采用微乳液水热辅助法合成了三种不同尺寸的手榴弹状ZnO微/纳结构.通过设计热化学循环,建立了纳米ZnO与块体ZnO体系热力学性质之间的关系.并结合微量热技术对不同尺寸ZnO微/纳体系的热力学性质进行了计算.结果表明,尺寸效应对微/纳体系热力学性质有显著的影响:随着反应物尺度的减小,体系的标准摩尔反应焓、标准摩尔反应Gibbs自由能、标准摩尔反应熵均降低,而材料自身的标准摩尔生成焓、标准摩尔生成Gibbs自由能、标准摩尔熵均增加. Three different sizes of grenade ZnO micro / nanostructures were synthesized by the microemulsion hydrothermal method.The relationship between the nano-ZnO and the thermodynamic properties of bulk ZnO was established by designing the thermochemical cycle. The results show that the size effect has a significant effect on the thermodynamic properties of the micro / nano system: With the decrease of the scale of the reactants, the standard molar enthalpy of the reaction, the standard molar reaction Gibbs free energy, standard molar reaction entropy decreased, and the standard molar enthalpy of formation of the material itself, the standard molar Gibbs free energy, the standard molar entropy increased.