Structural Regulation and Crystal Phase Stability Mechanism of Nano-Zirconia Synthesized via Supercritical Hydrothermal Method

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

doi:10.7652/xjtuxb202602007

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Structural Regulation and Crystal Phase Stability Mechanism of Nano-Zirconia Synthesized via Supercritical Hydrothermal Method

Special Topic Frontier Applications of Supercritical Fluids | 更新时间：2026-02-09

- Structural Regulation and Crystal Phase Stability Mechanism of Nano-Zirconia Synthesized via Supercritical Hydrothermal Method
- Journal of Xi'an Jiaotong University Vol. 60, Issue 2, Pages: 71-81(2026)
- 作者机构：
  
  西安交通大学能源与动力工程学院，710049，西安
  西安稀有金属材料研究院有限公司，710016，西安
- 作者简介：
- 基金信息：
- DOI：10.7652/xjtuxb202602007
  CLC： TB321;O792
- Received：11 June 2025，
  
  Published：10 February 2026
- 稿件说明：
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JIANG Guanyu, LIU Lu, WANG Shuzhong, et al. Structural Regulation and Crystal Phase Stability Mechanism of Nano-Zirconia Synthesized via Supercritical Hydrothermal Method[J]. Journal of Xi'an Jiaotong University, 2026, 60(2): 71-81.
DOI：

JIANG Guanyu, LIU Lu, WANG Shuzhong, et al. Structural Regulation and Crystal Phase Stability Mechanism of Nano-Zirconia Synthesized via Supercritical Hydrothermal Method[J]. Journal of Xi'an Jiaotong University, 2026, 60(2): 71-81. DOI： 10.7652/xjtuxb202602007.

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，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

To investigate the uniformity of dopant distribution and long-term crystal phase stability in nano-zirconia，the thermodynamic stability and phase stabilization mechanisms of Ce/Y-doped nano-zirconia during supercritical hydrothermal synthesis were elucidated at the atomic scale by combining multiscale characterization with density functional theory calculations.The phase composition，crystal structures，and elemental chemical states of the nano-zirconia particles were analyzed using X-ray diffraction，Raman spectroscopy，and X-ray photoelectron spectroscopy. The effects of different dopant types（Y and Ce）and concentrations（with molar fractions of 3%，6%，9%，and 12%）on the crystal evolution of as-synthesized nano-zirconia were systematically investigated. Concurrently，the electronic structure reconstruction，oxygen vacancy formation energy，and defect synergy mechanisms were analyzed.A quantitative structure-activity relationship linking doping concentration，crystal phase stability，and defect evolution was established.The results show that as the doping concentration increases，the defect formation energies of the monoclinic，tetragonal，and cubic phases of nano-zirconia decrease，which facilitates the crystal phase transformation.The critical molar fraction for the transition from the tetragonal to the cubic phase is 8.26% for Y-doped nano-zirconia and 9% for Ce-doped nano-zirconia.Under experimental conditions of 400℃ and 25 MPa，a doping molar fraction of 6% for Y/Ce yields a fully stabilized tetragonal nano-zirconia phase.These findings provide a theoretical basis for the further development of high-performance nano-zirconia-based composite materials.

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JIANG Guanyu

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Related Institution

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

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