Cycle / Years
40th cycle [2024-2027]
Contacts
Supervisor(s)
Prof. Fabio Marchetti, Prof. Gianluca Ciancaleoni
Title of the PhD project
New [FeFe]-Hydrogenase mimics for electrocatalytic H2 production
Abstract of the PhD project
The efficient and sustainable production of molecular hydrogen (H2), for instance via electrochemical processes, represents a fundamental step in the transition to a carbon-neutral economy. Many efforts have been directed to developing efficient proton reduction catalysts based on earth-abundant metals. In this context, nature provides an elegant example with [FeFe]-hydrogenase enzymes.
The main objective of this PhD project is the design and synthesis of new, easily-accessible and efficient water-soluble complexes that mimic [FeFe]-hydrogenase, and their evaluation in the electrocatalytic production of H2 from acidic solutions. DFT studies will assist in selecting ligands and substituents, and elucidating mechanistic aspects, to provide robust structure/activity relationships.
Academic Fields and Disciplines (SSD), main and secondary
General and Inorganic Chemistry - CHIM03
Educational and third mission activities
• Teaching Support - General Chemistry, for the Bachelor’s Degree in Food Science, Department of Agricultural, Food and Agro-Environmental Sciences, University of Pisa, September 2026 - February 2027.
• Support for work-experience activities (PCTO) for upper secondary school students, July 14th 2026.
• Laboratory Support - Inorganic Chemistry, for the Bachelor’s Degree in Chemistry for Industry and the Environment, Department of Chemistry and Industrial Chemistry, University of Pisa, April - May 2026.
• Dissemination activity for High School classes, IIS Giosuè Carducci Volterra, Pisa, January 31st 2026.
• Laboratory Support – General and Inorganic Chemistry, for the Bachelor’s Degree in Chemistry for Industry and the Environment, Department of Chemistry and Industrial Chemistry, University of Pisa, November – December 2025.
• Guest Lecturer – Organometallic Chemistry and Transition Elements, Department of Chemistry and Industrial Chemistry, University of Pisa, October 2025.
International
9th May 2025-10th Jult 2025: Two months studying period in the research group of Professor Wolfgang Weigand at Friedrich Schiller University, Jena (Germany).
Activities: Synthesis of classic dinuclear iron mimetics complexes of [FeFe]-hydrogenase. Synthesis of conjugated organic molecules to be used as photosensitive ligands for the mimetics. Cyclic voltammetry measurements for electrochemical characterization. Photocatalysis measurements to evaluate photocatalytic activity.
Publications
• S. Benetti, A. Cinci, C. Zappelli, F. Marchetti, "Diiron(I) Bis(cyclopentadienyl) Complexes with Bridging Iminium Ligands: From Foundational Organometallic Chemistry to Unique Reactivity and Biological Potential", Acc. Chem. Res., 2026, 59, 1227 (DOI:10.1021/acs.accounts.6c00038).
• I. Basma, H. Abul-Futouh, A. Cinci, S. J. Abaalkhail, A. A. Alayyaf, P. Köhler, W. Weigand, “Design and Structural Characterization of Ferrocenyl Bithiophene Thioketone-Based Iron Complexes”, Inorganics, 2026, 14, 14 (DOI: 10.3390/inorganics14010014).
• L. Biancalana, N. Di Fidio, D. Licursi, S. Zacchini, A. Cinci, A. M. Raspolli Galletti, F. Marchetti, C. Antonetti, “New ruthenium(II) isocyanide catalysts for the transfer hydrogenation of ethyl levulinate to γ-valerolactone in C2-C6 alcohols”, J. of Catalysis, 2024, 439, 115761 (DOI: 10.1016/j.jcat.2024.115761).
• A. Cinci, G. Ciancaleoni, S. Zacchini, F. Marchetti, “Cyanide Addition to Diiron and Diruthenium Bis-Cyclopentadienyl Complexes with Bridging Hydrocarbyl Ligands”, Inorganics, 2024, 12, 147 (DOI: 10.3390/inorganics12060147).
Oral communications at conferences
• A. Cinci, G. Bresciani, T. Funaioli, L. Biancalana, S. Zacchini, G. Ciancaleoni, F. Marchetti, “Unusual Ancillary Ligands For [FeFe]-Hydrogenase To Unlock New Electrocatalytic Structures”, INORG26 51st Congress of the Inorganic Chemistry Division & 2nd Edition of the Italian–French Coordination Chemistry Days, Molecular Biotechnology Center, 2026 September 1-4, oral presentation.
• A. Cinci, G. Bresciani, T. Funaioli, L. Biancalana, S. Zacchini, G. Ciancaleoni, F. Marchetti, “Bis-Cyclopentadienyl Cationic [FeFe]-Hydrogenase Mimetics”, ICH2026, 14th International Conference on Hydrogenase and Other Redox Metalloenzymes, University of Leicester, UK, 2026 July 26-30, oral presentation.
Poster communications at conferences
• A. Cinci, G. Bresciani, T. Funaioli, L. Biancalana, S. Zacchini, G. Ciancaleoni, F. Marchetti, “Expanding the [FeFe]-Hydrogenase Toolbox with Cyclopentadienyl and Heterocarbyne Ligands”, Chemistry For The Future International Conference, University of Pisa, 2026 July 1-3, poster presentation.
• A. Cinci, T. Funaioli, G. Ciancaleoni, L. Biancalana, S. Zacchini, F. Marchetti, “New [FeFe]-hydrogenase mimics for electrocatalytic H2 production”, INORG25 50th Conference of the Divisione di Chimica Inorganica SCI, Centro congressi Federico II, 2025 September 9-12, poster presentation.
• A. Cinci, T. Funaioli, G. Ciancaleoni, L. Biancalana, S. Zacchini, F. Marchetti, “New findings on [Fe2Cp2(CO)4] toward the development of potential electrocatalysts for H2 production”, ISOC XV International School of Organometallic Chemistry, University of Camerino, 2025 September 4-7, poster presentation.
• S. Stampatori, A. Cinci, D. Riccio, S. Zacchini, F. Marchetti, G. Pampaloni, L. Biancalana, “New Reactivity Pathways in Ruthenium(II) η6-Arene Complexes”, Chemistry for the Future International Conference, University of Pisa, 2023 June 28-30, poster presentation.
Other achievements
• Organization of Chemistry For the Future Conference 2026 (CFF2026), University of Pisa, Department of Chemistry and Industrial Chemistry, 2026 July 1st – 3rd.
Funding
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