文献类型：期刊文献

英文题名：Surface Reconstruction for Forming the [IrO6]-[IrO6] Framework: Key Structure for Stable and Activated OER Performance in Acidic Media

作者：Ma, Cheng-Long[1];Wang, Zhi-Qiang[2,3];Sun, Wei[4];Cao, Li-Mei[1];Gong, Xue-Qing[2,3];Yang, Ji[1]

机构：[1]East China Univ Sci & Technol, Sch Resources & Environm Engn, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Ctr Computat Chem, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[3]East China Univ Sci & Technol, Sch Chem & Mol Engn, Res Inst Ind Catalysis, Shanghai 200237, Peoples R China;[4]Hainan Univ, Coll Ecol & Environm, Haikou 570228, Hainan, Peoples R China

年份：2021

卷号：13

期号：25

起止页码：29654

外文期刊名：ACS APPLIED MATERIALS & INTERFACES

收录：;EI(收录号：20212910648418);WOS:【SCI-EXPANDED(收录号:WOS:000670430100039)】；

基金：We would like to thank the Shanghai Synchrotron Radiation Facility (SSFR, beamline BL14W1) and the National Synchrotron Radiation Laboratory (NSRL, Beamline BL11U) for providing beam time and the Research Center of Analysis and Test of East China University of Science and Technology for the help on material characterization analysis. Additional support was provided by Feringa Nobel Prize Scientist Joint Research Center.

语种：英文

外文关键词：oxygen evolution reaction; pyrochlore; surface reconstruction; Lu2Ir2O7; iridium-based derivatives

摘要：The surface reconstruction of iridium-based derivatives (A(x)Ir(y)O(z)) was extensively demonstrated to have an excellent oxygen evolution reaction (OER) performance in an acidic medium. It is urgent to use various spectroscopy and computational methods to explore the electronic state changes in the surface reconstruction process. Herein, the underestimated Lu2Ir2O7 was synthesized and investigated. Four typical forms of electrochemistry impedance spectra involved in the reconstruction process revealed three dominating forms of reconstructed pyrochlore in the OER stage, including the inner intact pyrochlore, mid metastable [IrO6]-[IrO6] framework, and the outer collapse amorphous layer. The enhancing electron transport efficiency of the corner-shared [IrO6]-[IrO6] framework was revealed as a critical role in acidic systems. The density of state (DOS) for the constructed [IrO6]-[IrO6] framework corroborated the enhancement of Ir-O hybridization and the downshift of the d-band center. Additionally, we contrast the pristine and reconstruction properties of the Pr2Ir2O7, Eu2Ir2O7, and Lu2Ir2O7 in alkaline and acidic media. The DOS and the XANES results reveal the scale relationship between the O 2p band center and the intrinsic activity for bulk pyrochlore in alkaline media. The highest O 2p center and the highest Ir-O hybridization of Lu2Ir2O7 exhibited the best OER performance among the Ir-based pyrochlore, up to a ninefold improvement in Ir-mass activity compared to IrO2. Our findings emphasize the electrochemical behavior of the reconstruction process for activated water-splitting performance.