锡基钙钛矿水热合成及高温相变和表面活性位研究
收稿日期: 2024-04-09
网络出版日期: 2025-04-21
基金资助
国家自然科学基金项目(22102069)
Hydrothermal synthesis of tin-based perovskite and study on high-temperature crystalline phase transition and surface active sites
Received date: 2024-04-09
Online published: 2025-04-21
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。
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 . DOI: 10.19964/j.issn.1006-4990.2024-0199
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.
| [1] | ARTINI C.Crystal chemistry，stability and properties of interlanthanide perovskites：A review［J］.Journal of the European Ceramic Society，2017，37（2）：427-440. |
| [2] | LI Hanxi， LAI Cui， WEI Zhen，et al.Strategies for improving the stability of perovskite for photocatalysis：A review of recent progress［J］.Chemosphere，2023，344：140395. |
| [3] | JIANG Mingquan， LU Junhan， CHEN Yi，et al.Non-hydrolytic sol-gel synthesis of BaTiO3 nano-powder：Effect of calcination temperature and modified titanium source on particles［J］.Materials Today Communications，2024，38：108494. |
| [4] | MISHRA G， MINOR C， TIWARI A.High throughput synthesis of BaSnO3 microcrystals by molten salt technique［J］.Materials Chemistry and Physics，2023，295：127042. |
| [5] | BIKYASHEV E A， KUBRIN S P， POPOV A V，et al.Evolution of the structure of MSnO3（M=Ba，Sr） perovskites during hydrothermal synthesis and their photocatalytic activity［J］.Dalton Transactions，2023，52（47）：17881-17893. |
| [6] | Masoumeh H， Mojgan G， Elmuez A D，et al.CaSnO3/g-C3N4 S-scheme heterojunction photocatalyst for the elimination of erythrosine and eriochrome black T from water under visible light［J］.Results in Engineering，2024，21：101903. |
| [7] | MURALIDHARAN M， SELVAKUMAR S， SIVAKUMAR K，et al.Effect of Yb doping on structural，optical and induced ferromagnetism in SrSnO3 perovskite nanostructures［J］.Physica B：Condensed Matter，2021，615：413039. |
| [8] | ASISI JANIFER M， ANAND S， JOSEPH PRABAGAR C，et al.Structural and optical properties of BaSnO3 ceramics by solid state reaction method［J］.Materials Today：Proceedings，2021，47：2067-2070. |
| [9] | MANOHARAN A， SURESH B， AJAY K，et al.Mixed ferro to diamagnetic transition in Hf doped CaSnO3 perovskite system［J］.Solid State Communications，2023，360：115033. |
| [10] | MURALIDHARAN M， AJAYKUMARI P， AVINASH M，et al.Optical，magnetic and defect studies of Ni2+ doped SrSnO3 nanostructures［J］.Ceramics International，2024，50（8）：12840-12851. |
| [11] | ZHANG Weifeng， TANG Junwang， YE Jinhua.Structural，photocatalytic，and photophysical properties of perovskite MSnO3（M=Ca，Sr，and Ba） photocatalysts［J］.Journal of Materials Research，2007，22（7）：1859-1871. |
| [12] | SHRIVASTAVA S， NEHRA S， KUMAR S，et al.Temperature-dependent dielectric measurements and structural properties of barium stannate（BaSnO3）［J］.Journal of Alloys and Compounds，2023，957：170458. |
| [13] | MURALEEDHARAN S， ASHOK A M.Nitrogen doping for effective enhancement of optoelectronic performance of ASnO3（A-Ca，Sr，Ba） transparent conducting oxides deposited by doctor blade method［J］.Optik，2023，287：171096. |
| [14] | 李小强，陈欣，李洪波，等.碳包覆CaSnO3纳米纤维作为高性能锂离子电池负极材料［J］.无机化学学报，2021，37（4）：700-708. |
| LI Xiaoqiang， CHEN Xin， LI Hongbo，et al.Carbon-coated CaSnO3 nanofibers as high performance anode materials for lithium ion batteries［J］.Chinese Journal of Inorganic Chemistry，2021，37（4）：700-708. | |
| [15] | CHANTELLE L， KENNEDY B J， DE OLIVEIRA C P，et al.Europium induced point defects in SrSnO3-based perovskites employed as antibacterial agents［J］.Journal of Alloys and Compounds，2023，956：170353. |
| [16] | CHU Xiangfeng， GAN Zhengqiang， BAI Linshan，et al.The acetic acid vapor sensing properties of BaSnO3 microtubes prepared by electrospinning method［J］.Materials Science and Engineering：B，2020，259：114606. |
| [17] | GLERUP M， KNIGHT K S， POULSEN F W.High temperature structural phase transitions in SrSnO3 perovskite［J］.Materials Research Bulletin，2005，40（3）：507-520. |
| [18] | SINGH PAL R， RANA S， KUMAR SHARMA S，et al.Enhancement of oxygen vacancy sites of La2- x M x Ce2O7- δ （M=Ca，Ba，Sr） catalyst for the low temperature oxidative coupling of methane：A combined DFT and experimental study［J］.Chemical Engineering Journal，2023，458：141379. |
| [19] | CHOUDHARY V R， RANE V H.Acidity/basicity of rare-earth oxides and their catalytic activity in oxidative coupling of methane to C2-hydrocarbons［J］.Journal of Catalysis，1991，130（2）：411-422. |
| [20] | 黄学辉，夏莹，张丽丽，等.纳米类钙钛矿化合物La4BaCu5- x- y Fe x Co y O13+ δ 的制备及表征［J］.陶瓷学报，2010，31（4）：561-564. |
| HUANG Xuehui， XIA Ying， ZHANG Lili，et al.Prepar-ation and characterization of perovskite-like compounds La 4 BaCu5- x- y Fe x Co y O13+ δ with doping in the "B" position［J］.Journal of Ceramics，2010，31（4）：561-564. | |
| [21] | FAISAL M， HARRAZ F A， ISMAIL A A，et al.Novel synthesis of polyaniline/SrSnO3 nanocomposites with enhanced photocatalytic activity［J］.Ceramics International，2019，45（16）：20484-20492. |
| [22] | WANG Menghui， ZHU Changzu， HU Huashuai，et al.Correlation between radiation resistance and structural factors of ABO3-type perovskites［J］.Nuclear Instruments and Methods in Physics Research Section B：Beam Interactions with Materials and Atoms，2023，536：88-96. |
| [23] | GAO Wanlin， ZHOU Tuantuan， WANG Qiang.Controlled synthesis of MgO with diverse basic sites and its CO2 capture mechanism under different adsorption conditions［J］.Chemical Engineering Journal，2018，336：710-720. |
| [24] | FRAILE J M， GARCíA N， MAYORAL J A，et al.The influence of alkaline metals on the strong basicity of Mg-Al mixed oxides：The case of transesterification reactions［J］.Applied Catalysis A：General，2009，364（1/2）：87-94. |
| [25] | KU? S， OTREMBA M， TóRZ A，et al.Further evidence of responsibility of impurities in MgO for variability in its basicity and catalytic performance in oxidative coupling of methane［J］.Fuel，2002，81（13）：1755-1760. |
| [26] | COOK R L， SAMMELLS A F.On the systematic selection of perovskite solid electrolytes for intermediate temperature fuel cells［J］.Solid State Ionics，1991，45（3/4）：311-321. |
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