Influence of crystalline phase structure of rare earth oxides on active oxygen and basic sites

IF 3.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Solid State Sciences Pub Date : 2024-11-01 DOI:10.1016/j.solidstatesciences.2024.107738

Jianping Fu , Xuefang Wen , Zhiyong Xu, Yongsheng Guo, Chunshan Ke, Junwei Xu

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Abstract

Herein, the effects of crystalline phase structures of rare earth oxides on active oxygen and basic sites were investigated. The fluorite structure shows the best lattice oxygen mobility and redox properties due to its open structure and weakest Ln-O bond strength. For Pr₆O₁₁ and Tb₄O₇, the presence of polyvalent cation states further enhances these properties. Based on the basicity and number of basic sites, the surfaces of A-type, B-type, and C-type lanthanide sesquioxides facilitate the generation of chemisorbed oxygen species in the following order: A-type > B-type > C-type. Furthermore, the basicity and amount of chemisorbed oxygen species are dependent on the electronegativity of rare earth elements, which decreases gradually from La to Lu. This is because from La₂O₃ to Lu₂O₃, electrons are less biased toward oxygen, the basicity of lattice oxygen decreases, and fewer electrons are produced for gaseous oxygen activation and chemisorbed oxygen generation.

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稀土氧化物晶相结构对活性氧和碱性位点的影响

本文研究了稀土氧化物晶相结构对活性氧和碱性位点的影响。萤石结构因其开放结构和最弱的 Ln-O 键强度而显示出最佳的晶格氧迁移率和氧化还原特性。对于 Pr6O11 和 Tb4O7，多价阳离子态的存在进一步增强了这些特性。根据碱性和碱性位点的数量，A 型、B 型和 C 型镧系倍半氧化物的表面按以下顺序促进化学吸附氧的生成：A型；B型；C型。此外，化学吸附氧的碱性和数量取决于稀土元素的电负性，从 La 到 Lu，电负性逐渐降低。这是因为从 La2O3 到 Lu2O3，电子对氧的偏向性降低，晶格氧的碱性降低，用于气态氧活化和化学吸附氧生成的电子减少。

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来源期刊

Solid State Sciences 化学-无机化学与核化学

CiteScore

6.60

自引率

2.90%

发文量

214

审稿时长

27 days

期刊介绍： Solid State Sciences is the journal for researchers from the broad solid state chemistry and physics community. It publishes key articles on all aspects of solid state synthesis, structure-property relationships, theory and functionalities, in relation with experiments. Key topics for stand-alone papers and special issues: -Novel ways of synthesis, inorganic functional materials, including porous and glassy materials, hybrid organic-inorganic compounds and nanomaterials -Physical properties, emphasizing but not limited to the electrical, magnetical and optical features -Materials related to information technology and energy and environmental sciences. The journal publishes feature articles from experts in the field upon invitation. Solid State Sciences - your gateway to energy-related materials.