Ru–bis(pyridine)pyrazolate (bpp)-Based Water-Oxidation Catalysts Anchored on TiO2: The Importance of the Nature and Position of the Anchoring Group

Laia Francàs, Craig Richmond, Pablo Garrido-Barros, Nora Planas, Stephan Roeser, Jordi Benet-Buchholz, Lluís Escriche, Xavier Sala, Antoni Llobet

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19 Citations (Scopus)


© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Three distinct functionalisation strategies have been applied to the in,in-[{RuII(trpy)}2(μ-bpp)(H2O)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 TiO2-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. In or out? Ru-bis(2-pyridyl)pyrazole (Hbpp) complexes have been anchored on a TiO2 surface through functionalisation of terpyridine and bis(pyridyl)pyrazolate ligands (see the picture). The nature of the anchoring group and its geometrical design strongly influence the performance of the anode with regard to the electrocatalytic oxidation of water to dioxygen.
Original languageEnglish
Pages (from-to)5261-5268
JournalChemistry - A European Journal
Issue number15
Publication statusPublished - 4 Apr 2016


  • organic-inorganic hybrid materials
  • redox chemistry
  • ruthenium
  • supported catalysts
  • surfaces and interfaces
  • water splitting


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