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Oxygen evolution reaction (OER) under acidic conditions becomes of significant importance for the practical use of a proton exchange membrane (PEM) water electrolyzer. In particular, maximizing the mass activity of iridium (Ir) is one of the maiden issues. Herein, the authors discover that the Ir‐doped calcium copper titanate (CaCu₃Ti₄O₁₂, CCTO) perovskite exhibits ultrahigh mass activity up to 1000 A gIr−1 for the acidic OER, which is 66 times higher than that of the benchmark catalyst, IrO2. By substituting Ti with Ir in CCTO, metal‐oxygen (M‐O) covalency can be significantly increased leading to the reduced energy barrier for charge transfer. Further, highly polarizable CCTO perovskite referred to as "colossal dielectric", possesses low defect formation energy for oxygen vacancy inducing a high number of oxygen vacancies in Ir‐doped CCTO (Ir‐CCTO). Electron transfer occurs from the oxygen vacancies and Ti to the substituted Ir consequentially resulting in the electron‐rich Ir and ‐deficient Ti sites. Thus, favorable adsorptions of oxygen intermediates can take place at Ti sites while the Ir ensures efficient charge supplies during OER, taking a top position of the volcano plot. Simultaneously, the introduced Ir dopants form nanoclusters at the surface of Ir‐CCTO, which can boost catalytic activity for the acidic OER. [ABSTRACT FROM AUTHOR]

Abstract Oxygen evolution reaction (OER) under acidic conditions becomes of significant importance for the practical use of a proton exchange membrane (PEM) water electrolyzer. In particular, maximizing the mass activity of iridium (Ir) is one of the maiden issues. Herein, the authors discover that the Ir‐doped calcium copper titanate (CaCu₃Ti₄O₁₂, CCTO) perovskite exhibits ultrahigh mass activity up to 1000 A gIr−1 for the acidic OER, which is 66 times higher than that of the benchmark catalyst, IrO2. By substituting Ti with Ir in CCTO, metal‐oxygen (M‐O) covalency can be significantly increased leading to the reduced energy barrier for charge transfer. Further, highly polarizable CCTO perovskite referred to as “colossal dielectric”, possesses low defect formation energy for oxygen vacancy inducing a high number of oxygen vacancies in Ir‐doped CCTO (Ir‐CCTO). Electron transfer occurs from the oxygen vacancies and Ti to the substituted Ir consequentially resulting in the electron‐rich Ir and ‐deficient Ti sites. Thus, favorable adsorptions of oxygen intermediates can take place at Ti sites while the Ir ensures efficient charge supplies during OER, taking a top position of the volcano plot. Simultaneously, the introduced Ir dopants form nanoclusters at the surface of Ir‐CCTO, which can boost catalytic activity for the acidic OER.

Development of efficient and stable electrocatalysts for oxygen evolution reaction (OER) under acidic conditions is desirable goal for commercializing proton exchange membrane (PEM) water electroyzer. Herein, we report iridium-doped hydrogenated titanate (Ir–HTO) nanobelts as a promising catalyst with a low-Ir content for the acidic OER. Addition of low-Ir (∼ 3.36 at%) into the single-crystalline HTO nanobelts with large exposed {100} facets significantly boost catalytic activity and stability for OER under acidic conditions. The Ir-HTO outperforms the commercial benchmark IrO 2 catalyst; an overpotential for delivering 10 mA cm−2 current density was reduced to about 25% for the Ir-HTO. Moreover, the catalytic performance of Ir-HTO is positioned as the most efficient electrocatalyst for the acidic OER. An improved intrinsic catalytic activity and stability are also confirmed for the Ir-HTO through in-depth electrochemical characterizations. Therefore, our results suggest that low-Ir doped single-crystalline HTO nanobelts can be a promising catalyst for efficient and durable OER under acidic conditions. • We developed an Ir-doped catalyst for the acidic oxygen evolution reaction (OER). • Ir was incorporated into a H 2 Ti 3 O 7 nanobelts (Ir–HTO) with large exposed {100} facets. • The single-crystalline nature of HTO increased the active sites for the OER. • The Ir-HTO nanobelts have a low Ir content (about 3–4 wt%) at the atomic scale. • The Ir-HTO nanobelts have high catalytic activity and durability for acidic OER. [ABSTRACT FROM AUTHOR]

Oxygen evolution reaction (OER) under acidic conditions becomes of significant importance for the practical use of a proton exchange membrane (PEM) water electrolyzer. In particular, maximizing the mass activity of iridium (Ir) is one of the maiden issues. Herein, the authors discover that the Ir-doped calcium copper titanate (CaCu₃Ti₄O₁₂, CCTO) perovskite exhibits ultrahigh mass activity up to 1000 A g Ir -1 for the acidic OER, which is 66 times higher than that of the benchmark catalyst, IrO 2 . By substituting Ti with Ir in CCTO, metal-oxygen (M-O) covalency can be significantly increased leading to the reduced energy barrier for charge transfer. Further, highly polarizable CCTO perovskite referred to as "colossal dielectric", possesses low defect formation energy for oxygen vacancy inducing a high number of oxygen vacancies in Ir-doped CCTO (Ir-CCTO). Electron transfer occurs from the oxygen vacancies and Ti to the substituted Ir consequentially resulting in the electron-rich Ir and -deficient Ti sites. Thus, favorable adsorptions of oxygen intermediates can take place at Ti sites while the Ir ensures efficient charge supplies during OER, taking a top position of the volcano plot. Simultaneously, the introduced Ir dopants form nanoclusters at the surface of Ir-CCTO, which can boost catalytic activity for the acidic OER., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)