Computational Simulations of Adsorption Behavior of Anionic Surfactants at the Portlandite-Water Interface under...

The adsorption behaviors of two kinds of anionic surfactants (called HSO₄ and HPO₄, respectively) with different negatively charged hydrophilic head groups (sulfate and phosphate groups) under different concentrations of sulfate and calcium ions at the portlandite-water interface are investigated by molecular dynamics simulations. Although the adsorption strength of HPO₄ is much greater than that of HSO₄, the desorption energy of HSO₄ is slightly greater at an early stage of desorption due to a more perpendicular orientation and denser packing of hydrophobic tail chains. After adding ions, the sulfate ion has a significant weakening effect due to competitive adsorption, and the negative influence of the calcium ion is weaker, and it even slightly promotes the adsorption at low concentration. Due to the stronger electrostatic interaction of phosphate head groups with the portlandite surface, adsorption strength and adsorption stability for HPO₄ are always greater than that of HSO₄ under the interference of sulfate ions. The competitive adsorption of the sulfate ion significantly weakens the interaction of hydrophilic head groups with portlandite and the dense packing of two surfactants. The calcium ion with low concentration approaches the portlandite surface and acts as an ion bridge to slightly enhance the adsorption of the surfactant. The ion bridging effect is stronger in the HPO₄ system than in the HSO₄ system.