Developing durable non-noble-metal catalysts for acidic water oxidation remains challenging. Here, the authors show that neodymium doping stabilizes active Mn3+ species, enabling manganese oxide to op...

The local pH environment within bipolar membrane (BPM) junctions is complex and not well understood, yet it is important to control for advancing the performance of BPM-based electrochemical systems. We report a voltammetric strategy using an ultrathin Ni mesh pH probe to spatially resolve pH changes in the BPM junction during model BPM electrolyzer operation. Under reverse bias, we observe depletion of OH– at the anion-exchange layer (AEL) interface, with a degree diminishing with increasing distance from the AEL. These gradients correlate with current-dependent water dissociation (WD) and are modulated by the electric field and the surface charge state of the catalyst. By correlating spatial pH profiles with the surface-charging behavior of WD catalysts, we explore a mechanism of catalyst-mediated H+ and OH– transfer facilitated by hydrogen-bonding networks. These findings highlight the role of local chemistry and electrostatics in BPM performance and offer new methods to probe and engineer catalytic junctions in electrochemical energy devices.