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要旨

Producing indispensable hydrogen and oxygen for social development via water electrolysis shows more prospects than other technologies. Although electrocatalysts have been explored for centuries, a universal activity descriptor for both hydrogen-evolution reaction (HER) and oxygen-evolution reaction (OER) is not yet developed. Moreover, a unifying concept is not yet established to simultaneously understand HER/OER mechanisms. Here, the relationships between HER/OER activities in three common electrolytes and over ten representative material properties on 12 3d-metal-based model oxides are rationally bridged through statistical methodologies. The orbital charge-transfer energy (& UDelta;) can serve as an ideal universal descriptor, where a neither too large nor too small & UDelta; (& AP;1 eV) with optimal electron-cloud density around Fermi level affords the best activities, fulfilling Sabatier's principle. Systematic experiments and computations unravel that pristine oxide with & UDelta; & AP; 1 eV possesses metal-like high-valence configurations and active lattice-oxygen sites to help adsorb key protons in HER and induce lattice-oxygen participation in the OER, respectively. After reactions, partially generated metals in the HER and high-valence hydroxides in the OER dominate proton adsorption and couple with pristine lattice-oxygen activation, respectively. These can be successfully rationalized by the unifying orbital charge-transfer theory. This work provides the foundation of rational material design and mechanism understanding for many potential applications.
A universal activity descriptor (orbital charge-transfer energy) is successfully extracted from various materials' physicochemical properties for both hydrogen-evolving and oxygen-evolving reactions in multiple electrolytes. Systematic experiments and computations reveal the life-cycle HER and OER mechanisms and identify the unifying orbital charge-transfer theory as a powerful mechanism analysis tool and foundation.image