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用于电化学析氧反应的原位转变钴金属有机框架电催化剂

In Situ Transformed Cobalt Metal-Organic Framework Electrocatalysts for the Electrochemical Oxygen Evolution Reaction.

作者信息

Sahoo Malaya K, Samantara Aneeya K, Behera J N

机构信息

National Institute of Science Education and Research (NISER), Khordha 752050, Odisha, India.

Homi Bhabha National Institute, (HBNI), Mumbai, India.

出版信息

Inorg Chem. 2020 Sep 8;59(17):12252-12262. doi: 10.1021/acs.inorgchem.0c01300. Epub 2020 Aug 26.

DOI:10.1021/acs.inorgchem.0c01300
PMID:32845136
Abstract

The development of an active and efficient electrocatalyst for the oxygen evolution reaction remains indispensable for the smooth running of an electrolyzer. Herein, we have synthesized two cobalt metal-organic frameworks (Co-MOFs) with the formulas [CHCoNO] (compound ) and [CHCoNO] (compound ) using pyrazine and 4,4'-bipyridine as linkers in dimethylformamide medium by a solvothermal method. Both Co-MOFs shows strong antiferromagnetic interactions with Θ = -70 and -61 K for compounds and , respectively. The in situ transformation of both compounds catalyzes the OER efficiently in alkaline medium, affording a current density of 10 mA/cm at overpotentials of 276 ± 3 and 302 ± 3 mV by compounds and , respectively. Moreover, compound shows a very high turnover frequency (15.087 s), lower Tafel slope (56 mV/dec), and greater Faradaic efficiency of 95.42% in comparison to compound . The transformations of the Co-MOFs have been accessed by employing powder X-ray diffraction (PXRD), high-resolution transmission electron microscopic (HRTEM) analysis, and X-ray photoelectron spectroscopy, which reveal the formation of uniform hexagonal Co(OH) plates. Therefore, the as-developed Co-MOF is found to be an efficient pre-electrocatalyst for the OER in alkaline medium. These results not only reveal the preparation of OER electrocatalysts from a Co-MOF but also establish a method to derive a potentially active electrocatalyst to substitute for the traditional noble-metal-based materials.

摘要

开发一种用于析氧反应的活性高效电催化剂对于电解槽的平稳运行仍然不可或缺。在此,我们通过溶剂热法在二甲基甲酰胺介质中使用吡嗪和4,4'-联吡啶作为连接体合成了两种钴金属有机框架(Co-MOFs),化学式分别为[CHCoNO](化合物 )和[CHCoNO](化合物 )。两种Co-MOFs均表现出强反铁磁相互作用,化合物 和 的θ分别为-70 K和-61 K。两种化合物的原位转变在碱性介质中均能高效催化析氧反应,化合物 和 分别在276±3和302±3 mV的过电位下提供10 mA/cm的电流密度。此外,与化合物 相比,化合物 表现出非常高的周转频率(15.087 s)、更低的塔菲尔斜率(56 mV/dec)和更高的法拉第效率95.42%。通过粉末X射线衍射(PXRD)、高分辨率透射电子显微镜(HRTEM)分析和X射线光电子能谱对Co-MOFs的转变进行了研究,结果表明形成了均匀的六方Co(OH)板。因此,所开发的Co-MOF被发现是碱性介质中析氧反应的一种高效预电催化剂。这些结果不仅揭示了由Co-MOF制备析氧电催化剂的方法,还建立了一种衍生潜在活性电催化剂以替代传统贵金属基材料的方法。

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