Surface, Kinetics And Electrocatalytic Properties Of The Ti/(ti + Ru + Ce)o2-system For The Oxygen Evolution Reaction In Alkaline Medium

Ti-supported (Ti + Ru + Ce)O2 electrodes, prepared at 450 °C, were characterised by XRD, open-circuit potential (Eoc), capacity data (C) and morphology factor (φ) determinations. XRD measurements showed mixed oxides present a low degree of crystallinity. E oc-data and CV-spectra support surface electrochemistry of mixed oxides is governed by the Ru(III)/Ru(IV) redox couple. In situ surface characterisation revealed the active surface area increases on increasing nominal CeO2-content. φ-Values remained in the 0.18-0.3 interval supporting the coatings have a low electrochemical porosity. Kinetics was studied recording polarisation and chronopotentiometric curves, which permitted to determine the Tafel slope and reaction order (with respect to OH -), in the low and high overpotential domains. Tafel slope data, b, presented a dependence on overpotential and oxide composition indicating the OER electrode mechanism depends on these variables. A unit reaction order with respect to OH- was found for all electrode compositions investigated. The theoretical analysis of the electrode mechanism permitted to analyse the changes in the experimental Tafel slopes taking into account modifications in the apparent electronic transfer coefficient, αap. Analysis of the true and apparent electrocatalytic activities revealed the O 2-evolution reaction rate is affected by oxide composition due to morphologic effects. © 2005 Elsevier Ltd. All rights reserved.511428092818Trasatti, S., (1981) Electrodes of Conductive Metallic Oxides, , Elsevier AmsterdamTrasatti, S., (2000) Electrochim. Acta, 45, p. 2377Trasatti, S., (1991) Electrochim. Acta, 36, p. 225Comninellis, C., Vercesi, G.P., (1991) J. Appl. Electrochem., 21, p. 335Tamura, H., Iwakura, C., (1982) Int. J. Hydrogen Energy, 7, p. 857De Faria, L.A., Boodts, J.F.C., Trasatti, S., (1996) J. Appl. Electrochem., 26, p. 1195De Faria, L.A., Boodts, J.F.C., Trasatti, S., (1997) Electrochim. Acta, 42, p. 3525Burke, L.D., McCarthy, M.M., (1998) J. Electrochem. Soc., 135, p. 1175Da Silva, L.M., Boodts, J.F.C., De Faria, L.A., (2001) Electrochim. Acta, 46, p. 1369Jin, S., Ye, S., (1996) Electrochim. Acta, 41, p. 827Nijjer, S., Thonstad, J., Haarberg, G.M., (2001) Electrochim. Acta, 46, p. 3503De Pauli, C.P., Trasatti, S., (2002) J. Electroanal. Chem., 538-539, p. 145Musiani, M., Furlanetto, F., Bertoncello, R., (1999) J. Electroanal. Chem., 465, p. 160Alves, V.A., Da Silva, L.A., Boodts, J.F.C., (1998) Electrochim. Acta, 44, p. 1525Shub, D.M., Reznik, M.F., (1985) Élektrokhimiya, 21, p. 937Shalaginov, V.V., Markina, O.V., Shub, D.M., (1980) Élektrokhimiya, 16, p. 271Da Silva, L.M., Boodts, J.F.C., De Faria, L.A., (2003) J. Braz. Chem. Soc., 14, p. 388Da Silva, L.M., Fernandes, K.C., De Faria, L.A., Boodts, J.F.C., (2004) Electrochim. Acta, 49, p. 4893Boodts, J.F.C., Trasatti, S., (1990) J. Electrochem. Soc., 137, p. 3784De Faria, L.A., Boodts, J.F.C., Trasatti, S., (1992) Electrochim. Acta, 37, p. 2511Da Silva, L.M., De Faria, L.A., Boodts, J.F.C., (2001) Electrochim. Acta, 47, p. 395Alves, V.A., Da Silva, L.A., Boodts, J.F.C., (2000) Quím. Nova, 23, p. 608De Faria, L.A., (1993), Ph.D. Thesis, Institute of Physics and Chemistry, São Paulo State UniversityDa Silva, L.M., Boodts, J.F.C., De Faria, L.A., (2000) Electrochim. Acta, 45, p. 2719Hu, J.M., Meng, H.M., Zhang, J.Q., Cao, C.N., (2002) Corros. Sci., 44, p. 1655Pourbaix, M., (1974) Atlas of Electrochemical Equilibria in Aqueous Solutions, , NACE International TexasDa Silva, L.M., Franco, D.V., De Faria, L.A., Boodts, J.F.C., (2004) Electrochim. Acta, 49, p. 3977Ardizzone, S., Fregonara, G., Trasatti, S., (1990) Electrochim. Acta, 35, p. 263Shub, D.M., Reznik, M.F., (1985) Élektrokhimiya, 21, p. 855Da Silva, L.M., De Faria, L.A., Boodts, J.F.C., (2003) Electrochim. Acta, 48, p. 699Darowicki, K., Orlikowski, J., (1999) J. Electrochem. Soc., 146, p. 663Consonni, V., Trasatti, S., Pollak, F., O'Grady, W.E., (1987) J. Electroanal. Chem., 228, p. 393Yeager, E., (1976) Electrocatalysis on Nonmetallic Surfaces, , A.D. Franklin U.S. Government Printing Office Washington D.CKrishtalik, L.I., (1983) Comprehensive Treatise of Electrochemistry, 7. , J.O'M. Böckris B.E. Conway E. Yeager R.E. White Plenum PressBöckris, J.O'M., (1956) J. Chem. Phys., 24, p. 817Rüetschi, P., (1959) J. Electrochem. Soc., 106, p. 819Filoche, M., Sapoval, B., (2000) Electrochim. Acta, 46, p. 213Mulder, W.H., Sluyters, J.H., Nyklos, L., (1990) J. Electroanal. Chem., 285, p. 103Ho, C.N., Hwang, B.J., (1994) J. Electroanal. Chem., 377, p. 17