Abstract
CaMoO4 nanocakes with uniform size and morphology were prepared on a large scale via a room temperature reverse-microemulsion method. The products were characterized in detail by X-ray powder diffraction, field-emission scanning electron microscopy, transmission electron microscopy, and high-resolution transmission electron microscopy. By establishing the relations between the thermodynamic functions of nano-CaMoO4 and bulk-CaMoO4 reaction systems, the equations for calculating the surface thermodynamic functions of nano-CaMoO4 were derived. Then, combined with in-situ microcalorimetry, the molar surface enthalpy, molar surface Gibbs free energy, and molar surface entropy of the prepared CaMoO4 nanocakes at 298.15 K were successfully obtained as (19.674 ± 0.017) kJ·mol−1, (619.704 ± 0.016) J·mol−1, and (63.908 ± 0.057) J·mol−1·K−1, respectively.
Highlights
The thermodynamic properties are some of the most important attributes of nanomaterials
In 2001, Hill [1,2,3] started to work on the nanothermodynamics area, and his research has opened up the door for the development of the discipline of nanothermodynamics
We report a simple and facile route for the large scale synthesis of uniform, singlecrystalline and well-defined CaMoO4 nanocakes, and presented an effective and general route for acquiring the surface thermodynamic functions of nanomaterials by in-situ microcalorimetry
Summary
The thermodynamic properties are some of the most important attributes of nanomaterials. Surface thermodynamic properties, including surface Gibbs free energy, surface enthalpy and surface entropy, are an important expression of surface effects, and they have a direct relationship with the chemical thermodynamics [5], chemical kinetics [6], catalysis [7,8], sense [9], adsorption [10], phase transition [11], electrochemistry [12] of nanomaterials. The study of the surface thermodynamic properties of nanomaterials and their structure-function relationships with particle size, morphology and structure is valuable to understand the nature of chemical reactions, but, till the development of the surface thermodynamics of nanomaterials is quite poor [13]. How to acquire surface thermodynamic functions of nanomaterials such as molar surface Gibbs free energy, molar surface enthalpy and molar surface entropy is still a great challenge
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