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解锁类沸石结构作为一种新型间隙氧化物离子导体家族:对载流子俘获、集体局部畸变和相关无序的见解。

Unlocking zeolite-like structures as a new family of interstitial oxide ion conductors: insights into carrier trapping, collective local distortion, and correlated disorder.

作者信息

Wei Xianyi, Li Xiaohui, Rakhmatullin Aydar, Wang Xiaoge, Li Cheng, Xu Hankun, Deng Sihao, He Lunhua, Lin Kun, Li Qiang, Sun Junliang, Xing Xianran, Kuang Xiaojun

机构信息

Guangxi Key Laboratory of Electrochemical and Magnetochemical Functional Materials, College of Chemistry and Bioengineering, Guilin University of Technology Guilin 541004 People's Republic of China

Conditions Extremes et Materiaux: Haute Temperature et Irradiation (CEMHTI-CNRS), CEMHTI UPR3079, University of Orléans F-45071 Orléans France.

出版信息

Chem Sci. 2025 Jul 16. doi: 10.1039/d5sc02898a.

Abstract

Zeolites have emerged as indispensable materials for applications ranging from catalysis and separation to adsorption and ion exchange, owing to their uniquely ordered porous architectures composed of well-defined channels and cavities. Inspired by the promising oxygen defect tolerance observed in various open structural frameworks, herein, we have developed a new zeolite-like feldspar structure, ABCO with 4- and 8-membered rings, in the case of Sr La GaGeO , as a new family of interstitial oxide ion conductors due to its open structural framework for accommodating and transporting interstitial oxide ions. Average structural analysis revealed that the interstitial oxygen occupies the centers of 4-membered rings, existing in a coordination equilibrium quasi-free state that confers high mobility; however, this contrasts with the experimentally observed low mobility. Local structural analysis further revealed that the local collective distortions in GaO and GeO tetrahedra, together with the correlated disorder of interstitial oxygen coordinated with Ge, hidden within the average structure, are critical to interstitial oxygen mobility from the 4-membered ring to the 8-membered ring. Our findings demonstrate zeolite-like structures as a new family of interstitial oxide ion conductors, offering new insights into the intricate interplay between oxide ion mobility, collective distortions, and correlated disorder at the local scale.

摘要

由于沸石具有由明确界定的通道和空腔组成的独特有序多孔结构,它们已成为从催化、分离到吸附和离子交换等各种应用中不可或缺的材料。受各种开放结构框架中观察到的有前景的氧缺陷耐受性的启发,在此,我们开发了一种新的类沸石长石结构,对于SrLaGaGeO而言,它具有4元和8元环,作为一种新的间隙氧化物离子导体家族,因为其开放结构框架可容纳和传输间隙氧化物离子。平均结构分析表明,间隙氧占据4元环的中心,以配位平衡准自由状态存在,赋予其高迁移率;然而,这与实验观察到的低迁移率形成对比。局部结构分析进一步表明,GaO和GeO四面体中的局部集体畸变,以及与Ge配位的间隙氧的相关无序,隐藏在平均结构中,对于间隙氧从4元环向8元环的迁移至关重要。我们的研究结果证明类沸石结构作为一种新的间隙氧化物离子导体家族,为局部尺度上氧化物离子迁移率、集体畸变和相关无序之间的复杂相互作用提供了新的见解。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7f3e/12376938/ef62535a9c5d/d5sc02898a-f1.jpg

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