Polyelectrolyte (PE) hydrogels are ubiquitous in nature.
Tailoring
the interactions between PE gels and salt provides versatile implements
to overcome their critical drawbacks such as weak and brittle nature.
Adding salts to PE gels introduces both counterions and co-ions, and
the variations of PE chain conformations and their macroscopic properties
have been mainly attributed to the interplay between PE charged groups
and their counterions, yet the role of co-ions is generally ignored.
This work demonstrates that by changing co-ion species with larger
atomic sizes, monovalent haloids are capable of triggering the phase
separation of common poly(acrylic acid) single network (PAAc-SN) hydrogels
into polymer-sparse and polymer-rich regions, accompanied by remarkable
enhancement in strength and toughness. The capabilities of co-ions
inducing phase separation of PAAc-SN gels follow a reverse Hofmeister
series: Cl– < Br– < I–. Due to the enhanced polymer–polymer interactions
and viscoelastic energy dissipation, the phase-separated PAAc-SN gels
exhibit exceptional mechanical properties, with fracture stress and
tearing energy of 96.7-folds and 1636-folds larger than those of the
as-prepared gels, respectively. The largest fracture stress and tearing
energy reach 8.8 ± 1.3 MPa and 29.8 ± 2.4 kJ/m2, exceeding most state-of-the-art PE hydrogels. A combination of
FTIR, 1H NMR, and all-atom molecular dynamics simulations
reveals that the reverse Hofmeister series-aided phase separation
originates from changes of network chain conformation through the
following influences rooted in the larger size of co-ions: (i) enhancing
hydrophobic polymer–polymer interactions; (ii) accelerating
the ion pair formation between carboxyl groups and their sodium counterions.
These results not only provide a new method for hydrogel strengthening
and toughening but also emphasize the significant role of co-ions
in tuning the properties of PE gels.