Reversible perovskite electrocatalysts for oxygen reduction/oxygen evolution.

The identification of electrocatalysts mediating both the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are prerequisite for the development of reversible fuel cells and rechargeable metal-air batteries. The question remains as to whether a bifunctional catalyst, or a single catalyst site, will exhibit potentials converging to +1.23 VRHE. Transition metal-based perovskites provide tunable catalysts where site substitution can influence both ORR and OER, however substitution in the pseudo-binary phases results in an anti-correlation in ORR and OER activities. We reveal that La x Mn y Ni1-y O3-δ , compositions with lanthanum A-site sub-stoichiometry exhibit reversible activity correlating with the appearance of the Mn3+/Mn4+ redox couple. The Mn3+/Mn4+ couple is associated with Mn4+ co-existing with Mn3+ in the bulk, as La3+ is substituted by Ni2+ at the A-site to create a mixed valent system. We also show that a direct A-site substitution by the Ca2+ cation in La x Ca1-x Mn y O3-δ perovskites also results in the creation of Mn4+, the appearance of the Mn3+/Mn4+ redox couple, and a concomitant reversible activity. These results highlight a general strategy of optimizing oxide electrocatalysts with reversible activity.

Real-time tracking of metal nucleation via local perturbation of hydration layers.

The real-time visualization of stochastic nucleation events at electrode surfaces is one of the most complex challenges in electrochemical phase formation. The early stages of metal deposition on foreign substrates are characterized by a highly dynamic process in which nanoparticles nucleate and dissolve prior to reaching a critical size for deposition and growth. Here, high-speed non-contact lateral molecular force microscopy employing vertically oriented probes is utilized to explore the evolution of hydration layers at electrode surfaces with the unprecedented spatiotemporal resolution, and extremely low probe-surface interaction forces required to avoid disruption or shielding the critical nucleus formation. To the best of our knowledge, stochastic nucleation events of nanoscale copper deposits are visualized in real time for the first time and a highly dynamic topographic environment prior to the formation of critical nuclei is unveiled, featuring formation/re-dissolution of nuclei, two-dimensional aggregation and nuclei growth.Electrochemical deposition is important for industrial processes however, tracking the early stages of metallic phase nucleation is challenging. Here, the authors visualize the birth and growth of metal nuclei at electrode surfaces in real time via high-speed non-contact lateral molecular force microscopy.

Redox transitions in an electrolyte-free myoglobin fluid.

Redox responses associated with the heme prosthetic group in a myoglobin-polymer surfactant solvent-free liquid are investigated for the first time in the absence of an electrolyte solution. Cyclic voltammograms from the biofluid exhibit responses that are consistent with planar diffusion of mobile charges in the melt. Temperature-dependent dynamic electrochemical and rheological responses are rationalized in terms of the effective electron hopping rate between heme centers and the transport of intrinsic ionic species in the viscous protein liquid.