H 2 -Evolving Dye-Sensitized Photocathode Based on a Ruthenium Diacetylide/Cobaloxime Supramolecular Assembly

Siliu Lyu (1) , Julien Massin (2) , Michéle Pavone (3) , Ana Muñoz-García (3) , Christine Labrugère (4) , Thierry Toupance (5) , Murielle Chavarot-Kerlidou (2) , Vincent Artero (2) , Céline Olivier (1)

1 ISM - Institut des Sciences Moléculaires
2 SolHyCat - Solar fuels, hydrogen and catalysis
3 University of Naples Federico II = Università degli studi di Napoli Federico II
4 PLACAMAT - Plateforme Aquitaine de Caractérisation des Matériaux
5 LCOO - Laboratoire de chimie organique et organométallique

The development of NiO-based molecular photocathodes is attracting growing interest in the field of dye-sensitized photoelectrochemical cells (DS-PEC) for efficient conversion of sunlight into fuel. For this purpose different strategies are developed to assemble the molecular components together in order to build functional devices. Here, an original dye-catalyst supramolecular assembly was designed and obtained via axial coordination of a cobalt-based H2-evolving catalyst, i.e. a cobaloxime complex, to a pyridyl-functionalized rutheniumdiacetylide photosensitizer. The new supramolecular assembly was successfully employed for the construction of efficient NiO-based photocathodes for solar hydrogen production. We report a joint experimental and theoretical study of the new photocatalytic system, including electrochemical and XPS analyses. Photo-electrochemical generation of H2 under pertinent aqueous conditions eventually led to a faradaic efficiency of 27 %

Mots clés: Molecular photocatalyst; Dye-sensitized photoelectrochemical cell; Nickel oxide; Ruthenium diacetylide complex; Cobaloxime

Domaines: Chimie

Siliu Lyu, Julien Massin, Michéle Pavone, Ana Muñoz-García, Christine Labrugère, et al.. H 2 -Evolving Dye-Sensitized Photocathode Based on a Ruthenium Diacetylide/Cobaloxime Supramolecular Assembly. ACS Applied Energy Materials, 2019, 2 (7), pp.4971-4980. ⟨10.1021/acsaem.9b00652⟩. ⟨hal-02344754⟩