Acta Phys. -Chim. Sin. ›› 2016, Vol. 32 ›› Issue (12): 2891-2897.doi: 10.3866/PKU.WHXB201609133

• ARTICLE • Previous Articles     Next Articles

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

Huan-Feng TANG1,Zai-Yin HUANG1,2,3,*(),Ming XIAO1,Min LIANG1,Li-Ying CHEN1   

  1. 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:2016-08-10 Published:2016-11-30
  • Contact: Zai-Yin HUANG E-mail:huangzaiyin@163.com
  • Supported by:
    the National Natural Science Foundation of China(21273050,21573048)

Abstract:

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.

Key words: In-situ microcalorimetry, Reaction kinetics, Kinetic model, Nanomaterial, Cubic cuprous oxide

MSC2000: 

  • O643