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具有高稳定性和对海水中尿素电催化氧化性能的双金属镍钴金属有机框架

Bimetallic NiCo Metal-Organic Frameworks with High Stability and Performance Toward Electrocatalytic Oxidation of Urea in Seawater.

作者信息

Sanati Soheila, Abazari Reza, Kirillov Alexander M

机构信息

Department of Chemistry, Faculty of Science, University of Maragheh, Maragheh P.O. Box 55181-83111, Iran.

Centro de Química Estrutural, Institute of Molecular Sciences, Departamento de Engenharia Química, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, Lisbon 1049-001, Portugal.

出版信息

Inorg Chem. 2024 Aug 26;63(34):15813-15820. doi: 10.1021/acs.inorgchem.4c01850. Epub 2024 Aug 14.

Abstract

The urea oxidation reaction (UOR) is an alternative anodic reaction for hydrogen generation via water splitting. The significance of UOR lies in both H production and the decontamination of urea-containing wastewater. Commercial electrocatalysts in this field are generally based on noble metals and show several limitations. Bimetal-organic frameworks (BMOFs) can be excellent candidates for the replacement of noble-metal-based catalysts beacuse of their promising features, such as a tunable structure, high surface area, and abundant sites for electrocatalysis. In this study, a series of nickel-cobalt BMOFs (Ni-Co-BMOFs: and refer to a molar fraction of Ni and Co) were synthesized and applied as electrocatalysts in UOR. In particular, a NiCo-MOF material with a structure similar to that of its parent Co-MOF, revealed exceptional electrocatalytic performance, as evidenced by low values of overpotential (1.33 V vs RHE at 10 mA cm), TOF (0.47 s), and Tafel slope (125 mV dec). At a 40 mA cm current density, NiCo-MOF also showed excellent stability during the 72 h tests. This performance of NiCo-BMOF can be assigned to the synergistic effect between Co and Ni, abundant active sites, porosity, and a tunable structure, all of which result in an increased reaction rate due to the acceleration of charge and mass transfers. Thus, the present work introduces an efficient noble-metal-free UOR for energy generation from urea-based wastewater.

摘要

尿素氧化反应(UOR)是一种通过水分解产生氢气的替代阳极反应。UOR的意义在于制氢以及对含尿素废水的净化。该领域的商业电催化剂通常基于贵金属,存在一些局限性。双金属有机框架(BMOFs)因其具有诸如可调节结构、高比表面积和丰富的电催化位点等有前景的特性,有望成为替代基于贵金属催化剂的优秀候选材料。在本研究中,合成了一系列镍钴BMOFs(Ni-Co-BMOFs: 和 分别指Ni和Co的摩尔分数)并将其用作UOR中的电催化剂。特别是,一种结构与其母体Co-MOF相似的NiCo-MOF材料表现出卓越的电催化性能,过电位低(在10 mA cm时相对于可逆氢电极(RHE)为1.33 V)、周转频率(TOF,0.47 s)和塔菲尔斜率(125 mV dec)即为证明。在40 mA cm的电流密度下,NiCo-MOF在72小时测试期间也表现出优异的稳定性。NiCo-BMOF的这种性能可归因于Co和Ni之间的协同效应、丰富的活性位点、孔隙率和可调节结构,所有这些都因电荷和质量传递的加速而导致反应速率增加。因此,本工作引入了一种用于从尿素基废水中产生能量的高效无贵金属UOR。

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