Kinetics and mechanism of heterogeneous voltage-driven water-dissociation catalysis

The water-dissociation (WD) reaction (H2O -> H+ + OH-) affects the rates of electrocatalytic reactions and the performance of bipolar membranes (BPMs), but how WD is driven by voltage and catalyzed is not understood. We report BPM electrolyzers with two reference electrodes (REs) to measure temperature-dependent WD current and overpotential (eta(wd)) without soluble electrolyte. Using TiO2-P25-nanoparticle catalyst and Arrhenius-type analysis, we found E-a,E-wd of 25-30 kJ/mol, independent of eta(wd), and a pre-exponential factor proportional to eta(wd) that decreases similar to 10-fold in D2O. We propose a new WD mechanism where metal-oxide nanoparticles, polarized by the BPM-junction voltage, serve as proton (1) acceptors (from water) on the negatively charged side of the particle to generate free OH-, (2) donors on the positively charged side to generate H3O+, and (3) surface proton conductors that connect spatially separate donor/acceptor sites. Increasing electric field with hwd orients water for proton transfer, increasing the pre-exponential factor, but is insufficient to lower E-a.