Catégorie : Articles

The first paper of Carlos on hydrofluxes is out! These original solvents, at the edge of water and molten salts, promise many discoveries for crystallization and materials discovery in the future. Stay tuned!

Crystallization of Manganese(V) Oxides by Hydroflux Synthesis: Control of Anisotropic Growth and Electrochemical Stability, C. V. M. Inocêncio, A. Torres-Pardo, D. Montero, L. Roach, P.-O. Autran, C. Sassoye, C. Aymonier, A. Varela, M. Parras, C. Laberty-Robert, D. Portehault*, Inorganic Chemistry, 10.1021/acs.inorgchem.4c05439

Transforming Nanocrystals into Superhard Boron Carbide Nanostructures, F. Igoa Saldaña, T. Gaudisson, S. Le Floch, B. Baptiste, L. Delbes, V. Malarewicz, O. Beyssac, K. Béneut, C. Coelho Diogo, C. Gervais, G. Rousse, K. Rasim, Y. Grin, A. Maître, Y. Le Godec*, D. Portehault*, ACS Nano,  10.1021/acsnano.4c08599

In a study led by Glenna Drisko and M. A. Parker at ICMCB, we designed a redox pathway involving a silicon Zintl phase and a custom-made silicon complex to fabricate size-controlled silicon particles. Anissa contributed significantly to the ‘Zintl’ part during her Ph.D.

Unveiling the Potential of Redox Chemistry to Form Size-Tunable, High-Index Silicon Particles, M. A. Parker, S. Khaddad, N. Fares, A. Ghoridi, D. Portehault, S. Bonhommeau, Y. Amarouchene, P. Rosa, M. Gonidec, G. L Drisko, Chemisty of Materials, (2024)

A great achievement by Daniel during his Ph.D. work: We unveil a path in molten salts to transition metal silicoborides through structural transformations driven by boron-based covalent bonds. Specific charge transfer between atoms provide guidelines to design corrosion-resistant and Earth-abundant water oxidation electrocatalysts. Among a range of methods, we made extensive use of synchrotron-based in situ XRD in molten salts.

Covalent Transition Metal Borosilicides: Reaction Pathways in Molten Salts for Water Oxidation Electrocatalysis, D. Janisch, F. Igoa Saldaña, E. De Rolland Dalon, C. VM Inocêncio, Y. Song, P.-O. Autran, A. Miche, S. Casale, D. Portehault, Journal of the American Chemical Society,  146, 21824 (2024)

Last months have seen the achievements of two important works in the group, both related to the design of nano-objects with complex crystal structure and/or internal nanostructure:

The first one is the discovery of a new zinc and silicon compound that exhibits a new crystal structure, polar, which is of interest for photoelectrocatalytic water splitting. To solve the crystal structure we had to deploy a wide range of techniques, especially 3D electron diffraction. A nice collaboration with P. Boullay at CRISMAT, and with many others, including UCMadrid and other teams of the LCMCP and of Sorbonne Université.

Molten Salts-Driven Discovery of a Polar Mixed-Anion 3D framework at the nanoscale: Zn₄Si₂O₇Cl₂, Charge Transport and Photoelectrocatalytic Water Splitting
R. Kumar, Y. Song, A. Ghoridi, P. Boullay, G. Rousse, C. Gervais, C. Coelho Diogo, H. Kabbour, C. Sassoye, P. Beaunier, V. Castaing, B. Viana, M. L. Ruiz Gonzalez, J. Gonzalez Calbet, C. Laberty-Robert, D. Portehault*, Angewandte Chemie International Edition, 135, e202303487 (2023)

The second milestone is the setup of a method to achieve core-shell nanoparticles made of intermetallic compounds, this case silicides, bearing strong covalency. To do so, we have developed an approach to control atomic diffusion into nanoparticles dispersed within molten salts. We have then shown that the core-shell structure impacts deeply electrocatalytic and magnetic properties. Beautiful work from Yang and Isabel, but also many others of the group and of collaborators from UCMadrid, SOLEIL synchrotron and Sorbonne Université.

Heterostructured Cobalt Silicide Nanocrystals: Synthesis in Molten Salts, Ferromagnetism, and Electrocatalysis, Y. Song, I. Gómez-Recio, A. Ghoridi, F. Igoa Saldaña, D. Janisch, C. Sassoye, V. Dupuis, D. Hrabovsky, M. L. Ruiz-González, J. M. González-Calbet, S. Casale, A. Zitolo, B. Lassalle-Kaiser, C. Laberty-Robert, D. Portehault*, Journal of the American Chemical Society, 145, 19207 (2023)

Geoinspired syntheses of materials and nanomaterials, D. portehault*, I. Gómez-Recio, M. A. Baron, V. Musumeci, C. Aymonier, V. Rouchon, Y. Le Godec, Chemical Society Reviews, 51, 4828 (2022)

We have joined the efforts of Prof. Sylvie Begin-Colin and Prof. Ovidiu Ersen at IPCMS Strasbourg to shed more light on the processes at play during colloidal synthesis of iron oxide nanocrystals. In situ transmission electron microscopy reveals that molecular precursors self-assemble into vesicles, in which nanocrystals nucleate.

In situ liquid transmission electron microscopy reveals self-assembly-driven nucleation in radiolytic synthesis of iron oxide nanoparticles in organic media, N. Ortiz Peña, D. Ihiawakrim, S. Creţu, G. Cotin, C. Kiefer, S. Begin-Colin, C. Sanchez, D. Portehault, O. Ersen, Nanoscale, 14, 10950 (2022)

A Confinement‐Driven Nucleation Mechanism of Metal Oxide Nanoparticles Obtained via Thermal Decomposition in Organic Media, G. Cotin, B. Heinrich, F. Perton, C. Kiefer, G. Francius, D. Mertz, B. Freis, B. Pichon, J.‐M. Strub, S. Cianférani, N. Ortiz Peña, D. Ihiawakrim, D. Portehault, O. Ersen, A. Khammari, M. Picher, F. Banhart, C. Sanchez, S. Begin‐Colin, Small, 18, 2200414 (2022)

We designed the first nanocrystals of sodium carbaboride in molten salts, and unveiled the deviation to ideal stoichiometry that is made possible by a specific molten salt-derived synthesis route and by the nanoscale of the objects. The nanocrystals can act as precursors towards functional boron carbides. This work is part of a Forum of Inorganic Chemistry.

Electron Precise Sodium Carbaboride Nanocrystals from Molten Salts: Single Sources to Boron Carbides, S. Delacroix, F. Igoa, Y. Song, Y. Le Godec, C. Coelho-Diogo, C.  Gervais, G. Rousse, D. Portehault*, Inorganic Chemistry, 10.1021/acs.inorgchem.0c03501

We report herein new oxides and oxyfluorides built on the apatite crystal framework and hosting Mn⁵⁺, a rare oxidation state of manganese, very scarcely observed in oxides. We take the opportunity of isolating these new solids to provide the first spectroscopic characterization of Mn⁵⁺ by EELS and to show the significant ionic conductivity of these solids.

This work was hosted by the department of Solid State Chemistry of the Universidad Complutense de Madrid. A strongly collaborative work with the RMES group of LCMCP lab, the Solid-State Chemistry and Energy Lab at Collège de France, and ILL at Grenoble.

Hydroxyapatites as Versatile Inorganic Hosts of Unusual Pentavalent Manganese Cations, A. Varela, I. Gómez-Recio, L. Serrador, M. Hernando, E. Matesanz, A. Torres-Pardo, M. T. Fernández-Díaz, J. L. Martínez, F. Gonell, G. Rousse, C. Sanchez, C. Laberty-Robert, D. Portehault, J. M. González-Calbet, M. Parras, Chemistry of Materials, DOI: 10.1021/acs.chemmater.0c03673

Correlative Microscopy Insight on Electrodeposited Ultrathin Graphite Oxide Films, N. Ortiz Peña, D. Ihiawakrim, V. Ball, S. Stanescu, M. Rastei, C. Sanchez, D. Portehault, O. Ersen, Journal of Physical Chemistry Letters, DOI: 10.1021/acs.jpclett.0c02482