From pixels to pores: 3D-(im)printed hierarchically porous polymer monoliths

Bridging molecular recognition with scalable materials is a central challenge in polymer science. Here, we present the first comprehensive characterization of LCD-based 3D-printed molecularly imprinted polymers (3DMIPs) with digitally programmable macrogeometries and tunable hierarchical porosity, revealing their optimization potential. As a case study, 3DMIPs targeting the specific enrichment of cannabidiol (CBD) are demonstrated. A highly porous lattice yields a 10.3-fold CBD enrichment, an imprinting factor of 3.7, and a CBD uptake of 1.65 mg/g, outperforming a coarser analog. Imaging and porosimetry reveal the pore architecture, pore interconnectivity, and pore size distribution, which, together with the macrogeometry, critically influence mass transfer and binding efficiency in these functional 3D materials. The 3DMIPs exhibit excellent thermal stability, highlighting suitability for practical applications. This work addresses the trade-off between molecular recognition, scalability, and design freedom, positioning 3DMIPs as a promising candidate for various applications, such as purifying health-promoting substances from complex plant matrices.