超临界水热合成纳米氧化锆结构调控和晶型稳定机理研究

姜观宇; 刘璐; 王树众; 邓雪涛; 杨健乔

doi:10.7652/xjtuxb202602007

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超临界水热合成纳米氧化锆结构调控和晶型稳定机理研究

专题超临界流体前沿应用 | 更新时间：2026-02-09

- 超临界水热合成纳米氧化锆结构调控和晶型稳定机理研究
- Structural Regulation and Crystal Phase Stability Mechanism of Nano-Zirconia Synthesized via Supercritical Hydrothermal Method
- 西安交通大学学报 2026年60卷第2期页码：71-81
- 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：
  
  作者简介：姜观宇（1997—），男，助理教授；
  王树众（通信作者），男，教授，博士生导师。
- 基金信息：
  
  陕西省重点研发计划资助项目。(2024GX-YBXM-314)
- DOI：10.7652/xjtuxb202602007
  中图分类号： TB321;O792
- 收稿：2025-06-11，
  
  纸质出版：2026-02-10
- 稿件说明：
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姜观宇, 刘璐, 王树众, 等. 超临界水热合成纳米氧化锆结构调控和晶型稳定机理研究[J]. 西安交通大学学报, 2026,60(2):71-81.

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.
姜观宇, 刘璐, 王树众, 等. 超临界水热合成纳米氧化锆结构调控和晶型稳定机理研究[J]. 西安交通大学学报, 2026,60(2):71-81. DOI： 10.7652/xjtuxb202602007.

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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references

闫硕,鲍崇高,李世佳,等.光固化成型工艺制备跨尺度多孔结构氧化锆陶瓷[J].硅酸盐学报, 2025 , 53 (9):2696-2705.

YAN Shuo, BAO Chonggao, LI Shijia, et al.Digital light processing of cross-scale porous zirconia ceramics[J]. Journal of the Chinese Ceramic Society, 2025, 53(9):2696-2705.

MAITI T K, MAJHI J, MAITI S K, et al.Zirconia-and ceria-based electrolytes for fuel cell applications:critical advancements toward sustainable and clean energy production[J].Environmental Science and Pollution Research, 2022, 29(43):64489-64512.

郭霞.纳米氧化锆基固体电解质的可控制备及离子导电性[D].呼和浩特:内蒙古工业大学, 2021.

CHEN Shaojiang, TENNAKOON A, YOU K E, et al.Ultrasmall amorphous zirconia nanoparticles catalyse polyolefin hydrogenolysis[J].Nature Catalysis, 2023, 6(2):161-173.

CHEN Y W, MOUSSI J, DRURY J L, et al.Zirconia in biomedical applications[J].Expert Review of Medical Devices, 2016, 13(10):945-963.

MASOODIYEH F, KARIMI-SABET J, KHANCHI A R, et al.Zirconia nanoparticle synthesis in sub and supercritical water:particle morphology and chemical equilibria[J].Powder Technology, 2015, 269:461-469.

CHEVALIER J, GREMILLARD L, VIRKAR A V, et al.The tetragonal-monoclinic transformation in zirconia:lessons learned and future trends[J].Journal of the American Ceramic Society, 2009, 92(9):1901-1920.

JING P P, GONG Y L, XIANG Y, et al.Biocompatibility study of Fe-doped zirconia-toughened alumina ceramic for artificial joints[J].Ceramics International, 2024, 50(11, Part B):20108-20117.

曹贺辉.稀土元素掺杂对氧化锆陶瓷力学性能的优化作用[J].佛山陶瓷, 2025, 35(5):29-31.

CAO Hehui.Optimizing the mechanical properties of zirconia ceramics with rare earth elements[J].Foshan Ceramics, 2025, 35(5):29-31 .

ALTOWYAN A S, KAYNAR U H, AYDIN H, et al. Enhanced photoluminescence properties of Eu 3+ /Li + codoped ZrO 2 :a focus on red and far-red emissions[J ] . Journal of Photochemistry and Photobiology: A Chemistry, 2025, 466:116408.

NOSENKO V, VORONA I, TRACHE VSKY V, et al. Cu-related paramagnetic centers in Cu-and (Cu, Y)-doped ZrO 2 nanopowders[J ] .Materials, 2025, 18(3):605.

XU Jiawen, SHI Xiumin, YI Mingyue, et al.Lithiumdoped ZrO 2 nanoparticles for SERS-based norfloxacin drug detection[J ] .Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy, 2025, 326:125239.

杨澜,胡彦杰.火焰喷雾热解法制备纳米ZrO 2 及其正极包覆应用[J ] .硅酸盐学报, 2024, 52 (12 ):3781-3788.

YANG Lan, HU Yanjie.Coating cathode material LiNi 0.8 Co 0.1 Mn 0.1 O 2 with Nano ZrO 2 prepared via flame spray pyrolysis[J ] .Journal of the Chinese Ceramic Society, 2024, 52(12):3781-3788.

谭海翔,韦世强,秦文忠,等.稳定氧化锆纳米材料制备方法及应用[J].大众科技, 2023, 25(7):52-55.

TAN Haixiang, WEI Shiqiang, QIN Wenzhong, et al. Preparation method and application of stabilized zirconia nanomaterials[J].Popular Science & Technology, 2023, 25(7):52-55.

LU Jinfeng, MINAMI K, TAKAMI S, et al.Super-critical hydrothermal synthesis and in situ organic modification of indium tin oxide nanoparticles using continuous-flow reaction system[J]. ACS Applied Materials & Interfaces, 2012 , 4(1 ):351-354.

ZHANG Yishu, WANG Shuzhong, LI Yanhui, et al. Inorganic salts in sub-/supercritical water:part A behavior characteristics and mechanisms[J].Desalination, 2020, 496:114674.

DING Weijing, CHEN Yunan, GE Zhiwei, et al.A molecular simulation study on solvation free energy and structural properties of polycyclic aromatic hydrocarbons in supercritical water environment[J].Journal of Molecular Liquids, 2020, 318:114274.

MARIDURAI T, BALAJI D, SAGADEVAN S.Synthesis and characterization of yttrium stabilized zirconia nanoparticles[J].Materials Research, 2016, 19(4):812-816.

卢祺.钕掺杂氧化钇稳定氧化锆彩色陶瓷的制备及其性能研究[D].包头:内蒙古科技大学, 2022.

TORRES D I, LLOPIS J.Infrared photoluminescence and Raman spectra in the Y 2 O 3 -ZrO 2 system[J ] .Superlattices and Microstructures, 2009, 45 (4/5 ):482-488 .

ZHU Wenliang, NAKASHIMA S, MARIN E, et al. Microscopic mapping of dopant content and its link to the structural and thermal stability of yttria-stabilized zirconia polycrystals[J].Journal of Materials Science, 2020, 55(2):524-534.

MA Bin, LI Yao, SU Ke.Characterization of ceria-yt-tria stabilized zirconia plasma-sprayed coatings[J]. Applied Surface Science, 2009, 255(16):7234-7237.

ZENG Zhaoyubo, LIU Yunzhong, QIAN Feng, et al. Role of a low level of La 2 O 3 dopant on the tetragonalto-monoclinic phase transformation of ceria-yttria costabilized zirconia[J ] .Journal of the European Ceramic Society, 2019, 39(14):4338-4346.

曹峥.掺杂氧化锆基陶瓷材料热物理性能和高温相稳定性的研究[D].北京:北京科技大学, 2023.

COTES S, GARGANO P H, FORTI M D, et al.Stabilization of charged substitutional ions in tetragonal zirconia[J].Materials Today:Proceedings, 2022, 51 (Part 1):488-495.

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