Modulation of electrochemical hydrogen evolution rate by araliphatic thiol monolayers on gold

被引：28
作者：
Muglali, Mutiu I. [1 ]
Erbe, Andreas [1 ]
Chen, Ying [1 ,2 ]
Barth, Christoph
Koelsch, Patrick [3 ,4 ]
Rohwerder, Michael [1 ]
机构：
[1] Max Planck Inst Eisenforsch GmbH, Dept Interface Chem & Surface Engn, D-40237 Dusseldorf, Germany
[2] Ruhr Univ Bochum, Ctr Electrochem Sci, D-44780 Bochum, Germany
[3] Karlsruhe Inst Technol, Inst Toxicol & Genet, D-76021 Karlsruhe, Germany
[4] Univ Washington, Dept Bioengn, Surface Anal Ctr Biomed Problems, Seattle, WA 98195 USA
来源：
ELECTROCHIMICA ACTA | 2013年 / 90卷
关键词：
Reductive SAM desorption; Hydrogen evolution; Catalysis; Sum frequency generation spectroscopy; Spectroscopic ellipsometry; SELF-ASSEMBLED MONOLAYERS; SCANNING-TUNNELING-MICROSCOPY; SUM-FREQUENCY GENERATION; FIELD-DRIVEN TRANSFORMATIONS; REDUCTIVE DESORPTION PROCESS; SINGLE-CRYSTAL ELECTRODE; BIPHENYL BASED THIOLS; IN-SITU; ALKANETHIOL MONOLAYERS; SPECTROSCOPIC ELLIPSOMETRY;
D O I：
10.1016/j.electacta.2012.11.116
中图分类号：
O646 [电化学、电解、磁化学];
学科分类号：
081704 ;
摘要：
Electroreductive desorption of a highly ordered self-assembled monolayer (SAM) formed by the araliphatic thiol (4-(4-(4-pyridyl)phenyl)phenyl)methanethiol leads to a concurrent rapid hydrogen evolution reaction (HER). The desorption process and resulting interfacial structure were investigated by voltammetric techniques, in situ spectroscopic ellipsometry, and in situ vibrational sum-frequency-generation (SFG) spectroscopy. Voltammetric experiments on SAM-modified electrodes exhibit extraordinarily high peak currents, which differ between Au(1 1 1) and polycrystalline Au substrates. Association of reductive desorption with HER is shown to be the origin of the observed excess cathodic charges. The studied SAM preserves its two-dimensional order near Au surface throughout a fast voltammetric scan even when the vertex potential is set several hundred millivolt beyond the desorption potential. A model is developed for the explanation of the observed rapid HER involving ordering and pre-orientation of water present in the nanometer-sized reaction volume between desorbed SAM and the Au electrode, by the structurally extremely stable monolayer, leading to the observed catalysis of the HER. (c) 2012 Elsevier Ltd. All rights reserved,
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页码：17 / 26
页数：10
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