XXV CONGRESSO DELLA SOCIETA' CHIMICA ITALIANA - ABSTRACT FORM
Selezionare la tipologia del contributo*: Poster Indicare l'area di preferenza principale*: Chimica inorganica
New insights on the activity of Group VI metal (Mo, W) based
organometallic compounds for electrocatalytic reduction of
carbon dioxide
Luca Nencini , Federico Franco, Claudio Cometto, Fabrizio Sordello, Carlo Nervi, Roberto Gobetto, Claudio Minero
Dipartimento di Chimica, Università di Torino, Via Pietro Giuria 7, 10125, Torino, Italia
[email protected]
The electrocatalytic conversion of CO2 into higher energy carbon products is nowadays
very attractive for its environmental and economic implications, due to the transformation of a low reactivity species into renewable fuels. In this scenario, scientific research has mainly directed towards the discovery of new efficient organometallic molecular catalysts, containing abundant and cheap transition metals. In particular, whereas the majority of the reported studies is mainly focused on the
catalytic activity of Group VII metal-based molecular systems (Mn(I)1, Re(I)2), much
less attention has been paid on the possible usage of complexes with Group VI
transition metals (Cr, Mo and W) as electrocatalysts for CO2 reduction, although many
examples from biology and organometallic science could support this idea3.
For this reason, we synthesized some tetracarbonyl Group VI metal-based coordination
compounds containing polypyridyl ligands, [M0(CO)
4(L)] (M=Mo, W;
L=2,2’-bipyridine and derivatives; 2,2’-dipyridylamine). Unlike the other structurally similar Group VII metal based counterparts, the complexes under study are characterized by zero-valent metal centers with the presence of a CO molecule instead of an anionic
ligand (Cl- or others). This issue could imply new interesting mechanistic insights about
the catalytic process. The electrocatalytic activity of these compounds was tested by means of such electrochemical techniques, as cyclic voltammetry and bulk electrolysis,
performing the experiments either under Ar atmosphere and in CO2 saturation
conditions. Our results revealed that some activity is present towards CO2 as a substrate,
even though at very negative potentials, being close to the values for the direct CO2
reduction (about -2.0 V vs SCE). Further investigation on the identity of the reaction products, together with the understanding of the mechanistic details of the catalytic
process are still in progress.
1 Bourrez, M.; Molton, F.; Chardon-Noblat, S.; Deronzier, A.; Angew. Chem. 50 (2011) 9903-9906
2 Hawecker, J.; Lehn, J. M.; Ziessel, R. J.Chem.Soc., Chem.Commun. (1984), 328-330
