Interplay between A-site and oxygen-vacancy ordering, and mixed electron/oxide-ion conductivity in n = 1 Ruddlesden–Popper perovskite Sr2Nd2Zn2O7†

IF 7.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Danhe Li, Guangxiang Lu, Zien Cheng, Maxim Avdeev, Jungu Xu, Zhengyang Zhou, Rihong Cong, Tao Yang and Pengfei Jiang
{"title":"Interplay between A-site and oxygen-vacancy ordering, and mixed electron/oxide-ion conductivity in n = 1 Ruddlesden–Popper perovskite Sr2Nd2Zn2O7†","authors":"Danhe Li, Guangxiang Lu, Zien Cheng, Maxim Avdeev, Jungu Xu, Zhengyang Zhou, Rihong Cong, Tao Yang and Pengfei Jiang","doi":"10.1039/D4SC05323K","DOIUrl":null,"url":null,"abstract":"<p >Oxygen vacancies in Ruddlesden–Popper (RP) perovskites (PV) [AO][ABO<small><sub>3</sub></small>]<small><sub><em>n</em></sub></small> play a pivotal role in engineering functional properties and thus understanding the relationship between oxygen-vacancy distribution and physical properties can open up new strategies for fine manipulation of structure-driven functionalities. However, the structural origin of preferential distribution for oxygen vacancies in RP structures is not well understood, notably in the single-layer (<em>n</em> = 1) RP-structure. Herein, the <em>n</em> = 1 RP phase Sr<small><sub>2</sub></small>Nd<small><sub>2</sub></small>Zn<small><sub>2</sub></small>O<small><sub>7</sub></small> was rationally designed and structurally characterized by combining three-dimensional (3D) electron diffraction and neutron powder diffraction. Sr<small><sub>2</sub></small>Nd<small><sub>2</sub></small>Zn<small><sub>2</sub></small>O<small><sub>7</sub></small> adopts a novel 2-fold <em>n</em> = 1 RP-type <em>Pmmn</em>-superstructure due to the concurrence of A-site column ordering and oxygen-vacancy array ordering. These two ordering models are inextricably linked, and disrupting one would thus destroy the other. Oxygen vacancies are structurally confined to occupy the equatorial sites of “BO<small><sub>6</sub></small>”-octahedra, in stark contrast to the preferential occupation of the inner apical sites in <em>n</em> ≥ 2 structures. Such a layer-dependent oxygen-vacancy distribution in RP structures is in fact dictated by the reduction of the cationic A–A/B repulsion. Moreover, the intrinsic oxygen vacancies can capture atmospheric O<small><sub>2</sub></small>, consequently resulting in a mixed oxide ion and p-type electrical conductivity of 1.0 × 10<small><sup>−4</sup></small> S cm<small><sup>−1</sup></small> at temperatures &gt; 800 °C. This value could be further enhanced to &gt; 1.0 × 10<small><sup>−3</sup></small> S cm<small><sup>−1</sup></small> by creating additional oxygen vacancies on the equatorial sites through acceptor doping. Bond valence site energy analysis indicates that the oxide ion conduction in Sr<small><sub>2</sub></small>Nd<small><sub>2</sub></small>Zn<small><sub>2</sub></small>O<small><sub>7</sub></small> is predominated by the one-dimensional pathways along the [Zn<small><sub>2</sub></small>O<small><sub>7</sub></small>] ladders and is triggered by the gate-control-like migration of the equatorial bridging oxygens to the oxygen-vacant sites. Our results demonstrate that control of anion and cation ordering in RP perovskites opens a new path toward innovative structure-driven property design.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" 4","pages":" 1932-1947"},"PeriodicalIF":7.6000,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/sc/d4sc05323k?page=search","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemical Science","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2025/sc/d4sc05323k","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0

Abstract

Oxygen vacancies in Ruddlesden–Popper (RP) perovskites (PV) [AO][ABO3]n play a pivotal role in engineering functional properties and thus understanding the relationship between oxygen-vacancy distribution and physical properties can open up new strategies for fine manipulation of structure-driven functionalities. However, the structural origin of preferential distribution for oxygen vacancies in RP structures is not well understood, notably in the single-layer (n = 1) RP-structure. Herein, the n = 1 RP phase Sr2Nd2Zn2O7 was rationally designed and structurally characterized by combining three-dimensional (3D) electron diffraction and neutron powder diffraction. Sr2Nd2Zn2O7 adopts a novel 2-fold n = 1 RP-type Pmmn-superstructure due to the concurrence of A-site column ordering and oxygen-vacancy array ordering. These two ordering models are inextricably linked, and disrupting one would thus destroy the other. Oxygen vacancies are structurally confined to occupy the equatorial sites of “BO6”-octahedra, in stark contrast to the preferential occupation of the inner apical sites in n ≥ 2 structures. Such a layer-dependent oxygen-vacancy distribution in RP structures is in fact dictated by the reduction of the cationic A–A/B repulsion. Moreover, the intrinsic oxygen vacancies can capture atmospheric O2, consequently resulting in a mixed oxide ion and p-type electrical conductivity of 1.0 × 10−4 S cm−1 at temperatures > 800 °C. This value could be further enhanced to > 1.0 × 10−3 S cm−1 by creating additional oxygen vacancies on the equatorial sites through acceptor doping. Bond valence site energy analysis indicates that the oxide ion conduction in Sr2Nd2Zn2O7 is predominated by the one-dimensional pathways along the [Zn2O7] ladders and is triggered by the gate-control-like migration of the equatorial bridging oxygens to the oxygen-vacant sites. Our results demonstrate that control of anion and cation ordering in RP perovskites opens a new path toward innovative structure-driven property design.

Abstract Image

n = 1 Ruddlesden - Popper钙钛矿Sr2Nd2Zn2O7中a位与氧空位排序的相互作用及混合电子/氧化离子电导率
Ruddlesden - Popper (RP)钙钛矿(PV) [AO][ABO3]n中的氧空位在工程功能性质中起着关键作用,因此了解氧空位分布与物理性质之间的关系可以为精细操纵结构驱动的功能开辟新的策略。然而,氧空位在RP结构中优先分布的结构起源尚不清楚,特别是在单层(n =1) RP结构中。本文采用三维电子衍射和中子粉末衍射相结合的方法,对n = 1 RP相Sr2Nd2Zn2O7进行了合理设计和结构表征。Sr2Nd2Zn2O7采用了一种新颖的2倍n = 1 rp型pmmn上层结构,由于a位柱有序和氧空位阵列有序同时存在。这两种排序模式是密不可分的,打乱其中一种就会毁掉另一种。氧空位在结构上局限于占据“BO6”-八面体的赤道位,与n≥2结构中优先占据内顶位形成鲜明对比。在RP结构中,这种依赖于层的氧空位分布实际上是由阳离子a−a /B斥力的减少所决定的。此外,固有氧空位可以捕获大气中的O2,从而导致混合氧化物离子和p型电导率为1.0 × 10-4 S cm-1。800°C。该值可以进一步增强为>;1.0 × 10-3 S cm-1通过受体掺杂在赤道位上产生额外的氧空位。键价位能分析表明,Sr2Nd2Zn2O7中氧化离子的传导主要是沿[Zn2O7]阶梯的一维通道,并由赤道桥接氧向氧空位的门控式迁移触发。我们的研究结果表明,控制RP钙钛矿中阴离子和阳离子的顺序为创新结构驱动的性能设计开辟了一条新的道路。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
求助全文
约1分钟内获得全文 求助全文
来源期刊
Chemical Science
Chemical Science CHEMISTRY, MULTIDISCIPLINARY-
CiteScore
14.40
自引率
4.80%
发文量
1352
审稿时长
2.1 months
期刊介绍: Chemical Science is a journal that encompasses various disciplines within the chemical sciences. Its scope includes publishing ground-breaking research with significant implications for its respective field, as well as appealing to a wider audience in related areas. To be considered for publication, articles must showcase innovative and original advances in their field of study and be presented in a manner that is understandable to scientists from diverse backgrounds. However, the journal generally does not publish highly specialized research.
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术官方微信