Comprehensive evaluation of photoelectrochemical performance dependence on geometric features of ZnO nanorod electrodes.

The impact of geometric features, light absorption spectra, and electrochemical active surface area on photoelectrochemical properties was investigated in this work. Nanoforests of ZnO nanorods with rationally controlled morphologies were grown on ITO substrates by the hydrothermal method and utilized as a model for this purpose. The size of the nanorods was systematically adjusted by varying the concentration of polyethyleneimine as a cation surfactant in the growth solution. It was found that the emergent geometric characteristics (i.e. the aspect ratio) increased almost at the same pace as the electrochemically active surface area, but the light scattering effect slightly increased as a result of the random spatial orientation of the nanorods. The large surface area and the void space between nanorods increased the photon-to-current conversion efficiency by promoting the hole transfer process at the electrode/electrolyte interface. A maximum photocurrent density of 0.06 mA cm-2 (0.5 V vs. NHE) for smaller diameter and length ZnO nanorods (ZnO-P1) was obtained under 365 nm UV light illumination. Additionally, we provide visual evidence that a shorter photogenerated hole diffusion distance results in improved charge separation efficiency using Mn2+ as the photogenerated hole imaging agent. Therefore, the present work demonstrates a facile strategy for nanoforest morphology improvement for generating strong contact at the ZnO NR electrode/electrolyte interface, which is favourable in energy conversion and storage technologies.

Incorporation of the New anti-Octadecaborane Laser Dyes into Thin Polymer Films: A Temperature-Dependent Photoluminescence and Infrared Spectroscopy Study.

New anti-octadecaborane(22) laser dyes have been recently introduced. However, their application in solid thin films is limited, despite being very desirable for electronics. Spectroscopic methods, photoluminescence (PL), and infrared reflection-absorption spectroscopy (IRRAS), are here used to reveal structural responses to a temperature change in thin polymer films made of π- and σ-conjugated and non-conjugated polymers and anti-octadecaborane(22) and its tetra-alkylatedderivatives. It has been observed that borane clusters are not firmly fixed within polymer matrices and that their ability for diffusion out of the polymer film is unprecedented, especially at higher temperatures. This ability is related to thermodynamic transitions of polymer macromolecular chains. PL and IRRAS spectra have revealed a clear correlation with ß-transition and α-transition of polymers. The influence of structure and molecular weight of a polymer and the concentration and the substitution type of clusters on mobility of borane clusters within the polymer matrix is demonstrated. A solution is proposed that led to an improvement of the temperature stability of films by 45 °C. The well-known spectroscopic methods have proved to be powerful tools for a non-routine description of the temperature behavior of both borane clusters and polymer matrices.

Boosting the Photoelectrochemical Performance of Au/ZnO Nanorods by Co-Occurring Gradient Doping and Surface Plasmon Modification.

Band bending modification of metal/semiconductor hybrid nanostructures requires low-cost and effective designs in photoelectrochemical (PEC) water splitting. To this end, it is evinced that gradient doping of Au nanoparticles (NPs) inwards the ZnO nanorods (NRs) through thermal treatment facilitated faster transport of the photo-induced charge carriers. Systematic PEC measurements show that the resulting gradient Au-doped ZnO NRs yielded a photocurrent density of 0.009 mA/cm2 at 1.1 V (vs. NHE), which is 2.5-fold and 8-fold improved compared to those of Au-sensitized ZnO and the as-prepared ZnO NRs, respectively. The IPCE and ABPE efficiency tests confirmed the boosted photoresponse of gradient Au-incorporated ZnO NRs, particularly in the visible spectrum due to the synergistic surface plasmonic effect of Au NPs. A gradient Au dopant profile promoted the separation and transfer of the photo-induced charge carriers at the electrolyte interface via more upward band bending according to the elaborated electrochemical impedance spectroscopy and Kelvin probe force microscopy analyses. Therefore, this research presents an economical and facile strategy for preparing gradient plasmonic noble NP-incorporated semiconductor NRs, which have excellent potential in energy conversion and storage technologies.

Development of New Health Risk Assessment of Nanoparticles: EPA Health Risk Assessment Revised.

The concentration of nanoparticles in the ambient air can lead to induced toxicities; however, it appears that nanoparticles' unique properties are completely omitted when assessing health risks. This paper aims to enhance the EPA health risk assessment by incorporating two new variables that consider the size of nanoparticles: the toxicity multiplier and the size multiplier. The former considers the qualitative aspect of the size of particles within a concentration, whilst the latter takes into account the effects associated with the number of particles of the specific i-th size distribution interval. To observe the impact of the new variables, a case study was performed. The studied element was cadmium, which was measured using ICP-MS to discover concentrations of size fractions, ranging from <15.1 to <9830 nm. Next, the cadmium concentration is assessed using both the current state-of-the-art method and the proposed method with adjustments. Based on the new approach, the final risk was 1.1 × 10−5, which was almost 24 times higher compared with the current method. The contribution of nanoparticles to the risk value grew from barely 6% to an alarming 88%. Therefore, the enhanced method can lead to more realistic results when assessing the health risks of nanoparticles.

The Photostability of Novel Boron Hydride Blue Emitters in Solution and Polystyrene Matrix.

In recent work, the boron hydride anti-B18H22 was announced in the literature as a new laser dye, and, along with several of its derivatives, its solutions are capable of delivering blue luminescence with quantum yields of unity. However, as a dopant in solid polymer films, its luminescent efficiencies reduce dramatically. Clarification of underlying detrimental effects is crucial for any application and, thus, this contribution makes the initial steps in the use of these inorganic compounds in electrooptical devices based on organic polymer thin films. The photoluminescence behavior of the highly luminescent boron hydrides, anti-B18H22 and 3,3',4,4'-Et4-anti-B18H18, were therefore investigated. The quantum yields of luminescence and photostabilities of both compounds were studied in different solvents and as polymer-solvent blends. The photophysical properties of both boranes are evaluated and discussed in terms of their solvent-solute interactions using photoluminescence (PL) and NMR spectroscopies. The UV degradability of prepared thin films was studied by fluorimetric measurement. The effect of the surrounding atmosphere, dopant concentration and the molecular structure were assessed.