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

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–molecule 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.

Formation of atomic-sized contacts controlled by electrochemical methods

Electrochemical methods have recently become an interesting tool for fabricating and characterizing nanostructures at room temperature. Simplicity, low cost and reversibility are some of the advantages of this technique that allows to work at the nanoscale without requiring sophisticated instrumentation. In our experimental setup, we measure the conductance across a nanocontact fabricated either by dissolving a macroscopic gold wire or by depositing gold in between two separated gold electrodes. We have achieved a high level of control on the electrochemical fabrication of atomic-sized contacts in gold. The use of electrochemistry as a reproducible technique to prepare nanocontacts will open several possibilities that are not feasible with other methodologies. It involves, also, the possibility of reproducing experiments that today are made by more expensive, complicated or irreversible methods. As example, we show here a comparison of the results when looking for shell effects in gold nanocontacts with those obtained by other techniques.

Electrochemical features of Pt(S)[n(110) × (100)] surfaces in acidic media

Experiments have been carried out in sulfuric and perchloric acid solutions on Pt(S)[n(110) × (100)] electrodes. The comparison between the two different electrolytic media reveals an important influence of the anion in the voltammetric features. Total charge curves have been obtained with the CO charge displacement method in combination with voltammetric measurements. From these curves, the dependence of the pztc with the step density and the strength of the anion adsorption have been analyzed. The problem of the so-called third peak is treated for a series of electrodes that contain (110) terraces, revealing the requirement of (110) domains for occurrence of this adsorption state.

Characterization of a zeolite-templated carbon by electrochemical quartz crystal microbalance and in situ Raman spectroscopy

Electrochemical quartz crystal microbalance was used to monitor the mass changes during the electrochemical characterization of a zeolite-templated carbon (ZTC) in 1 M H2SO4 medium. Under electrochemical oxidation conditions, a high anodic current and a net mass increase were recorded, resulting in the increase of the specific capacitance owing to the contribution of the pseudocapacitance, mainly derived from the hydroquinone–quinone redox couple. Under more severe electrochemical conditions, a net mass loss was observed, revealing that electrochemical gasification took place. Surface chemistry, before and after the electrochemical treatments, was analyzed through temperature programmed desorption experiments. Furthermore, in situ Raman spectroscopy was used to further characterize the structural changes produced in ZTC under the electrochemical conditions applied, supporting that high potential values produce the electrochemical oxidation and degradation of the carbon material.