Dr Luca Gonsalvi                                                        

 

 

 

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Group Leader
Current Research Themes

Hydrogen Production and Storage from Organic Hydrides by Homogeneous Catalysis

This research interest falls in the area of Energy Storage, in particular the quest for novel catalysts for hydrogen production from chemical reservoirs in the frame of the emerging Hydrogen Economy. Hydrogen can be in principle released from hydrogen-rich organic compounds by breaking and recombining chemical bonds. An example is the reaction involving Formic Acid (FA, HCOOH), which can be dehydrogenated into a mixture of CO2 and H2 gas in the presence of suitable homogeneous (soluble) or heterogeneous (solid) catalysts, able to decrease the activation energy of the reaction, enabling running the same under mild conditions of temperatures and atmospheric pressure.  The reverse reaction, CO2 hydrogenation, may in principle be used to regenerate FA under suitable conditions, enabling the sustainable use of such an organic hydride as H-storage material.

We are studying the properties of transition metals such as Ru, Fe, Ir and Mn stabilized by a series of polydentate ligands such as PPn, PNnP, NPn, NPyN, P-NPyN-P, etc in the two processes run in organic solvents or solventless conditions. In parallel, we are evaluating structural modifications of water soluble phosphines to carry out these reactions in water under mild pressure and temperature conditions.

 

Collaborations: TU Wien (A), CEA Saclay (F), EPFL Lausanne (CH), UCCS Universite' d'Artois Lens (F), LIKAT Rostock (D).

 

Transition Metal Complexes in Water: Chemistry, Catalysis and Antitumoral Organometallics

 

Our research interest in the quest for versatile water soluble phosphines for applications in catalysis and other aspects, has led us during the years to the development of structural modifications of  the water soluble cage like phosphine 1,3,5-triaza-7-phosphaadamantane (PTA), including functionalizations at "upper" and "lower" rim, selective bond cleavage to give a series of mono- and bidentate P,N and P,O ligands. These complexes were applied to regioselective C=C and C=O catalytic hydrogenations and transfer hydrogenations, olefin hydroformylations and CO2/bicarbonate reduction to formate in water. Ancillary ligands such as arene, pyrazolyl borate, substituted cyclopentadienyls were also used.

The catalytic studies are often accompanied by detailed mechanistic investigations, both in vitro (solution NMR, also under high-pressure conditions) and in silico (DFT calculations).

Selected compounds are routinely tested for in vitro evaluation of  antimetastatic activity using HT29 colon carcinoma, A549 lung carcinoma and T47D breast carcinoma cells.

 

Collaborations: EPFL Lausanne (CH), UCCS Universite' d'Artois Lens (F)

 

White Phosphorus Chemical Activation

Another topic of interest (until 2014) involved the study of activation of the tetrahedral allotrope of phosphorus (P4, white phosphorus) as a possible feedstock for the synthesis of H3PO2, PH3 and organophosphorus derivatives. Rh and Ir complexes such as [M(dppm)2]OTf are able to activate P4 and generate a novel P5 unit of the kind Ph2PCH2PPh2PPPP by insertion on the M-dppm bond. The use of Pt(0) allows for further bond cleavage as in the case of Co complexes.

The synthetic work in the quest of novel P-Metal architectures is accompanied by dynamic NMR studies, X-ray crystallographic analysis and DFT calculations.

Recent Selected Publications

[1] Mellone, I.; Bertini, F.; Peruzzini, M.; Gonsalvi, L.* "An active, stable and recyclable Ru(II) tetraphosphine-based catalytic system for hydrogen production by selective formic acid dehydrogenation" Catal. Sci. & Technol. 2016, 6, 6504-6512. [article]

[2] Bertini, F.; Gorgas, N.; Stoeger, B.; Peruzzini, M.; Veiros, L. F.; Kirchner, K.;* Gonsalvi, L.* "Efficient and Mild Carbon Dioxide Hydrogenation to Formate Catalyzed by Fe(II)-Hydridocarbonyl Complexes bearing 2,6-(diaminopyridyl)diphosphine Pincer Ligands" ACS Catal. 2016, 6, 2889−2893. [article] Highly cited article

[3] Kalsin, A.M.*; Peganova, T. A.; Novikov, V. V.; Peruzzini, M.; Gonsalvi, L.* "Cooperative effects of ruthenium micellar catalysts and added surfactants in transfer hydrogenation of ketones in water" Catal. Sci. & Technol. 2015, 5, 4458-4465. [article]

[4] Bertini, F.; Mellone, I.; Ienco, A.; Peruzzini, M.; Gonsalvi, L.* "Iron(II) Complexes of the Linear rac-Tetraphos-1 Ligand as Efficient Homogeneous Catalysts for Sodium Bicarbonate Hydrogenation and Formic Acid Dehydrogenation" ACS Catal. 2015, 5, 1254−1265. [article]

[5] Guerriero, A.; Bricout, H.; Sordakis, K.; Peruzzini, M.; Monflier, E. Hapiot, F.;* Laurenczy, G.;* Gonsalvi, L.* "Hydrogen Production by Selective Dehydrogenation of HCOOH Catalyzed by Ru-biaryl Sulfonated Phosphines in Aqueous Solution" ACS Catal. 2014, 4, 3002-3012. [article]

 


Senior Researcher

ICCOM-CNR 

Via Madonna del Piano 10,

50019 Sesto Fiorentino (Fl) Italy

Office +39 055 5225251 Lab +39 055 5225237
Fax +39 055 5225203 E-mail l.gonsalviATiccom.cnr.it

 

Biography

First Degree

Laurea in Chimica (M.Sc.) 

University of Parma (Italy) 

Ph.D.

Organometallic Chemistry and Catalysis 

University of Sheffield (UK)

Post Doctoral 

Catalytic Oxidations, 

Delft University of Technology (NL)

 

Dr Luca Gonsalvi graduated in Chemistry in 1994 from his hometown University of Parma, where he worked on olefin hydroformylation via Rh complexes tethered to modified silica under the supervision of Prof G. Predieri both as student and as fixed-term research assistant.

 

In 1996 he started his PhD research at the University of Sheffield in the Catalytic Mechanisms Research Group. The project, supervised by Dr A. Haynes and in collaboration with BP Chemicals Ltd. involved the study of stereoelectronic ligand effects in methanol carbonylation. The thesis, defended in November 1999, was awarded the Turner Prize in Chemistry of The University of Sheffield.

 

In December 1999, he joined Prof. R. A. Sheldon's group at Delft University of Technology as PDRA to develop a clean catalytic route to esters via selective alpha-oxidation of ethers and acetals, sponsored by the Dutch Innovation Oriented Program for Catalysis (IOP-Katalyse), in collaboration with DSM Research and other companies.

 

From December 2001, he has joined ICCOM as Staff Researcher, developing aqueous phase LTM-catalysed processes, white phosphorus activation and organometallic chemistry water soluble compounds.

 

Since 2009 he is Group Leader at ICCOM of a Research Unit working on the themes: "Hydrogen Storage and Production from Organic Hydrides by Homogeneous Catalysis" and "Homogenous Catalysis in Water".

 

In 2010, he was promoted to CNR Senior Researcher.

 

In 2014, he received the ASN Italian Habilitation as Associate Professor in General and Inorganic Chemistry. In 2017, he received the ASN Italian Habilitation as Full Professor in General and Inorganic Chemistry.

 

International Projects

 

 

HYDROCHEM

 

  AQUACHEM

 

https://media.licdn.com/media/p/1/000/29d/34e/25b6d99.png SUSPHOS

 

COST ACTION D29

 

 

COST ACTION CM0802

 

 

 

COST ACTION CM1205

 

 

 

Recent National Projects

 

ENERGYLAB

 

PirodePIRODE

 

 

logo2EFOR

 

 

FIRENZE HYDROLAB

 

 

 

Conference Organization

 

 

 

 

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