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通过氧-氧自由基耦合机制用于析氧反应的极其活跃且稳健的铱-锰双原子电催化剂

Extremely Active and Robust Ir-Mn Dual-Atom Electrocatalyst for Oxygen Evolution Reaction by Oxygen-Oxygen Radical Coupling Mechanism.

作者信息

Liu Wenbo, Long Guifa, Xiang Zhipeng, Ren Tianlu, Piao Jinhua, Wan Kai, Fu Zhiyong, Liang Zhenxing

机构信息

Guangdong Provincial Key Laboratory of Fuel Cell Technology, School of Chemistry and Chemical Engineering, South China University of Technology, 510641, Guangzhou, P. R. China.

Guangxi Key Laboratory of Chemistry and Engineering of Forest Products, School of Chemistry and Chemical Engineering, Guangxi Minzu University, 530008, Nanning, P. R. China.

出版信息

Angew Chem Int Ed Engl. 2024 Oct 21;63(43):e202411014. doi: 10.1002/anie.202411014. Epub 2024 Sep 12.

Abstract

A novel Ir-Mn dual-atom electrocatalyst is synthesized by a facile ion-exchange method by incorporating Ir in SrMnO, which yields an extremely high activity and stability for the oxygen evolution reaction (OER). The ion exchange process occurs in a self-limitation way, which favors the formation of Ir-Mn dual-atom in the IrMnO unit. The incorporation of Ir modulates the electronic structure of both Ir and Mn, thereby resulting in a shorter distance of the Ir-Mn dual-atom (2.41 Å) than the Mn-Mn dual-atom (2.49 Å). The modulated Ir-Mn dual-atom enables the same spin direction O (↑) of the adsorbed *O intermediates, thus facilitating the direct coupling of the two adsorbed *O intermediates to release O via the oxygen-oxygen radical coupling mechanism. Electrochemical tests reveal that the Ir-SrMnO exhibits a superior OER's activity with a low overpotential of 207 mV at 10 mA cm and achieves a mass specific activity of 1100 A g at 1.5 V. The proton-exchange-membrane water electrolyzer with the Ir-SrMnO catalyst exhibits a low electrolysis voltage of 1.63 V at 1.0 A cm and a stable 2000-h operation with a decay of only 15 μV h at 0.5 A cm.

摘要

通过一种简便的离子交换方法,将铱(Ir)掺入SrMnO中,合成了一种新型的Ir-Mn双原子电催化剂,该催化剂对析氧反应(OER)具有极高的活性和稳定性。离子交换过程以自限方式发生,有利于在IrMnO单元中形成Ir-Mn双原子。Ir的掺入调节了Ir和Mn的电子结构,从而导致Ir-Mn双原子的间距(2.41 Å)比Mn-Mn双原子的间距(2.49 Å)更短。调制后的Ir-Mn双原子使吸附的O中间体具有相同的自旋方向O(↑),从而促进两个吸附的O中间体通过氧-氧自由基偶联机制直接偶联以释放O。电化学测试表明,Ir-SrMnO在10 mA cm时具有207 mV的低过电位,表现出优异的OER活性,在1.5 V时实现了1100 A g的质量比活性。采用Ir-SrMnO催化剂的质子交换膜水电解槽在1.0 A cm时具有1.63 V的低电解电压,在0.5 A cm下稳定运行2000小时,衰减仅为15 μV h。

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