Descrizione del progetto
Catalizzatori sostenibili basati su metalli alcalino terrosi
All’interno del ciclo dell’azoto, le forme ossidata (NOx), neutra (N2) e ridotta (NH3) passano dall’una all’altra attraverso una rete complicata di processi. Al contrario, la manipolazione dell’azoto nell’industria necessita spesso di metodi di forza bruta. Il processo di Haber-Bosch per la conversione di N2 in NH3 è uno dei processi industriali più dispendiosi in termini di consumo energetico. Finanziato dal programma di azioni Marie Skłodowska-Curie, il progetto NITRO-EARTH studierà la chimica metallorganica dei complessi imido [RN(2ˉ)] e nitrido [N(3ˉ)] dei metalli alcalino terrosi, in particolare Mg e Ca. L’obiettivo finale consiste nella creazione di una nuova classe di catalizzatori di metalli alcalino terrosi come alternativa sostenibile a quelli basati sui metalli di transizione.
Obiettivo
NITRO-EARTH is aiming to investigate the hardly explored nitrogen chemistry of the alkaline-earth metals (Ae) in order to disclose new reactivity and catalysis. In the biogeochemical nitrogen cycle oxidized (NOx), neutral (N2) and reduced (NH3) forms of N are interconverted by a complicated network of processes. In contrast, manipulation of N in industry is challenging and often needs brute-force methods. The Haber-Bosch process for N2-to-NH3 conversion is, despite being metal-catalysed, one of the most energy consuming industrial processes. This proposal focusses on the organometallic chemistry of imido [RN(2ˉ)] and nitrido [N(3ˉ)] complexes of the alkaline-earth metals, in particular Mg and Ca. While the amide (R2Nˉ) chemistry of the Ae metals is well-established, Ae-imido complexes are rare and Ae-nitrido compounds solely exist as insoluble salts, e.g. Mg3N2. Given the importance of imido and nitrido ligands in transition metal chemistry, access to soluble Ae=NR and Ae≡N complexes promises a rich reactivity and is the prelude of new catalytic processes based on abundant, generally biocompatible, alkaline-earth metals. The various pathways to reach the target include utilization of recently introduced, highly reducing Mg(0) complexes by HARDER and nitreones which have been investigated by PATEL. Also HARDER’s recently discovered N2 fixation with Ca will play a role in the synthetic approach. Owing to the highly ionic character and negative charge on N in Ae=NR or Ae≡N complexes, these novel complexes will be extremely potent nucleophiles or deprotonating reagents. This will be strongly dependent on nuclearity and aggregation which will be controlled by a library of bulky ligands currently available in the HARDER group. The work will be heavily supported by ab initio calculations. The project ultimately leads to the generation of a new class of alkaline-earth metal catalysts which may provide sustainable alternative for transition metal based catalysts.
Campo scientifico
Parole chiave
Programma(i)
- HORIZON.1.2 - Marie Skłodowska-Curie Actions (MSCA) Main Programme
Meccanismo di finanziamento
HORIZON-TMA-MSCA-PF-EF - HORIZON TMA MSCA Postdoctoral Fellowships - European FellowshipsCoordinatore
91054 Erlangen
Germania