Two-dimensional self-assembly of melem and melemium cations at pH-controlled aqueous solution–Au(111) interfaces under electrochemical control

doi:10.1007/s11705-016-1564-4

Front. Chem. Sci. Eng.

2016, Vol. 10

Issue (2) : 294-300 https://doi.org/10.1007/s11705-016-1564-4

RESEARCH ARTICLE

Two-dimensional self-assembly of melem and melemium cations at pH-controlled aqueous solution–Au(111) interfaces under electrochemical control

Shinobu Uemura^1,^*(

),Kenki Sakata²,Masashi Aono²,Yusuke Nakamura²,Masashi Kunitake^2,^*(

)

¹. Department of Advanced Materials Sciences, Faculty of Engineering, Kagawa University, Kagawa 761-0396, Japan
². Graduate School of Science and Technology, Kumamoto University, Kumamoto 860-8555, Japan

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Abstract

Two-dimensional self-assembly of melem at pH-controlled aqueous solution-Au(111) interfaces has been investigated by electrochemical scanning tunneling microscopy. In the solutions with pH>pK_b1 of melem, two ordered self-assembled structures (honeycomb and close-packed structures) and one disordered fibrillar structure were observed as a function of the surface coverage of melem controlled by the electrode potential. In contrast, in the acidic solution with pH<pK_b1 of melem, only the self-assembled honeycomb network was observed in a relatively wide potential range probably due to the presence of monoprotonated melem cations. Dots attributed to counteranions were frequently observed in the pores of the honeycomb network. The lack of close-packed and fibrillar structures at low pH (<pK_b1) is attributed to ionic repulsion of melemium cations.

Keywords self-assembly scanning tunneling microscopy electrochemistry structural phase transition melem

Corresponding Author(s): Shinobu Uemura,Masashi Kunitake

Online First Date: 24 March 2016 Issue Date: 19 May 2016

Cite this article:

Shinobu Uemura,Kenki Sakata,Masashi Aono, et al. Two-dimensional self-assembly of melem and melemium cations at pH-controlled aqueous solution–Au(111) interfaces under electrochemical control[J]. Front. Chem. Sci. Eng., 2016, 10(2): 294-300.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-016-1564-4
https://academic.hep.com.cn/fcse/EN/Y2016/V10/I2/294

Fig.1 Chemical structures of (a) melem and (b and c) monoprotonated melemium cations

Fig.2 (a), (b), and (d) Typical STM images and (e) the structural model of melem at the 0.1 mol?L^?1 HClO₄ solution-Au(111) interface. (c) High-resolution image of melem at the weakly basic solution-Au(111) interface. (a) E_s = -0.04 V, I_t = 30 nA, and E_bias = -0.20 V. (d) E_s = +0.43 V, I_t = 10 nA, and E_bias = -0.30 V

Fig.3 (a?c) Typical STM images and (d?f) the corresponding schematic structural models of melem at the 0.1 mol?L^?1 NaClO₄ aqueous solution with pH ≈ 6-Au(111) interface. (a) E_s = ?0.30 V, I_t = 10 nA, and E_bias = ?0.20 V. (b) E_s = ?0.10 V, I_t = 2.0 nA, and E_bias = ?0.20 V. (c) E_s = 0.35 V, I_t = 1.0 nA, and E_bias = ?0.40 V

Fig.4 Serial STM images of melem fibrils. Solution conditions: 1.5 × 10^?5 mol?L^?1 melem in 0.02 mol?L^?1 NaClO₄ aqueous solution. The same aggregates are indicated by white arrows. The scale bar is 5 nm. E_s = 0.50 V, I_t = 2.0 nA, and E_bias = ?0.40 V

Fig.5 (a) and (b) Cyclic voltammograms of melem using Au(111) electrodes and (c) schematic illustration of the potential ranges of each structure. In (a), the red solid line is 9 × 10^?6 mol?L^?1 melem in 0.1 mol?L^?1 HClO₄ and the black dashed line is bare Au(111) in 0.1 mol?L^?1 HClO₄. In (b), the grey solid line is 9 × 10^?6 mol?L^?1 melem in weakly basic aqueous solution with pH>9 and the grey dashed line is bare Au(111) in weakly basic aqueous solution with pH>9. The data (b) are adopted with permission from Ref. 15. Copyright 2011 American Chemical Society

Tab.1 Peak potentials and the charge of the peak from cyclic voltammograms in 9.0 × 10^-⁶ mol?L^?1 melem aqueous solutions using an Au(111) electrode

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