| 1 | Correlating the electronic structure of perovskite La_(1-x)SrxCoO_(3) with activity for the oxygen evolution reaction:The critical role of Co 3d hole state显示文摘Perovskite LaCoO_(3) is being increasingly explored as an effective low-cost electrocatalyst for the oxygen evolution reaction(OER).Sr doping in LaCoO_(3)(La1-xSrxCoO_(3))has been found to substantially increase its catalytic activity.In this work,we report a detailed study on the evolution of the electronic structure of La1-xSrxCoO_(3) with 0≤x≤1 and its correlation with electrocatalytic activity for the OER.A combination of X-ray photoemission spectroscopy(XPS)and X-ray absorption spectroscopy(XAS)was used to unravel the electronic density of states(DOS)near the Fermi level(EF),which provide insights into the key electronic structure features for the enhanced OER catalytic activity.Detailed analysis on the Co L-edge XAS suggest that LaCoO_(3) has a low spin state with t_(2g)^(6) e_(g)^(0) configuration at room temperature.This implies that the high OER catalytic activity of LaCoO_(3) should not be rationalized by the occupancy of eg=1 descriptor.Substituting Sr^(2+) for La^(3+) in LaCoO_(3) induces Co4+oxidation states and effectively dopes hole states into the top of valence band.A semiconductor-to-metal transition is observed for x>0.2,due to the holeinduced electronic DOS at the EF and increased hybridization between Co 3 d and O 2 p.Such an electronic modulation enhances the surface adsorption of the*OH intermediate and reduces the energy barrier for interfacial charge transfer,thus improving the OER catalytic activity in La_(1-x)Sr_(x)CoO_(3).In addition,we found that the La_(1-x)Sr_(x)CoO_(3) surface undergoes amorphization after certain period of OER measurement,leading to a partial deactivation of the electrocatalyst.High Sr doping levels accelerated the amorphization process. | Zechao Shen Mei Qu Jueli Shi Freddy E.Oropeza Victor A.de la Peña O’Shea Giulio Gorni C.M.Tian Jan P.Hofmann Jun Cheng Jun Li Kelvin H.L.Zhang | 2022 | Journal of Energy Chemistry2022，31，2： | 1 |
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