Image de Jerome Canivet

Jerome Canivet

Chercheur

Numéro ORCID : 0000-0002-0458-3085


445 424 (Standard + 33 [0] 472 445 300)
P105

Mots clés

Molecular Catalysts, Metal-Organic Frameworks, Porous Polymers, Post-Synthetic Functionnalization, Confinement, Fine Chemicals, Photocatalysis

Education

University of Lyon (France): Professorial Thesis (Habilitation à Diriger des Recherches), 2017

University of Neuchâtel (Switzerland): Ph. D., Organometallic Synthesis and Molecular Catalysis, 2007

University of Lille (France): M. S., Organic and Macromolecular Chemistry, 2003

University of Lille (France): B. S., Physical and Chemical Sciences, 2001

 

Career

2011- now: Permanent CNRS researcher at IRCELYON, Engineering and Processes Intensification team, France.

2009-2011: Postdoctoral research project done at the CNRS with Dr. David Farrusseng, Metal-organic frameworks as catalysts, IRCELYON, France.

2007-2009: Postdoctoral research project done at the Noyori’s Laboratory under the direction of the Prof. Kenichiro Itami, Catalyzed direct CH arylation, University of Nagoya, Japan.

2003-2007: Ph.D research project done at the Laboratory of Organometallic Chemistry and Molecular Catalysis directed by the Prof. Georg Süss-Fink, Synthesis of water-soluble arene ruthenium, rhodium and iridium complexes and study of their catalytic potential for the transfer hydrogenation reaction in aqueous solution, Chemistry Institute of Neuchâtel, Switzerland.

 

Awards - Grants

2019: Emergence@International travel grant from Institute of Chemistry - CNRS (Japan lecture tour)

2018: Young Researcher Award from the Catalysis Division of the French Chemcial Society (DivCat)

2007: SNF Postdoctoral Fellowship for Prospective Researchers, Swiss National Science Foundation (supported by Prof. J.-E. Bäckvall, Stockholm University, Sweden). 

2007: JSPS Postdoctoral Fellowship for Foreign Researchers, Japan Society for the Promotion of Science (supported by Prof. K. Itami, Nagoya University, Japan).

 

Research impact

November 2019: 43 scientific papers (J.Am.Chem.Soc.,  Angew. Chem.,  Chem.Commun, J.Catal.,... ), H index = 24, 2600 citations, 3 book chapters, 5 patents

for updated scientific production see

ORCID

Researcher ID

Environmentally friendly and cost efficient processes attract continuously growing interest for applications in catalysis and organic synthesis.

The main aim of my PhD work (2003-2007), in the Süss-Fink group at Neuchâtel University, Switzerland, was to develop efficient catalysts in aqueous solution, especially for transfer hydrogenation of ketones and imines to give an environmentally friendly access to alkaloids via asymmetric catalysis in water.

NADH


In this “green chemistry” concept, I extended my field of research to other catalytic reactions like carbon-carbon coupling and to self-assembled materials. Thus I joint the Itami group (2007-2009), first as a part of the Noyori Laboratory, in Nagoya, Japan, as a JSPS postdoctoral fellow in order to develop new systems (molecular catalysts and/or nanoparticles) able to catalyze the heteroarenes functionalization (via CH activation) under mild conditions, enhancing the cost efficiency of the process.

coupling 

Since 2009, I joint the group of Engineering and Process Intensification at the CNRS in the Institute of Researches on Catalysis en Environment of Lyon (IRCELYON) in order to develop new catalysts based on the MOFs technology, expanding the field of applications of these promising porous crystalline materials. I therefore developed new catalytic species confined into the MOFs cavities in order to obtain innovative selectivities with heterogeneized molecular catalysts.

MOF_cat
 

I developed the concept of solid macroligand, using MOF and microporous polymers as valuable representatives. We show that polymer-based macroligands allow designing heterogeneous catalysts with similar versatility than found in molecular chemistry and homogeneous catalysis.

Our main finding is that the Hammett parameter is a performing descriptor of all the active sites, irrespective of their nature (heterogeneous or molecular) and the Hammett parameter can be directly linked to the catalytic performance of the catalysts with no gap between homogeneous and heterogeneous catalyses. While the usefulness of the Hammett parameter is well established in molecular chemistry, no such evidence was present for heterogeneous/heterogenized catalysts so far. This perfect correlation has been established for Rh-based catalytic systems in both CO2 photoreduction (ACS Catal. 2018) and ketones transfer hydrogenation (ChemCatChem 2018).

Linear correlation between catalytic activity and Hammett constant determined/calculated for the active site established for both heterogeneous and molecular catalytic systems.

The established correlation between the catalytic activity and the Hammett parameter highlights the crucial impact of the local electronic environment surrounding the active catalytic center over the long-range framework structure, as demonstrated for two different MOF and four CMP-based catalysts. The general linear trend gives also insight into the contribution of the diffusion limitation inside the porous network of such heterogeneous catalysts or of unexpected reactivity of functional groups at the macroligand.

This opens new perspectives for the rational design of efficient heterogeneous catalysts based on molecular species.

Both MOF and Microporous Polymers thus appear as very appealing platforms and their use as macroligands for the heterogenization of molecular catalysts is further reducing the gap between homogeneous and heterogeneous catalysis.

Molecular Catalysts Confined inside Cavities: The Concept of Solid Porous Macroligands

Thanks to their hybrid formulation, MOFs shall bridge the gap between pure inorganic and organic materials, thereby pushing the frontiers of knowledge ever further. Initially, MOFs were regarded only as a new type of molecular sieve material with a pore size between those of inorganic zeolites (<1 nm) and ordered mesoporous silica materials (>2 nm). On the other hand, their stimuli-induced flexibility, or more generally their softness, is common trait with organic enzymes. It is indeed acknowledged that MOFs could mimic enzymes using the concept of molecular recognition, allowing high chemo-, regio- and enantioselectivity – the ultimate goal in catalysis.

Enz_MOF_Zeol2

Novel porous platforms allows adressing new challenges in heterogeneous catalysis whicle tackling issues on stability and control over active site: Metal-Organic Frameworks (MOF), Covalent Organic Frameworks (COF) and Conjugated Microporous Polymers (CMP). From MOF to COF and CMP, they present decreasing ordered structure and control over the porosity but increasing chemical stability.

They thus appear as very appealing platforms and their use as macroligands for the heterogenization of molecular catalysts is further reducing the gap between homogeneous and heterogeneous catalysis.

 

For track records see ORCID

Follow us on Twitter  MOF@IRCELYON

Heterogenization of Active Molecular Catalysts within Solid Porous Macroligands

For Light alkenes di- and oligomerization

 

Ni_oligom2
 see J. Am. Chem. Soc. 2013, 135, 4195-4198

 


For Enantioselective catalysis (aldol reaction, hydrogenation)

Abstract Image

see J. Am. Chem. Soc. 2015, 137, 9409-9416

 

For Photocatalysis

 

Abstract Image

 

see ACS Catal. 2018, 8, 1653-1661

 

Understanding Host-Guest interactions using DFT combined with DNP-SENS

see Chem.Eur.J. 2016, 46, 16531-16538

2019: ITbm/GTR Seminar Series, Nagoya, Japan
Heterogenized molecular catalysis: Unifying two world

2019: Elicat Summer School on Catalysis, Villeurbanne, France
Application of Metal-Organic Frameworks to Catalysis

2017: Elicat Summer School on Catalysis, Villeurbanne, France
Metal-Organic Frameworks: Extended Molecular Networks vs. Surface Science

2014: IGER/ITbM/RCMS Seminar Series, Nagoya, Japan
Metal-Organic Frameworks: A new tale of the Emperor's new clothes