Research progress for perovskite-structure exsolution materials
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摘要: 纳米结构催化材料被认为是各种能量转换和存储系统的有利设计理念。负载在氧化物载体上的纳米金属催化剂已被应用于燃料电池、气体传感器和化学重整装置等众多领域。然而，纳米金属催化剂经常存在耐久性问题。尽管表面修饰的纳米金属催化剂可以提供足够的催化活性，但其在恶劣的操作环境中的耐久性问题仍然存在。最近，原位出溶产生的纳米催化剂已被证明可以克服传统纳米金属催化剂的应用局限。出溶被定义为钙钛矿氧化物中具有催化活性的掺杂剂作为高度分散的纳米金属催化剂在其表面上出溶的过程。特别地，嵌入钙钛矿氧化物的出溶纳米催化剂比传统的纳米金属催化剂表现出更高的纳米颗粒密度和更强的抗烧结能力。本文概述了用于能源应用中出溶材料的最新进展，包括基本机制、主体氧化物的设计策略和实际应用。还讨论了这些材料的未来前景和进一步优化的途径。Abstract: Nanostructured catalytic materials are considered to be a favorable design concept for various energy conversion and storage systems. Nanosized metal catalysts supported on oxide scaffolds have been adopted in numerous fields, including fuel cells, gas sensors, and chemical reforming devices. Nevertheless, nanometal catalysts often suffer from durability issues. Although surface-decorated nanometal catalysts can deliver sufficient catalytic activity, some of them still exhibit durability issues in severe operating environments. Recently, nanocatalysts produced by in situ exsolution have been demonstrated to overcome the practical limitations of conventional nanometal catalysts. The exsolution is defined as a process in which a catalytically active dopant in perovskite oxide is exsolved on its surface as highly dispersed nanometal catalysts. In particular, exsolution nanocatalysts embedded on perovskite oxides exhibit higher nanoparticle densities and greater resistance to particle agglomeration than conventional nanometal catalysts. This perspective presents an overview of recent advances in exsolution materials for energy applications including fundamental mechanisms, design strategies for host oxides, and practical applications. The future prospects of these materials and the scope for further optimization are also discussed.
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Key words:
- perovskite /
- metal nanoparticles /
- energy devices /
- electrocatalyst /
- ex-solution
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图 1 促进钙钛矿氧化物B位阳离子出溶的各种效应及其多功能应用示意图[1]
Figure 1. Schematic of various effects in facilitating the exsolution of B-site cations for perovskite oxides and its multifunctional applications[1]
SOFC—Solid oxide fuel cells; SOEC—Solid oxide electrolysis cells; CB—Conduction band; VB—Valence band; hv—Photon energy; HER—Hydrogen evolution reaction; OER—Oxygen evolution reaction; PO2—Oxygen partial pressure
图 5 (a) 在纯H2 (左)和20% H2 (右)中还原5、10、15、20和30 h颗粒的SEM图像；(b) 不同氧分压(PO2)下平均粒径和还原时间之间的关系[34]
Figure 5. (a) SEM images of the particles reduced in pure H2 (left) and 20% H2 (right) for 5, 10, 15, 20, and 30 h; (b) Relationship between average particle size and reduction time under different oxygen partial pressure (PO2) conditions[34]
图 7 电化学转换和触发效应：(a) 电化学转换方法的示意图；(b) TGA曲线和施加电势下的电池电流；(c) 气体还原和电化学转换的特性[39]
Figure 7. Electrochemical switching and triggering effects: (a) Schematic illustration of the electrochemical swit ching method; (b) TGA curve and cell current under an applied potential; (c) Properties of gas reduction and electrochemical switching[39]
表 1 还原气氛处理的出溶钙钛矿在电催化领域的应用
Table 1. Summary on the exsolution on perovskites under reducing gas for electrocatalysis
Catalysts Atmosphere Exsolved metal Application Ref. La0.43Sr0.37Cu0.12Ti0.88O3–δ Pure H2 at 400-700℃ Cu SOFC [41] La0.65Sr0.3Cr0.85Ni0.15O3−δ 5% H2-Ar at 1200℃ Ni SOFC [45] Sm0.80-xSr0.20Fe0.80Ti0.15Ru0·05O3−δ 5% H2/Ar at 900℃ Ru SOFC [46] La0.4Sr0.6Co0.2Fe0.7Mo0.1O3–δ 5% H2/Ar at 700℃ Co-Fe SOEC [47] Pr0.8Sr1.2(Fe, Ni)0.8Nb0.2O4–δ 20% H2/Ar at 850℃ Ni-Fe SOEC [48] La0.43Ca0.37Ni0.06Ti0.94O3–δ 10% H2/N2 at 900℃ Ni SOEC [49] Sr2Fe1.3Ni0.2Mo0.5O6–δ H2 (3% H2O) at 800℃ Ni-Fe SOFC/SOEC [50] La0.9Mn0.6Ni0.4O3−δ 5% H2/Ar at 650℃ Ni Li-O2 batteries [51] LaMn0.75Co0.25O3−δ 5% H2/Ar at 830℃ Co Zi-air batteries [52] 
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