Spectroelectrochemical analysis of the water oxidation mechanism on doped nickel oxides

Metal oxides and oxyhydroxides exhibit state-of-the-art activity for the oxygen evolution reaction (OER); however, their reaction mechanism, particularly the relationship between charging of the oxide and OER kinetics, remains elusive. Here, we investigate a series of Mn-, Co-, Fe-, and Zn-doped nickel oxides using operando UV–vis spectroscopy coupled with time-resolved stepped potential spectroelectrochemistry. The Ni2+/Ni3+ redox peak potential is found to shift anodically from Mn- < Co- < Fe- < Zn-doped samples, suggesting a decrease in oxygen binding energetics from Mn- to Zn-doped samples. At OER-relevant potentials, using optical absorption spectroscopy, we quantitatively detect the subsequent oxidation of these redox centers. The OER kinetics was found to have a second-order dependence on the density of these oxidized species, suggesting a chemical rate-determining step involving coupling of two oxo species. The intrinsic turnover frequency per oxidized species exhibits a volcano trend with the binding energy of oxygen on the Ni site, having a maximum activity of ∼0.05 s–1 at 300 mV overpotential for the Fe-doped sample. Consequently, we propose that for Ni centers that bind oxygen too strongly (Mn- and Co-doped oxides), OER kinetics is limited by O–O coupling and oxygen desorption, while for Ni centers that bind oxygen too weakly (Zn-doped oxides), OER kinetics is limited by the formation of oxo groups. This study not only experimentally demonstrates the relation between electroadsorption free energy and intrinsic kinetics for OER on this class of materials but also highlights the critical role of oxidized species in facilitating OER kinetics

A ternary PEDOT-TiO2-reduced graphene oxide nanocomposite for supercapacitor applications

A ternary composite of PEDOT was prepared with TiO2 via emulsion polymerization method adjusting various weight ratios of TiO2 to PEDOT and synthesized rGO was then blended with this composite. The FTIR, UV–Vis and XRD analysis displayed characteristic features of PEDOT and TiO2. The morphology of the nano-hybrid structure was additionally investigated by SEM analysis. Pore size and surface area analysis of particles were characterized by BET method. The electrochemical analysis showed that the specific capacitance (Csp) for PEDOT-TiO2-15-rGO was 18.9 F.cm-2 at 0.1 mA g-1 current density

Silicon surface passivation by PEDOT: PSS functionalized by SnO2 and TiO2 nanoparticles

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Direct Observation of the Chemical Transformations in BiVO4 Photoanodes upon Prolonged Light-Aging Treatments

Exposing BiVO4 photoanodes to light-aging treatments is known to produce a significant photocurrent enhancement. Until now, the interpretation given to this phenomenon is associated to the formation of oxygen vacancies and little is reported about chemical changes in the material. Herein, the chemical segregation of Bi species toward the surface upon light-aging treatment is demonstrated, which takes place with the concomitant formation of intra-bandgap states associated to the oxygen vacancies. It is further demonstrated that these intra-bandgap states are photoactive and generate photocurrent under infrared excitation. These results highlight the importance of understanding light-induced effects while employing multinary metal oxide photoelectrodes