Gradual Morphological Tuning in Polymer Microspheres via Pickering Emulsion Synthesis: Architecture-Controlled Dye...

Polymeric microspheres synthesized via Pickering emulsion polymerization offer structural tunability, making them attractive platforms for dye adsorption. This study investigates the adsorption behavior of methylene blue onto two classes of polymeric microspheres-poly(methacrylic acid) crosslinked with ethylene glycol dimethacrylate (PM), containing both micro- and nanopores, and poly(methacrylic acid) crosslinked with divinylbenzene (PD), containing only nanopores. The adsorption kinetics were modeled using a dual-process approach that distinguishes between diffusion-controlled transport and surface-controlled kinetic adsorption. We quantified the relative contributions of these mechanisms and correlated them with particle architecture. In the PM particles, diffusion plays a significant role in smaller particles with larger macropores, enabling methylene blue to penetrate the interior. As the particle size increased and macroporosity decreased, adsorption becomes increasingly dominated by surface kinetics. In contrast, PD particles -which lack macropores-showed the opposite trend: smaller particles were primarily governed by fast surface adsorption, while in larger particles, diffusion through nanopores became increasingly relevant. Correlation analysis between adsorption rate constants and structural parameters such as particle diameter and pore sizes revealed strong, opposing trends. In PD particles, a near-perfect inverse correlation was observed between the diffusion and kinetic components, indicating competitive suppression, where the dominance of one mechanism limited the contribution of the other. These results demonstrated that internal pore architecture played a central role in controlling the adsorption mechanism. Tuning particle size and porosity allowed deliberate control over the balance between diffusion and surface kinetics, enabling the rational design of microparticle adsorbents with tailored uptake behavior for water purification and dye removal applications.