Metal Organic Framework-based electrocatalysts towards bio-inspired water splitting reaction - Finanziamento dell’Unione Europea – NextGenerationEU – missione 4, componente 2, investimento 1.1.

MOF2O aims at developing Metal Organic Frameworks (MOFs)-based electro-catalysts for the Oxygen Evolution Reaction (OER), one of the two half-reactions of the water splitting process, mastered by Nature using the Mn-complex in Photosystem II. MOFs can be identified as the link between oxidic porous catalysts and homogeneous complexes, being constituted by metal oxidic clusters connected by organic linkers. They are intrinsically tunable by changing either the metal in the cluster and the length/functionality of the organic linkers, opening up new possibilities in the bio-inspired design of the active site and its environment. The project will start implementing two parallel synthetic strategies for MOFs preparation: i) synthesize already known structures that partially exposes their clusters (e.g., MIL-88 and ZIF-8) or with linkers that naturally can bear metallic ions (e.g., porphyrins in PCN-224); ii) preparing MOFs with robust structure and modify part of the linkers making them able to bear active species (e.g., UiO-67). The materials will be prepared by Dr. A. Lazzarini in University of L’Aquila, where also their routine characterization (PXRD, TGA, BET, NMR, SEM) will be performed; the synthesized materials will also be electrochemically characterized with cyclic voltammetry in collaboration with Prof. L. Rossi from University of L’Aquila. Afterwards, more advanced physico-chemical characterization will be performed by Prof. E. Borfecchia and Dr. M. Signorile at the University of Torino, in order to elucidate structural/electronic properties for the MOF framework and the possible active sites. A multi-technique approach synergizing laboratory methods (IR, Raman, UV-Vis under in situ conditions, also using probe molecules) and synchrotron X-ray absorption/emission spectroscopies will allow us to disclose the finest details of the investigated MOFs, including assessment of their hydro-stability in the presence of model electrolytes. To pinpoint structure-activity relationships, the project will also involve electrocatalytic testing of the most promising materials, exploiting a recently acquired DEMS setup. In parallel, we will perform spectroelectrochemical studies with both vibrational and X-ray spectroscopies to capture the material response under realistic OER-conditions and access deeper insights into the reaction mechanism. These latter cutting-edge studies will be carried out in close collaboration with Prof. H. Dau from Free University of Berlin, expert in heterogeneous electro-catalysts for water splitting, enabling a fruitful cross-fertilization within the project network. Taken together, the fundamental and application-oriented knowledge generated in MOF2O will guide the development of stable and highly performing MOF-based OER electro-catalysts, making a step further towards an efficient use of water splitting to face the ongoing challenges in the energy sector.