Nanostructured Systems for Electrocatalysis of Reduction Reactions for Energy Conversion Applications

Isopi, Jacopo (2021) Nanostructured Systems for Electrocatalysis of Reduction Reactions for Energy Conversion Applications, [Dissertation thesis], Alma Mater Studiorum Università di Bologna. Dottorato di ricerca in Chimica, 33 Ciclo. DOI 10.48676/unibo/amsdottorato/9771.
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Oxygen Reduction Reaction (ORR) requires a platinum-based catalyst to reduce the activation barrier. One of the most promising materials as alternative catalysts are carbon-based, graphene and carbon nanotubes (CNT) derivatives. ORR on a carbon-based substrate involves the less efficient two electrons process and the optimal four electrons process. New synthetic strategies to produce tunable graphene-based materials utilizing graphene oxide (GO) as a base inspired the first part of this work. Hydrogen Evolution Reaction (HER) is a slow process requiring also platinum or palladium as catalyst. In the second part of this work, we develop and use a technique for Ni nanoparticles electrodeposition using NiCl2 as precursor in the presence of ascorbate ligands. Electrodeposition of nano-nickel onto flat glassy carbon (GC) and onto nitrogen-doped reduced graphene oxide (rGO-N) substrates are studied. State of the art catalysts for CO2RR requires rare metals rhenium or rhodium. In recent years significant research has been done on non-noble metals and molecular systems to use as electro and photo-catalysts (artificial photosynthesis). As Cu-Zn alloys show good CO2RR performance, here we applied the same nanoparticle electrosynthesis technique using as precursors CuCl2 and Cl2Zn and observed successful formation of the nanoparticles and a notable activity in presence of CO2. Using rhenium complexes as catalysts is another popular approach and di-nuclear complexes have a positive cooperative effect. More recently a growing family of pre-catalysts based on the earth-abundant metal manganese, has emerged as a promising, cheaper alternative. Here we study the cooperative effects of di-nuclear manganese complexes derivatives when used as homogeneous electrocatalysts, as well as a rhenium functionalized polymer used as heterogeneous electrocatalyst.

Tipologia del documento
Tesi di dottorato
Isopi, Jacopo
Dottorato di ricerca
Settore disciplinare
Settore concorsuale
Parole chiave
Electrochemistry Catalyst Graphene Nanoparticles ORR HER CO2RR GQD Dinuclear Complexes
Data di discussione
20 Maggio 2021

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