Half-metallization Atom-Fingerprints Achieved at Ultrafast Oxygen-Evaporated Pyrochlores for Acidic Water Oxidation.

ABSTRACT

The stability and catalytic activity of acidic oxygen evolution reaction (OER) are strongly determined by the coordination states and spatial symmetry among metal sites at catalysts. Herein, an ultrafast oxygen evaporation technology to rapidly soften the intrinsic covalent bonds using ultrahigh electrical pulses is suggested, in which prospective charged excited states at this extreme avalanche condition can generate a strong electron-phonon coupling to rapidly evaporate some coordinated oxygen (O) atoms, finally leading to a controllable half-metallization feature. Simultaneously, the relative metal (M) site arrays can be orderly locked to delineate some intriguing atom-fingerprints at pyrochlore catalysts, where the coexistence of metallic bonds (M─M) and covalent bonds (M─O) at this symmetry-breaking configuration can partially restrain crystal field effect to generate a particular high-spin occupied state. This half-metallization catalyst can effectively optimize the spin-related reaction kinetics in acidic OER, giving rise to 10.3 times (at 188 mV overpotential) reactive activity than pristine pyrochlores. This work provides a new understanding of half-metallization atom-fingerprints at catalyst surfaces to accelerate acidic water oxidation.