Catalytic Activity and Stability of Oxides: The Role of Near-Surface Atomic Structures and Compositions

ConspectusElectrocatalysts play an important role in catalyzing the kinetics for oxygen reduction and oxygen evolution reactions for many air-based energy storage and conversion devices, such as metal–air batteries and fuel cells. Although noble metals have been extensively used as electrocatalysts, their limited natural abundance and high costs have motivated the search for more cost-effective catalysts. Oxides are suitable candidates since they are relatively inexpensive and have shown reasonably high activity for various electrochemical reactions. However, a lack of fundamental understanding of the reaction mechanisms has been a major hurdle toward improving electrocatalytic activity. Detailed studies of the oxide surface atomic structure and chemistry (e.g., cation migration) can provide much needed insights for the design of highly efficient and stable oxide electrocatalysts.In this Account, we focus on recent advances in characterizing strontium (Sr) cation segregation and enrichment near the surface of Sr-substituted perovskite oxides under different operating conditions (e.g., high temperature, applied potential), as well as their influence on the surface oxygen exchange kinetics at elevated temperatures. We contrast Sr segregation, which is associated with Sr redistribution in the crystal lattice near the surface, with Sr enrichment, which involves Sr redistribution via the formation of secondary phases. The newly developed coherent Bragg rod analysis (COBRA) and energy-modulated differential COBRA are uniquely powerful ways of providing information about surface and interfacial cation segregation at the atomic scale for these thin film electrocatalysts. <i>In situ</i> ambient pressure X-ray photoelectron spectroscopy (APXPS) studies under electrochemical operating conditions give additional insights into cation migration. Direct COBRA and APXPS evidence for surface Sr segregation was found for La<sub>1–<i>x</i></sub>Sr<sub><i>x</i></sub>CoO<sub>3−δ</sub> and (La<sub>1–<i>y</i></sub>Sr<sub><i>y</i></sub>)<sub>2</sub>CoO<sub>4±δ</sub>/La<sub>1–<i>x</i></sub>Sr<sub><i>x</i></sub>CoO<sub>3−δ</sub> oxide thin films, and the physical origin of segregation is discussed in comparison with (La<sub>1–<i>y</i></sub>Sr<sub><i>y</i></sub>)<sub>2</sub>CoO<sub>4±δ</sub>/La<sub>1–<i>x</i></sub>Sr<sub><i>x</i></sub>Co<sub>0.2</sub>Fe<sub>0.8</sub>O<sub>3−δ</sub>. Sr enrichment in many electrocatalysts, such as La<sub>1–<i>x</i></sub>Sr<sub><i>x</i></sub>MO<sub>3−δ</sub> (M = Cr, Co, Mn, or Co and Fe) and Sm<sub>1–<i>x</i></sub>Sr<sub><i>x</i></sub>CoO<sub>3</sub>, has been probed using alternative techniques, including low energy ion scattering, secondary ion mass spectrometry, and X-ray fluorescence-based methods for depth-dependent, element-specific analysis. We highlight a strong connection between cation segregation and electrocatalytic properties, because cation segregation enhances oxygen transport and surface oxygen exchange kinetics. On the other hand, the formation of cation-enriched secondary phases can lead to the blocking of active sites, inhibiting oxygen exchange. With help from density functional theory, the links between cation migration, catalyst stability, and catalytic activity are provided, and the oxygen <i>p</i>-band center relative to the Fermi level can be identified as an activity descriptor. Based on these findings, we discuss strategies to increase a catalyst’s activity while maintaining stability to design efficient, cost-effective electrocatalysts.