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CoCeMO 三金属氧化物的一般合成 用于析氧反应的阳离子交换反应。

General synthesis of CoCeMO trimetallic oxides a cation exchange reaction for the oxygen evolution reaction.

机构信息

Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science and Collaborative Innovation Center of Suzhou Nano Science and Technology, Soochow University, Suzhou 215123, P. R. China.

Key Laboratory of Rare Mineral of Hubei Province, Ministry of Natural Resources, Hubei Geological Experimental Testing Center, Wuhan 430034, P. R. China.

出版信息

Dalton Trans. 2023 Apr 25;52(16):5312-5320. doi: 10.1039/d3dt00318c.

Abstract

Cobalt-based spinel oxides are considered potential candidates for the oxygen evolution reaction (OER) due to their abundant valence changes and promising electrochemical activity, but their low intrinsic activity hinders their practical applications. Herein, we synthesize a series of CoCeMO (M = Zn, Ni, Ru, Er, Mg, Mn, Sn) derived from CoCeM coordination-driven self-assembled aggregates (CDSAAs) using a general ion exchange and subsequent calcination method. Interestingly, CoCeMO exhibit different morphologies from porous nanospheres, particle-stacked nanospheres, to hollow nanospheres as the third metal element is altered. Markedly, CoCeZnO porous nanospheres (PNs) exhibit the best OER performance. The XPS results reveal that the existence of CeO and Zn ions significantly increased the Co/Co ratio and the content of oxygen vacancies in CoO. Furthermore, Co can be used as highly reactive sites to form CoOOH and the high content of oxygen vacancies can optimize the oxygen-containing intermediate adsorption energy, both of which can effectively improve the OER performance. Therefore, well-designed CoCeZnO PNs demonstrate high OER activity with a lower overpotential ( = 333 mV) than that of commercial RuO (344 mV) in 10 mA cm, a Tafel slope of 98 mV dec, and a long-term durability of 45 h. This work may provide some inspiration for the design of trimetallic oxide nanomaterials.

摘要

钴基尖晶石氧化物因其丰富的价态变化和有前途的电化学活性而被认为是氧析出反应(OER)的潜在候选物,但由于其内在活性较低,限制了其实际应用。在此,我们采用通用的离子交换和随后的煅烧方法,从 CoCeM 配位驱动自组装聚集体(CDSAAs)合成了一系列 CoCeMO(M=Zn、Ni、Ru、Er、Mg、Mn、Sn)。有趣的是,随着第三金属元素的改变,CoCeMO 表现出不同的形态,从多孔纳米球、颗粒堆积纳米球到空心纳米球。显著的是,CoCeZnO 多孔纳米球(PNs)表现出最佳的 OER 性能。XPS 结果表明,CeO 和 Zn 离子的存在显著提高了 Co/Co 比和 CoO 中氧空位的含量。此外,Co 可以用作高反应性位点,形成 CoOOH,并且高含量的氧空位可以优化含氧中间体的吸附能,这两者都可以有效地提高 OER 性能。因此,设计良好的 CoCeZnO PNs 在 10 mA cm 时表现出高 OER 活性,过电位( = 333 mV)低于商用 RuO(344 mV),塔菲尔斜率为 98 mV dec,长期耐久性为 45 h。这项工作可能为三金属氧化物纳米材料的设计提供一些启示。

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