Citation: TANG Huan-Feng, HUANG Zai-Yin, XIAO Ming, LIANG Min, CHEN Li-Ying. An Investigation into the Reaction Kinetics of Cubic Nano-Cu₂O in Theory and Experiment[J]. Acta Physico-Chimica Sinica, ;2016, 32(12): 2891-2897. doi: 10.3866/PKU.WHXB201609133 shu

An Investigation into the Reaction Kinetics of Cubic Nano-Cu₂O in Theory and Experiment

1.
College of Chemistry and Chemical Engineering, Guangxi University for Nationalities, Nanning 530006, P. R. China;
2.
Key Laboratory of Forest Chemistry and Engineering, Guangxi University for Nationalities, Nanning 530006, P. R. China;
3.
Guangxi Colleges and Universities Key Laboratory of Food Safety and Pharmaceutical Analytical Chemistry, Nanning 530006, P. R. China

Received Date: 10 August 2016
Revised Date: 12 September 2016

Fund Project: The project was supported by the National Natural Science Foundation of China (21273050, 21573048).

To investigate the kinetic behaviors of nanoparticle heterogeneous reactions, we introduced a liquidphase reduction method to control the synthesis of cubic cuprous oxide with a particle size of 55 nm. Based on the differences between nano-Cu₂O and bulk Cu₂O, in-situ microcalorimetry was used to acquire fine thermodynamic information of Cu₂O systems in HNO₃. The reaction kinetic parameters of Cu₂O were calculated by a combination of thermodynamic principles and kinetic transition state theory, whose results are discussed and verified with the kinetic models of a cube that has been built. The results demonstrate that unlike the higher reaction rate constant than bulk Cu₂O, nano-Cu₂O shows lower kinetic parameters, including apparent activation energy, pre-exponential factor, activation enthalpy, activation entropy and activation Gibbs free energy. Both the reaction rate constant and activation Gibbs free energy increase with increasing temperature. The kinetic models show that the main factors affecting the reaction kinetic parameters are as follows:(i) the partial molar surface enthalpy affects the apparent activation energy; (ii) the partial molar surface entropy affects the preexponential factor; and (iii) the partial molar surface Gibbs free energy affects the reaction rate constant. We also provide a universal theoretical model and experimental method for gaining and analyzing kinetic parameters of nanomaterial heterogeneous reactions.
- In-situ microcalorimetry,
- Reaction kinetics,
- Kinetic model,
- Nanomaterial,
- Cubic cuprous oxide
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沈阳化工大学材料科学与工程学院沈阳 110142

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通讯作者: 陈斌, bchen63@163.com

An Investigation into the Reaction Kinetics of Cubic Nano-Cu₂O in Theory and Experiment