Nanoparticles containing Metal, Phosphorus, Carbon, or more!


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.

Both metal carbides and metal phosphides exhibit a covalent character because of the fairly low electronegativity of carbon and phosphorus. Binary compounds are well-known from solid-state chemistry and metallurgy. However, they are few routes to prepare nanoparticles, despite their applications in a number of fields, such as optics (luminescence), catalysis and electro-catalysis. We work on innovative synthetic routes to produce nanoparticles with chosen composition and surface properties.

Related papers:

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

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

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.

Ensemble versus Local Restructuring of Core-shell Nickel-Cobalt Nanoparticles upon Oxidation and Reduction Cycles

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 early transition metal carbide nanoparticles on graphitic carbons

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

The Birth of Nickel Phosphides Catalysts: Monitoring Phosphorus Insertion into Nickel

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

White phosphorus as single source of "P" in the synthesis of nickel phosphide

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

White phosphorus and metal nanoparticles: a versatile route to metal phosphide nanoparticles

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

Review papers:

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

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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