Archives des Themes team C - LCC CNRS Toulouse

Homogeneous catalysts

Evelyne PREVOTS — Thu, 16 Oct 2025 15:20:51 +0000

Homogeneous catalysts

LCC

Homogeneous catalysts for fine chemicals and energy

We are developing new organometallic and supramolecular catalysts (host-guest complexes) for enantioselective cascade reactions such as asymmetric hydroaminomethylation.

Beyond atom-economic reactions, in the context of current green chemistry and solar energy storage requirements, we are also developing new catalysts for biomass conversion (platform molecule synthesis), plastic recycling, reversible dihydrogen storage (LOHC, (de)hydrogenation), as well as photoisomerisation reactions for solar energy storage.

Asymmetric hydroaminomethylation (HAM) reaction. We are studying asymmetric hydroformylation/reductive amination and asymmetric hydroformylation/condensation/asymmetric hydrogenation cascades to design new chiral organometallic systems with high activity and excellent selectivity.

Fig. Tandem hydroaminomethylation reaction for synthesising amines from alkenes. Credit: Philippe Serp

References

Highly efficient palladium-catalyzed carbonylation reactions of terpenes, Oukhrib A., Kalck P., Urrutigoïty M., Coord. Chem. Rev. 2025, 531, 216453/1-10., 10.1016/j.ccr.2025.216453 – hal-05068408, https://doi.org/10.1016/j.ccr.2025.216453

Recent advances in the methanol carbonylation reaction into acetic acid, Kalck P., Le Berre C., Serp P., Coord. Chem. Rev. 2020, 402, 213078, https://doi.org/10.1016/j.ccr.2019.213078

Biomass conversion

Fig. Polyoxometalate mediated oxidation of polyols derived from biomass into formic acid and formaldehyde. Credit: Bidyut B. Sarma

We are developing the synthesis of new bio-based nitrogenous monomers for the synthesis of biopolymers, as well as an industrial approach to glucose hydrogenolysis (synthesis of platform molecules).

Conversion of biomass-derived molecules into platform molecules using polyoxometalates.

Flow photochemistry and photoisomerisation for solar energy storage

We focus on the use of microreactors (micro-scale flow chemistry) for photochemical syntheses, as these are highly scale-dependent. Our model reaction was initially [2+2] cycloaddition. Our work has enabled us to improve our fundamental understanding of the elementary phenomena involved and to identify and quantify the phenomena that promote or limit them. The methodology developed makes it possible to envisage a change of scale (industrial production, for example) and to support the transposition of photochemical reactions from batch to continuous reactors.
We also study photo-oxygenation reactions involving singlet oxygen generated by photosensitisation of oxygen using a dye called a photosensitiser (PS). The issues associated with the use of a photosensitiser (stability, efficiency, regeneration, recycling) are similar to those encountered with a catalyst.

Reference

Efficient Photooxygenation Process of Biosourced α-Terpinene by Combining Controlled LED-Driven Flow Photochemistry and Rose Bengal-Anchored Polymer Colloids
R. Radjagobalou, J.-F. Blanco, L. Petrizza, M. Le Bechec, O. Dechy-Cabaret, S. Lacombe, M. Save, K. Loubiere
ACS Sustainable Chem. Eng., 2020, 8, 50, 18568–18576. DOI

We are also interested in MOST systems, which are A/B switchable chemical systems capable of (i) converting solar energy into storable chemical energy via a photochemical transformation from A to B and (ii) releasing the stored energy on demand in the form of heat via the reverse catalytic transformation from B to A. In this context, the work carried out by our team focuses in particular on the preparation and evaluation, in batch and continuous micro-scale, of catalysts for the reverse reaction from B to A for Norbornadiene/Quadricyclane (NBD/QC) systems.

Fig. Catalysts for MOST systems: reversible thermal energy storage. (Credit @Odile Dechy Cabaret)

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LCC CNRS

Laboratoire de chimie de coordination du CNRS

205 route de Narbonne, BP 44099
31077 Toulouse cedex 4
France

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+ 33 5 61 33 31 00

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L’article Homogeneous catalysts est apparu en premier sur LCC CNRS Toulouse.

Single-site catalysts

Evelyne PREVOTS — Thu, 16 Oct 2025 15:06:50 +0000

Single-site catalysts

LCC

Back to team C

Projects in this area are based on single-site catalytic systems (supported molecular catalysts and isolated atoms) immobilised on supports, with the aim of developing processes with low environmental impact (atom economy, catalyst recycling, implementation in continuous and/or solvent-free processes).

Reference

Stabilization of metal single atoms on carbon and TiO2 supports for CO2 hydrogenation: The importance of regulating charge transfer
Rivera-Cárcamo C., Scarfiello C., García A. B., Tison Y., Martinez H., Baaziz W., Ersen O., Le Berre C., Serp P.
Advanced Materials Interfaces 2021, 8(8), 2001777/1-17.
https://doi.org/10.1002/admi.202001777, https://hal.archives-ouvertes.fr/hal-03043523

Fig. High-resolution TEM image of a single Pt atom catalyst on an MgO support. The bright spots indicated by the arrows are the isolated atoms. Credit: Bidyut B. Sarma

Supported molecular catalysts

Immobilisation of molecular metal catalyst over supports has the advantage of leading to the development of catalytic phases that can be more easily separated from the reaction medium, or even reused, as well as the possibility of continuous use.
In the case of carbonaceous supports, it has been shown that these can play a significant role in the catalytic reaction. We are studying the influence of various factors (such as the nature of the interaction and the distance between the catalytically active center and the support, the nature and morphology of the latter, etc.) on catalytic performance (activity, selectivity, stability). In this context, we are developing specific ligands to enable the immobilisation of different transition metal complexes from the right-hand side of the periodic table.
The systems developed are used in particular in the asymmetric hydrogenation reaction of various substrates using gold- and rhodium-based catalysts in batch and flow processes.
We are also interested in developing catalysts for various (co)polymerisation reactions: iron and nickel catalysts for ethylene polymerisation, palladium for CO/olefin copolymerisation, and more recently, various systems for the synthesis of polycarbonates by copolymerisation of bio-based epoxides obtained from terpenes and CO2; the latter also acting as a solvent in a process operating in a supercritical environment.
We are also interested in developing supported catalysts for MOST systems that convert solar energy into thermal energy. Cobalt complexes have been adsorbed onto various carbonaceous supports to create recyclable catalytic systems that can be used in fixed beds for continuous flow operation.

Fig. Copolymerisation of cyclohexene with CO₂ on an Fe catalyst immobilised in a CNT. (crédit J. Durand).

References

High pressure equilibrium data of CO₂/cyclohexene oxide and CO₂/limonene oxide systems in the context of polycarbonate synthesis using CO2 as a co-monomer, Pasini E. V., Durand J., Camy S., Fluid Phase Equilib. 2025, 595, 114406/1-11., https://www.sciencedirect.com/science/article/abs/pii/S0378381225000767

Supported Co-based catalytic systems for the epoxidation of terpenes using O2 as oxidant, Rais M., Soulié J., Tendero C., Durand J., Eur. J. Inorg. Chem. 2025, 28(5), e202400293/1-14., 10.1002/ejic.202400293 – hal-04836205 https://doi.org/10.1002/ejic.202400293

Single atom catalyst

Single-atom catalysis has become a major area of research in heterogeneous catalysis in recent years. In these systems, the absence of ensemble effects and the existence of strong electronic effects from the support induce reactivity that is very different from that of metal particles. We are developing synthesis strategies aimed at stabilizing isolated metal atoms on oxide or carbonaceous supports and studying the reactivity of these species in hydrogenation reactions.

References

Acetophenone hydrogenation and consecutive hydrogenolysis with Pd/CNT catalysts: Highlighting the synergy between single atoms and nanoparticles by kinetic modeling, Bernardin V., Vanoye L., Rivera-Cárcamo C., Serp P., Favre-Réguillon A., Philippe R., Catalysis Today 2023, 422, 114196/1-9., https://doi.org/10.1016/j.cattod.2023.114196, https://hal.science/hal-04107663

Adjustment of the single atom/nanoparticle ratio in Pd/CNT catalysts for phenylacetylene selective hydrogenation, Audevard J., Navarro-Ruiz J., Bernardin V., Tison Y., Corrias A., Del Rosal I., Favre-Réguillon A., Philippe R., Gerber I. C., Serp P., ChemCatChem 2023, 15(11), e202300036/1-18., https://doi.org/10.1002/cctc.202300036, https://hal.science/hal-04102599

Fig. Model of a single palladium atom (PdSA) stabilised on a sheet of oxidised graphene (crédits J. Navarro Ruiz, LPCNO, Toulouse, France).

Single atom catalysts (SAC) for photocatalytic/electrocatalytic applications.

This work is being conducted in collaboration with Friedrich-Alexander University (FAU) in Erlangen-Nuremberg, Germany, and the Indian Institute of Chemical Technology (IICT) in India. As part of this work, we are studying the global and local structure of SACs using X-ray absorption spectroscopy (XAS), diffuse reflection infrared spectroscopy (DRIFTS) and high-resolution transmission electron microscopy (HR-TEM). SACs are ultimately used for the hydrogen evolution reaction under the effect of light or electricity.

References

Single-atom catalysts on C₃N₄: Minimizing single atom Pt loading for maximized photocatalytic hydrogen production efficiency, Lazaar N., Wu S., Qin S., Hamrouni A., Sarma B. B., Doronkin D. E., Denisov N., Lachheb H., Schmuki P., Angew. Chem., Int. Ed. 2025, 64(6), e202416453/1-8., 10.1002/anie.202416453 – hal-04927966, https://doi.org/10.1002/anie.202416453

Pd single atoms on g-C₃N₄photocatalysts: minimum loading for maximum activity, Jeyalakshmi V., Wu S., Qin S., Zhou X., Sarma B. B., Doronkin D. E., Kolařík J., Šoóš M., Schmuki P., Chem. Sci. 2025, 16(11), 4788-4795., 10.1039/D4SC08589B – hal-05064320, https://doi.org/10.1039/D4SC08589B

Atomically dispersed Cu–Ni dual-metal sites on g-C3N4 for synergistic enhancement of photocatalytic hydrogen evolution, Islam H., Jaksani B., Iqbal A., Varangane S., Annadata H. V., Ghosh B., Sarma B. B., Thapa R., Pal U., ACS Appl. Energy Mater. 2025, 8(13), 9770-9780., 10.1021/acsaem.5c01346 – hal-05183801, https://doi.org/10.1021/acsaem.5c01346

Fig. Single metal atom incorporated into C₃N₄, TiO₂ for the hydrogen evolution reaction (crédit : Bidyut B. Sarma)

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LCC CNRS

Laboratoire de chimie de coordination du CNRS

205 route de Narbonne, BP 44099
31077 Toulouse cedex 4
France

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+ 33 5 61 33 31 00

Contact

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L’article Single-site catalysts est apparu en premier sur LCC CNRS Toulouse.

Heterogeneous catalysts

Evelyne PREVOTS — Thu, 16 Oct 2025 14:46:38 +0000

Heterogeneous catalysts

LCC

Back to team C

The aim is to develop innovative strategies (confined catalysis, catalyst cocktails, Pickering interfacial catalysis, self-assembling catalysts) for the development of high-performance heterogeneous (nano)catalysts for fine chemical reactions (selective hydrogenation) or energy-related reactions (Fischer-Tropsch synthesis, CO₂ activation, ORR).

Cocktail catalyst

The aim is to develop supported catalysts by integrating ultra-rational use of the active phase (often consisting of a critical metal) but also of the support, which can also contribute to catalysis, in order to achieve cooperative catalysis from multifunctional catalysts.

This original concept, combining the activities of several metallic species (nanoparticles, isolated atoms) and the support (via hydrogen spillover), has been exploited to significantly improve the performance of palladium catalysts for hydrogenation reactions and nickel catalysts for CO₂ reduction.

Fig. Cocktail catalyst (credit Philippe Serp Toulouse).

References

Synergy between supported metal single atoms and nanoparticles and their relevance in catalysis
Serp P.
ChemCatChem 2023, 15(15), e202300545/1-12.
https://doi.org/10.1002/cctc.202300545
https://hal.science/hal-04174631

“Cocktail”-type catalysis on bimetallic systems for cinnamaldehyde selective hydrogenation: Role of isolated single atoms, nanoparticles and single atom alloys
Audevard J., Navarro-Ruiz J., Bernardin V., Philippe R., Corrias A., Tison Y., Favre-Réguillon A., Del Rosal I., Gerber I. C., Serp P.
Journal of Catalysis 2023, 425, 245-259.
https://doi.org/10.1016/j.jcat.2023.06.023
https://hal.science/hal-04139552

Effects of Pd and Co intimacy in Pd-modified Co/TiO₂ catalysts for direct CO₂ hydrogenation to fuels: the closer not the better
Scarfiello C., Durupt A., Tison Y., Pham Minh D., Soulantica K., Serp P.
Catalysis Science & Technology 2024, 14(10), 2896-2907.
https://doi.org/10.1039/d4cy00324a
https://hal.science/hal-04552701

Acetophenone hydrogenation and consecutive hydrogenolysis with Pd/CNT catalysts: Highlighting the synergy between single atoms and nanoparticles by kinetic modeling
Bernardin V., Vanoye L., Rivera-Cárcamo C., Serp P., Favre-Réguillon A., Philippe R.
Catalysis Today 2023, 422, 114196/1-9.
https://doi.org/10.1016/j.cattod.2023.114196
https://hal.science/hal-04107663

Adjustment of the single atom/nanoparticle ratio in Pd/CNT catalysts for phenylacetylene selective hydrogenation
Audevard J., Navarro-Ruiz J., Bernardin V., Tison Y., Corrias A., Del Rosal I., Favre-Réguillon A., Philippe R., Gerber I. C., Serp P.
ChemCatChem 2023, e202300036/1-18.
https://doi.org/10.1002/cctc.202300036
https://hal.science/hal-04102599

Mechanism of hydrogen spillover on metal-doped carbon materials: surface carboxylic groups are key
Navarro-Ruiz J., Audevard J., Vidal M., Campos C. H., Del Rosal I., Serp P., Gerber I. C.
ACS Catalysis 2024, 14(9), 7111-7126.
https://doi.org/10.1021/acscatal.4c00293
https://hal.science/hal-04587084

Probing basal and prismatic planes of graphitic materials for metal single atom and subnanometer cluster stabilization
Vidal M., Pandey J., Navarro-Ruiz J., Langlois J., Tison Y., Yoshii T., Wakabayashi K., Nishihara H., Frenkel A. I., Stavitski E., Urrutigoïty M., Campos C. H., Godard C., Placke T., del Rosal I., Gerber I. C., Petkov V., Serp P.
Chemistry – A European Journal 2024, 30(50), e202400669/1-18.
https://doi.org/10.1002/chem.202400669
https://hal.science/hal-04677240

Deactivation of Pd/C catalysts by irreversible loss of hydrogen spillover ability of the carbon support
Vanoye L., Guicheret B., Rivera-Cárcamo C., Audevard J., Navarro-Ruiz J., del Rosal I., Gerber I. C., Campos C. H., Machado B., Volkman J., Philippe R., Serp P., Favre-Réguillon A.
Journal of Catalysis 2023, 424, 173-188.
https://doi.org/10.1016/j.jcat.2023.05.006
https://hal.science/hal-04113228

Preparation of self-assembled supported catalysts.

The use of self-assembly reactions is a promising avenue for the development of original nano-architectures for catalytic applications.

Inspired by metal-organic frameworks, we have developed an original synthesis route that allows us to obtain assemblies of metal NPs (as well as isolated metal atoms) covalently bound by organic ligands. To date, several metals (Ru, Co, Rh, Au) and three organic motifs have been studied: C₆₀, triphenylene- and adamantane-based ligands.

The ability to control the dimensionality of the assembly is one of the major challenges in the design and understanding of these advanced materials, which have proven to be highly active and selective in fine chemical reactions.

References

Covalent assemblies of metal nanoparticles – strategies for synthesis and catalytic applications
Y. Min, M. R. Axet, P. Serp
Dans “Recent Advances in Nanoparticle Catalysis“, edited by Nicholas Turner, Carmen Claver and Piet van Leeuwen, Springer, 2020, pp 129-197. DOI

3D Ruthenium Nanoparticle Covalent Assemblies from Polymantane Ligands for Confined Catalysis
Y. Min, H. Nasrallah, D. Poinsot, P. Lecante, Y. Tison, H. Martinez, P. Roblin, A. Falqui, R. Poteau, I. del Rosal, I. C. Gerber, J.-C. Hierso, M. R. Axet, P. Serp
Chem. Mater., 2020, 32, 2365-2378. DOI

Nanocatalysts for high selectivity enyne cyclization: oxidative surface reorganization of gold sub-2-nm nanoparticle networks
H. Nasrallah, Y. Min, D. Poinsot, T.-A. Nguyen, J. Roger, O. Heintz, F. Jolibois, R. Poteau, I. C. Gerber, Y. Coppel, M. L. Kahn, M. Rosa Axet, P. Serp, J.-C. Hierso
J. Am. Chem. Soc. Gold, 2021, 1, 187-200. DOI

Fig. : Covalent network of metallic nanoparticles (credit P. Serp).

Supported catalysis in a confined environment

Confinement effects in heterogeneous catalysis have been the subject of particular attention because they can affect catalytic activity, selectivity and stability.

Although most studies focus on oxide-type materials, particularly zeolites, carbonaceous materials, especially carbon nanotubes, also allow such effects to occur.

Strategies are therefore being studied to selectively confine the active phase in order to highlight confinement effects in various reactions (hydrogenation, Fischer-Tropsch synthesis).

Reference

Beyond confinement effects in Fischer-Tropsch Co/CNT catalysts
A. C. Ghogia, B. F. Machado, S. Cayez, A. Nzihou, P. Serp, K. Soulantica, D. Pham Minh
J. Catal., 2021, 397, 156-171. DOI

Fig. Confinement effects in supported catalysis (credit: P. Serp).

Supported catalysis for CO2 hydrogenation

This activity focuses on the hydrogenation reaction of CO₂, with the objectives of controlling the selectivity of the reaction (CH₄, CO, hydrocarbons) and lowering reaction temperatures.

CO₂ methanation reaction. Our activities focus on developing catalysts capable of producing methane through the Sabatier reaction at low temperatures. Our efforts have concentrated on optimising a TiO₂support, both by adjusting the nature of the phases present (rutile and anatase) and by modifying the surface.

Direct Fischer-Tropsch reaction from CO₂. The hydrogenation of CO₂ via the Fischer-Tropsch synthesis process (CO₂-FTS) produces ultra-clean synthetic fuel. This reaction is generally carried out in two stages (indirect route), combining the production of synthesis gas by reverse reaction of the gas with water in a first reactor, and a CO-FTS process in a second reactor. The direct pathway allows both reactions to be carried out at a lower temperature and in a single reactor if cobalt is used. It is this pathway, which requires the use of multifunctional catalysts, that is the subject of our research.

References

Origin of the synergetic effect between TiO2 crystalline phases in the Ni/TiO2 catalyzed CO2 methanation reaction
Messou, M. Borges Ordoño, A. Urakawa, F. Meunier, B. F. Machado, V. Collière, R. Philippe, V. Bernardin, P. Serp, C. Le Berre
J. Catal., 2021, 398, 14-28.

Tuning CO₂ hydrogenation selectivity on Ni/TiO₂ catalysts via sulfur addition
Le Berre, A. Falqui, A. Casu, T. T. Debela, M. Barreau, C. H. Hendon, P. Serp
Catal. Sci. Technol., 2022, 12, 6856-6864.

Low temperature Sabatier CO₂ methanation
Molinet Chinaglia, S. Shafiq, P. Serp
ChemCatChem, 2024, 16, e202401213.

Modified Co/TiO₂ catalysts for CO₂ hydrogenation to fuels
Scarfiello, K. Soulantica, S. Cayez, A. Durupt, G. Viau, N. Le Breton, A. K. Boudalis, F. Meunier, G. Clet, M. Barreau, D. Salusso, S. Zafeiratos, D. Pham Minh, P. Serp
J. Catal., 2023, 428, 115202.

Effects of Pd and Co intimacy in Pd-modified Co/TiO₂ catalysts for direct CO₂ hydrogenation to fuels
Scarfiello, A. Durupt, Y. Tison, D. Pham Minh, K. Soulantica, P. Serp
Catal. Sci. Technol., 2024, 14, 2896-2907.

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LCC CNRS

Laboratoire de chimie de coordination du CNRS

205 route de Narbonne, BP 44099
31077 Toulouse cedex 4
France



+ 33 5 61 33 31 00

Contact

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L’article Heterogeneous catalysts est apparu en premier sur LCC CNRS Toulouse.

In situ/operando spectroscopy

Evelyne PREVOTS — Wed, 15 Oct 2025 10:25:08 +0000

In situ/operando spectroscopy

LCC

Back to team C

In situ/operando spectroscopy

We use various spectroscopic techniques to observe the changes that occur during the reaction. We implement reaction conditions that are as close as possible to those used in the laboratory.

We use low-energy X-rays to identify phase/crystallinity changes during the reaction, high-energy X-rays at the synchrotron to identify changes in oxidation state and coordination, Fourier transform infrared spectroscopy to identify functional groups, and microscopy to determine metal dispersion/agglomeration.

Reference

Operando spectroscopy to understand dynamic structural changes of solid catalysts
Sarma B. B., Grunwaldt J.-D.
CHIMIA 2024, 78(5), 288-296.
https://doi.org/10.2533/chimia.2024.288
https://hal.science/hal-04593870

Fig. Various in situ/operando techniques for monitoring dynamic changes in the catalyst

Dynamic behaviour of single atom catalysts and clusters

Solid catalysts exhibit highly dynamic behaviour and tend to restructure during the reaction. Among them, single atom catalysts (SACs) or atomically dispersed catalysts are more vulnerable when the dynamic behaviour of catalysts plays a key role. SACs have the potential to achieve maximum efficiency (theoretically), but on the other hand, due to their high surface energy, they tend to agglomerate, which alters the reaction pathway. It is therefore difficult to know whether the active site is an isolated metal or a metal island. To understand dynamic behaviour, in situ/operando spectroscopy is essential. For example, in our recent work, we have shown that Rh SACs during ethylene hydroformylation form Rh clusters, leading to two different pathways (hydroformylation reaction and CO hydrogenation).

Reference

Understanding the role of supported Rh atoms and clusters during hydroformylation and CO hydrogenation reactions with in situ/operando XAS and DRIFT spectroscopy
Sarma B. B., Neukum D., Doronkin D. E., Lakshmi Nilayam A. R., Baumgarten L., Krause B., Grunwaldt J.-D.
Chemical Science 2024, 15(31), 12369-12379.
http://dx.doi.org/10.1039/D4SC02907K
https://hal.science/hal-04692606

Fig. Dynamic behaviour of the single-atom rhodium catalyst during the hydroformylation reaction. Credit : Bidyut B. Sarma

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LCC CNRS

Laboratoire de chimie de coordination du CNRS

205 route de Narbonne, BP 44099
31077 Toulouse cedex 4
France



+ 33 5 61 33 31 00

Contact

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L’article In situ/operando spectroscopy est apparu en premier sur LCC CNRS Toulouse.