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

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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

更新时间：2025-09-29

- 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 Stability Mechanism of Nano-Zirconia Synthesized by Supercritical Hydrothermal Technology
- 西安交通大学学报 2025年
- 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：
  
  陕西省重点研发计划(2024GX-YBXM-314)
- DOI：
  中图分类号： TB321;O792
- 收稿：2025-06-11，
  
  修回：2025-09-14，
  
  录用：2025-09-29，
- 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/OL]. 西安交通大学学报, 2025.

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.
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/OL]. 西安交通大学学报, 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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references

Kelly JR , Denry I . Stabilized zirconia as a structural ceramic: An overview [J ] . Dental Materials , 2008 , 24 ( 3 ): 289 - 298 .

Maiti TK , Majhi J , Maiti SK , 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 ] . 内蒙古工业大学 , 2021 .

Chen S , 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 , Joelle M , L. DJ , et al . Zirconia in biomedical applications [J ] . Expert Review of Medical Devices , 2016 , 13 ( 10 ): 945 - 963 .

Masoodiyeh F , Karimi-Sabet J , Khanchi AR , 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 AV , et al . The Tetragonal-Monoclinic Transformation in Zirconia: Lessons Learned and Future Trends [J ] . 2009 , 92 ( 9 ): 1901 - 1920 .

Jing PP , Gong YL , 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.

Srdić VV , Rakić S , Cvejić Ž . Aluminum doped zirconia nanopowders: Wet-chemical synthesis and structural analysis by Rietveld refinement [J ] . Materials Research Bulletin , 2008 , 43 ( 10 ): 2727 - 2735 .

Altowyan AS , Kaynar UH , Aydin H , et al . Enhanced photoluminescence properties of Eu 3+ /Li + co-doped 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 , Trachevsky V , et al . Cu-Related Paramagnetic Centers in Cu- and (Cu,Y)-Doped ZrO 2 Nanopowders [J ] . Materials , 2025 , 18 ( 3 ): 605 .

Xu J , Shi X , Yi M , et al . Lithium-doped 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 .

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 ( 07 ): 52 - 55 .

Lu J , Minami K , Takami S , et al . Supercritical 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 Y , Wang S , Li Y , et al . Inorganic salts in sub-/supercritical water—Part A: Behavior characteristics and mechanisms [J ] . Desalination , 2020 , 496 : 114674 .

Ding W , Chen Y , Ge Z , 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 : 812 - 816 .

Naumenko A , Berezovska N , Biliy M , et al . Vibrational analysis and Raman spectra of tetragonal zirconia [J ] . Physics and Chemistry Solid State , 2008 , 9 ( 1 ): 121 - 125 .

Torres DI , Llopis J . Infrared photoluminescence and Raman spectra in the Y 2 O 3 –ZrO 2 system [J ] . Superlattices Microstructures , 2009 , 45 ( 4 ): 482 - 488 .

Zhu W , 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 B , Li Y , Su K . Characterization of ceria–yttria stabilized zirconia plasma-sprayed coatings [J ] . Applied Surface Science , 2009 , 255 ( 16 ): 7234 - 7237 .

Zeng Z , Liu Y , Qian F , et al . Role of a low level of La 2 O 3 dopant on the tetragonal-to-monoclinic phase transformation of ceria-yttria co-stabilized zirconia [J ] . Journal of the European Ceramic Society , 2019 , 39 ( 14 ): 4338 - 4346 .

Wu N-L , Wang S-Y , Rusakova IA . Inhibition of Crystallite Growth in the Sol-Gel Synthesis of Nanocrystalline Metal Oxides [J ] . Science , 1999 , 285 ( 5432 ): 1375 - 1377 .

Cotes S , Gargano PH , Forti MD , et al . Stabilization of charged substitutional ions in tetragonal zirconia [J ] . Materials Today: Proceedings , 2022 , 51 : 488 - 495 .

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