锡基钙钛矿水热合成及高温相变和表面活性位研究

doi:10.19964/j.issn.1006-4990.2024-0199

摘要/Abstract

摘要：

为探讨锡基钙钛矿的高温晶相变化及表面活性位如酸、碱位点之间的关系，采用水热法制备了一系列ASn（OH）₆（A＝Ca、Sr、Ba）前驱体，并在800 ℃空气氛围下焙烧获得纯相的ASnO₃（A＝Ca、Sr、Ba）钙钛矿型复合氧化物。使用XRD、FT-IR、Raman、XPS和TEM等技术对其结构进行表征，结果表明，CaSnO₃和SrSnO₃为正交晶相，BaSnO₃为具有肖特基缺陷的立方晶相，随着温度从室温升高至800 ℃，CaSnO₃和BaSnO₃不发生晶相变化，而SrSnO₃在高温下会由正交晶相（Pnma）向正交晶相（Imma）转变。表面酸碱性位点与A位离子的碱性密切相关，A位离子碱性越强，碱性位点越丰富，酸性位点越少。结果表明：中等强度碱中心量与氧空位浓度相关；氧空位浓度取决于平均金属-氧键键能，平均金属-氧键键能越低，氧空位和中等强度碱中心越丰富。钙钛矿型复合氧化物是优良的氧离子导体，在一些临氧的多相催化反应中均表现出良好的反应性能，阐明其高温相变和表面活性位有助于进一步理解其在该类反应中的构效关系。

关键词: 水热法, 钙钛矿合成, 高温相变, 表面活性中心, 氧空位

Abstract:

To investigate the high-temperature crystalline phase transitions of tin-based perovskites and the relationship between surface active sites such as acidic and basic sites，a series of ASn（OH）₆（A=Ca，Sr，Ba） precursors were prepared by hydrothermal method，and pure phase ASnO₃（A=Ca，Sr，Ba） perovskite-type composite oxides were obtained by calcination under 800 ℃ under air atmosphere.The bulk and surface structure of these samples were characterized using techniques such as XRD，FTIR，Raman，XPS，and TEM.The results showed that CaSnO₃ and SrSnO₃ were orthorhombic phases，while BaSnO₃ exhibited a cubic phase with Schottky defects.As the temperature increased from room temperature to 800 ℃，CaSnO₃ and BaSnO₃ did not undergo any crystalline phase transition，while SrSnO₃ transformed from orthorhombic phase（Pnma） to orthorhombic phase（Imma） at high temperatures.Their surface acid-base sites were closely related to the alkalinity of A-site cations.The results showed that the stronger the alkalinity of A-site cations，the richer the basic sites，and the fewer the acidic sites.The moderate basic site was related to the concentration of oxygen vacancies.The concentration of oxygen vacancies depended on the average metal oxygen bond energy.The lower this bond energy，the more abundant oxygen vacancies and moderate basic sites.Floody-type composite oxide was an excellent oxygen ion conductor，which showed good response performance in some aerobic multi-phase catalytic reactions.The cleptication of its high temperature phase change and surface activity position was conducive to further understand their research on the research relationship in this type of reaction.

Key words: hydrothermal method, perovskite synthesis, high temperature crystalline phase transition, surface active sites, oxygen vacancy

中图分类号:

TQ134.32

陈冠宜, 徐骏伟. 锡基钙钛矿水热合成及高温相变和表面活性位研究[J]. 无机盐工业, 2025, 57(4): 37-44.

CHEN Guanyi, XU Junwei. Hydrothermal synthesis of tin-based perovskite and study on high-temperature crystalline phase transition and surface active sites[J]. Inorganic Chemicals Industry, 2025, 57(4): 37-44.

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