The charge state of surfaces in contact with aqueous electrolytes is crucial for the performance and stability of dielectric surfaces in general and lyophobic colloids in particular. Thus far the role of adsorbed molecular CO2 remained largely unexplored. The aim of the present investigation is to study the de-charging and re-charging for two model surfaces upon addition of CO2 and/or 1:1 electrolytes (NaCl, HCl) under precisely controlled boundary conditions up to millimolar concentrations of additives. Starting from the salt- and CO2-free state, the ζ-potential magnitudes drop linearly with the logarithm of the CO2-concentrations over several orders of magnitude in CO2-concentrations. Hydrophobic Polystyrene nearly fully discharges, hydrophilic SiO2 reveals a 60% charge reduction. From the surface specific effects of instead adding NaCl or HCl, we discriminate and parameterize empirically the relative contribution of three individual mechanisms for decreasing the ζ-potential magnitudes (screening, pH-driven charge regulation, dielectric charge regulation) combining during CO2-addition. Moreover, depending on the achieved CO2-induced de-charging, the behavior upon subsequent addition of NaCl and HCl switches between two limiting cases. Screening dominates for surfaces in the native state without CO2, but a significant re-charging is observed for surfaces conditioned under excess CO2-concentrations.
Keywords: Adsorption; Charge state; Dielectric surfaces; Zeta potentials.
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