Sophie Carenco | Publications


2021 (5)
2020 (3) 2019 (12) 2018 (5) 2017 (3)
2016 (4) 2015 (2) 2014 (4) 2013 (7)
2012 (7) 2011 (1) 2010 (2) 2008 (1)

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Recent Papers

Phosphines Modulating the Catalytic Silane Activation on Nickel-Cobalt Nanoparticles, Tentatively Attributed to Frustrated Lewis Pairs in a Colloidal Solution

We propose the concept of a NanoFLP in a colloidal solution where one partner is a phosphine Lewis base and the other is the Lewis acid surface of a NiCo nanoparticle. We attempt to apply this concept to the hydrosilylative reduction of benzaldehyde. We identify a correlation between the Tolman cone angle and the silane conversion, consistent with both mechanisms; however, we found no clear correlation between the Tolman electronic parameter and the reaction outcome. Structural analyses evidenced that the nanoparticles are not altered during the reaction, which led us to propose the formation of a NanoFLP as a transient species in solution.


A. Palazzolo, S. Carenco. Chem. Mater. 2021, acs.chemmater.1c03105.

Guidelines for the Molybdenum Oxidation State and Geometry from X-ray Absorption Spectroscopy at the Mo L2,3 -Edges

X-ray absorption near-edge structure (XANES) is a particularly well-adapted technique to study the L2,3-edges of Mo (2520–2625 eV). It provides information on both the electronic and local structures of metal-containing species and allows drawing structure–activity relationships. However, L2,3-edges are difficult to interpret, especially for 4d and 5d transition metals. In this work, we provide a method for their interpretation based on a library of spectra of simple Mo compounds. We suggest using the L3-edge to determine the oxidation state and the L2-edge to gain insight on the geometry around Mo atoms. This method is then applied to a series of molybdenum sulfide compounds to rationalize their structures.


A.P. Freitas, R. F. André, C. Poucin, T. K.-C. Le, J. Imbao, B. Lassalle-Kaiser, S. Carenco. Guidelines for the Molybdenum Oxidation State and Geometry from X-Ray Absorption Spectroscopy at the Mo L2,3-Edges. J. Phys. Chem. C 2021, 10.1021/acs.jpcc.1c01875.

Early Transition Metal Nano-carbides and Nano-hydrides from Solid-State Metathesis initiated at Room Temperature

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

Influence of Copper Precursor on the Catalytic Transformation of Oleylamine during Cu Nanoparticles Synthesis

Copper nanoparticle synthesis was studied by thorough characterization of the organic reactions happening during the synthesis. The reduction of copper(II) acetate by oleylamine resulted in a high amount of water and few by-products while the reduction of copper(II) acetylacetonate resulted in a low amount of water and many products. The nanoparticles showed different abilities to further dehydrogenate and transaminate oleylamine in the synthesis reaction pot. This was explained by the presence of a copper oxide phase in the nanoparticles prepared from copper acetate.


A. Pesesse, S. Carenco, Cat. Sci. Tech.., 2021, 10.1039/D1CY00639H.

Interlayer Silylation of Layered Octosilicate with Organoalkoxysilanes: Effects of Tetrabutylammonium Fluoride as a Catalyst and Functional Groups of Silanes

Interlayer silylation of layered sodium octosilicate (Na-Oct) with various organoalkoxysilanes was conducted using hexadecyltrimethylammonium ion-exchanged layered octosilicate as an intermediate in the presence or absence of tetrabutylammonium fluoride (TBAF). The degree of silylation was increased by adding TBAF. It is suggested that fluoride ions perform a nucleophilic attack on the alkoxysilanes, which promotes the silylation reaction.Several functional groups were grafted with this procedure. Overall TBAF appears as a relevant catalyst for the covalent interlayer surface modification of layered silicates with organic functional groups.


M. Yatomi, M. Koike, N. Rey, Y. Murakami, S. Saito, H. Wada, A. Shimojima, D. Portehault, S. Carenco, C. Sanchez, C. Carcel, M. Wong Chi Man and K. Kuroda, Eur. J. Inorg. Chem., 2021, ejic.202100050.

A Single Molecular Stoichiometric P‐Source for Phase‐Selective Synthesis of Crystalline and Amorphous Iron Phosphide Nanocatalysts

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

Unraveling the Role of Alkali Cations in the Growth Mechanism of Gd2O2S Nanoparticles

Alkali cations are required for the colloidal synthesis of Ln2O2S nanoplates in organic solvent. We challenge the commonly accepted scenario of partial lanthanide substitution by the alkali. We demonstrate the formation of an alkali-stabilized oleate mesophase acting as a template for nanoparticle nucleation and growth.


C. Larquet, D. Carriere, A.-M. Nguyen, T. K.-C. Le, X. Frogneux-Plé, I. Génois, P. Le Griel, A. Gauzzi, C. Sanchez, S. Carenco, Chem. Mater. 2020, doi:10.1021/acs.chemmater.9b04059

[Article] Nanotechnologies : les chimistes au cœur des dernières avancées

"Domaine prioritaire dans la R&D des pays industrialisés, les nanotechnologies seront à l’horizon 2030 essentielles aux ingénieurs pour faire face aux crises environnementales, à la raréfaction de matières premières stratégiques et à la demande croissante d’énergie. Les chimistes y jouent un rôle de premier plan."

Cet article publié dans le dossier spécial sur la chimie de La Jaune et la Rouge discute du rôle des chimistes dans les nanotechnologies. Sommaire du dossier | Lire l'article.


S. Carenco, La Jaune et la Rouge 2019, 749, 46-47.

Morphological and Structural Evolution of Co3O4 Nanoparticles Revealed by in Situ Electrochemical Transmission Electron Microscopy during Electrocatalytic Water Oxidation

We implement an in situ electrochemical Transmission Electron Microscopy (in situ EC-TEM) methodology for studying electrocatalysts of the oxygen evolution reaction (OER) during operation, by using model cobalt oxide Co3O4 nanoparticles. Surface amorphization occurs, yielding a nanometric cobalt (oxyhydr)oxide-like phase during OER. This process is irreversible and occurs to an extent that has not been described before. Furthermore, pH and counterions of the electrolytes impact this restructuration, shedding light on the materials properties in neutral phosphate electrolytes.


N. Ortiz Peña, D. Ihiawakrim, M. Han, B. Lassalle-Kaiser, S. Carenco, C. Sanchez, C. Laberty-Robert, D. Portehault, O. Ersen, ACS Nano 2019, 13, 11372.

Bimetallic Phosphide (Ni,Cu)2P Nanoparticles by Inward Phosphorus Migration and Outward Copper Migration

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.

Band Gap Engineering from Cation Balance: The Case of Lanthanide Oxysulfide Nanoparticles

(Gd,Ce)2O2S anisotropic nanoparticles with hexagonal structure exhibit colors varying from white to brown with increasing Ce concentration. Bandgap engineering is thus possible, from 4.7 eV to 2.1 eV. Surprisingly, due to the limited thickness of the lamellar nanoparticles, the bandgap of the nanoparticles is direct as validated by density functional theory on slabs. The fine control of the bandgap over a wide range, solely triggered by the cation ratio, is rarely described in the literature and highly promising for further development of this class of compounds.


C. Larquet, A.-M. Nguyen, E. Glais, L. Paulatto, C. Sassoye, M. Selmane, P. Lecante, C. Maheu, C. Geantet, L. Cardenas, C. Chanéac, A.Gauzzi, C. Sanchez, S. Carenco, Chem. Mater. 2019, 31, 5014-23.

Direct Synthesis of N-Heterocyclic Carbene-Stabilized Copper Nanoparticles from a N-Heterocyclic Carbene-Borane

N-Heterocyclic carbene-stabilized copper nanoparticles are synthesized using a NHC-borane and mesitylcopper(I) in thermal conditions (refluxing toluene for 2.5 h). Nanoparticles with a size distribution of 11.6 ± 1.8 nm were obtained. The interaction between Cu NPs and NHC ligands was probed by XPS, showing the covalent binding of the NHC to the surface of the nanoparticles.

Mechanistic studies suggest that the NHC-borane plays two roles: contributing to the reduction of [CuMes]2 to release Cu0 species and providing NHC ligands to stabilize the copper nanoparticles.


X. Frogneux, L. Hippolyte, D. Mercier, D. Portehault, C. Chaneac, C. Sanchez, P. Marcus, F. Ribot, L. Fensterbank, S. Carenco, Chem. Eur. J. 2019, 25, 11481-85.

Different reactivity of rutile and anatase TiO2 nanoparticles: synthesis and surface states of nanoparticles of mixed-valence Magnéli oxides

Understanding the surface reactivity of titanium oxides Magnéli phases that contain both Ti(IV) and Ti(III) is of prime importance. This article describes a new synthetic route to 50 nm carbon-free Ti4O7 and Ti6O11 nanoparticles.The surface reactivity of the Magnéli nanoparticles was quantitatively evaluated under different atmospheres with synchrotron radiation-based X-ray photoelectron spectroscopy, highlighting oxidized surfaces with lower conductivity than the core. This finding sheds a new light on the charge transfer occuring in these materials.


E. Baktash, J. Capitolis, L. Tinat, C. Larquet, T. H. C. Chan Chang, J.-J. Gallet, F. Bournel, C. Sanchez, S. Carenco, D. Portehault. Chem. Eur. J. 2019, 25, 11114-20.

Dumbbell-Shaped T8-POSS with Functional Organic Linkers

New dumbbell‐shaped octasilsesquioxanes (T8-POSS) are obtained by the condensation of organobridged silane precursors with partially condensed POSS. The synthesis based on corner-capping proceeds under mild reaction conditions (60 °C in toluene) upon a nucleophilic fluoride-catalyzed condensation. Two dumbbell-type T8-POSS, one with a non-symmetrical urea-thiourea linker and the other one with a symmetrical malonamide linker, are described.


N. Rey, S. Carenco, C. Carcel, A. Ouali, D. Portehault, M. Wong Chi Man, C. Sanchez, Eur. J. Inorg. Chem. 2019, 27, 3148-56.

Radical-Initiated Dismutation of Hydrosiloxanes by Catalytic Potassium-Graphite

Formation of higher-value products from cheaper silicone precursors such as polymethylhydrosiloxane (PMHS) is a challenge for silicon chemistry. Here, we show that catalytic amount of potassium graphite can be used as an efficient radical initiator for the cleavage of Si–O bonds of hydrosiloxanes. Mechanistic investigations suggest that both the dismutation of the initial hydrosiloxane and the reduction of carbonyl derivatives by hydrosilylation are initiated with a radical pathway.


X. Frogneux, A. Pesesse, S. Delacroix, F. Ribot, S. Carenco, ChemCatChem 2019, 11, 3781-85.

Thermal Stability of Oleate-Stabilized Gd2O2S Nanoplates in Inert and Oxidizing Atmospheres

Capping ligands play an important role in the chemistry of nanoparticles. Ultrathin monodisperse Ln2O2Sx oxysulfide nanoparticles (Ln = lanthanide) show promising luminescence and light absorption properties. Here, we show that the thermal stability of Gd2O2Sx nanocrystals is limited because of their non‐stoichiometric composition and strongly depends on the annealing atmosphere. Annealing the nanoparticles in air enables removing the ligands without altering the nanocrystals structure.


C. Larquet, D. Hourlier, A.-M. Nguyen, A. Torres-Pardo, A. Gauzzi, C. Sanchez, S. Carenco, ChemNanoMat 2019, 5, 539-46.

Tunable Magnetic Properties of (Gd,Ce)2O2S Oxysulfide Nanoparticles

Gadolinium oxysulfide nanoparticles are suitable candidates for bimodal imaging Here, we synthesized and characterized bimetallic (Gd,Ce)2O2S nanoparticles and demonstrated that they are paramagnetic over a wide temperature range including the body one. The mixture of Gd and Ce magnetic centers enables a fine control of the magnetic properties up to high Ce concentrations (80%) and over a large range of magnetic moments, while photoemission properties are guaranteed up to 20% of Ce owing to a regular dispersion of the Ce centers.


C. Larquet, Y. Klein, D. Hrabovsky, A. Gauzzi, C. Sanchez, S. Carenco, EurJIc. 2019, 6, 762-765 | EurJIc Cover.


Metal Oxysulfides: From Bulk Compounds to Nanomaterials

This review summarizes the syntheses and applications of metal oxysulfides. Bulk compounds of rare earth and transition metals are discussed in the section Introduction. After a presentation of their main properties and applications, their structures are presented and their syntheses are discussed. The section Bulk Materials and Their Main Applications is dedicated to the growing field of nanoscaled metal oxysulfides. Lanthanide-based nanoparticles are discussed first, followed by transition-metal based nanoparticles.


C. Larquet, S. Carenco, Frontiers in Chem. 2020, doi:10.3389/fchem.2020.00179

Describing inorganic nanoparticles in the context of surface reactivity and catalysis

Surface and core of inorganic nanoparticles may undergo profound transformations in their environment of use. Accurate description is key to understand and control surface reactivity.

Through a selection of case studies, this feature article proposes a journey from surface science to nanoparticle design, while illustrating state-of-the-art spectroscopies that help provide a relevant description of inorganic nanoparticles in the context of surface reactivity.


S. Carenco, Chem. Commun. 2018, 54, 6719-6727

Designing Nanoparticles and Nanoalloys with Controlled Surface and Reactivity

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

Nanoscaled Metal Borides and Phosphides: Recent Developments and Perspectives

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

Carbon monoxide-induced dynamic metal-surface nanostructuring

Carbon monoxide is a ubiquitous molecule in surface science, materials chemistry, catalysis and nanotechnology. Its interaction with a number of metal surfaces is at the heart of major processes, such as Fischer-Tropsch synthesis or fuel-cell optimization. Recent works have highlighted the ability of metal surfaces and nanoparticles to undergo restructuring after exposure to CO under fairly mild conditions, generating nanostructures. This Minireview deals with such nanostructuring, and discusses the driving force in reversible and non-reversible situations.


S. Carenco, Chem. Eur. J . 2014, 20, 10616

Electron Microscopy for the Chemists of Materials

Electron microscopy is a central tool in materials sciences and nanochemistry. Combining tomography with electron energy loss spectroscopy and high-magnification imaging in high-angle annular dark-field mode provides access to all features of the same object.

In this feature article, we teamed up with colleagues from Strasbourg, CEA Le Ripault, Toulouse and Paris to illustrate a few contributions of electron microscopy techniques in the field of nanomaterials: silica fibers, porous metal oxides, MOFs and metal phosphide nanoparticles.


S. Carenco, S. Moldovan, L. Roiban, I. Florea, D. Portehault, K. Vallé, P. Belleville, C. Boissière, L. Rozes, N. Mézailles, M. Drillon, C. Sanchez, O. Ersen Nanoscale 2016, 8, 1260

Exploring nanoscaled matter from speciation to phase diagrams: metal phosphide nanoparticles as a case of study

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


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