Chen Gao, Zhu Yanping, Chen Hao Ming, Hu Zhiwei, Hung Sung-Fu, Ma Nana, Dai Jie, Lin Hong-Ji, Chen Chien-Te, Zhou Wei, Shao Zongping
State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, Nanjing, 210009, China.
Department of Chemistry, National Taiwan University, Taipei, 106, Taiwan.
Adv Mater. 2019 Jul;31(28):e1900883. doi: 10.1002/adma.201900883. Epub 2019 May 17.
Rationally designing active and durable catalysts for the oxygen evolution reaction (OER) is of primary importance in water splitting. Perovskite oxides (ABO ) with versatile structures and multiple physicochemical properties have triggered considerable interest in the OER. The leaching of A site cations can create nanostructures and amorphous motifs on the perovskite matrix, thus facilitating the OER process. However, selectively dissolving A site cations and simultaneously obtaining more active amorphous motifs derived from the B site cations remains a great challenge. Herein, a top-down strategy is proposed to transform bulk crystalline perovskite (LaNiO ) into a nanostructured amorphous hydroxide by FeCl post-treatment, resulting in an extremely low overpotential of 189 mV at 10 mA cm . The top-down-constructed amorphous catalyst with a large surface area has dual NiFe active sites, where high-valence Ni -based edge-sharing octahedral frameworks are surrounded by interstitial distorted Fe octahedra and contribute to the superior OER performance. This top-down strategy provides a valid way to design novel perovskite-derived catalysts.
合理设计用于析氧反应(OER)的活性和耐用催化剂在水分解中至关重要。具有多样结构和多种物理化学性质的钙钛矿氧化物(ABO₃)引发了人们对OER的极大兴趣。A位阳离子的浸出可以在钙钛矿基体上产生纳米结构和无定形图案,从而促进OER过程。然而,选择性溶解A位阳离子并同时获得更多源自B位阳离子的活性无定形图案仍然是一个巨大的挑战。在此,提出了一种自上而下的策略,通过FeCl₃后处理将块状结晶钙钛矿(LaNiO₃)转变为纳米结构的无定形氢氧化物,在10 mA cm⁻²的电流密度下产生了极低的189 mV过电位。这种自上而下构建的具有大表面积的无定形催化剂具有双NiFe活性位点,其中高价Ni基边共享八面体框架被间隙扭曲的Fe八面体包围,这有助于实现优异的OER性能。这种自上而下的策略为设计新型钙钛矿衍生催化剂提供了一种有效的方法。