Adsorption of fluids in a pore with chemical heterogeneities: The cooperative effect

In this work, we study the cooperative adsorption of fluids in a heterogeneous pore, in which the pore walls are composed of homogeneous substrates with chemical groups (CGs) decorating them. The adsorption caused by the homogeneous substrates alone and that by CGs do not add up to the overall adsorption, indicating the existence of a cooperative effect. The cooperative effect is the source of cooperative adsorption, and is characterized in this work by the ratio of the overall adsorption to the sum of adsorption by the substrate only and that by CGs. It is found that the cooperative adsorption does not depend monotonically on the substrate or the CGs. Two different origins of the cooperative adsorption play different roles depending on which one dominates the overall adsorption. Our simulations reveal that, when the homogeneous substrate dominates the overall adsorption, weakening of the attractive fluid-substrate interaction or alternatively strengthening of the fluid-CGs interaction leads to a stronger cooperative effect and enhances the cooperative adsorption. However, when CGs dominate the overall adsorption, weakening of the attractive fluid-CG interaction or strengthening the fluid-substrate interaction results in strong cooperative adsorption. In order to investigate the effects of the distribution of CGs on cooperative adsorption, a design-test method is generalized and used in this work. Simulation results show that the overall adsorption can be significantly affected by the CG distribution.