Screening highly active perovskites for hydrogen-evolving reaction via unifying ionic electronegativity descriptor.

Guan, Daqin; Zhou, Jing; Huang, Yu-Cheng; Dong, Chung-Li; Wang, Jian-Qiang; Zhou, Wei; Shao, Zongping · Nat Commun · 2019

basic_science · Level V

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Abstract

Facile and reliable screening of cost-effective, high-performance and scalable electrocatalysts is key for energy conversion technologies such as water splitting. ABO<sub>3-δ</sub> perovskites, with rich constitutions and structures, have never been designed via activity descriptors for critical hydrogen evolution reaction (HER). Here, we apply coordination rationales to introduce A-site ionic electronegativity (AIE) as an efficient unifying descriptor to predict the HER activities of 13 cobalt-based perovskites. Compared with A-site structural or thermodynamic parameter, AIE endows the HER activity with the best volcano trend. (Gd<sub>0.5</sub>La<sub>0.5</sub>)BaCo<sub>2</sub>O<sub>5.5+δ</sub> predicted from an AIE value of ~2.33 exceeds the state-of-the-art Pt/C catalyst in electrode activity and stability. X-ray absorption and computational studies reveal that the peak HER activities at a moderate AIE value of ~2.33 can be associated with the optimal electronic states of active B-sites via inductive effect in perovskite structure (~200 nm depth), including Co valence, Co-O bond covalency, band gap and O 2p-band position.