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Ru–bis(pyridine)pyrazolate (bpp)‐Based Water‐Oxidation Catalysts Anchored on TiO 2 : The Importance of the Nature and Position of the Anchoring Group
Author(s) -
Francàs Laia,
Richmond Craig,
GarridoBarros Pablo,
Planas Nora,
Roeser Stephan,
BenetBuchholz Jordi,
Escriche Lluís,
Sala Xavier,
Llobet Antoni
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201504015
Subject(s) - catalysis , chemistry , terpyridine , pyridine , sulfonate , carboxylate , reactivity (psychology) , electrochemistry , polymer chemistry , oxide , tin oxide , electrolysis , adsorption , inorganic chemistry , combinatorial chemistry , electrode , stereochemistry , organic chemistry , metal , medicine , alternative medicine , pathology , sodium , electrolyte
Three distinct functionalisation strategies have been applied to the in , in ‐[{Ru II (trpy)} 2 (μ‐bpp)(H 2 O) 2 ] 3+ (trpy=2,2′:6′,2′′‐terpyridine, bpp=bis(pyridine)pyrazolate) water‐oxidation catalyst framework to form new derivatives that can adsorb onto titania substrates. Modifications included the addition of sulfonate, carboxylate, and phosphonate anchoring groups to the terpyridine and bis(pyridyl)pyrazolate ligands. The complexes were characterised in solution by using 1D NMR, 2D NMR, and UV/Vis spectroscopic analysis and electrochemical techniques. The complexes were then anchored on TiO 2 ‐coated fluorinated tin oxide (FTO) films, and the reactivity of these new materials as water‐oxidation catalysts was tested electrochemically through controlled‐potential electrolysis (CPE) with oxygen evolution detected by headspace analysis with a Clark electrode. The results obtained highlight the importance of the catalyst orientation with respect to the titania surface in regard to its capacity to catalytically oxidize water to dioxygen.