Highly monodisperse sodium citrate-coated spherical silver nanoparticles (Ag NPs) with controlled sizes ranging from 10 to 200 nm have been synthesized by following a kinetically controlled seeded-growth approach via the reduction of silver nitrate by the combination of two chemical reducing agents: sodium citrate and tannic acid. The use of traces of tannic acid is fundamental in the synthesis of silver seeds, with an unprecedented (nanometric resolution) narrow size distribution that becomes even narrower, by size focusing, during the growth process. The homogeneous growth of Ag seeds is kinetically controlled by adjusting reaction parameters: concentrations of reducing agents, temperature, silver precursor to seed ratio, and pH. This method produces long-term stable aqueous colloidal dispersions of Ag NPs with narrow size distributions, relatively high concentrations (up to 6 × 1012 NPs/mL), and, more important, readily accessible surfaces. This was proved by studying the catalytic properties of as-synthesized Ag NPs using the reduction of Rhodamine B (RhB) by sodium borohydride as a model reaction system. As a result, we show the ability of citrate-stabilized Ag NPs to act as very efficient catalysts for the degradation of RhB while the coating with a polyvinylpyrrolidone (PVP) layer dramatically decreased the reaction rate.

We herein present a comprehensive study on how the catalytic performance and reusability of Au nanocrystals (NCs) are affected by systematic variations of crystal size, surface coating and composition.

The rational design of advanced nanomaterials with enhanced optical properties can be reached only with the profound thermodynamic and kinetic understanding of their synthetic processes. In this work, the synthesis of monodisperse AuAg nanoshells with thin shells and large voids is achieved through the development of a highly reproducible and robust methodology based on the galvanic replacement reaction. This is obtained thanks to the systematic identification of the role played by the different synthetic parameters involved in the process (such as surfactants, co-oxidizers, complexing agents, time, and temperature), providing an unprecedented control over the material's morphological and optical properties. Thus, the timeand size-resolved evolution of AuAg nanoshells surface plasmon resonance band is described for 15, 30, 60, 80, 100, and 150 nmsized particles spanning almost through the entire visible spectrum. Its analysis reveals a four-phase mechanism coherent with the material's morphological transformation. Simulations based on Mie's theory confirm the observed optical behavior in AuAg nanoshells formation and provide insights into the influence of the Au/Ag ratio on their plasmonic properties. The high degree of morphological control provided by this methodology represents a transferable and scalable strategy for the development of advanced-generation plasmonic nanomaterials.

A novel synthetic strategy based on the controlled corrosion of silver templates allows us to prepare PtAg@Pt single-crystal hollow NCs with high-index planes at room temperature with enhanced surface reactivity.

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In the present work, hollow PdAg-CeO2 heterodimer nanocrystals (NCs) were prepared and tested as catalysts for the selective hydrogenation of alkynes. These nanostructures combine for the first time the beneficial effect of alloying Pd with Ag in a single NC hollow domain with the formation of active sites at the interface with the CeO2 counterpart in an additive manner. The PdAg-CeO2 NCs display excellent alkene selectivity for aliphatic alkynes. For the specific case of hydrogenation of internal alkynes such as 4-octyne, very low over-hydrogenation and isomerization products were observed over a full conversion regime, even after prolonged reaction times. These catalytic properties were remarkably superior in comparison to standard catalysts. The promotion of Ag on the moderation of the reactivity of the Pd phase, in combination with the creation of interfacial sites with the CeO2 moiety in the same nanostructure, is pointed as the responsible of such a remarkable catalytic performance.

Abstract:The design of new protocols for the colloidal synthesis of complex nanocrystals (NCs) with advanced functionalities, comprising both hybrid and hollow structures, and the study of their fundamental properties is of paramount importance for the development of a new generation of nanostructured materials. The possibility of tailoring the dimensional regime of NCs, along with its composition and structure, represents a landmark achievement in the control of their unique physico-chemical properties. These properties, alongside with the ability to cheaply produce high quality NCs in fairly large amounts by wetchemistry techniques, leads to their potential applicability from materials science to nanomedicine. Within this context, this review is focused on describing a successful framework for designing synthetic strategies for the production of advanced complex NCs, integrating the development of new synthetic methods with its structural characterization, monitoring of their properties, and study of its reactivity. As a result, it is expected to provide new routes to produce robust and easy-to-process NCs in a wide range of sizes, shapes and configurations that can be explored to achieve the combination of all degrees of control, aiming to produce a complete and diverse library of material combinations that will expand its applicability in a wide diversity of fields.