The particle migration and coalescence(PMC) kinetics of a supported metal are the main deactivation mechanisms restricting the successful industrialization of nanoparticles, but the theoretical insights regarding thes...The particle migration and coalescence(PMC) kinetics of a supported metal are the main deactivation mechanisms restricting the successful industrialization of nanoparticles, but the theoretical insights regarding these kinetics are lacking. One key issue is the lack of a physical model to predict the effects of metal-support interaction(MSI) on PMC kinetics. In this paper, we report a theoretical study of PMC kinetics and their dependence on MSI. A new particle diffusion model is proposed based on the surface premelting hypothesis that considers the contact angle of a hemispherical particle on the support. Enhanced MSI suppresses PMC by increasing the radius of curvature and the interfacial adhesion energy, even though the accompanying reduction in the geometry factor partially promotes PMC kinetics. The increased surface energy increases the chemical potential of the atoms in the particle, which is conducive to PMC; an increased surface energy also results in enhanced MSI, which suppresses PMC. The competition between these two contradictory effects leads to a critical contact angle where the surface energy has no influence on the diffusion and resulting PMC kinetics. The proposed diffusion theory mode lincluding the effects of the support and the corresponding kinetic simulations, shed light onto the support-dependence of PMC kinetics and provide a foundation for further optimization and design of supported particles with better stability.展开更多
基金supported by the National Key R&D Program of China(Grant Nos.2018YFA0208603,2017YFB0602205)the Chinese Academy of Sciences(Grant No.QYZDJ-SSW-SLH054)the National Natural Science Foundation of China(Grant No.91645202)
文摘The particle migration and coalescence(PMC) kinetics of a supported metal are the main deactivation mechanisms restricting the successful industrialization of nanoparticles, but the theoretical insights regarding these kinetics are lacking. One key issue is the lack of a physical model to predict the effects of metal-support interaction(MSI) on PMC kinetics. In this paper, we report a theoretical study of PMC kinetics and their dependence on MSI. A new particle diffusion model is proposed based on the surface premelting hypothesis that considers the contact angle of a hemispherical particle on the support. Enhanced MSI suppresses PMC by increasing the radius of curvature and the interfacial adhesion energy, even though the accompanying reduction in the geometry factor partially promotes PMC kinetics. The increased surface energy increases the chemical potential of the atoms in the particle, which is conducive to PMC; an increased surface energy also results in enhanced MSI, which suppresses PMC. The competition between these two contradictory effects leads to a critical contact angle where the surface energy has no influence on the diffusion and resulting PMC kinetics. The proposed diffusion theory mode lincluding the effects of the support and the corresponding kinetic simulations, shed light onto the support-dependence of PMC kinetics and provide a foundation for further optimization and design of supported particles with better stability.
