Interfacial impregnation chemistry in the synthesis of cobalt catalysts supported on titania.
The interfacial chemistry of the impregnation step involved in the synthesis of cobalt catalysts supported on titania was investigated with regard to the mode of interfacial deposition of the aqua complex [Co(H(2)O)(6)](2+) on the "titania/electrolyte solution" interface, the structure of the inner-sphere complexes formed, and their relative interfacial concentrations. Several methodologies based on the application of deposition experiments and electrochemical techniques were used in conjunction with diffuse-reflectance spectroscopy and EPR spectroscopy. These suggested the formation of mononuclear/oligonuclear inner-sphere complexes on deposition of the [Co(H(2)O)(6)](2+) ions at the "titania/electrolyte solution" interface. The joint application of semiempirical quantum-mechanical calculations, stereochemical considerations, and modeling of the deposition data revealed the exact structure of these complexes and allowed their relative concentrations at various Co(II) surface concentrations to be determined. It was found that the interface speciation depends on the Co(II) surface concentration. Mononuclear complexes are formed at the compact layer of the "titania/electrolyte solution" interface for low and medium Co(II) surface concentrations. Formation of mono-hydrolyzed Ti(2)O-TiO and the dihydrolyzed TiO-TiO disubstituted configurations is very probable. In the first configuration one water ligand of the [Co(H(2)O)(6)](2+) ion is substituted by a bridging surface oxygen atom and another by a terminal surface oxygen atom. In the second configuration two water ligands of the [Co(H(2)O)(6)](2+) ion are substituted by two terminal surface oxygen atoms. Binuclear and trinuclear inner-sphere complexes are formed, in addition to the mononuclear ones, at relatively high Co(II) surface concentrations.
Petsi
Theano
T
Department of Chemistry, University of Patras, 26500 Patras, Greece.
Panagiotou
George D
GD
Garoufalis
Christos S
CS
Kordulis
Christos
C
Stathi
Panagiota
P
Deligiannakis
Yiannis
Y
Lycourghiotis
Alexis
A
Bourikas
Kyriakos
K