Atomic-Scale Surface Segregation in Copper-Gold Nanoparticles.

We combine electron microscopy measurements of the surface compositions in Cu-Au nanoparticles and atomistic simulations to investigate the effect of gold segregation. While this mechanism has been extensively investigated within Cu-Au in the bulk state, it was never studied at the atomic level in nanoparticles. By using energy dispersive x-ray analysis across the (100) and (111) facets of nanoparticles, we provide evidence of gold segregation in Cu_{3}Au and CuAu_{3} nanoparticles in the 10 nm size range grown by epitaxy on a salt surface with high control of the nanoparticles morphology. To get atomic-scale insights into the segregation properties in Cu-Au nanoparticles on the whole composition range, we perform Monte Carlo calculations employing N-body interatomic potentials highlighting a complete segregation of Au in the (100) and (111) facets for gold nominal composition above 70% and 60%, respectively. Furthermore, we show that there is no size effect on the segregation behavior since we evidence the same oscillating concentration profile from the surface to the nanoparticle's core as in the bulk. These results shed new light on the interpretation of the enhanced reactivity, selectivity, and stability of Cu-Au nanoparticles in various catalytic reactions.

Synthesis and structural properties of high-entropy nanoalloys made by physical and chemical routes.

The development of synthesis methods with enhanced control over the composition, size and atomic structure of High Entropy Nano-Alloys (HENA) could give rise to a new repertoire of nanomaterials with unprecedented functionalities, notably for mechanical, catalytic or hydrogen storage applications. Here, we have developed two original synthesis methods, one by a chemical route and the other by a physical one, to fabricate HENA with a size between 3 and 10 nm and a face centered cubic structure containing three (CoNiPt), four (CoNiPtCu and CoNiPtAu) or five (CoNiPtAuCu) metals close to the equiatomic composition. The key point in the proposed chemical synthesis method is to compensate the difference in reactivity of the different metal precursors by increasing the synthesis temperature using high boiling solvents. Physical syntheses were performed by pulsed laser ablation using a precise alternating deposition of the individual metals on a heated amorphous carbon substrate. Finally, we have exploited aberration-corrected transmission electron microscopy to explore the nanophase diagram of these nanostructures and reveal intrinsic thermodynamic properties of those complex nanosystems. In particular, we have shown (i) that the complete mixing of all elements can only occur close to the equiatomic composition and (ii) how the Ostwald ripening during HENA synthesis can induce size-dependent deviations from the equiatomic composition leading to the formation of large core-shell nanoparticles.

Revealing Size Dependent Structural Transitions in Supported Gold Nanoparticles in Hydrogen at Atmospheric Pressure.

The enhancement of the catalytic activity of gold nanoparticles with their decreasing size is often attributed to the increasing proportion of low-coordinated surface sites. This correlation is based on the paradigmatic picture of working gold nanoparticles as perfect crystal forms having complete and static outer surface layers whatever their size. This picture is incomplete as catalysts can dynamically change their structure according to the reaction conditions and as such changes can be eventually size-dependent. In this work, using aberration-corrected environmental electron microscopy, size-dependent crystal structure and morphological evolution in gold nanoparticles exposed to hydrogen at atmospheric pressure, with loss of the face-centered cubic crystal structure of gold for particle size below 4 nm, are revealed for the first time. Theoretical calculations highlight the role of mobile gold atoms in the observed symmetry changes and particle reshaping in the critical size regime. An unprecedented stable surface molecular structure of hydrogenated gold decorating a highly distorted core is identified. By combining atomic scale in situ observations and modeling of nanoparticle structure under relevant reaction conditions, this work provides a fundamental understanding of the size-dependent reactivity of gold nanoparticles with a precise picture of their surface at working conditions.

On the Influence of Oxygen on the Degradation of Fe-N-C Catalysts.

Fe-N-C catalysts containing atomic FeNx sites are promising candidates as precious-metal-free catalysts for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells. The durability of Fe-N-C catalysts in fuel cells has been extensively studied using accelerated stress tests (AST). Herein we reveal stronger degradation of the Fe-N-C structure and four-times higher ORR activity loss when performing load cycling AST in O2 - vs. Ar-saturated pH 1 electrolyte. Raman spectroscopy results show carbon corrosion after AST in O2 , even when cycling at low potentials, while no corrosion occurred after any load cycling AST in Ar. The load-cycling AST in O2 leads to loss of a significant fraction of FeNx sites, as shown by energy dispersive X-ray spectroscopy analyses, and to the formation of Fe oxides. The results support that the unexpected carbon corrosion occurring at such low potential in the presence of O2 is due to reactive oxygen species produced between H2 O2 and Fe sites via Fenton reactions.

Nanostructured Nickel Aluminate as a Key Intermediate for the Production of Highly Dispersed and Stable Nickel Nanoparticles Supported within Mesoporous Alumina for Dry Reforming of Methane.

Two routes of preparation of mesoporous Ni-alumina materials favoring the intermediate formation of nanostructured nickel-aluminate are presented. The first one involves an aluminum containing MOF precursor used as sacrificial template to deposit nickel while the second is based on a one-pot synthesis combined to an EISA method. As shown by a set of complementary techniques, the nickel-aluminate nanospecies formed after calcination are homogeneously distributed within the developed mesoporous alumina matrices whose porous characteristics vary depending on the preparation method. A special attention is paid to electron-microscopy observations using especially STEM imaging with high chemical sensitivity and EDS elemental mapping modes that help visualizing the extremely high nickel dispersion and highlight the strong metal anchoring to the support that persists after reduction. This leads to active nickel nanoparticles particularly stable in the reaction of dry reforming of methane.

Direct Measurement of the Surface Energy of Bimetallic Nanoparticles: Evidence of Vegard's Rulelike Dependence.

We use in situ transmission electron microscopy to monitor in real time the evaporation of gold, copper, and bimetallic copper-gold nanoparticles at high temperature. Besides, we extend the Kelvin equation to two-component systems to predict the evaporation rates of spherical liquid mono- and bimetallic nanoparticles. By linking this macroscopic model to experimental TEM data, we determine the surface energies of pure gold, pure copper, Cu_{50}Au_{50}, and Cu_{25}Au_{75} nanoparticles in the liquid state. Our model suggests that the surface energy varies linearly with the composition in the liquid Cu-Au nanoalloy; i.e., it follows a Vegard's rulelike dependence. To get atomic-scale insights into the thermodynamic properties of Cu-Au alloys on the whole composition range, we perform Monte Carlo simulations employing N-body interatomic potentials. These simulations at a microscopic level confirm the Vegard's rulelike behavior of the surface energy obtained from experiments combined with macroscopic modeling.

Driving reversible redox reactions at solid-liquid interfaces with the electron beam of a transmission electron microscope.

Liquid-cell transmission electron microscopy (LCTEM) has opened up a new way to study chemical reactions at the interface between solids and liquids. However, understanding the effects of the electron beam in the liquid cell has been clearly identified as one of the most important challenges to assess correctly and quantitatively LCTEM data. Here we show that the electron beam can be used to drive reversible deposition/dissolution cycles of copper shells over gold nanoparticles in methanol. Besides revealing the influence of irreversible processes on the kinetic of growth/etching cycles, this study of nanostructure behaviour as a function of the dose rate highlights the possibility to switch the oxidising or reducing nature of liquid environment only with the electron beam. The chemical and electronic processes possibly involved in these tunable redox reactions are qualitatively discussed together with their possible impacts on electrochemical LCTEM experiments.

Thermodynamics of faceted palladium(-gold) nanoparticles supported on rutile titania nanorods studied using transmission electron microscopy.

Many physical properties of nanoparticles (NPs) are driven by their equilibrium shape (ES). Thus, knowing the kinetic and thermodynamic parameters that affect the particle morphology is key for the rational design of NPs with targeted properties. Here, we report on the thermodynamic ES of supported monometallic palladium and bimetallic palladium-gold (Pd-Au) single-crystalline truncated nano-octahedra (TOs) studied using aberration-corrected transmission electron microscopy (TEM). Monometallic palladium and bimetallic Pd62Au38 and Pd43Au57 TOs were grown by pulsed laser deposition on rutile titania (r-TiO2) nanorods exposing mainly (110) facets. Particle structure and dimension were first obtained from aberration-corrected high resolution TEM (HRTEM) images acquired parallel to the metal-oxide interface. By fitting an extended Wulff-Kaishev rule to the HRTEM data of the truncated octahedral thermodynamic ES in the size range of 2 to 5 nm, we secondly determined the interface and excess line energies associated with the particle-oxide-vacuum triple phase junction in Pd and Pd43Au57 TOs in the epitaxial relationship Pd(-Au)(111)101‖r-TiO2(110)[1-1-1] and in Pd62Au38 TOs in the epitaxial relationship Pd62Au38(100)101‖r-TiO2(110)[1-10]. Our results show a decrease in particle adhesion to the oxide support upon alloying Pd with Au. The loss in adhesion is tentatively attributed to an increase of the lattice strain induced at the metal-oxide interface as gold atoms are added to the palladium lattice.

Exploring the Formation of Symmetric Gold Nanostars by Liquid-Cell Transmission Electron Microscopy.

The shape-dependent properties of gold nanostars (NSs) have motivated massive research efforts in the field of colloidal chemistry to gain a better control over the morphology of these promising nanostructures. Nevertheless, this challenge requires a better understanding of the atomic-scale processes leading to the formation of stellated nanoparticles. We hereby report an unprecedented in situ study focused on the seed-mediated synthesis of symmetric gold NSs performed by radiolysis in methanol. We take advantage of the spatial and temporal resolutions of liquid-cell transmission electron microscopy to unravel the key effects of the growth speed, seed-crystal morphology, and dimethylamine functionalization on the formation mechanisms, shape, and stability of NSs enclosed by high-index facets. Surprisingly, the stellation processes transforming icosahedral nanoparticles into NSs with 20 sharp arms entails a continuous restructuring of NS facets driven by surface diffusion, which provide a fresh look at faceting mechanisms.

Atomic-Scale Snapshots of the Formation and Growth of Hollow PtNi/C Nanocatalysts.

Determining the formation and growth mechanism of bimetallic nanoparticles (NPs) with atomic detail is fundamental to synthesize efficient "catalysts by design". However, an understanding of the elementary steps which take place during their synthesis remains elusive. Herein, we have exploited scanning transmission electron microscopy coupled to energy-dispersive X-ray spectroscopy, operando wide angle and small-angle X-ray scattering, and electrochemistry to unveil the formation and growth mechanism of hollow PtNi/C NPs. Such NPs, composed of a PtNi shell surrounding a nanoscale void, catalyze efficiently and sustainably the oxygen reduction reaction (ORR) in an acidic electrolyte. Our step-by-step study reveals that (i) Ni-rich/C NPs form first, before being embedded in a NixByOz shell, (ii) the combined action of galvanic displacement and the nanoscale Kirkendall effect then results in the sequential formation of Ni-rich core@Pt-rich/C shell and ultimately hollow PtNi/C NPs. The electrocatalytic properties for the ORR and the stability of the different synthesis intermediates were tested and structure-activity-stability relationships established both in acidic and alkaline electrolytes. Beyond its interest for the ORR electrocatalysis, this study also presents a methodology that is capable to unravel the formation and growth mechanism of various nanomaterials including preferentially shaped metal NPs, core@shell NPs, onion-like NPs, Janus NPs, or a combination of several of these structures.

New insights into the mixing of gold and copper in a nanoparticle from a structural study of Au-Cu nanoalloys synthesized via a wet chemistry method and pulsed laser deposition.

Gold-copper nanoparticles (Au-Cu NPs) were elaborated by both chemical (polyol reduction method) and physical (laser deposition) routes. The size, composition and crystal structure of these bimetallic nanoalloys were then characterized by aberration corrected transmission electron microscopy (TEM). Using a one-pot polyol method, Au-Cu nanocubes (NCs) with nominal compositions Au3Cu and AuCu3 were synthesized. The size and composition of the NCs were tuned by varying the amount and the ratio of Au(iii) and Cu(ii) ions used as metallic precursors in the reaction. While the particle shape and size were well-controlled, single particle X-ray spectroscopy showed that, irrespective of the targeted compositions, the Cu content in all NCs was about 11-12 at%, i.e. in both samples, the real composition was different from the nominal one. This was ascribed to an incomplete alloying of the two constituent metals of the alloy in the cubes due to different reduction kinetics of the two metallic precursors. To shed light on the alloying of gold and copper at the nanoscale, Au-Cu NPs with targeted compositions Au3Cu and AuCu3 were deposited on amorphous carbon by laser ablation of two monometallic sources, and their structural properties were studied by TEM. These studies show that Au-Cu nanoalloys were synthesized in both samples and that the complete mixing of Au and Cu atoms achieved with this synthesis technique led to the production of Au-Cu NPs with well-controlled compositions. These results constitute a first but major step towards a complete understanding of the details of kinetics and thermodynamics determining the mixing of gold and copper atoms at the nanoscale. Such an understanding is essential for producing Au-Cu bimetallic nanoalloys with well-defined structural properties via wet chemical synthesis.

Au-Rh and Au-Pd nanocatalysts supported on rutile titania nanorods: structure and chemical stability.

Au, Rh, Pd, Au-Rh and Au-Pd nanoparticles (NPs) were synthesized by colloidal chemical reduction and immobilized on hydrothermally-prepared rutile titania nanorods. The catalysts were characterized by aberration-corrected TEM/STEM, XPS, and FTIR, and were evaluated in the hydrogenation of tetralin in the presence of H2S. Oxidizing and reducing thermal treatments were employed to remove the polyvinyl alcohol (PVA) surfactant. Reduction in H2 at 350 °C was found efficient for removing the PVA while preserving the size (ca. 3 nm), shape and bimetallic nature of the NPs. While Au-Pd NPs are alloyed at the atomic scale, Au-Rh NPs contain randomly distributed single-phase domains. Calcination-reduction of Au-Rh NPs mostly leads to separated Au and Rh NPs, while pre-reduction generates a well-defined segregated structure with Rh located at the interface between Au and TiO2 and possibly present around the NPs as a thin overlayer. Both the titania support and gold increase the resistance of Rh and Pd to oxidation. Furthermore, although detrimental to tetralin hydrogenation initial activity, gold stabilizes the NPs against surface sulfidation in the presence of 50 ppm H2S, leading to increased catalytic performances of the Au-Rh and Au-Pd systems as compared to their Rh and Pd counterparts.

Selective hydrogenation of butadiene over TiO2 supported copper, gold and gold-copper catalysts prepared by deposition-precipitation.

Oxide supported copper and gold catalysts are active for the selective hydrogenation of polyunsaturated hydrocarbons but their low activity compared to palladium catalysts and the deactivation of copper catalysts limit their use. There are only a very limited number of studies concerned with the use of bimetallic Au-Cu catalysts for selective hydrogenation reactions and the aim of this work was to prepare TiO2-supported monometallic Au and Cu and bimetallic AuCu (Cu/Au atomic ratio of 1 and 3) catalysts and to evaluate their catalytic performance in the selective hydrogenation of butadiene. Small gold, copper and gold-copper nanoparticles (average particle size < 2 nm) were obtained on TiO2 using the preparation method of deposition-precipitation with urea followed by reduction under H2 at 300 °C. Very small clusters were observed for Cu/TiO2 (∼1 nm) which might result from O2 induced copper redispersion, as also supported by the XPS analyses. The alloying of copper with gold was found to inhibit its redispersion and also limits its reoxidation, as attested by XPS. The bimetallic character of the AuCu nanoparticles was confirmed by XPS and EDX-HAADF. Cu/TiO2 was initially more active than Au/TiO2 in the selective hydrogenation of butadiene at 75 °C but it deactivated rapidly during the first hours of reaction whereas the gold catalyst was very stable up to 20 hours of reaction. The bimetallic AuCu/TiO2 catalysts displayed an activation period during the first hours of the reaction, which was very pronounced for the sample containing a higher Cu/Au atomic ratio. This initial gain in activity was tentatively assigned to copper segregation at the surface of the bimetallic nanoparticles, induced by the reactants. When the AuCu/TiO2 catalysts were pre-exposed to air at 75 °C before butadiene hydrogenation, surface copper segregation occurred, leading to higher initial activity and the suppression of the activation period. Under the same conditions, Cu/TiO2 totally lost its activity, probably due to irreversible copper oxidation.

Plasmon spectroscopy and imaging of individual gold nanodecahedra: a combined optical microscopy, cathodoluminescence, and electron energy-loss spectroscopy study.

Imaging localized plasmon modes in noble-metal nanoparticles is of fundamental importance for applications such as ultrasensitive molecular detection. Here, we demonstrate the combined use of optical dark-field microscopy (DFM), cathodoluminescence (CL), and electron energy-loss spectroscopy (EELS) to study localized surface plasmons on individual gold nanodecahedra. By exciting surface plasmons with either external light or an electron beam, we experimentally resolve a prominent dipole-active plasmon band in the far-field radiation acquired via DFM and CL, whereas EELS reveals an additional plasmon mode associated with a weak dipole moment. We present measured spectra and intensity maps of plasmon modes in individual nanodecahedra in excellent agreement with boundary-element method simulations, including the effect of the substrate. A simple tight-binding model is formulated to successfully explain the rich plasmon structure in these particles encompasing bright and dark modes, which we predict to be fully observable in less lossy silver decahedra. Our work provides useful insight into the complex nature of plasmon resonances in nanoparticles with pentagonal symmetry.

Corrosion Products Formed on MgZr Alloy Embedded in Geopolymer Used as Conditioning Matrix for Nuclear Waste-A Proposition of Interconnected Processes.

Geopolymer has been selected as a hydraulic mineral binder for the immobilization of MgZr fuel cladding coming from the dismantling of French Uranium Natural Graphite Gas reactor dedicated to a geological disposal. In this context, the corrosion processes and the nature of the corrosion products formed on MgZr alloy in a geopolymer matrix with and without the corrosion inhibitor NaF have been determined using a multiscale approach combining in situ Grazing Incidence hard X-ray Diffraction, Raman microspectroscopy, Scanning and Transmission Electron Microscopies coupled to Energy Dispersive X-ray Spectroscopy. The composition, the morphology, and the porous texture of the corrosion products were characterized, and the effect of the corrosion inhibitor NaF was evidenced. The results highlighted the formation of Mg(OH)2-xFx. In addition, in presence of NaF, NaMgF3 forms leading to a decrease of the thickness and the porosity of the corrosion products layer. Moreover, a precipitation of magnesium silicates within the porosity of the geopolymer was evidenced. Finally, we propose a detailed set of interconnected processes occurring during the MgZr corrosion in the geopolymer.

Studying the Effects of Temperature on the Nucleation and Growth of Nanoparticles by Liquid-Cell Transmission Electron Microscopy.

Temperature control is a recent development that provides an additional degree of freedom to study nanochemistry by liquid cell transmission electron microscopy. In this paper, we describe how to prepare an in situ heating experiment for studying the effect of temperature on the formation of gold nanoparticles driven by radiolysis in water. The protocol of the experiment is fairly simple involving a special liquid cell with uniform heating capabilities up to 100 °C, a liquid-cell TEM holder with flow capabilities and an integrated interface for controlling the temperature. We show that the nucleation and growth mechanisms of gold nanoparticles are drastically impacted by the temperature in liquid cell. Using STEM imaging and nanodiffraction, the evolution of the density, size, shape and atomic structure of the growing nanoparticles are revealed in real time. Automated image processing algorithms are exploited to extract useful quantitative data from video sequences, such as the nucleation and growth rates of nanoparticles. This approach provides new inputs for understanding the complex physico-chemical processes at play during the liquid-phase synthesis of nanomaterials.

Quantitative In Situ Visualization of Thermal Effects on the Formation of Gold Nanocrystals in Solution.

Understanding temperature effects in nanochemistry requires real-time in situ measurements because this key parameter of wet-chemical synthesis simultaneously influences the kinetics of chemical reactions and the thermodynamic equilibrium of nanomaterials in solution. Here, temperature-controlled liquid cell transmission electron microscopy is exploited to directly image the radiolysis-driven formation of gold nanoparticles between 25 °C and 85 °C and provide a deeper understanding of the atomic-scale processes determining the size and shape of gold colloids. By quantitatively comparing the nucleation and growth rates of colloidal assemblies with classical models for nanocrystal formation, it is shown that the increase of the molecular diffusion and the solubility of gold governs the drastic changes in the formation dynamics of nanostructures in solution with temperature. In contraction with the common view of coarsening processes in solution, it is also demonstrated that the dissolution of nanoparticles and thus the Ostwald ripening is not only driven by size effects. Furthermore, visualizing thermal effects on faceting processes at the single nanoparticle level reveals how the competition between the growth speed and the surface diffusion dictates the final shape of nanocrystals.

Introducing cobalt as a potential plasmonic candidate combining optical and magnetic functionalities within the same nanostructure.

The control of magnetic properties at the nanoscale is a current topic of intense research. It was shown that combining both magnetic and plasmonic nanoparticles (NPs) led to the improvement of their magneto-optical signal. In this context, common strategies consist of the design of bimetallic NPs. However, the understanding of the physics leading to the coupling between magnetic and plasmonic NPs is lacking, preventing any significant progress for the development of future photonic devices. In this article, we propose to focus our attention on an efficient and commonly used magnetic metal, cobalt, and evaluate its plasmonic properties at the nanoscale through the use of NP regular arrays, as a potential candidate combining both optical and magnetic functionalities within the same metal. We show that such NPs display plasmonic properties within a large spectral range from the UV to the NIR spectral range, with efficient quality factors, when the inter-particle distance is properly selected. These as-fabricated simple materials could find applications in integrated photonic devices for telecommunications.

Selective shortening of gold nanorods: when surface functionalization dictates the reactivity of nanostructures.

The selective shortening of gold nanorods (NRs) is a directional etching process that has been intensively studied by UV-Vis spectroscopy because of its direct impact on the optical response of these plasmonic nanostructures. Here, liquid-cell transmission electron microscopy is exploited to visualize this peculiar corrosion process at the nanoscale and study the impacts of reaction kinetics on the etching mechanisms. In situ imaging reveals that anisotropic etching requires a chemical environment with a low etching power to make the tips of NRs the only reaction site for the oxidation process. Then, aberration-corrected TEM and atomistic simulations were combined to demonstrate that the disparity between the reactivity of the body and the ends of NRs does not derive from their crystal structure but results from an inhomogeneous surface functionalization. In a general manner, this work highlights the necessity to consider the organic/inorganic natures of nanostructures to understand their chemical reactivity.