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:
A Robust Synthesis of Co2P and Ni2P Nanocatalysts from Hexaethylaminophosphine and Phosphine-Enhanced Phenylacetylene Hydrogenation
We selected a commercial aminophosphine, HETAP, as the phosphorus precursor to develop a robust synthesis crystalline Co2P and Ni2P nanoparticles with high yields on a 9 mmol scale. Moreover, modification of the nanoparticles via the addition of a molecular Lewis base triggered catalytic activity of the colloidal suspension at low temperature for the hydrogenation of phenylacetylene. We delineated the most efficient phosphines in the case of a Ni2P catalyst, using a stereoelectronic map of 13 phosphines.
A. Ropp , S. Carenco, Inorg. Chem. 2024, DOI 10.1021/acs.inorgchem.4c02743
Phosphine-Enhanced Semi-Hydrogenation of Phenylacetylene by Cobalt Phosphide Nano-Urchins
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, ChemPlusChem2023, DOI 10.1002/cplu.202300469.
Nickel Carbide (Ni3C) Nanoparticles for Catalytic Hydrogenation of Model Compounds in Solvent
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
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, ChemNanoMat2020, 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, ChemCatChem2017, 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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