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

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关键词：纳米氧化锆；超临界水热合成；掺杂；晶型稳定

中图分类号：TB321;O792文献标志码：A

DOI：10.7652/xjtuxb202602007 文章编号：0253-987X（2026）02-0071-11

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

JIANG Guanyu1，LIU Lul²，WANG Shuzhong1 ，DENG Xuetaol，YANG Jianqiaol （1. School of Energy and Power Engineering，Xi'an Jiaotong University，Xi'an 71Oo49，China; 2.Xi’anRare Materials Institute Co.，Ltd.，Xi'an71ool6，China）

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 difraction， Raman spectroscopy， and X-ray photoelectron spectroscopy. The effects of different dopant types （Y and Ce） and concentrations （with molar fractions of 3% ， 6% ， （2号 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∘C and 25MPa ，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-zirconiabased composite materials.

Keywords： nano-zirconia; supercritical hydrothermal technology; doping; crystal stability

纳米氧化锆（ ZrO2 ）作为一种高性能陶瓷材料，因其高熔点（约 2700∘C ）、优异的化学稳定性、高离子导电性以及独特的相变增韧特性，在结构材料[1]、固体氧化物燃料电池[2-3]、催化载体[4]、生物医学[5-6]等领域展现出广阔的应用前景。（剩余13541字）