Book Description

At solid-gas electrochemical interfaces, gas molecules interact dynamically with surface ions and electrons. A fundamental understanding of the technologically important interfaces can lead to better fuel cells and electrolyzers. In the bulk of typical oxygen-ion-conducting solids, oxygen vacancies and mobile electrons migrate under the influence of concentration and electrostatic potential gradients. Similarly, at gas-solid interfaces, these charge carriers migrate across an electrochemical double layer. The two-way traffic of ions and electrons contrasts sharply with conventional metal-based electrocatalysis, in which only electrons are transferred. This type of ion insertion reaction is ubiquitous in energy conversion and storage devices, such as lithium ion batteries, water-splitting membranes and solid oxide fuel cells. CeO2-[delta] (ceria) is a model oxygen-ion-conducting electrode, which is commonly employed to catalyze H2 oxidation and H2O dissociation reactions, as well as CO oxidation and CO2 dissociation reactions. In my thesis studies, I developed synchrotron-based ambient pressure X-ray photoelectron spectroscopy to characterize the electrochemical double layer under reaction conditions. Concentrations and binding energy of oxygen ions, localized electrons, and surface reaction intermediates were quantified using core level and valence band X-ray photoelectron spectroscopy as a function of electrochemical overpotentials. These measurements reveal that localized electrons and oxygen vacancies segregate persistently from the bulk to the surface, resulting in concentrations up to four orders of magnitude greater on the surface than in the bulk. Under water splitting conditions, H2O molecules incorporate rapidly into surface oxygen vacancies. Spectroscopy and electrochemistry results suggest that the electron transfer between Ce 4f states and OH adsorbates is rate determining. Under CO oxidation and CO2 dissociation conditions, on the other hand, carbonate is the stable adsorbate. The larger footprint of carbonate relative to hydroxyl adsorbate gives rise to adsorbate-adsorbate interactions, resulting in a coverage-dependent reaction pathway. Lastly, measurement of surface dipole potential energy in both cases reveals intrinsic dipole moments of adsorbates as the origin of electrostatic potential gradient near the surface. Combined, these in-situ investigations unravel the electrochemical reaction pathway, particularly the role of point defects at ceria/gas interfaces, and establish a rational path towards enhancing the efficacy of oxide electrocatalysts.