Cu segregation in Au-Cu nanoparticles exposed to hydrogen atmospheric pressure: how is fcc symmetry maintained?

In a recent work [A. Nassereddine et al., Small 2021, 17, 2104571] we reported the atomic-scale structure and dynamics of sub-4 nm sized Au nanoparticles (NPs) supported on titania in H2 at atmospheric pressure obtained by using aberration-corrected environmental transmission electron microscopy (ETEM), density functional theory (DFT) optimizations and ab initio molecular dynamic (AIMD) simulations. Our results showed unstable Au NPs losing their face-centred cubic (fcc) symmetry (from fcc to non-fcc symmetries) and revealed the drastic effect of hydrogen adsorption. In this work, we use the same approach to study the dynamics of equiatomic Au-Cu NPs in the same range of size and the results show an enhanced structural stability upon alloying by Cu. In spite of the morphology evolution from facetted to rounded shapes, the observed Au-Cu NPs are found to keep their fcc symmetry under atmospheric hydrogen pressure. AIMD simulation evidences a Cu segregation process from the sub-surface toward the upper surface layer, and a reversed segregation of Au atoms from the surface towards the sub-surface sites. The analysis of the chemical ordering in the core shows a tendency to a local chemical ordering where Au-Cu hetero-atomic bindings are favoured. The segregating Cu seems to play a major role in reducing the fluxionality of Au-Cu NPs in H2 and thus, maintaining their fcc symmetry.

Characterization of the boron profile and coordination in altered glass layers by EEL spectroscopy.

Electron energy-loss spectroscopy was used to characterize the boron profile and its coordination (BIII and BIV), along the complex alteration layer of glass samples altered for 511 days at 50 °C in solution containing FeCl2, MgCl2 and/or CaCl2. To reach this goal, the impact of both TEM operating conditions and sample preparation on the determination of the boron coordination was first studied using mineralogical and pristine glasses reference samples. Then, the boron concentration profiles were characterized in the glass alteration layer. These profiles were found to be S-shaped with a thickness around forty nanometers. The proportion of BIII was found to decrease with the boron total concentration (from the pristine glass to the gel layer), which suggests a higher bonding strength for BIV bonds than that of BIII bonds under the alteration conditions. These findings are of tremendous interest to advance further in the understanding of glass alteration mechanisms.

Nanoscale temperature measurement during temperature controlled in situ TEM using Al plasmon nanothermometry.

Over recent years, the advent of microelectromechanical system (MEMS)-type microheaters has pushed the limits of temperature controlled in situ transmission electron microscopy (TEM). In particular, by enabling the observation of the structure of materials in their application environments, temperature controlled TEM provides unprecedented insights into the link between the properties of materials and their structure in real-world problems, a clear knowledge of which is necessary for rational development of functional materials with new or improved properties. While temperature is the key parameter in such experiments, accessing the precise temperature of the sample at the nanoscale during observations still remains challenging. In the present work, we have applied aluminium plasmon nanothermometry technique that monitors the temperature dependence of the volume plasmon of Al nanospheres using electron energy loss spectroscopy for in situ local temperature determination over MEMS-type microheaters. With access to local temperatures between room temperature to 550 ∘C, we have assessed the spatial and temporal stabilities of these microheaters when they operate at different setpoint temperatures both under vacuum and in the presence of a static H2 gas environment. Temperature comparisons performed under the two environments show discrepancies between local and setpoint temperatures.

Nanoalloying bulk-immiscible iridium and palladium inhibits hydride formation and promotes catalytic performances.

The hydrogen sorption properties of oxide-supported Ir-Pd nanoalloys have been determined for the first time, and correlated with their catalytic behavior. The addition of Ir to Pd suppresses hydride formation and leads to improved catalytic performances with respect to pure metals in the preferential oxidation of CO in H2 excess (PROX).

Two-dimensional quasistatic stationary short range surface plasmons in flat nanoprisms.

We report on the nanometer scale spectral imaging of surface plasmons within individual silver triangular nanoprisms by electron energy loss spectroscopy and on related discrete dipole approximation simulations. A dependence of the energy and intensity of the three detected modes as function of the edge length is clearly identified both experimentally and with simulations. We show that for experimentally available prisms (edge lengths ca. 70 to 300 nm) the energies and intensities of the different modes show a monotonic dependence as function of the aspect ratio of the prisms. For shorter or longer prisms, deviations to this behavior are identified thanks to simulations. These modes have symmetric charge distribution and result from the strong coupling of the upper and lower triangular surfaces. They also form a standing wave in the in-plane direction and are identified as quasistatic short range surface plasmons of different orders as emphasized within a continuum dielectric model. This model explains in simple terms the measured and simulated energy and intensity changes as function of geometric parameters. By providing a unified vision of surface plasmons in platelets, such a model should be useful for engineering of the optical properties of metallic nanoplatelets.

Direct imaging of surface plasmon resonances on single triangular silver nanoprisms at optical wavelength using low-loss EFTEM imaging.

Using low-loss energy-filtering transmission electron microscopy (EFTEM) imaging, we map surface plasmon resonances (SPRs) at optical wavelengths on single triangular silver nanoprisms. We show that EFTEM imaging combining high spatial sampling and high energy resolution enables the detection and for the first time, to the best of our knowledge, mapping at the nanoscale of an extra multipolar SPR on these nanoparticles. As illustrated on a 276.5 nm long nanoprism, this eigenmode is found to be enhanced on the three edges where it exhibits a two-lobe distribution.