Immobilizing Molecular Metal Dithiolene-Diamine Complexes on 2D Metal-Organic Frameworks for Electrocatalytic H₂ Production

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• 作者：Dr. Renhao Dong ; Dr. Zhikun Zheng ; Dr. Diana C. Tranca ; Dr. Jian Zhang ; Dr. Naisa Chandrasekhar ; Dr. Shaohua Liu ; Dr. Xiaodong Zhuang ; Prof. Dr. Gotthard Seifert and Prof. Dr. Xinliang Feng
• 刊名：Chemistry - A European Journal
• 出版年：2017
• 出版时间：February 16, 2017
• 年：2017
• 卷：23
• 期：10
• 页码：2255-2260
• 全文大小：2028K
• ISSN：1521-3765

文摘

Carbon electrocatalysts consisting of metal complexes such as MN_x or MS_x are promising alternatives to high-cost Pt catalysts for the hydrogen evolution reaction (HER). However, the exact HER active sites remain elusive. Here, molecular metal dithiolene-diamine (MS₂N₂, M=Co and Ni), metal bis(dithiolene) (MS₄), and metal bis(diamine) (MN₄) complexes were selectively incorporated into carbon-rich 2D metal–organic frameworks (2D MOFs) as model carbon electrocatalysts. The 2D MOF single layers, powders, and composites with graphene were thus prepared and showed definite active sites for H₂ generation. The electrocatalytic HER activity of the 2D MOF-based catalysts with different metal complexes follow the order of MS₂N₂>MN₄>MS₄. Moreover, the protonation preferentially occurred on the metal atoms, and the concomitant heterolytic elimination of H₂ was favored on the M–N units in the MS₂N₂ active centers. The results provide an in-depth understanding of the catalytic active sites, thus making way for the future development of metal complexes in carbon-rich electrode materials for energy generation.