Adsorption of polyelectrolytes to like-charged substrates induced by multivalent counterions as exemplified by poly(styrene sulfonate) and silica
文献信息
Plinio Maroni, Michal Borkovec
The present study demonstrates that multivalent counterions trigger adsorption of polyelectrolytes on a like-charged substrate. In particular, adsorption of polystyrene sulfonate on silica is studied experimentally in NaCl, MgCl2, and LaCl3 solutions by optical reflectivity. While adsorption is negligible in the presence of Na+, the polyelectrolyte adsorbs in the presence of Mg2+ and La3+. The adsorbed amount of the polyelectrolyte goes through a maximum as a function of the salt concentration. This maximum increases with increasing valence and shifts to lower salt concentrations. At low salt concentration, the adsorption is negligible. At intermediate salt level, ripening and multilayer formation leads to continuous growth of the adsorbed layer. At higher salt level, blocking and formation of a monolayer lead to saturation. These results are tentatively interpreted in terms of a charge reversal of the polyelectrolyte–metal complex. The molecular mass of the polyelectrolyte has an important effect on the adsorption behavior, whereby the tendency towards ripening becomes more pronounced at large molecular mass.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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