Novel ruthenium bipyridyl dyes with s-donor ligands and their application in dye-sensitized solar cells

Two series of novel ruthenium bipyridyl dyes incorporating sulfur-donor bidentate ligands with general formula \[Ru(R-bpy)2C2N2S2] and \[Ru(R-bpy)2(S2COEt)]\[NO3] (where R =H, CO2Et, CO2H; C2N2S2 = cyanodithioimidocarbonate and S2COEt = ethyl xanthogenate) have been synthesized and characterized spectroscopically, electrochemically and computationally. The acid derivatives in both series (C2N2S2 3 and S2COEt 6) were used as a photosensitizer in a dye-sensitized solar cell (DSSC) and the incident photo-to-current conversion efficiency (IPCE), overall efficiency (_) and kinetics of the dye/TiO2 system were investigated. It was found that 6 gave a higher efficiency cell than 3 despite the latter dye’s more favorable electronic properties, such as greater absorption range, higher molar extinction coefficient and large degree of delocalization of the HOMO. The transient absorption spectroscopy studies revealed that the recombination kinetics of 3 were unexpectedly fast, which was attributed to the terminal CN on the ligand binding to the TiO2, as evidenced by an absorption study of R =H and CO2Et dyes sensitized on TiO2, and hence leading to a lower efficiency DSSC.

Electron diffusion and back reaction in dye-sensitized solar cells : the effect of nonlinear recombination kinetics

The electron collection efficiency in dye-sensitized solar cells (DSCs) is usually related to the electron diffusion length, L = (Dτ)^1/2, where D is the diffusion coefficient of mobile electrons and τ is their lifetime, which is determined by electron transfer to the redox electrolyte. Analysis of incident photon-to-current efficiency (IPCE) spectra for front and rear illumination consistently gives smaller values of L than those derived from small amplitude methods. We show that the IPCE analysis is incorrect if recombination is not first-order in free electron concentration, and we demonstrate that the intensity dependence of the apparent L derived by first-order analysis of IPCE measurements and the voltage dependence of L derived from perturbation experiments can be fitted using the same reaction order, γ ≈ 0.8. The new analysis presented in this letter resolves the controversy over why L values derived from small amplitude methods are larger than those obtained from IPCE data.

Títulos valores a la luz de la ley 527 de 1999,

La Ley 527 de 1999 regula lo relativo al Comercio Electrónico en Colombia. Esta ley sigue de cerca la Ley Modelo que sobre la materia preparó la Comisión de las Naciones Unidas para el Derecho Mercantil Internacional

Do static sources respond to massive scalar particles from the Hawking radiation as uniformly accelerated ones do in the inertial vacuum?

We examine the recently found equivalence for the response of a static scalar source interacting with a massless Klein-Gordon field when the source is (i) static in Schwarzschild spacetime, in the Unruh vacuum associated with the Hawking radiation, and (ii) uniformly accelerated in Minkowski spacetime, in the inertial vacuum, provided that the source's proper acceleration is the same in both cases. It is shown that this equivalence is broken when the massless Klein-Gordon field is replaced by a massive one.

Interaction of Hawking radiation with static sources in de Sitter and Schwarzschild-de Sitter spacetimes

We study and look for similarities between the response rates R-dS(a(0),Lambda) and R-SdS(a(0),Lambda,M) of a static scalar source with constant proper acceleration a(0) interacting with a massless, conformally coupled Klein-Gordon field (i) in de Sitter spacetime, in the Euclidean vacuum, which describes a thermal flux of radiation emanating from the de Sitter cosmological horizon and (ii) in Schwarzschild-de Sitter spacetime, in the Gibbons-Hawking vacuum, which describes thermal fluxes of radiation emanating from both the hole and the cosmological horizons, respectively, where Lambda is the cosmological constant and M is the black hole mass. After performing the field quantization in each of the above spacetimes, we obtain the response rates at the tree level in terms of an infinite sum of zero-energy field modes possessing all possible angular momentum quantum numbers. In the case of de Sitter spacetime, this formula is worked out and a closed, analytical form is obtained. In the case of Schwarzschild-de Sitter spacetime such a closed formula could not be obtained, and a numerical analysis is performed. We conclude, in particular, that R-dS(a(0),Lambda) and R-SdS(a(0),Lambda,M) do not coincide in general, but tend to each other when Lambda-->0 or a(0)-->infinity. Our results are also contrasted and shown to agree (in the proper limits) with related ones in the literature.

Quantum Dot-Sensitized Solar Cells Based on Directly Adsorbed Zinc Copper Indium Sulfide Colloids

Heavy metal-based quantum dots (QDs) have demonstrated to behave as efficient sensitizers in QD-sensitized solar cells (QDSSCs), as attested by the countless works and encouraging efficiencies reported so far. However, their intrinsic toxicity has arisen as a major issue for the prospects of commercialization. Here, we examine the potential of environmentally friendly zinc copper indium sulfide (ZCIS) QDs for the fabrication of liquid-junction QDSSCs by means of photoelectrochemical measurements. A straightforward approach to directly adsorb ZCIS QDs on TiO2 from a colloidal dispersion is presented. Incident photon-to-current efficiency (IPCE) spectra of sensitized photoanodes show a marked dependence on the adsorption time, with longer times leading to poorer performances. Cyclic voltammograms point to a blockage of the channels of the mesoporous TiO2 film by the agglomeration of QDs as the main reason for the decrease in efficiency. Photoanodes were also submitted to the ZnS treatment. Its effects on electron recombination with the electrolyte are analyzed through electrochemical impedance spectroscopy and photopotential measurements. The corresponding results bring out the role of the ZnS coating as a barrier layer preventing electron leakage toward the electrolyte, as argued in other QD-sensitized systems. The beneficial effect of the ZnS coating is ultimately reflected on the power conversion efficiency of complete devices, reaching values of 2 %. In a more general vein, through these findings, we aim to call the attention to the potentiality of this quaternary alloy, virtually unexplored as a light harvester for sensitized devices.

Sol–gel copper chromium delafossite thin films as stable oxide photocathodes for water splitting

Significant effort is being devoted to the study of photoactive electrode materials for artificial photosynthesis devices. In this context, photocathodes promoting water reduction, based on earth-abundant elements and possessing stability under illumination, should be developed. Here, the photoelectrochemical behavior of CuCrO2 sol–gel thin film electrodes prepared on conducting glass is presented. The material, whose direct band gap is 3.15 eV, apparently presents a remarkable stability in both alkaline and acidic media. In 0.1 M HClO4 the material is significantly photoactive, with IPCE values at 350 nm and 0.36 V vs. RHE of over 6% for proton reduction and 23% for oxygen reduction. This response was obtained in the absence of charge extraction layers or co-catalysts, suggesting substantial room for optimization. The photocurrent onset potential is equal to 1.06 V vs. RHE in both alkaline and acidic media, which guarantees the combination of the material with different photoanodes such as Fe2O3 or WO3, potentially yielding bias-free water splitting devices.

La villa de la C/ Olimpo y la organización territorial de la periferia urbana de Lucentum (Alicante)

Esta investigación establece la secuencia estratigráfica, cronológica y funcional de un núcleo de poblamiento suburbano del municipio romano de Lucentum, con el fin de dibujar las líneas maestras de la evolución productiva de su ager periurbano. El yacimiento presenta cuatro fases principales que abarcan un dilatado arco temporal: estructuras de época tardorrepublicana (fase I, ss. II-I aC), una reestructuración viaria y urbanística de época augustea (fase II), el desarrollo de una villa con estructuras de transformación mercantil datada a partir de época tardojulia o flavia (fase III) y, por último, una fase bajoimperial (fase IV, ss. IV-v dC), en la que la villa sufre fuertes reestructuraciones.