Structural Regulation and Crystal Stability Mechanism of Nano-Zirconia Synthesized by Supercritical Hydrothermal Technology

JIANG Guanyu; LIU Lu; WANG Shuzhong; DENG Xuetao; YANG Jianqiao

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Structural Regulation and Crystal Stability Mechanism of Nano-Zirconia Synthesized by Supercritical Hydrothermal Technology

更新时间：2025-09-29

- Structural Regulation and Crystal Stability Mechanism of Nano-Zirconia Synthesized by Supercritical Hydrothermal Technology
- JOURNAL OF XI’AN JIAOTONG UNIVERSITY (2025)
- 作者机构：
  
  1.西安交通大学能源与动力工程学院,陕西省西安市710049
  2.西安稀有金属材料研究院有限公司,陕西省西安市710016
- 作者简介：
- 基金信息：
- DOI：
  CLC： TB321;O792
- Received：11 June 2025，
  
  Revised：2025-09-14，
  
  Accepted：29 September 2025，
- 稿件说明：
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JIANG Guanyu, LIU Lu, WANG Shuzhong, et al. Structural Regulation and Crystal Stability Mechanism of Nano-Zirconia Synthesized by Supercritical Hydrothermal Technology[J/OL]. JOURNAL OF XI’AN JIAOTONG UNIVERSITY, 2025.
DOI：

JIANG Guanyu, LIU Lu, WANG Shuzhong, et al. Structural Regulation and Crystal Stability Mechanism of Nano-Zirconia Synthesized by Supercritical Hydrothermal Technology[J/OL]. JOURNAL OF XI’AN JIAOTONG UNIVERSITY, 2025. DOI：

摘要

为了探究纳米氧化锆掺杂剂分布均匀性和长效晶型稳定性，本文基于超临界水热合成技术，结合多尺度表征与密度泛函理论（DFT）计算，从原子尺度揭示了Ce/Y掺杂纳米氧化锆晶型及结构热力学的稳定性机理。通过X射线衍射、拉曼光谱和X射线光电子能谱分析了纳米氧化锆颗粒的物相组成、晶型种类和元素化学态；系统研究了不同掺杂离子种类（Y和Ce）和不同掺杂浓度（摩尔分数分别为3、6、9和12）对合成态纳米氧化锆晶体演化的影响规律；同步解析了其电子结构重构、氧空位形成能及缺陷协同作用机制；建立了掺杂浓度-晶型稳定性-缺陷演变的定量构效关系。研究结果表明：随着掺杂浓度的增加，纳米氧化锆的单斜相、四方相和立方相缺陷形成能降低，导致纳米氧化锆结构易发生转变；Y掺杂纳米氧化锆由四方相转变为立方相的临界摩尔分数为8.26，Ce掺杂纳米氧化锆结构转变的临界摩尔分数为9；在温度为400 ℃和压力为25 Mpa的实验条件下，掺杂摩尔分数为6的Y/Ce可获得完全稳定的纳米氧化锆四方相。该结果为进一步开发高性能纳米氧化锆基复合材料提供理论依据。

Abstract

In order to obtain the distribution of dopants and long-term phase stability of nano-zirconia

the thermodynamic stability and phase stabilization mechanisms of Ce/Y-doped nano-zirconia systems in supercritical hydrothermal synthesis process were revealed by combining with multiscale characterization methods and density functional theory (DFT) calculations at the atomic scale in this work. The phase composition

crystal types

and elemental chemical states of nanoparticles were identified by X-ray diffraction

Raman spectroscopy and X-ray photoelectron spectroscopy. Through systematic investigation of the crystal evolution law of nano-zirconia under varied doping ion types (Y and Ce) and doping concentrations (molar fractions of 3

and 12)

its electronic structure reconstruction

oxygen vacancy formation energy

and defect synergistic effect were simultaneously analyzed. Furthermore

a quantitative relationship between doping concentration

phase stability

and defect evolution was established. The research results indicate that the defect formation energy for monoclinic

tetragonal

and cubic phases all reduced as the doping concentration increased

so facilitating structural transformation in the case of dopants. The critical mole fraction for the transition of tetragonal phase to cubic phase for Ce-doped zirconia was 9. When it comes to Y-doped zirconia

the critical mole fraction turn out to be 8.26. It was found that 6 molar fraction of Y/Ce doping under 400 ℃ and 25 MPa can achieve complete stabilization of tetragonal zirconia. The results can serve as a foundation for developing next-generation high-performance zirconia-based nanocomposites.

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Related Author

JIANG Guanyu

LIU Lu

WANG Shuzhong

DENG Xuetao

YANG Jianqiao

Related Institution

School of Energy and Power Engineering, Xi'an Jiaotong University

Xi'an Rare Materials Institute Co., Ltd.

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