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.

Aplicación teórica del árbol de evaluación del Marine Stewardship Council, como herramienta de gestión de pesca sostenible, a la pesquería de la chirla, Chamelea gallina (Linnaeus, 1758), con draga hidráulica en el Golfo de Cádiz

La etiqueta azul del Marine Stewardship Council, pesca sostenible certificada, indica que un producto de pescado, fresco o transformado, procede de un recurso natural, salvaje, gestionado de manera respetuosa con el medio. Para obtenerla es necesario cumplir una serie de requisitos que son evaluados por una empresa certificadora (a la cual MSC ha dado el visto bueno y que es, a su vez, evaluada por otro organismo que asegura su completa imparcialidad). MSC presenta un modo de gestionar pesquerías que, según la propia organización, asegura la continuidad de la especie objetivo, de otras especies dependientes de ésta y del medio donde habitan. Sin embargo, obtener dicha eco-etiqueta azul es complejo y, sobre todo, económicamente difícil. El objetivo de este artículo es comprobar si el enfoque ecosistémico de este estándar ayudaría a paliar el impacto negativo de una pesquería que es fuente de riqueza, alimento y empleo perdurable en el Golfo de Cádiz. Es decir, aplicar los principios y criterios de MSC como herramienta de gestión de la pesquería de la chirla, Chamelea gallina (Linnaeus, 1758), con draga hidráulica.

Interplay Between Structure, Stoichiometry, and Electron Transfer Dynamics in SILAR-based Quantum Dot-Sensitized Oxides

We quantify the rate and efficiency of picosecond electron transfer (ET) from PbS nanocrystals, grown by successive ionic layer adsorption and reaction (SILAR), into a mesoporous SnO2 support. Successive SILAR deposition steps allow for stoichiometry- and size-variation of the QDs, characterized using transmission electron microscopy. Whereas for sulfur-rich (p-type) QD surfaces substantial electron trapping at the QD surface occurs, for lead-rich (n-type) QD surfaces, the QD trapping channel is suppressed and the ET efficiency is boosted. The ET efficiency increase achieved by lead-rich QD surfaces is found to be QD-size dependent, increasing linearly with QD surface area. On the other hand, ET rates are found to be independent of both QD size and surface stoichiometry, suggesting that the donor–acceptor energetics (constituting the driving force for ET) are fixed due to Fermi level pinning at the QD/oxide interface. Implications of our results for QD-sensitized solar cell design are discussed.