Boosting the reactivity of nanoparticles towards small molecules

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Small molecules such as CO2 have been activated on metal nanoparticles for ages, eg. in the Sabatier process using nickel nanoparticles. However, the harsh conditions required with noble-metal free catalysts preclude the catalytic process from formingfunctional molecules. Rather, simple molecules such as methane are obtained, which stands as a strong limitation. In the NanoFLP projet, we aim at boosting the reactivity of these nanoparticles using adequate surface ligands in order to operate the catalytic reactions at room temperature and ambient pressure.

Funding

This project has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant agreement No. 758480).

ERC

Recent publications on the NanoFLP project

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.

ChemMater2021

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.

JPCC2021

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.

GreenChem2021

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.

CatSciTech2021

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

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.

ChemComm2018

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

Other related papers

Synthesis and Structural Evolution of Nickel-Cobalt Nanoparticles Under H2 and CO2

CO2 can be converted into hydrocarbon using cobalt-based catalysts. However and to our surprise, core-shell nickel-cobalt nanoparticles produced oxygenated molecules instead (CO, methanol, formaldehyde).

We showed that, as a result of the heating and the presence of reactive gas, nickel was able to migrate to the surface of the nanoparticle. Alongside, small amounts of phosphorus were also found to get exposed to the surface. This phosphorus actually comes from the ligands (TOP) that were required in the first step of the nanoparticles synthesis but partially decomposed upon heating.

The active catalyst should not be seen as a cobalt surface, but rather as a nickel-cobalt alloy containing significant level of phosphide species.

Small2015

S. Carenco, C.-H. Wu, A. Shavorskiy, S. Alayoglu, G. A. Somorjai, H. Bluhm, M. Salmeron, Small 2015, 11, 3045

The Active State of Supported Ruthenium Oxide Nanoparticles during Carbon Dioxide Methanation

CO2 methanation is an old process but it is one of the keys to produce chemicals of interest. One of the research trend is to go to lower reaction temperatures, which promote highly selective reactions (i.e. formation of methane without carbon monoxyde by-products). Ruthenium nanoparticles are active at low temperature in this process.

Near-Ambient-Pressure X-Ray Photoelectron Spectroscopy (NAP-XPS) was used to monitoring ruthenium nanoparticles deposited on a tailored TiO2 surface. We showed that the ruthenium is metallic under model reaction conditions and we also were able to analyze the nature of the adsorbates as a function of the temperature.

JPCC2016

S. Carenco, C. Sassoye, M. Faustini, P. Eloy, D. P. Debecker, H. Bluhm, M. Salmeron, J. Phys. Chem. C 2016, 120, 15354

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.

ChemEurJ2014

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

Related content

CNRSleJournal

Interview pour CNRS Le Journal (8 juillet 2019)

"La jeune garde des nanoparticules". Read Online. Read printed version. Interview réalisée par Martin Koppe.

InnovationReview

Interview pour Innovation Review (13 septembre 2017)

"L'ERC, un outil essentiel dans le financement de la recherche fondamentale". Read Online. Interview de trois lauréats français, réalisée par Florent Detroy.

Team of the NanoFLP project

Antoine

Antoine Pesesse
PhD student (2018-)

Rémi

Rémi André
PhD student (2018-2021) then Post-Doctoral Fellow

Cyprien

Cyprien Poucin
PhD student (2019-)

Alexy

Alexy De Jesus Almeida Freitas
Post-Doctoral Fellow (2019-2021)

Alberto

Alberto Palazzolo
Post-Doctoral Fellow (2019-2021)

Anthony

Anthony Ropp
PhD student (2021-)

 

Contact information

Sorbonne Université - LCMCP
Tour 34-44, bureau 412, CC174
4 Place Jussieu
75252 Paris Cedex 05, FRANCE
sophie.carenco*sorbonne-universite.fr (* is @)
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