sophiecarenco

Few years ago, I visited a Space Museum in Manchester. In the exhibits, some dark rocks taken out of meteorite... they were made of combination of elements that are seldom encoutered on Earth surface, because our atmosphere contains way too much oxygen gas. What a surprise, when I realized some of them were those I was targeting in the lab! Metal-phosphorus alloys, metal-carbon compounds... a bunch of fun compounds that were prepared by the fathers&mothers of chemistry, but that we are now revisiting at the nanoscale.

We report the positive effect of phosphine additives on the activity of cobalt phosphide nano-urchins for the semi-hydrogenation of phenylacetylene. While the nanocatalyst's activity was low under mild conditions (7 bar of H₂, 100 °C), the addition of a catalytic amount of phosphine remarkably increased the conversion, e. g., from 13 % to 98 % in the case of PⁿBu₃. A stereo-electronic map was proposed: the strongest effect was observed for low to moderately hindered phosphines, associated with strong electron donor abilities.

A. Ropp, R. F. André, S. Carenco, ChemPlusChem 2023, DOI 10.1002/cplu.202300469.

We investigated here crystalline nickel carbide nanoparticles as catalysts in colloidal suspension for hydrogenation reactions under H₂ (7 bar) and below 100°C. Polar solvents appeared comparatively more favorable than less polar ones for the hydrogenation of two model substrates: nitrobenzene and phenylacetylene. Furthermore, the presence of water in the solvent mix was mostly favorable to the hydrogenation yield. We expanded the scope to a variety of aldehydes, ketones, esters, nitriles and unsaturated hydrocarbons.

R. F. André, L. Meyniel, S. Carenco, Cat. Sci. Tech. 2022, doi 10.1039/D2CY00894G

Transition metal carbides (TMCs) have attracted great interest due to their mechanical and catalytic properties but their syntheses generally require energy-consuming processes with temperatures above 800 °C. We report here a solid-state metathesis reaction between metal chlorides (ZrCl₄, NbCl₅, MoCl₃, MoCl₅, HfCl₄, TaCl₅, WCl₆) and potassium dispersed in carbon. Within seconds, it produces carbide or metallic nanoparticles of diameter below 50 nm supported on carbon. Based on thermodynamic and kinetic considerations, we propose a mechanism explaining the coexistence of several phases (metal, carbide, hydride) and their occurrence at each step of the reaction.

R. F. André, F. D'Accriscio, A. P. Freitas, G. Crochet, C. Bouillet, M. Bahri, O. Ersen, C. Sanchez, S. Carenco, Green Chem., 2021, 10.1039/D1GC01097B

We report the synthesis of air-stable P₄(MesCO)₄. We used it to prepare FeP and Fe₂P nanoparticles at 250 °C. X‐Ray photoelectron spectroscopy (XPS) and atomic pair distribution function (PDF) reveal the local order and bonding in the amorphous and crystalline materials. Crystalline FeP forms via an intermediate amorphous phase with a local order similar to that of the crystalline sample. We explore the electrocatalytic properties for the hydrogen evolution reaction (HER) in acidic and neutral electrolytes. In both electrolytes, amorphous FeP is a more efficient catalyst than crystalline FeP and Fe₂P.

F. D’Accriscio, E. Schrader, C. Sassoye, M. Selmane, R. F. André, S. Lamaison, D. Wakerley, M. Fontecave, V. Mougel, G. Le Corre, H. Grützmacher, C. Sanchez, S. Carenco, ChemNanoMat 2020, cnma.202000198.2020, doi:10.1002/cnma.202000198

Copper and nickel are particularly interesting first-raw metals for their abundance and relevance in several branches of catalysis. In order to synthesize crystalline bimetallic phosphide Ni-Cu-P nanoparticles, core-shell copper‑nickel nanoparticles were reacted with white phosphorus (P₄). Surprisingly, hollow monocrystalline (Ni,Cu)₂P nanoparticles were formed alongside Cu nanoparticles and crystallized in a phase isostructural to Ni₂P.

A.-M. Nguyen, M. Bahri, S. Dreyfuss, S. Moldovan, A. Miche, C. Méthivier, O. Ersen, N. Mézailles, S. Carenco, Chem. Mater. 2019, 31, 6124-34.

Bimetallic nanoparticles are widely studied, for example in catalysis. However, possible restructuring in the environment of use, such as segregation or alloying, may occur. Taken individually, state‐of‐the‐art analytical tools fail to give an overall picture of these transformations.

In collaboration with Cecile S. Bonifacio and Judith C. Yang from Pittsburg University, we studied nickel-cobalt nanoparticles exposed to reactive gases. Combination of an ensemble technique (NAP-XPS) and a local one (environmental TEM) was pivotal for describing the nanoparticles transformations.

S. Carenco, C. S. Bonifacio, J. C. Yang, Chem. - A Eur. J. 2018, 24, 12037-43.

An expeditious synthesis of metal carbide nanoparticles onto various carbon supports is demonstrated. The procedure is versatile and readily yields TiC, VC, Mo2C and W2C nanoparticles on different types of carbons. The reaction is initiated at room temperature and proceeds within seconds.

This novel synthetic route paves the way to a large variety of metal carbide-carbon nanocomposites that may be implemented in emerging nanotechnology fields.

D. Ressnig, S. Moldovan, O. Ersen, P. Beaunier, D. Portehault, C. Sanchez, S. Carenco, Chem. Commun. 2016, 52, 9546

Using in situ ambient-pressure X-ray photoelectron spectroscopy, the formation of nickel phosphide on the surface of a nickel foil was investigated, at temperatures like those employed to form nickel phosphide nanoparticles in colloidal route using tri-n-octylphosphine as a phsophorus source.

Our results demonstrate that even below 150 °C, significant phosphorus and carbon incorporation can occur during metal nanoparticles syntheses that employ TOP as stabilizing agent. These findings provide new insight on the surface chemistry of metal phosphide nanoparticles, increasingly employed in several fields of catalysis.

S. Carenco, Z. Liu, M. Salmeron, ChemCatChem 2017, 9, 2318–2323

We demonstrated that the stoichiometric reaction of elemental phosphorus with M(0) sources of nickel (complex or nanoparticles) yields nickel phosphide compound.
This paper was the milestone of all our work on metal phosphide nanoparticles.

S. Carenco, I. Resa, X. Le Goff, P. Le Floch, N. Mézailles, Chem. Commun. 2008, 22, 2568

We generalized the phosphidation reaction to several M(0) nanoparticles. In particular, we obtained indium phosphide nanoparticles from two different routes.

S. Carenco, M. Demange, J. Shi, C. Boissière, C. Sanchez, P. Le Floch, N. Mézailles, Chem. Commun. 2010, 46, 5578

This Personal Account is about the design, synthesis and monitoring of metal alloy nanoparticles.

Nanoalloys represent a playground to establish structure-properties relationships within the nano-matter. The rational design of nanoalloys is discussed (reactants choice, composition control), in relation with their surface state. Consequences on heterogeneous and homogeneous catalytic reactions, as well as for energy storage and conversion, is illustrated through examples.

S. Carenco, Chem. Rec. 2018, 18, 1114-1124

In this extensive review, we discuss about the synthesis, properties and applications of metal phosphide and metal borides nanoparticles. We show the similarities between these two classes of compounds. We comment on the trends of the field as well as on the latest advances.

S. Carenco, D. Portehault, C. Boissière, N. Mézailles, C. Sanchez, Chem. Rev. 2013, 113, 7981

This critical review deals with the question of nanoscale phase diagram. Because of their high surface-to-volume ratio, nanoparticles sometimes show phase preferences for certain composition, or even display phase segregation phenomena that one would not expect at the bulk scale. Here, we took metal phosphides as a case study to discuss this exiting side of nanoscale matter.

S. Carenco, D. Portehault, C. Boissière, N. Mézailles, C. Sanchez, Adv. Mater. 2014, 26, 371