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镍(II)掺杂卟啉基共轭多孔聚合物的合成及其作为尿素氧化反应催化剂的研究。

Ni(II)-Incorporated Porphyrin-Based Conjugated Porous Polymer Derived from 2,6-Diformyl-4-methylphenol as a Catalyst for the Urea Oxidation Reaction.

机构信息

Department of Chemistry, Indian Institute of Engineering Science and Technology, Howrah711 103, West Bengal, India.

School of Material Sciences, Indian Association for the Cultivation of Science, Kolkata700 032, West Bengal, India.

出版信息

Inorg Chem. 2022 Nov 21;61(46):18390-18399. doi: 10.1021/acs.inorgchem.2c02211. Epub 2022 Nov 9.

Abstract

The urea oxidation reaction (UOR) is an excellent alternative to the sluggish oxygen evolution reaction (OER) as an anode reaction for hydrogen generation via electrochemical water splitting. Here, a porphyrin-based conjugated porous polymer (CPP) has been developed through the polycondensation reaction of 2,6-diformyl-4-methylphenol and pyrrole (DMP-POR). The nickel(II) complex of this conjugated polymer Ni-DMP-POR shows efficient UOR in an alkaline medium. The as-synthesized materials were characterized by solid-state C CP-MAS, thermogravimetric analysis (TGA), Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The porous property of the materials was characterized by N adsorption/desorption isotherms at 77 K. Both DMP-POR and Ni-DMP-POR showed excellent thermal stability. The Ni-DMP-POR exhibits very good UOR in 1 M KOH and 0.33 M urea with an overpotential of 260 mV at 10 mA cm and a Tafel slope of 48 mV dec. The catalyst also shows excellent chronoamperometric and chronopotentiometric stability, suggesting its future scope in sustainable hydrogen production from wastewater resources.

摘要

尿素氧化反应(UOR)是一种替代缓慢的析氧反应(OER)的理想阳极反应,可用于电化学水分解制氢。在此,通过 2,6-二醛基-4-甲基苯酚和吡咯(DMP-POR)的缩聚反应开发了一种基于卟啉的共轭多孔聚合物(CPP)。该共轭聚合物的镍(II)配合物在碱性介质中表现出高效的 UOR。所合成的材料通过固态 C CP-MAS、热重分析(TGA)、傅里叶变换红外(FT-IR)光谱、X 射线光电子能谱(XPS)、粉末 X 射线衍射(PXRD)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)进行了表征。通过在 77 K 下进行 N 吸附/解吸等温线对材料的多孔性质进行了表征。DMP-POR 和 Ni-DMP-POR 均表现出优异的热稳定性。Ni-DMP-POR 在 1 M KOH 和 0.33 M 尿素中表现出非常好的 UOR,在 10 mA cm 时的过电势为 260 mV,塔菲尔斜率为 48 mV dec。该催化剂还表现出出色的恒电流和恒电位稳定性,表明其在利用废水资源可持续生产氢气方面具有广阔的应用前景。

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