TY - JOUR
T1 - Deposition of an oxomanganese water oxidation catalyst on TiO2 nanoparticles
T2 - Computational modeling, assembly and characterization
AU - Li, Gonghu
AU - Sproviero, Eduardo M.
AU - Snoeberger, Robert C.
AU - Iguchi, Nobuhito
AU - Blakemore, James D.
AU - Crabtree, Robert H.
AU - Brudvig, Gary W.
AU - Batista, Victor S.
PY - 2009/8/31
Y1 - 2009/8/31
N2 - Inexpensive water oxidation catalysts are needed to develop photocatalytic solar cells that mimic photosynthesis and produce fuel from sunlight and water. This paper reports the successful attachment of a dinuclear di - oxo manganese water oxidation catalyst [H2O(terpy)Mniii(-O)2 Mniv(terpy)H2O](NO3)3 (1, terpy = 2,2′:6′2″-terpyridine) onto TiO2 nanoparticles (NPs) via direct adsorption, or in situ synthesis. The resulting surface complexes are characterized by EPR and UV-visible spectroscopy, electrochemical measurements and computational modeling. We conclude that the mixed-valence (iii,iv) state of 1 attaches to near-amorphous TiO2 NPs by substituting one of its water ligands by the TiO2 NP, as suggested by low-temperature (7 K) EPR data. In contrast, the analogous attachment onto well-crystallized TiO2 NPs leads to dimerization of 1 forming Mn(iv) tetramers on the TiO2 surface as suggested by EPR spectroscopy and electrochemical studies.
AB - Inexpensive water oxidation catalysts are needed to develop photocatalytic solar cells that mimic photosynthesis and produce fuel from sunlight and water. This paper reports the successful attachment of a dinuclear di - oxo manganese water oxidation catalyst [H2O(terpy)Mniii(-O)2 Mniv(terpy)H2O](NO3)3 (1, terpy = 2,2′:6′2″-terpyridine) onto TiO2 nanoparticles (NPs) via direct adsorption, or in situ synthesis. The resulting surface complexes are characterized by EPR and UV-visible spectroscopy, electrochemical measurements and computational modeling. We conclude that the mixed-valence (iii,iv) state of 1 attaches to near-amorphous TiO2 NPs by substituting one of its water ligands by the TiO2 NP, as suggested by low-temperature (7 K) EPR data. In contrast, the analogous attachment onto well-crystallized TiO2 NPs leads to dimerization of 1 forming Mn(iv) tetramers on the TiO2 surface as suggested by EPR spectroscopy and electrochemical studies.
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U2 - 10.1039/b818708h
DO - 10.1039/b818708h
M3 - Article
AN - SCOPUS:68149085970
VL - 2
SP - 230
EP - 238
JO - Energy and Environmental Science
JF - Energy and Environmental Science
SN - 1754-5692
IS - 2
ER -