalytic performance of NCs in industrially important reactions. This study reports a versatile method for synthesizing polyhedral NCs enclosed by a variety of high-index Pd facets. The method is based on the heteroepitaxial growth of Pd layers on concave trisoctahedral (TOH) gold NC seeds under careful control of the growth kinetics. Polyhedral Au@Pd NCs with three different classes of high-index facets, including concave TOH NCs with {hhl} facets, concave hexoctahedral (HOH) NCs with {hkl} facets, and tetrahexahedral (THH) NCs with {hk0} facets, can be formed in high yield. The Miller indices of NCs are also modifiable, and we have used the THH NCs as a demonstrative example. The catalytic activities of these NCs were evaluated by the structure-sensitive reaction of formic acid electro-oxidation. The results showed that the high-index facets are generally more active than the low-index facets. In summary, a seeded growth process based on concave high-index faceted monometallic TOH NC templates and careful control of the growth kinetics is a simple and effective strategy for the synthesis of noble metal NCs with high-index facets. It also offers tailorability of the surface structure in shape-controlled synthesis.

Synthesis of small silver nanocubes in a hydrophobic solvent by introducing oxidative etching with Fe(iii) species

The role of oxidative etching in the synthesis of noble-metal nanocrystals with a hydrophilic solvent (in particular, ethylene glycol) has been explored in our previous work. In this paper, we demonstrate that the mechanism of oxidative etching could be extended to the synthesis of single-crystal Ag nanocrystals in a hydrophobic solvent such as isoamyl ether. In this case, Fe(III) species in the form of FeCl3 or Fe(acac)3 had to be introduced into the hydrophobic system as an effective etching agent. The final product contained single-crystal Ag nanocubes (slightly truncated) with an edge length as small as ∼13.5 nm, a size that has been difficult to achieve using a hydrophilic system.