Tobias Binninger

In recent years, the oxygen evolution reaction (OER) has attracted increased research interest due to its crucial role in electrochemical energy conversion devices for renewable energy applications. The vast majority of OER catalyst materials investigated are metal oxides of various compositions. The experimental results obtained on such materials strongly suggest the existence of a fundamental and universal correlation between the oxygen evolution activity and the corrosion of metal oxides. This corrosion manifests itself in structural changes and/or dissolution of the material. We prove from basic thermodynamic considerations that any metal oxide must become unstable under oxygen evolution conditions irrespective of the pH value. The reason is the thermodynamic instability of the oxygen anion in the metal oxide lattice. Our findings explain many of the experimentally observed corrosion phenomena on different metal oxide OER catalysts.

The electrochemically active surface area (ECSA) of metal-oxide supported platinum catalysts as obtained from hydrogen underpotential deposition (H upd ) and from carbon monoxide stripping experiments was investigated. It was demonstrated that both methods fail to give meaningful values of the ECSA if they are performed in the conventional way as known for pure Pt and carbon supported Pt catalysts, respectively. For both methods, the reason for this failure is the lack of a correct baseline for the integration of the associated charges. It was found that the cyclic voltammogram recorded in CO saturated electrolyte gives an improved baseline for the H upd analysis. For CO stripping, a novel baseline method was developed by performing a "CO stripping simulation" (COSS) experiment in CO-free electrolyte. The first cycle of this COSS-experiment is an improved baseline for the integration of the CO stripping peak, since possible support reduction/oxidation currents can be accounted for. With these modifications, H upd and CO stripping voltammetry can be used for metal-oxide supported platinum to yield true, reproducible and consistent values for the ECSA.

Cell designs for the electrochemical reduction of CO 2 from gas phase were developed and investigated, and the critical elements for an efficient process were identified. Various types of polymeric membrane were used to build membrane electrode assembly adapted for CO 2 reduction in gas phase: protonic and anion exchange membrane (AEM), bipolar membrane and a modified bipolar like membrane configuration. Configurations using anion exchange ionomer in the cathodic catalytic layer in contact with an AEM allow for a great enhancement of the cathode reaction selectivity toward CO. However, a severe problem was identified when co-electrolysis is performed using only an AEM: this type of membrane acts as a CO 2 "pump" meaning that for each molecule of CO 2 reduced at the cathode, one or two CO 2 molecules are produced at the anode by oxidation of the carbonate/bicarbonate anion transported in the membrane. A bipolar membrane system was shown to soften this problem, but only a newly developed cell design was able to fully prevent the parasitic CO 2 pumping. Using this new cell configuration, the faradaic efficiency of an alkaline environment is maintained, the parasitic CO 2 pumping to the anode side is completely suppressed, and the overall cell voltage efficiency is highly improved.

An electrochemical three-electrode flow-cell is presented for in situ small-angle X-ray scattering (SAXS) and X-ray absorption spectroscopy (XAS) experiments in transmission mode at synchrotron X-ray sources. The cell also allows for in situ XAS performed in fluorescence mode. Constant experimental conditions, even under moderate gas evolution, are provided by the electrolyte flow with controlled gas saturation. A special configuration of working and counter electrode, respectively, yields low residual ohmic resistance in three-electrode measurements that enables the study of thick porous electrodes of active high surface area materials. The cell proved its functionality and reliability in two studies: First, an in situ anomalous SAXS experiment for the high-potential degradation properties of a Pt/IrO2-TiO2 catalyst for the oxygen reduction reaction at polymer electrolyte fuel cell cathodes; and second, an in situ XAS study of the electronic state of Ir centers inside an IrO2-TiO2 catalyst under oxygen evolution conditions.