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磁场增强的混合价态钴调制 LaCoO 催化剂上的电催化氧气析出。

Magnetic Field-Enhanced Electrocatalytic Oxygen Evolution on a Mixed-Valent Cobalt-Modulated LaCoO Catalyst.

机构信息

Key Laboratory of Functional Materials Physics and Chemistry of the Ministry of Education, Jilin Normal University, 130103, Changchun (P. R., China.

出版信息

Chemphyschem. 2023 Mar 14;24(6):e202200845. doi: 10.1002/cphc.202200845. Epub 2022 Dec 14.

Abstract

Extensive efforts to enhance the oxygen evolution reaction (OER) catalytic performance of transition metal oxides mainly concentrate on the extrinsic morphology tailoring, lattice doping, and electrode interface optimizing. Nevertheless, little room is left for performance improvement using these methods and an obvious gap still exists compared to the precious metal catalysts. In this work, a novel "mixed-valent cobalt modulation" strategy is presented to enhance the electrocatalytic OER of perovskite LaCoO (LCO) oxide. The valence transition of cobalt is realized by ethylenediamine post reduction procedure at room temperature, which further induces the variation of magnetic properties for LCO catalyst. The optimized LCO catalyst with Co /Co of 1.98 % exhibits the best OER activity, and the overpotential at 10 mA cm current density is decreased by 170 mV compared pristine LCO. Impressively, the ferromagnetic LCO catalyst can perform magnetic OER enhancement. By application of an external magnetic field, the overpotential of LCO at 10 mA cm can be further decreased by 20 mV compared to that of under zero magnetic field, which arises from the enhanced energy states of electrons and accelerated electron transfer process driven by magnetic field. Our findings may provide a promising strategy to break the bottleneck for further enhancement of OER performance.

摘要

研究人员为提高过渡金属氧化物的析氧反应(OER)催化性能进行了广泛的研究,主要集中在外延形态调控、晶格掺杂和电极界面优化等方面。然而,这些方法的性能提升空间有限,与贵金属催化剂相比仍存在明显差距。在这项工作中,提出了一种新颖的“混合价钴调制”策略来提高钙钛矿 LaCoO(LCO)氧化物的电催化 OER 性能。通过室温下乙二胺的后还原过程实现钴的价态转变,进一步引起 LCO 催化剂磁性能的变化。优化后的 Co/Co 为 1.98%的 LCO 催化剂表现出最佳的 OER 活性,在 10 mA cm电流密度下的过电位比原始 LCO 降低了 170 mV。引人注目的是,铁磁性 LCO 催化剂可以实现磁性 OER 增强。施加外部磁场后,LCO 在 10 mA cm 下的过电位比无磁场下进一步降低了 20 mV,这是由于磁场驱动电子增强了电子的能级和加速了电子转移过程。我们的发现可能为进一步提高 OER 性能提供了一种有前途的策略。

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