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Bis(diimino)metal complex nanosheets composed of metal ions and hexaaminobenzene ligands (MHABs) are fascinating two-dimensional materials which have been gaining significant attention as electrode materials and electrocatalysts owing to their electrical conductivities, redox properties, and porous structures obtained by the π-conjugated system and regular metal complex arrangement. Although electrochemical oxidation enables the simple and direct formation of MHABs on electrodes within a couple of minutes only, the obtained MHABs are relatively rough and of low crystallinity. This study investigated the effects of the applied potential during the synthesis, the type of base, and the concentrations of bases and building blocks on the synthesis of NiHAB nanosheets. Optical microscopy (OM), atomic force microscopy (AFM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and grazing-incidence X-ray scattering (GIXS) results revealed that a low oxidation potential, high concentration of the ammonia solution, and low concentration of the building blocks in the reaction solution provided a nanometre-thick NiHAB layer. Under the optimal reaction conditions, NiHAB nanosheets were successfully synthesized in a face-on orientation manner on gold electrodes using electrochemical oxidation methods. Furthermore, the anisotropic electrochemical synthesis of CuHAB was achieved under the optimised conditions. The mechanism of the MHAB growth process with an anisotropic orientation and nanometre thickness was proposed and attributed to the flat adsorption of π-conjugated oligomers composed of bis(diamino)metal moieties in a solution onto an electrode surface and the electrochemical oxidation and deprotonation of the adsorbates on the electrode.

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• cc-by-3.0
  

  CC BY 3.0 Deed

キーワード: coordination nanosheets, electrochemical oxidation, Bis(diimino)metal complex

刊行年月日: 2024-03-12

出版者: Royal Society of Chemistry (RSC)

掲載誌:

• New Journal of Chemistry (ISSN: 11440546) vol. 14 p. 6081-6087

研究助成金:

• Japan Society for the Promotion of Science 22K05055
• Japan Society for the Promotion of Science 22K14569
• Japan Society for the Promotion of Science JP19H05460
• Ministry of Education, Culture, Sports, Science and Technology JPMXP12-A-22-UT-0007
• Ministry of Education, Culture, Sports, Science and Technology JPMXP12-A-23-UT-0025

原稿種別: 出版者版 (Version of record)

MDR DOI:

公開URL: https://doi.org/10.1039/d3nj05650c

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更新時刻: 2024-05-08 16:30:28 +0900

MDRでの公開時刻: 2024-05-08 16:30:28 +0900