Bridging Macroscopic Diffusion and Microscopic Cavity Escape of Brownian and Active Particles in Irregular Porous Networks

While irregular and geometrically complex pore networks are ubiquitous in nature and industrial processes, there is no universal model describing nanoparticle transport in these environments. 3D super-resolution nanoparticle tracking was employed to study the motion of passive (Brownian) and active (self-propelled) species within complex networks, and universally identified a mechanism involving successive cavity exploration and escape. In all cases, the long-time ensemble-averaged diffusion coefficient was proportional to a quantity involving the characteristic length scale and time scale associated with microscopic cavity exploration and escape (<i>D</i> ∼ <i>r</i>²/<i>t</i>_trap), where the proportionality coefficient reflected the apparent porous network connectivity. For passive nanoparticles, this coefficient was always lower than expected theoretically for a random walk, indicating reduced network accessibility. In contrast, the coefficient for active nanomotors, in the same pore spaces, aligned with the theoretical value, suggesting that active particles navigate "intelligently" in porous environments, consistent with kinetic Monte Carlo simulations in networks with variable pore sizes. These findings elucidate a model of successive cavity exploration and escape for nanoparticle transport in porous networks, where pore accessibility is a function of motive force, providing insights relevant to applications in filtration, controlled release, and beyond.