Oxygen electrocatalysis plays a critical role in the efficiency of important energy conversion and storage systems. While many efforts have focused on designing efficient electrocatalysts for these processes, optimal catalysts that are inexpensive, active, selective, and stable are still being searched. Nonstoichiometric, mixed-metal oxides present a promising group of electrocatalysts for these processes due to the versatility of the surface composition and fast oxygen conducting properties. Herein, we demonstrate, using a combination of theoretical and experimental studies, the ability to develop design principles that can be used to engineer oxygen electrocatalysis activity of layered, mixed ionic-electronic conducting Ruddlesden-Popper (R-P) oxides. We show that a density function theory (DFT) derived descriptor, O binding energy on a surface oxygen vacancy, can be effective in identifying efficient R-P oxide structures for oxygen reduction reaction (ORR). Using a controlled synthesis method, well-defined nanostructures of R-P oxides are obtained, which along with thermochemical and electrochemical activity studies are used to validate the design principles. This has led to the identification of a highly active ORR electrocatalyst, nanostructured Co-doped lanthanum nickelate oxide, which when incorporated in solid oxide fuel cell cathodes significantly enhances the performance at intermediate temperatures (∼550 °C), while maintaining long-term stability. The reported findings demonstrate the effectiveness of the developed design principles to engineer mixed ionic-electronic conducting oxides for efficient oxygen electrocatalysis, and the potential of nanostructured Co-doped lanthanum nickelate oxides as promising catalysts for oxygen electrocatalysis.
First series Ruddlesden-Popper oxides (referred herein as R-P-1, with a formula A n+1 B n O 3n+1 where n = 1) have been used in a number of electrochemical and thermochemical reactions. In this review, we examine in detail the effect of the synthesis methods and the composition of the A and B sites on their electrocatalytic/catalytic activity. Effects on important activity parameters, such as surface exchange coefficient (k), oxygen diffusion coefficient (D), hyperstoichiometry (δ), and electronic conductivity are discussed. We find that synthesis plays an important role in their final structure and hyperstoichiometric oxygen content, which significantly impact their activity. In addition, we show that the composition of the A and B sites has an effect on the catalytic/electrocatalytic activity parameters, such as D, k, δ, and electrical conductivity. The use of these oxides for thermal-catalysis is also discussed. We find that while R-P-1 oxides have been widely implemented for high temperature electrocatalysis, their potential for thermal-catalysis has not been fully explored. Limited reports on thermal-catalysis suggest that the redox properties of the B-site transition metal in these oxides, as well as the oxide's ability to accept and release oxygen under reaction conditions play an important role in their catalytic activity. A perspective on catalysis by R-P-1 oxides is provided at the end of the review.
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