XXV CONGRESSO DELLA SOCIETA' CHIMICA ITALIANA - ABSTRACT FORM
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Novel Re(I) based catalysts for CO
2
Photo- and Electrocatalytic reduction at
low overpotential
Federico Franco, Claudio Cometto, Cunfa Sun, Luca Nencini, Fabrizio
Sordello, Claudio Garino, Roberto Gobetto, Carlo Nervi, Claudio Minero
Department of Chemistry and NIS, University of Turin, via P. Giuria 7, 10125 Torino, Italy
federico.franco@unito.it
Our research mainly focused on the synthesis of a series of novel Re(I)-carbonyl diimine complexes, to be used as catalysts for both photo- and electroreduction of CO2. In more detail, a new class of catalysts is characterized by the presence
of common polypyridyl ligands covalently attached to the highly fluorescent PNI cromophore (N-(diimine)-4-(1-piperidinyl) naphthalene-1,8-dicarboximide), which revealed to be able to provide a huge excited state lifetime enhancement in a Re(I) charge-transfer complex [1]. This feature may play a role in the process of photocatalytic CO2 reduction.
The electrochemical behaviour of the synthesized organometallic compounds 2-3 was studied either under inert atmosphere and in presence of CO2, in order to test
their electrocatalytic activities. A direct comparison with the activity of Re(CO)3(bipy)Cl (1), already known as an efficient molecular catalyst, is
reported [2]. Controlled-potential electrolysis measurements in homogeneous solution under continuous CO2 flow (in the figure below) revealed that the
PNI-containing Re(I) complexes 2-3 have sluggish kinetics towards CO2 as a
substrate, but, at the same time, they can operate at substantially lower overpotential (-1.96 V vs Fc/Fc+ couple) than 1.
[1] Yarnell, J. E.; Deaton, J. C.; McCusker, C. E.; Castellano, F. N.; Inorg. Chem., 2011, 50, 7820-7830
[2] Hawecker, J.; Lehn, J. M.; Ziessel, R. J., Chem.Commun., 1984, 328-330
Poster
