PO几何构型单元增强了CoO在酸性析氧反应中的电催化性能。
PO geometric configuration unit enhanced electrocatalytic performance of CoO in acidic oxygen evolution.
作者信息
Shang Fanfan, He Huijie, Li Peng, Cai Hairui, An Bei, Li Xiaoqian, Yang Shengchun, Sun Zhanbo, Wang Bin
机构信息
MOE Key Laboratory for Non-equilibrium Synthesis and Modulation of Condensed Matter, Key Laboratory of Shaanxi for Advanced Materials and Mesoscopic Physics, State Key Laboratory for Mechanical Behavior of Materials, School of Physics, Xi'an Jiaotong University, No. 28 West Xianning Road, Xi'an 710049, China.
MOE Key Laboratory for Non-equilibrium Synthesis and Modulation of Condensed Matter, Key Laboratory of Shaanxi for Advanced Materials and Mesoscopic Physics, State Key Laboratory for Mechanical Behavior of Materials, School of Physics, Xi'an Jiaotong University, No. 28 West Xianning Road, Xi'an 710049, China; National Innovation Platform (Center) for Industry-Education Integration of Energy Storage Technology, Xi'an Jiaotong University, No. 28 West Xianning Road, Xi'an 710049, China; Shaanxi Collaborative Innovation Center for Hydrogen Fuel Cell PerformanceImprovement, Xi'an Jiaotong University, No. 28 West Xianning Road, Xi'an 710049, China.
出版信息
J Colloid Interface Sci. 2023 Jul;641:329-337. doi: 10.1016/j.jcis.2023.03.036. Epub 2023 Mar 13.
It is challenging to develop high-efficient and stable nonprecious metal-based electrocatalyst for oxygen evolution reaction (OER) in acid for proton exchange membrane (PEM) water splitting. Herein, P atoms were introduced into the lattice of spinel CoO (P-CoO) to replace with octahedral coordinated Co via a hydrothermal process following a thermal treatment. The formation of PO geometric configuration unit in CoO can trigger electron rearrangement around Co ions, which resulted in the high-active Co site on the surface, significantly decreasing the energy barrier of rate-determining step for OER. Moreover, the weaker covalency of the Co 3d-O 2p bond and higher formation energy of oxygen vacancy around Co in P-CoO inhibited the participation of lattice oxygen during OER process, enabling that P-CoO can work stably in acidic media. The obtained P-CoO afforded satisfying stability over 30 h in a PEM electrolysis device with an overpotential of 400 mV@10 mA/cm in 0.1 M HClO.
开发用于质子交换膜（PEM）水电解中酸性析氧反应（OER）的高效稳定非贵金属基电催化剂具有挑战性。在此，通过热处理后的水热过程将P原子引入尖晶石CoO（P-CoO）的晶格中，以取代八面体配位的Co。CoO中PO几何构型单元的形成可引发Co离子周围的电子重排，从而在表面产生高活性Co位点，显著降低OER速率决定步骤的能垒。此外，P-CoO中Co 3d-O 2p键较弱的共价性以及Co周围氧空位较高的形成能抑制了OER过程中晶格氧的参与，使得P-CoO能够在酸性介质中稳定工作。所制备的P-CoO在PEM电解装置中于0.1 M HClO中在10 mA/cm²下过电位为400 mV时，在30 h以上表现出令人满意的稳定性。
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