Zhao Jia-Wei, Li Cheng-Fei, Shi Zi-Xiao, Guan Jie-Lun, Li Gao-Ren
MOE Laboratory of Bioinorganic and Synthetic Chemistry, The Key Lab of Low-Carbon Chemistry & Energy Conservation of Guangdong Province, School of Chemistry, Sun Yat-sen University, Guangzhou 510275, China.
Research (Wash D C). 2020 Jul 10;2020:6961578. doi: 10.34133/2020/6961578. eCollection 2020.
In the process of oxygen evolution reaction (OER) on perovskite, it is of great significance to accelerate the hindered lattice oxygen oxidation process to promote the slow kinetics of water oxidation. In this paper, a facile surface modification strategy of nanometer-scale iron oxyhydroxide (FeOOH) clusters depositing on the surface of LaNiO (LNO) perovskite is reported, and it can obviously promote hydroxyl adsorption and weaken Ni-O bond of LNO. The above relevant evidences are well demonstrated by the experimental results and DFT calculations. The excellent hydroxyl adsorption ability of FeOOH-LaNiO (Fe-LNO) can obviously optimize OH filling barriers to promote lattice oxygen-participated OER (LOER), and the weakened Ni-O bond of LNO perovskite can obviously reduce the reaction barrier of the lattice oxygen participation mechanism (LOM). Based on the above synergistic catalysis effect, the Fe-LNO catalyst exhibits a maximum factor of 5 catalytic activity increases for OER relative to the pristine perovskite and demonstrates the fast reaction kinetics (low Tafel slope of 42 mV dec) and superior intrinsic activity (TOFs of ~40 O S at 1.60 V vs. RHE).
在钙钛矿上的析氧反应（OER）过程中，加速受阻的晶格氧氧化过程以促进水氧化的缓慢动力学具有重要意义。本文报道了一种在LaNiO（LNO）钙钛矿表面沉积纳米级羟基氧化铁（FeOOH）簇的简便表面修饰策略，它能明显促进羟基吸附并削弱LNO的Ni-O键。上述相关证据通过实验结果和DFT计算得到了很好的证明。FeOOH-LaNiO（Fe-LNO）优异的羟基吸附能力能明显优化OH填充势垒以促进晶格氧参与的OER（LOER），而LNO钙钛矿中被削弱的Ni-O键能明显降低晶格氧参与机制（LOM）的反应势垒。基于上述协同催化作用，Fe-LNO催化剂相对于原始钙钛矿，OER的催化活性提高了最大5倍，表现出快速的反应动力学（低塔菲尔斜率为42 mV dec）和优异的本征活性（在1.60 V vs. RHE下TOFs约为40 O S）。
