MENDELEEV – green revolution by Merging mEtal–orgaNic frameworks with Deep Eutectic soLvEnts for the dEVelopment of sustainable technologies and artificial nitrogen fixation
Descrizione del progetto su una riga
The Research Project in a Nutshell
MENDELEEV Consortium assembles 3 Teams with complementary expertise, spanning organic, material chemistry, and crystallography. We aim to synergize our expertise in order to set-up radically new foundation of (Photo)Catalytic and Synthetic Chemistry and the green production of ammonia, based on the synergistic use of environmentally friendly media (Deep Eutectic Solvents, DESs) and Metal-Organic Frameworks (MOFs). MENDELEEV will pursue the following objectives and challenges: (a) design, preparation and characterization of novel MOFs using DESs as solvents and structure-directing agents; (b) employment of DESs for metal- and biocatalyzed processes using ad hoc functionalized MOFs with Earth-abundant metals to reshape fundamental cross-coupling reactions with the final aim to prepare key intermediates towards the synthesis of APIs; (c) artificial nitrogen fixation to ammonia using DES-mediated synthesis, MOFs as photocatalysts, and DESs as active reaction media. Extended dissemination and communication activities will be performed in order to both raise the awareness on project issues among the main stakeholders, draw the attention of the industrial world for the large exploitation potential of the project results, and bring the general public more aware of the topics of sustainability and clean chemistry and energy.
Objective 1
Design and preparation of novel Metal–Organic Frameworks (MOFs) in DESs and DES-based MOFs
Novel classes of MOFs will be designed and prepared via a ionothermal synthesis (that is using DESs both as solvents and potential templates or structure directing agents in the formation of solids), exploring different combination of either organic ligands or H-bond acceptors and donors as DES components, with metals belonging to early main group or first row d-block elements or Group IVB or rare Earth elements.
Objective 2
Catalysis with Earth-abundant elements using MOFs in renewable and nature-based DESs
We aim to rebuild the foundations of organometallic catalysis from an environmental-friendly standpoint, by developing unprecedented cross-coupling protocols for forging new C–C bonds based on the integrated use of early main group and first-row organometallics embedded or anchored on the pores of ad hoc designed MOFs with nature inspired DESs, acting as solvents and catalysts, jointly with more efficient purification methods and recyclable conditions, thereby minimizing the use of molecular solvents.
Objective 3
Artificial nitrogen fixation to ammonia using MOFs as organic photocatalysts and DESs as active reaction media
We will design and investigate new MOFs in DESs and DES-based MOFs with enhanced photocatalytic activities by forcing to optimization the role of the two strategic reactants, nitrogen and sunlight. This objective will be achieved by improving the light harvesting properties of MOF photocatalysts, via a careful design of the organic ligand components and the nature of the metal centers. We will exploit the virtually infinite variety of organic design, as already developed, though under different circumstances and design targets, in other fields of solar energy materials in the last decade.
Objective 4
Structural-based optimization of MOF properties
X-ray diffraction experiment will supply structural information at atomic resolution about DES components interacting with MOFs and newly synthesized DES-based MOFs . A structure-based optimization of functional properties of DES-based MOFs will be carried out by developing a virtual screening based on global optimization methods (simulated annealing, genetic algorithm) and machine learning approaches.
Objective 5
Dissemination and Communication of the scientific outcomes and applicative returns
Communication and Responsible Research and Innovation (RRI) activities of the project will have three main goals: (a) disseminate and maximize the impact of project outcomes, (b) evaluate the project societal impacts, increasing both researchers' and stakeholders’ awareness (i.e. involving aspects such as the impact of greenhouse gas emissions on climate change and the quest for renewable energy); and (c) disseminate to the general public the main topics related to the project’s activities, via writing of popular books and participation to scientific and book festivals and public events for researchers, science enthusiasts, schools and families (meetings, workshops, shows, and conferences).