Size-Dependent and Step-Modulated Supramolecular Electrochemical Properties of Catechol-Derived Adlayers at Pt(hkl) Surfaces

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• 作者：Margarita Rodr铆guez-L贸pez ; Enrique Herrero ; V铆ctor Climent ; Antonio Rodes ; Antonio Aldaz ; Juan M. Feliu ; Arnaldo Carrasquillo ; Jr.
• 刊名：Langmuir
• 出版年：2013
• 出版时间：October 22, 2013
• 年：2013
• 卷：29
• 期：42
• 页码：13102-13110
• 全文大小：391K
• 年卷期：v.29,no.42(October 22, 2013)
• ISSN：1520-5827

文摘

The electrochemical reactivity of catechol-derived adlayers is reported at platinum (Pt) single-crystal electrodes. Pt(111) and stepped vicinal surfaces are used as model surfaces possessing well-ordered nanometer-sized Pt(111) terraces ranging from 0.4 to 12 nm. The electrochemical experiments were designed to probe how the control of monatomic step-density and of atomic-level step structure can be used to modulate molecule鈥搈olecule interactions during self-assembly of aromatic-derived organic monolayers at metallic single-crystal electrode surfaces. A hard sphere model of surfaces and a simplified band formation model are used as a theoretical framework for interpretation of experimental results. The experimental results reveal (i) that supramolecular electrochemical effects may be confined, propagated, or modulated by the choice of atomic level crystallographic features (i.e.monatomic steps), deliberately introduced at metallic substrate surfaces, suggesting (ii) that substrate-defect engineering may be used to tune the macroscopic electronic properties of aromatic molecular adlayers and of smaller molecular aggregates.