Guan Daqin, Ryu Gihun, Hu Zhiwei, Zhou Jing, Dong Chung-Li, Huang Yu-Cheng, Zhang Kaifeng, Zhong Yijun, Komarek Alexander C, Zhu Ming, Wu Xinhao, Pao Chih-Wen, Chang Chung-Kai, 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, 211800, China.
Max-Planck-Institute for Chemical Physics of Solids, Nöthnitzer Str. 40, Dresden, 01187, Germany.
Nat Commun. 2020 Jul 6;11(1):3376. doi: 10.1038/s41467-020-17108-5.
Ion leaching from pure-phase oxygen-evolving electrocatalysts generally exists, leading to the collapse and loss of catalyst crystalline matrix. Here, different from previous design methodologies of pure-phase perovskites, we introduce soluble BaCl and SrCl into perovskites through a self-assembly process aimed at simultaneously tuning dual cation/anion leaching effects and optimizing ion match in perovskites to protect the crystalline matrix. As a proof-of-concept, self-assembled hybrid BaSrCoFeO (BSCF) nanocomposite (with BaCl and SrCl) exhibits the low overpotential of 260 mV at 10 mA cm in 0.1 M KOH. Multiple operando spectroscopic techniques reveal that the pre-leaching of soluble compounds lowers the difference of interfacial ion concentrations and thus endows the host phase in hybrid BSCF with abundant time and space to form stable edge/face-sharing surface structures. These self-optimized crystalline structures show stable lattice oxygen active sites and short reaction pathways between Co-Co/Fe metal active sites to trigger favorable adsorption of OH species.
从纯相析氧电催化剂中离子浸出普遍存在,这会导致催化剂晶体基质的坍塌和损失。在此,与之前纯相钙钛矿的设计方法不同,我们通过自组装过程将可溶性BaCl和SrCl引入钙钛矿中,旨在同时调节双阳离子/阴离子浸出效应并优化钙钛矿中的离子匹配,以保护晶体基质。作为概念验证,自组装的混合BaSrCoFeO(BSCF)纳米复合材料(含有BaCl和SrCl)在0.1 M KOH中,在10 mA cm时表现出260 mV的低过电位。多种原位光谱技术表明,可溶性化合物的预浸出降低了界面离子浓度的差异,从而赋予混合BSCF中的主体相充足的时间和空间来形成稳定的边/面共享表面结构。这些自优化的晶体结构显示出稳定的晶格氧活性位点以及Co-Co/Fe金属活性位点之间的短反应路径,以触发对OH物种的有利吸附。