Oxygen reduction reaction induced pH-responsive chemo-mechanical hydrogel actuators

We describe and characterize elementary designs for electrochemical micro- and macro-scale chemomechanical hydrogel actuators. The actuation of a pH-sensitive cross-linked polyacrylic acid (PAA) hydrogel is driven in the model devices through the oxygen reduction reaction (ORR) occurring at the electrodes of an embedded Au mesh micro-electrochemical array. Proton consumption by the ORR at the cathode of the embedded electrochemical cell leads to the formation of a localized pH gradient that in turn drives the strain response in the composite actuators. The dynamics result from the ionization of the carboxylic acid moieties of the PAA network in the high pH region, yielding an osmotic pressure that drives a volumetric expansion due to water imbibition. This system actuates both stably and reversibly; when the electrochemically-induced ORR is halted, the localized pH gradient dissipates due to diffusive mixing, which in turn relaxes the induced strains. Two approaches to the fabrication of hydrogel actuators were examined in this work. The first method adopted a design based on small flagella (∼0.2 mm × 1.5 mm × 60 μm, width × length × height) in which the actuating PAA structures are molded atop a set of fixed electrodes mounted on a supporting substrate. These hydrogel actuators show fast, large-amplitude, and largely reversible responses in the ORR mediated chemomechanical dynamics. We also investigated larger hydrogel actuators (∼4.5 mm × 11 mm × 1 mm, width × length × height), based on an autonomous design that embeds an open mesh stretchable micro-electrode array within the hydrogel. The significant and design-dependent impacts of mass transfer on the chemomechanical dynamics are evidenced in each case, a feature examined to elucidate more efficient mesoscopic design rules for actuators of this form.