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双金属浸出诱导催化剂重构用于高活性和高稳定性电化学水氧化
Bimetal Leaching Induced Reconstruction of Water Oxidation Electrocatalyst for Enhanced Activity and Stability
【摘要】 析氧反应(OER)催化剂在催化反应过程中不可避免地会发生表面重构,这一过程使得设计、构筑高性能和高稳定性的OER电催化剂充满挑战。在此,我们采用双金属浸出诱导表面重构的策略,构建了高活性和高稳定性的水氧化电催化剂。在该策略中,通过水热、离子交换和后续的退火工艺处理,将由α-CoMoO4、K2Co2(MoO4)3、Co3O4和CoFe2O4四种氧化物晶相组成的材料阵列转换为OER预催化剂。原位电化学拉曼光谱和非原位X射线衍射(XRD)分析表明,其中的不稳定成分K2Co2(MoO4)3的快速溶解引发了Mo和K的适度浸出,从而在低电压下加速了表面富集的α-Co(OH)2向CoOOH活性相的转化。此外,CoFe2O4相耦合重构产生新相CoO与无定形层CoOOH,从而形成了CoFe2O4@CoO@CoOOH紧密的多相结构,起到了“纳米栅栏”的作用,可有效防止催化剂的过度重构,从而赋予重构后的催化剂优异的催化活性和稳定性。本工作为设计高电流密度下具有优异活性和稳定性的OER催化剂提供了新的思路。
【Abstract】 Surface reconstruction inevitably occurs during pre-catalysis for the oxygen evolution reaction(OER); however, obtaining OER electrocatalysts with high performance and stability remains a challenge. In this study, we have developed a bimetallic leaching-induced surface reconstruction strategy to fabricate efficient electrocatalysts for water oxidation. Microcolumn arrays consisting of α-CoMoO4, K2Co2(MoO4)3, Co3O4, and CoFe2O4 four-phase oxides were integrated as pre-catalyst by a hydrothermal, ion-exchange, and subsequent annealing process. In situ Raman spectroelectrochemical and ex situ X-ray diffraction(XRD) studies revealed that the rapid dissolution of the unstable component K2Co2(Mo O4)3 triggered the adaptive leaching of Mo and K, which accelerated the transformation of the surface-enriched α-Co(OH)2 to the active phase of CoOOH at low voltage. Furthermore, the stable CoFe2O4 component couples the reconfigured new phase CoO with the amorphous layer CoOOH to form a compact hierarchical structure of CoFe2O4@CoO@CoOOH, which plays the role of a nanofence and effectively prevents the catalyst from over-reconstruction, thus achieving excellent catalytic stability. This work provides a novel idea for designing OER catalysts with excellent activity and stability at high current densities.
【Key words】 Oxygen evolution reaction; Surface reconstruction; Ion leaching; Water splitting; Electrocatalysis; Catalyst;
- 【文献出处】 物理化学学报 ,Acta Physico-Chimica Sinica , 编辑部邮箱 ,2024年08期
- 【分类号】O643.36
- 【下载频次】6