Perovskite oxides hold great promise as efficient electrocatalysts for various energy‐related applications owing to their low cost, flexible structure, and high intrinsic catalytic activity. However, conventional synthetic methods can only obtain perovskite catalysts with large particle sizes, small surface areas, and few morphological features, leading to limited catalytic activity and thus posing a major challenge toward real‐world applications. Reducing the size of bulk perovskites down to the nanosize represents an efficient way to improve the electrocatalytic performance. A comprehensive overview of recent progress in the nanostructuring of perovskites for catalyzing several key reactions in metal–air batteries, water splitting, and solid oxide fuel cells is provided. A range of synthetic protocols for making perovskite nanostructures are summarized, followed by an emphasis on how each method can be tailored to obtain high‐performing perovskite nanocatalysts. These recent advances highlight the enormous potential of nanosized perovskites for facilitating the electrocatalytic reactions. The remaining challenges and future directions are pointed out for the development of next‐generation perovskite‐based nanostructured catalysts.

Recent Advances in Novel Nanostructuring Methods of Perovskite Electrocatalysts for Energy-Related Applications

Electrocatalysis lies in the center of many clean energy conversion and storage technologies. Developing efficient electrocatalysts to promote the kinetics of the key chemical reactions involved in these processes represents an important research topic. Ruddlesden–Popper perovskites (An+1BnX3n+1), as a layered derivative of the perovskite family (ABX3), are an important class of solid-state materials, and are emerging as high-performing electrocatalysts due to their unique layered structure and rich chemical compositions. In this review, we provide a comprehensive understanding of the structure and properties of Ruddlesden–Popper perovskites in the context of their electrocatalysis applications. We also summarize the recent developments of Ruddlesden–Popper perovskites for catalyzing a breadth of electrochemical reactions at both low and high temperatures. We highlight how Ruddlesden–Popper perovskites can be tailored through a range of design strategies to achieve improved electrocatalysis. Finally, we provide perspectives on future research directions that further expand the electrocatalytic possibilities of Ruddlesden–Popper perovskites.

Ruddlesden–Popper perovskites in electrocatalysis

Oxide perovskites have emerged as an important class of materials with important applications in many technological areas, particularly thermocatalysis, electrocatalysis, photocatalysis, and energy storage. However, their implementation faces numerous challenges that are familiar to the chemist and materials scientist. The present work surveys the state-of-the-art by integrating these two viewpoints, focusing on the critical role that defect engineering plays in the design, fabrication, modification, and application of these materials. An extensive review of experimental and simulation studies of the synthesis and performance of oxide perovskites and devices containing these materials is coupled with exposition of the fundamental and applied aspects of defect equilibria. The aim of this approach is to elucidate how these issues can be integrated in order to shed light on the interpretation of the data and what trajectories are suggested by them. This critical examination has revealed a number of areas in which the review can provide a greater understanding. These include considerations of (1) the nature and formation of solid solutions, (2) site filling and stoichiometry, (3) the rationale for the design of defective oxide perovskites, and (4) the complex mechanisms of charge compensation and charge transfer. The review concludes with some proposed strategies to address the challenges in the future development of oxide perovskites and their applications.

Defect engineering of oxide perovskites for catalysis and energy storage: synthesis of chemistry and materials science.

/pdf/review-on-exsolution-and-its-driving-forces-in-perovskites-51uo2jv2gw.pdf

Review on exsolution and its driving forces in perovskites

Perovskite oxides have received a great deal of attention as promising electrodes in both solid oxide fuel cells (SOFCs) and solid oxide electrolyzer cells (SOECs) because of their reasonable reactivity, impurity tolerance, and tunable properties. In particular, exploration is still required for improving perovskite electrodes, which normally suffer from slow kinetics in electrocatalysis. Experimental studies have led to the development of new classes of perovskites with advanced characteristics and electrode kinetics at technical levels. In parallel with those developments, achievements in theoretical and computational studies have led to substantial understanding, at the atomic level, of their physicochemical properties and electrocatalytic behaviors. Their chemical and structural flexibilities enable perovskites to accommodate most metallic elements without destroying their complex matrix structures, thereby delivering a pathway to engineer their catalytic properties. In this Minireview, recent advances in perovskite electrodes are introduced, and perovskites with exsolved nanoparticles are discussed as enhanced electrocatalytic materials.

Enhancing Perovskite Electrocatalysis of Solid Oxide Cells Through Controlled Exsolution of Nanoparticles

Here, we report a new nickel-iron alloy nanoparticle-decorated LaSrFe0.75Ni0.25O4 K2NiF4-type oxide with Ruddlesden-Popper structure (RP-LSFN), performed as a high performance sulfur-resistant anode prepared by an infiltration method for solid oxide fuel cells (SOFCs) using LaSrFeNiO6-δ double perovskite (DP-LSFN) as the precursor. A reduction converts the DP-LSFN phase into mixed phases containing the RP-LSFN and FeNi3 nanoparticles. The morphology, thermal expansion behavior, sulfur tolerance and electrochemical activity for hydrogen oxidation of this FeNi3 nanoparticle-decorated, RP-LSFN infiltrated anode are investigated. An electrolyte-supported SOFC with this infiltrated anode generates a high power output of 541 mW cm-2 at 800 °C operated on 1000 ppm H2S-H2 as fuel and compares favorably to that with pure H2 fuel. A single cell with this anode demonstrates favorable stability at 800 °C during 90, 40 and 20 h operation with H2 containing 100, 200 and 1000 ppm H2S, respectively.

Nickel-Iron Alloy Nanoparticle-Decorated K2NiF4-Type Oxide as an Efficient and Sulfur-Tolerant Anode for Solid Oxide Fuel Cells

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Nickel-Iron Alloy Nanoparticle-Decorated K2NiF4-Type Oxide as an Efficient and Sulfur-Tolerant Anode for Solid Oxide Fuel Cells