Bipolar Membranes Via Divergent Synthesis: On the Interplay between Ion Exchange Capacity and Water Dissociation Catalysis

Bipolar membranes (BPMs) enable the operation of electrochemical reactors with electrode compartments in different chemical environments or pH. The transport properties at the microscopic scale are dictated by the composition and morphology of the interfacial junctions as well as the specific chemistry of the ion-exchange layers that support the current of protons and hydroxide ions. This work elucidates the relation between water-dissociation efficiency and the physicochemical properties of the individual ion-exchange membrane layers in the poly(styrene-<i>b</i>-poly(ethylene-<i>ran</i>-butylene)-<i>b</i>-polystyrene) (SEBS)-based BPM. The optimal water dissociation performance of three previously reported water-dissociation catalysts in the SEBS-based BPM was examined, with junction thickness of graphene oxide > TiO₂ > SnO₂, resulting in disparate junction morphologies at the BPM's interface. A hybrid junction system, which included both the effective water dissociation catalyst SnO₂ and direct contacting of the ion-exchange membrane layer, exhibited high water dissociation efficiency. This was likely due to the immediate ion transport pathway provided by direct membrane contact around the catalyst, which also improved the interfacial adhesion. A higher ion exchange capacity (IEC) in BPMs substantially enhanced the water dissociation performance in BPMs without water-dissociation catalysts. However, the incorporation of the effective SnO₂ catalyst into the BPMs with a lower IEC significantly improved performance, an effect attributed to the hybrid junction system. Additionally, the increase in water uptake and ion conductivity of the cation exchange layer with higher IEC suggested that the cation exchange layer and its interface to the water-dissociation catalyst layer may play a key role in water dissociation. This study identifies the key parameters of individual BPM components and their interactions to water dissociation performance, offering new insights to guide in the construction of future BPMs optimized for enhanced water dissociation efficiency at high current densities.