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
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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.
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