Nanorod Diffusion near the Solid–Liquid Interface with Varied Wall Nonuniformity

The complex diffusion behaviors of rod-shaped nanoparticles near the solid–liquid interface are closely related to various biological processes and technological applications. Despite recent advancements in understanding the diffusion dynamics of nanoparticles near some specific solid–liquid interfaces, systematical studies to tune the interfacial interaction or fabricating nonuniform wall to see their effects on the nanorod (NR) diffusion are still lacking. This work utilized molecular dynamics simulations to investigate the rotational and translational diffusion dynamics of a single NR near the solid–liquid interface. We constructed a patterned wall featuring adjustable nonuniformity, which was accomplished by modifying the interaction between NR and the wall, noting that the resulting nonuniformity limits both the translational and rotational diffusion of NR, evident from decreases in diffusion coefficients and exponents. By trajectory analysis, we categorized the diffusion modes of NRs near the patterned wall with varied nonuniformities into three types: Fickian diffusion, desorption-mediated flight, and in-plane diffusion. Furthermore, energy analysis based on the adsorption–desorption mechanism has demonstrated that the three diffusion states are driven by interactions between the NR and the wall, which are primarily influenced by rotational diffusion. These results could significantly deepen the understanding of anisotropic nanoparticle interfacial diffusion and would provide new insights into the transport mechanisms of nanoparticles within confined environments.