Two-dimensional (2D) substrates decorated with metal nanoparticles offer new opportunities to achieve high-performance catalytic behavior. However, little is known on how the substrates control the nucleation and growth processes of the nanoparticles. This paper presents the visualization of dynamic nucleation and growth processes of gold nanoparticles on ultrathin MoS2 nanoflakes by in situ liquid-cell transmission electron microscopy (TEM). The galvanic displacement resulting in Au nuclei formation on MoS2 was observed in real time inside the liquid cell. We found that the growth mechanism of Au particles on pristine MoS2 is in between diffusion-limited and reaction-limited, possibly due to the presence of electrochemical Ostwald ripening. A larger size distribution and more orientation variation is observed for the Au particles along the MoS2 edge than on the interior. Differing from pristine MoS2, sulfur vacancies on MoS2 induce Au particle diffusion and coalescence during the growth process. Density functional theory (DFT) calculations show that the size difference is because the exposed molybdenum atoms at the edge with dangling bonds can strongly interact with Au atoms, whereas sulfur atoms on the MoS2 interior have no dangling bonds and weakly interact with gold atoms. In addition, S vacancies on MoS2 generate strong nucleation centers that can promote diffusion and coalescence of Au nanoparticles. The present work provides key insights into the role of 2D materials in controlling the size and orientation of noble metal nanoparticles vital to the design of next generation catalysts.
2D materials such as transition metal dichalcogenides (TMDCs) are a promising scaffold material onto which noble metal nanoparticles may be directly synthesized via galvanic displacement for catalytic applications. In situ liquid TEM was used to directly observe the reduction of gold ions from a solution of AuCl3 onto MoS2 nanoflakes. The observed growth mechanism was influenced by sulfur vacancies on the MoS2 substrate and was found to be in-between diffusion-limited and growth-limited models, in agreement with Lifshitz–Slyozov–Wagner growth theory.