Photocatalytic behavior for the phenol degradation of ZnAl layered double hydroxide functionalized with SDS.

Functionalized ZnAl layered double hydroxide based photocatalyst was obtained by the addition of sodium dodecyl sulfate (SDS) during the synthesis by the coprecipitation method, and further calcination at 400 °C. Bare and modified materials were characterized by X-ray diffraction, nitrogen adsorption-desorption, IR, UV-Vis, EPR and XPS spectroscopies, SEM and HRTEM. The synthesized material was evaluated in the photodegradation of phenol in a 40 ppm aqueous solution (4.25 × 10-4 mol of phenol/L), under UV light irradiation. An increasing in the degradation of phenol from 62 to 95%, and from 62 to 82% in the mineralization of phenol was obtained using SDS functionalized ZnAl LDH, in comparison with the unmodified material. This increase could be attributed to the presence of sulfate radicals, confirmed by the EPR study.

Phonon fingerprints of CsPb2Br5.

CsPb2Br5 is a stable, water-resistant, material derived from CsPbBr3 perovskite and featuring two-dimensional Pb-Br framework separated by Cs layers. Both compounds can coexist at nanolength scale, which often produces conflicting optical spectroscopy results. We present a complete set of polarized Raman spectra of nonluminescent CsPb2Br5 single crystals that reveals the symmetry and frequency of nondegenerate Raman active phonons accessible from the basal (0 0 1) plane. The experimental results are in good agreement with density functional perturbation theory simulations, which suggests that the calculated frequencies of yet unobserved double degenerate Raman and infrared phonons are also reliable. Unlike CsPbBr3, the lattice dynamics of CsPb2Br5 is stable as evidenced by the calculated phonon dispersion. The sharp Raman lines and lack of a dynamic-disorder-induced central peak in the spectra at room temperature indicate that the coupling of Cs anharmonic motion to Br atoms, known to cause the dynamic disorder in CsPbBr3, is absent in CsPb2Br5.

HRTEM low dose: the unfold of the morphed graphene, from amorphous carbon to morphed graphenes.

We present experimental evidence under low-dose conditions transmission electron microscopy for the unfolding of the evolving changes in carbon soot during mechanical milling. The milled soot shows evolving changes as a function of the milling severity or time. Those changes are responsible for the transformation from amorphous carbon to graphenes, graphitic carbon, and highly ordered structures such as morphed graphenes, namely Rh6 and Rh6-II. The morphed graphenes are corrugated layers of carbon with cross-linked covalently nature and sp2- or sp3-type allotropes. Electron microscopy and numerical simulations are excellent complementary tools to identify those phases. Furthermore, the TEAM 05 microscope is an outstanding tool to resolve the microstructure and prevent any damage to the sample. Other characterization techniques such as XRD, Raman, and XPS fade to convey a true identification of those phases because the samples are usually blends or mixes of the mentioned phases.

Challenges of modelling real nanoparticles: Ni@Pt electrocatalysts for the oxygen reduction reaction.

Theoretical/computational methods have been extensively applied to screen possible nano-structures attempting to maximize catalytic and stability properties for applications in electrochemical devices. This work shows that the method used to model core@shell structures is of fundamental importance in order to truly represent the physicochemical changes arising from the formation of a core-shell structure. We demonstrate that using a slab approach for modelling nanoparticles the oxygen adsorption energies are qualitatively well represented. Although this is a good descriptor for the catalytic activity, huge differences are found for the calculated surface stability between the results of a nano-cluster and those of a slab approach. Moreover, for the slab method depending on the geometric properties of the core and their similarity to the elements of the core or shell, contradictory effects are obtained. In order to determine the changes occurring as the number of layers and nano particle size are increased, clusters of Ni@Pt from 13 to 260 atoms were constructed and analyzed in terms of geometric parameters, oxygen adsorption, and dissolution potential shift. It is shown that the results of modelling the Ni@Pt nanoparticles with a cluster approach are in good agreement with experimental geometrical parameters, catalytic activity, and stability of a carefully prepared series of Ni@Pt nanostructures where the shell thickness is systematically changed. The maximum catalytic activity and stability are found for a monolayer of Pt whereas adding a second and third layer the behavior is almost the same than that in pure Pt nanoparticles.

Maintaining the genuine structure of 2D materials and catalytic nanoparticles at atomic resolution.

The recent development of atomic resolution, low dose-rate electron microscopy allows investigating 2D materials as well as catalytic nano particles without compromising their structural integrity. For graphene and a variety of nanoparticle compositions, it is shown that a critical dose rate exists of <100 e(-)/Å(2) s at 80 keV of electron acceleration that allows maintaining the genuine object structures including their surfaces and edges even if particles are only 3 nm large or smaller. Moreover, it is demonstrated that electron beam-induced phonon excitation from outside the field of view contributes to a contrast degradation in recorded images. These degradation effects can be eliminated by delivering electrons onto the imaged area, only, by using a Nilsonian illumination scheme in combination with a suitable aperture at the electron gun/monochromator assembly.

Instrumental requirements for the detection of electron beam-induced object excitations at the single atom level in high-resolution transmission electron microscopy.

This contribution touches on essential requirements for instrument stability and resolution that allows operating advanced electron microscopes at the edge to technological capabilities. They enable the detection of single atoms and their dynamic behavior on a length scale of picometers in real time. It is understood that the observed atom dynamic is intimately linked to the relaxation and thermalization of electron beam-induced sample excitation. Resulting contrast fluctuations are beam current dependent and largely contribute to a contrast mismatch between experiments and theory if not considered. If explored, they open the possibility to study functional behavior of nanocrystals and single molecules at the atomic level in real time.

3-D reconstruction of the atomic positions in a simulated gold nanocrystal based on discrete tomography: prospects of atomic resolution electron tomography.

A novel reconstruction procedure is proposed to achieve atomic resolution in electron tomography. The method exploits the fact that crystals are discrete assemblies of atoms (atomicity). This constraint enables us to obtain a three-dimensional (3-D) reconstruction of test structures from less than 10 projections even in the presence of noise and defects. Phase contrast transmission electron microscopy (TEM) images of a gold nanocrystal were simulated in six different zone axes. The discrete number of atoms in every column is determined by application of the channelling theory to reconstructed electron exit waves. The procedure is experimentally validated by experiments with gold samples. Our results show that discrete tomography recovers the shape of the particle as well as the position of its 309 atoms from only three projections. Experiments on a nanocrystal that contains several missing atoms, both on the surface and in the core of the nanocrystal, while considering a high noise level in each simulated image were performed to prove the stability of the approach to reconstruct defects. The algorithm is well capable of handling structural defects in a highly noisy environment, even if this causes atom count "errors" in the projection data.