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Band engineering is thoroughly employed nowadays targeting technologically scalable photoanodes for solar water splitting applications. Most often complex and costly recipes are necessary, for average performances. Here we report very simple photoanode growth and thermal annealing, with effective band engineering results. Strongly enhanced photocurrent, of more than 200 %, is measured for Ti-doped hematite nanorods grown from aqueous solutions and annealed under Nitrogen atmosphere, compared to air annealed ones. Oxidized surface states and increased density of charge carriers are found responsible for the enhanced photoelectrochemical activity, as shown by electrochemical impedance spectroscopy and synchrotron X-rays spectromicroscopies. They are found related to oxygen vacancies, acting as n-dopants, and the formation of pseudo-brookite clusters by surface Ti segregation. Spectro-ptychography is used for the first time at Ti L3 absorption edge to isolate Ti chemical coordination arising from pseudo-brookite clusters contribution. Correlated with electron microscopy investigation and Density Functional Theory (DFT) calculations, our data unambiguously prove the origin of the enhanced photoelectrochemical activity of N2-annealed Ti-doped hematite nanorods. Finally, we present here a handy and cheap surface engineering method beyond the known oxygen vacancy doping, allowing a net gain in the photoelectrochemical activity for the hematite-based photoanodes.

International audience; A novel system of paramagnetic vesicles was designed using ion pairs of iron-containing surfactants. Unilamellar vesicles (diameter approximate to 200 nm) formed spontaneously and were characterized by cryogenic transmission electron microscopy, nanoparticle tracking, analysis, and light and small-angle neutron scattering. Moreover, for the first time, it is shown that magnetization measurements can be used to investigate self-assembly of such functionalized systems, giving information on the vesicle compositions and distribution Of surfactants between the bilayers and the aqueous bulk.

International audience; A detailed morphological and structural analysis of CeO2 nanoparticles has been performed using electron tomography in scanning transmission mode in high angle annular dark field. The nanoparticles have been prepared through a solvothermal synthesis assisted by microwave heating. An adequate choice of the synthesis parameters leads to particles with various well-defined morphologies: cubes, octahedrons, and nanorods. In the case of cubic CeO2 nanoparticles, the three-dimensional analysis allowed us to precisely calculate the type and the proportion of the minor facets exposed at the nanoparticle surface. For the CeO2 nanoparticles with an octahedron shape, it has been demonstrated that the ambiguous interpretation of the objects giving triangular views in classical transmission electron microscopy can be prevented; furthermore, precise assignments of their external shape, surface crystallography, and type of minor facets were realized. In the case of nanorods, it was shown that the external shape and the transversal symmetry are strongly dependent on the nanorod sizes. The presence of a well-defined porosity inside the rods was also evidenced thanks to the ability of the electron tomography to solve the internal structure of a nano-object.

We present here the application of the energy-filtered transmission electron microscopy (EFTEM) in the tomographic mode to determine the precise 3D distribution of nitrogen within nitrogen-doped carbon nanotubes (N-CNTs). Several tilt series of energy-filtered images were acquired on the K ionization edges of carbon and nitrogen on a multiwalled N-CNT containing a high amount of nitrogen. Two tilt series of carbon and nitrogen 2D maps were then calculated from the corresponding energy-filtered images by using a proper extraction procedure of the chemical signals. Applying iterative reconstruction algorithms provided two spatially correlated C and N elemental-selective volumes, which were then simultaneously analyzed with the shape-sensitive reconstruction deduced from Zero-Loss recordings. With respect to the previous findings, crucial information obtained by analyzing the 3D chemical maps was that, among the two different kind of arches formed in these nanotubes (transversal or rounded ones depending on their morphology), the transversal arches contain more nitrogen than do the round ones. In addition, a detailed analysis of the shape-sensitive volume allowed the observation of an unexpected change in morphology along the tube axis: close to the round arches (with less N), the tube is roughly cylindrical, whereas near the transversal ones (with more N), its shape changes to a prism. This relatively new technique is very powerful in the material science because it combines the ability of the classical electron tomography to solve 3D structures and the chemical selectivity of the EFTEM imaging.