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High crystallinity design of Ir-based catalysts drives catalytic reversibility for water electrolysis and fuel cells.

ABSTRACT: The voltage reversal of water electrolyzers and fuel cells induces a large positive potential on the hydrogen electrodes, followed by severe system degradation. Applying a reversible multifunctional electrocatalyst to the hydrogen electrode is a practical solution. Ir exhibits excellent catalytic activity for hydrogen evolution reactions (HER), and hydrogen oxidation reactions (HOR), yet irreversibly converts to amorphous IrO_x at potentials > 0.8 V/RHE, which is an excellent catalyst for oxygen evolution reactions (OER), yet a poor HER and HOR catalyst. Harnessing the multifunctional catalytic characteristics of Ir, here we design a unique Ir-based electrocatalyst with high crystallinity for OER, HER, and HOR. Under OER operation, the crystalline nanoparticle generates an atomically-thin IrO_x layer, which reversibly transforms into a metallic Ir at more cathodic potentials, restoring high activity for HER and HOR. Our analysis reveals that a metallic Ir subsurface under thin IrO_x layer can act as a catalytic substrate for the reduction of Ir ions, creating reversibility. Our work not only uncovers fundamental, uniquely reversible catalytic properties of nanoparticle catalysts, but also offers insights into nanocatalyst design.

SUBMITTER: Lee WH

PROVIDER: S-EPMC8277764 | biostudies-literature |

REPOSITORIES: biostudies-literature

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