Catalysts for Renewable Hydrogen Production and NADH Regeneration

Alceo Macchioni^a, Elisa Boccalon^a, Gabriel Menendez Rodriguez^a, Iolanda D'Ambrosio^a, Ferdinando Costantino^a, Cristiano Zuccaccia^a, Luca Rocchigiani^a

^aDepartment of Chemistry, Biology and Biotechnology, University of Perugia, Via Elce di Sotto 8, 06123, Perugia, Italy

Proceedings of The Future of Hydrogen: Science, Applications and Energy Transition (H2Future25)

Production

Ibiza, Spain, 2025 May 5th - 7th

Organizers: Teresa Andreu, Bahareh Khezri and Jose Mata

Oral, Alceo Macchioni, presentation 013
Publication date: 27th March 2025

The production of H₂ from renewable sources, ideally water and organic molecules coming from waste resources, is one of biggest challenge that the scientific community is facing nowadays. Implementing a catalytic protocol for H₂ production is an attractive strategy for increasing efficiency and scalability and reducing energy demand.

In our group we are developing catalysts for hydrogen evolution reaction [1] and reactions strictly related to H₂ production, such as water oxidation [2], dehydrogenation of formic acid [3], regeneration of the “natural form” of hydrogen, i.e. NADH [4], dehydrogenation of platform molecules, which are wastes or by-products of industrial processes [5]. We mainly focus on single-site catalytic systems of different nature including, homogeneous, heterogenized and heterogenous [6].

In this contribution, our recent results concerning with the rational development of iridium organometallic (electro-)catalysts for NADH regeneration approaching the performance of enzymes will be reported. Furthermore, it will be shown how decorating organoiridium catalysts with moieties that mimic the functional group of the substrate to activate, is a successful strategy to selectively dehydrogenate glycerol to produce renewable H₂ and lactate. Finally, some examples of the utilization of layered materials as catalysts for electrolytic water oxidation will be presented.

References:

[1] Trotta, C.; Dahiya, P.; Baldinelli, L.; Menendez Rodriguez, G.; Chakraborty, P.; Bistoni, G.; De Angelis, F.; Sundararaju, B.; Macchioni, A. A cobalt molecular catalyst for hydrogen evolution reaction with remarkable activity in phosphate buffered water solution. Catal. Sci. Technol., 2024, 14, 3699–3706

[2] Gatto, G.; De Palo, A.; Carrasco, A. C.; Pizarro, A. M.; Zacchini, S.; Pampaloni, G.; Marchetti, F.; Macchioni, A. Modulating the water oxidation catalytic activity of iridium complexes by functionalizing the Cp*-ancillary ligand: hints on the nature of the active species. Catal. Sci. Technol. 2021, 11, 2885−2895.

[3] Trotta, C.; Langellotti, V.; Manco, I.; MenendezRodriguez, G.; Rocchigiani, L.; Zuccaccia, C.; Ruffo, F.; Macchioni, A. Boosting Effect of Sterically Protected Glucosyl Substituents in Formic Acid Dehydrogenation by Iridium(III) 2-Pyridineamidate Catalysts. ChemSusChem 2024, No. e202400612.

[4] Menendez Rodriguez, G.; Trotta, C.; Tensi, L.; Macchioni, A. Reversible Electrocatalytic NAD+/NADH Interconversion Mediated by a Pyrazine-Amidate Iridium Complex. J. Am. Chem. Soc. 2024, 146, 34298−34303.

[5] Boccalon, E.; Menendez Rodriguez, G.; Trotta, C.; Ruffo, F.; Zuccaccia, C.; Macchioni, A. Acceptorless Dehydrogenation of Glycerol Catalysed by Ir(III) Complexes with Carbohydrate-Functionalised Ligands: A Sweet Pathway to Produce Hydrogen and Lactic Acid. Eur. J. Inorg. Chem. 2024, e202400507.

[6] Macchioni, A. The Middle-Earth between Homogeneous and Heterogeneous Catalysis in Water Oxidation with Iridium. Eur. J. Inorg. Chem. 2019, 7–1.

Acknowledgements:

This work has been funded by Fondazione Perugia Progetto n. 21101, Sviluppo di catalizzatori eterogenei innovativi per la produzione sostenibile di idrogeno verde. We thank the European Union − NextGenerationEU under the Italian Ministry of University and Research (MUR) National Innovation Ecosystem grant ECS00000041 – VITALITY and Universitá degli Studi di Perugia, within the project Progetti Fondo Ricerca di Ateneo 2021 and 2022, and PON − Ricerca e Innovazione − DM 1062 (J91B21003250006) for support.

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