Catalytic Activity and Stability of Oxides: The Role of Near-Surface Atomic Structures and Compositions (original) (raw)
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2017
Title of Dissertation: IN OPERANDO MECHANISTIC STUDIES OF HETEROGENEOUS ELECTROCATALYSIS ON SOLID OXIDE ELECTROCHEMICAL CELL MATERIALS Aaron Isaac Geller, Doctor of Philosophy, 2017 Directed by: Professor Bryan W. Eichhorn Department of Chemistry and Biochemistry This dissertation details the development and utilization of in operando protocols for observing electrochemical reactions on solid oxide electrochemical cells (SOCs) in order to better understand the fundamental chemistry governing their operation. Two key reactions in SOC processes are studied using ambient pressure Xray photoelectron spectroscopy (AP-XPS), the oxygen reduction and evolution reactions (ORR and OER). Measurements made on lanthanum strontium manganite (La1-xSrxMnO3±∂, LSM), a standard electrode material show that the surface composition does not match the bulk stoichiometry. Sr extrudes onto the LSM surface in the form of SrO and greater Mn reduction is observed. These phenomena are further augmented by app...
Catalysts
Perovskites of strontium cobalt oxyhalides having the chemical formulae Sr2CoO4-xHx (H = F, Cl, and Br; x = 0 and 1) were prepared using a solid-phase synthesis approach and comparatively evaluated as electrocatalysts for oxygen evolution in an alkaline solution. The perovskite electrocatalyst crystal phase, surface morphology, and composition were examined by X-ray diffraction, a scanning electron microscope, and energy-dispersive X-ray (EDX) mapping. The electrochemical investigations of the oxyhalides catalysts showed that the doping of F, Cl, or Br into the Sr2CoO4 parent oxide enhances the electrocatalytic activity for the oxygen evolution reaction (OER) with the onset potential as well as the potential required to achieve a current density of 10 mA/cm2 shifting to lower potential values in the order of Sr2CoO4 (1.64, 1.73) > Sr2CoO3Br (1.61, 1.65) > Sr2CoO3Cl (1.53, 1.60) > Sr2CoO3F (1.50, 1.56) V vs. HRE which indicates that Sr2CoO3F is the most active electrode amon...
A review of transition metal-based bifunctional oxygen electrocatalysts
Journal of the Chinese chemical society, 2019
Electrochemical energy storage and conversion devices play a key role in the development of clean, sustainable, and efficient energy systems to meet the sustainable growth of our society. However, challenging issues including the sluggish kinetics of oxygen electrode reactions involving the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) are present, limiting the implementation of devices such as metal-air batteries, water electrolyzers, and regenera-tive fuel cells. In this review, various monometallic and bimetallic transition metal oxides (TMOs) and hydroxides are summarized in terms of their application for ORR/OER, in which the merits and demerits of various precious metal and carbon-based metal oxide materials are discussed, with requirements for better electro-catalysts and catalyst support being introduced as well. Following this, different approaches to improve catalytic activity such as the introduction of doping and defects, the manipulation of crystal facets, and the engineering of supports, compositions , and morphologies are summarized in which TMOs with improved ORR/OER catalytic activities can be synthesized, further improving the speed, stability , and polarization of electrochemical energy storage and conversion devices. Finally, perspectives into the improvement of performance and the better understanding of ORR/OER mechanisms for bifunctional electrocatalysts using in situ spectroscopic techniques and density functional theory calculations are also discussed. K E Y W O R D S bifunctional, electrocatalysts, engineering, oxygen evolution reaction, oxygen reduction reaction, transition metals
Materials Technology for the Energy and Environmental Nexus, Volume 2, 2023
The smooth transition from finite non-renewables to renewable energy conversion technologies will require efficient electrocatalysts which can harness intermittent energies to store in the form of chemical bonds. The oxygen evolution reaction (OER) impedes the widespread usage of water electrolyzers to convert H 2 O into H 2 and persists as a bottleneck, including other energy conversion devices with sluggish four H + /e − kinetics. In this context, designing highly active and stable catalysts capable of driving a lower overpotential in the OER to produce continuous hydrogen (H 2) is a primary demanded. This chapter discussed the mechanism of the OER in conventional adsorbate oxygen and lattice oxygen participation in transition metal oxides (TMOs). Further, the influences of surface engineering, doping, and defects in the TMOs and understanding the electronic structure to screen electrodes towards the structure-activity relationship are highlighted. Specifically, the adsorption strength of O 2p is understood in detail as its binding ability over the surface of TMOs can be correlated directly to the OER activity. The iterative development of TMOs in terms of understanding electronic structural attributes is essential for the commercial deployment of energy conversion technologies. The comprehensive outlook of this chapter investigates thoroughly how TMOs can be used as significant materials for the OER in the near future.