Three-dimensional pore networks provide a critical structural link between carbon preparation and mass transport and adsorption behavior. However, their formation and functional roles cannot be fully resolved using two-dimensional images and bulk statistical descriptors. This study integrates in situ experiments, data analysis, and physical modeling to investigate pore evolution and coupled diffusion–adsorption mechanisms in porous carbons, focusing on pore formation, spatial connectivity, and their influence on molecular transport. In situ microscopy and quantitative morphological analysis identify the characteristic stages of pore nucleation, expansion, interconnection, and shrinkage during pyrolysis. Using 1,340 records of preparation conditions and pore properties, relationships between processing conditions and pore structural parameters are established. Gaussian random fields are coupled with phase-field simulations to construct hierarchical three-dimensional pore models. Experimental comparisons show that the generated structures reproduce the main features of measured pore size distributions, providing a spatial basis for analyzing pore connections, isolated pores, and local bottlenecks that are difficult to characterize using bulk descriptors. Voxel and pore-network models are further employed to simulate coupled CO₂ diffusion and adsorption, resolving the spatial concentration of local mass transport, molecular accessibility, and delayed gas-phase filling induced by wall adsorption. These simulations elucidate how pore architecture influences adsorption-site utilization under transient conditions. By linking material formation with transport through three-dimensional pore networks, this study provides a quantitative approach to understanding pore evolution and mass transport and adsorption mechanisms in porous carbons.
 

Porous carbon,Pore evolution,Three-dimensional modeling,phase-field model,Inverse design