Red-light sensitized hole-conducting polymer for energy conversion.

We report a novel hole conductive polymer with photoactive Os(ii) complexes in the side chains. This PPV derivative can be activated upon absorption of red visible light and delivers notable photocurrents when used as photocathode material. Thus, the polymer presents as a stepping stone towards developing soft matter alternatives to NiO photocathodes, which function under visible light irradiation. To show the concept we combine electrical impedance spectroscopy with steady state spectroscopy. As light-driven hole injection from Os complex to the PPV polymer is thermodynamically feasible both based on reductive quenching of photoexcited PPV and based on oxidative quenching of the photoexcited Os chromophores we investigate the impact of illumination wavelengths on the photocathode behavior and photochemical stability of the material. While both blue and red light excitation, i.e., excitation of the chromophoric units PPV and excitation of the metal-to-ligand charge transfer transitions in the side-chain pendant Os chromophores yield cathodic photocurrents, the photochemical stability is drastically enhanced upon red-light excitation. Hence, the results of the investigations discussed show the validity of the concept developing red-light sensitized hole-conducting polymers for energy conversion.

Probing the dye-semiconductor interface in dye-sensitized NiO solar cells.

The development of p-type dye-sensitized solar cells (p-DSSCs) offers an opportunity to assemble tandem photoelectrochemical solar cells with higher efficiencies than TiO2-based photoanodes, pioneered by O'Regan and Grätzel [Nature 353, 737-740 (1991)]. This paper describes an investigation into the behavior at the interfaces in p-DSSCs, using a series of BODIPY dyes, BOD1-3. The three dyes have different structural and electronic properties, which lead to different performances in p-DSSCs. We have applied photoelectron spectroscopy and transient absorption spectroscopy to rationalize these differences. The results show that the electronic orbitals of the dyes are appropriately aligned with the valence band of the NiO semiconductor to promote light-induced charge transfer, but charge-recombination is too fast for efficient dye regeneration by the electrolyte. We attribute this fast recombination, which limits the efficiency of the solar cells, to the electronic structure of the dye and the presence of Ni3+ recombination sites at the NiO surface.

Self-Assembled Graphene/MWCNT Bilayers as Platinum-Free Counter Electrode in Dye-Sensitized Solar Cells.

We describe the preparation and properties of bilayers of graphene- and multi-walled carbon nanotubes (MWCNTs) as an alternative to conventionally used platinum-based counter electrode for dye-sensitized solar cells (DSSC). The counter electrodes were prepared by a simple and easy-to-implement double self-assembly process. The preparation allows for controlling the surface roughness of electrode in a layer-by-layer deposition. Annealing under N2 atmosphere improves the electrode's conductivity and the catalytic activity of graphene and MWCNTs to reduce the I3- species within the electrolyte of the DSSC. The performance of different counter-electrodes is compared for ZnO photoanode-based DSSCs. Bilayer electrodes show higher power conversion efficiencies than monolayer graphene electrodes or monolayer MWCNTs electrodes. The bilayer graphene (bottom)/MWCNTs (top) counter electrode-based DSSC exhibits a maximum power conversion efficiency of 4.1 % exceeding the efficiency of a reference DSSC with a thin film platinum counter electrode (efficiency of 3.4 %). In addition, the double self-assembled counter electrodes are mechanically stable, which enables their recycling for DSSCs fabrication without significant loss of the solar cell performance.

Morphological and mechanical studies of Al2O3-Na2SiO3 as a skin barrier coated with TiO2 for carbon fiber reinforced composite materials.

The utilization of adhesive compounds in bonding lightweight and high-performance composite structures, including carbon fiber reinforced polymer (CFRP) composites, has garnered significant attention from researchers. This study presents the novel application of Al2O3 coated with TiO2 as a thermal protective layer for CFRP substrate. Initially, the CFRP substrate underwent a protective treatment involving the application of Al2O3 as a middle coat, followed by a further protective layer consisting of TiO2 as a top coat. The deposition of TiO2 onto an Al2O3-based thermal barrier coating (TBC) was carried out utilizing the flame spray method. The use of a TiO2 coating as a top coat was employed to enhance protection and heat dispersion across the middle coat and substrate. In order to achieve sufficient adhesion between the CFRP substrate, an intermediate coat consisting of Al2O3 with a Na2SiO3 binder, the impact of varying nozzle distances on adhesion strength and pull-off test outcomes was investigated, with a nozzle distance of 180 mm yielding the highest adhesion strength. The thermal stability of a CFRP substrate was enhanced through the deposition of a layer of TiO2 on Al2O3. The surface and cross-sectional morphologies of the composite were analyzed using a Scanning Electron Microscope (SEM). It was observed that the presence of a TBC on the composite surface effectively reduced the amount of heat that was transferred to the composite material. In order to assess the effectiveness of TBC on CFRP substrates, a series of experiments involving thermal torch and conductivity tests were undertaken. The interaction between the top and middle coats of a composite material results in enhanced mechanical properties, hence improving its thermal insulation capabilities. The artificially produced TBC coatings have the potential to function as adhesive materials, ensuring the sustained high performance of CFRP substrates.

Localizing the initial excitation - A case study on NiO photocathodes using Ruthenium dipyridophenazine complexes as sensitizers.

We report on the localization of the initially excited electronic state within the molecular framework of a series of [Ru(bpy)2dppz]2+ derivatives (bpy:2,2'-bipyridine, dppz: dipyrido-phenazine) as sensitizers in NiO based photocathodes. The introduction of conjugated linkers with phenylene and triazole moieties in the bpy ligand sphere separates the NiO surface from the metal center and hence is considered to stabilize the charge separated state, which results from light-driven hole injection. However, introduction of the conjugated linkers also alters the localization of the excess electron density in the excited state within the ligand sphere and impacts the extent to which the charge-separated state is formed. The study emphasizes that tuning the ligand with the lowest-energy π* orbital distal or proximal to the NiO surface significantly affects the initial charge-separation and the solar cell performance. The stability of the charge-separated state correlates with the observed photocurrents in dye-sensitized solar cells. Furthermore, the study challenges the widely accepted concept that the introduction of extended anchoring groups, i.e. increasing Ru - NiO distance, stabilizes the charge-separated state and suppresses charge recombination at the metal-oxide molecule interface.

Wafer-scale transfer route for top-down III-nitride nanowire LED arrays based on the femtosecond laser lift-off technique.

The integration of gallium nitride (GaN) nanowire light-emitting diodes (nanoLEDs) on flexible substrates offers opportunities for applications beyond rigid solid-state lighting (e.g., for wearable optoelectronics and bendable inorganic displays). Here, we report on a fast physical transfer route based on femtosecond laser lift-off (fs-LLO) to realize wafer-scale top-down GaN nanoLED arrays on unconventional platforms. Combined with photolithography and hybrid etching processes, we successfully transferred GaN blue nanoLEDs from a full two-inch sapphire substrate onto a flexible copper (Cu) foil with a high nanowire density (~107 wires/cm2), transfer yield (~99.5%), and reproducibility. Various nanoanalytical measurements were conducted to evaluate the performance and limitations of the fs-LLO technique as well as to gain insights into physical material properties such as strain relaxation and assess the maturity of the transfer process. This work could enable the easy recycling of native growth substrates and inspire the development of large-scale hybrid GaN nanowire optoelectronic devices by solely employing standard epitaxial LED wafers (i.e., customized LED wafers with additional embedded sacrificial materials and a complicated growth process are not required).

Experimental data of CaTiO3 photocatalyst for degradation of organic pollutants (Brilliant green dye) - Green synthesis, characterization and kinetic study.

The data presented here focuses on the physicochemical characterization of perovskite CaTiO3 nanoparticles (orthorhombic) as photocatalyts and the kinetic study of their photodegradation performance toward organic pollutant, i.e. brilliant green (BG) which is azo derivatives dye. The CaTiO3 nanoparticles was synthesized using chicken eggshell-derived CaCO3 and anatase TiO2 with molar ratio of (1:1), (1:3), (2:5), and (2:7). The physical and microstructural properties of CaTiO3 were characterized by X-ray diffractometer (XRD), scanning electron microscope (SEM), Fourier Transform Infrared (FTIR) and UV/vis spectrometer. The effect of initial dye concentration, catalyst composition, and catalyst dosage on the adsorption mechanism of dye on CaTiO3 was investigated in jacketed photoreactor under UV irradiation. The analysis reveals that BG molecules are efficiently chemisorbed, as indicated by pseudo first order kinetic, and degraded within 120 min. Considering the low-cost preparation process and high photocatalytic performance, the resultant CaTiO3 can further be used as an efficient photocatalyst for organic pollutant removal from aqueous and industrial wastewater.

Nanostructured Cu2O Synthesized via Bipolar Electrochemistry.

Cuprous oxide (Cu2O) was synthesized for the first time via an open bipolar electrochemistry (BPE) approach and characterized in parallel with the commercially available material. As compared to the reference, Cu2O formed through a BPE reaction demonstrated a decrease in particle size; an increase in photocurrent; more efficient light scavenging; and structure-correlated changes in the flat band potential and charge carrier concentration. More importantly, as-synthesized oxides were all phase-pure, defect-free, and had an average crystallite size of 20 nm. Ultimately, this study demonstrates the impact of reaction conditions (e.g., applied potential, reaction time) on structure, morphology, surface chemistry, and photo-electrochemical activity of semiconducting oxides, and at the same time, the ability to maintain a green synthetic protocol and potentially create a scalable product. In the proposed BPE synthesis, we introduced a common food supplement (potassium gluconate) as a reducing and complexing agent, and as an electrolyte, allowing us to replace the more harmful reactants that are conventionally used in Cu2O production. In addition, in the BPE process very corrosive reactants, such as hydroxides and metal precursors (required for synthesis of oxides), are generated in situ in stoichiometric quantity, providing an alternative methodology to generate various nanostructured materials in high yields under mild conditions.

Structure of Ni(OH)2 intermediates determines the efficiency of NiO-based photocathodes - a case study using novel mesoporous NiO nanostars.

We report the wet chemical synthesis of mesoporous NiO nanostars (NS) as photocathode material for dye-sensitized solar cells (DSSCs). The growth mechanism of NiO NS as a new morphology of NiO is assessed by TEM and spectroscopic investigations. The NiO NS are obtained upon annealing of preformed ß-Ni(OH)2 into pristine NiO with low defect concentrations and favorable electronic configuration for dye sensitization. The NiO NS consist of fibers self-assembled from nanoparticles yielding a specific surface area of 44.9 m2 g-1. They possess a band gap of 3.83 eV and can be sensitized by molecular photosensitizers bearing a range of anchoring groups, e.g. carboxylic acid, phosphonic acid, and pyridine. The performance of NiO NS-based photocathodes in photoelectrochemical application is compared to that of other NiO morphologies, i.e. nanoparticles and nanoflakes, under identical conditions. Sensitization of NiO NS with the benchmark organic dye P1 leads to p-DSSCs with a high photocurrent up to 3.91 mA cm-2 whilst the photoelectrochemical activity of the NiO NS photocathode in aqueous medium in the presence of an irreversible electron acceptor is reflected by generation of a photocurrent up to 23 µA cm-2.

In Vitro Lipophilic Antioxidant Capacity, Antidiabetic and Antibacterial Activity of Citrus Fruits Extracts from Aceh, Indonesia.

This study reports in vitro lipophilic antioxidant, inhibition of α-amylase and antibacterial activities of extracts of peel and pulp of citrus samples from Aceh, Indonesia. HPLC (high-performance liquid chromatography), phytochemical, and FTIR (fourier transform infrared) analysis detected carotenoids, flavonoids, phenolic acids and terpenoids, contributing to the biological potencies. Most peel and pulp extracts contained lutein and lower concentrations of zeaxanthin, α-carotene, ß-carotene and ß-cryptoxanthin. The extracts also contained flavanone glycosides (hesperidin, naringin and neohesperidin), flavonol (quercetin) and polymethoxylated flavones (sinensetin, tangeretin). L-TEAC (lipophilic trolox equivalent antioxidant capacity) test determined for peel extracts higher antioxidant capacity compared to pulp extracts. All extracts presented α-amylase inhibitory activity, pulp extracts showing stronger inhibitory activity compared to peel extracts. All extracts inhibited the growth of both gram (+) and gram (-) bacteria, with peel and pulp extracts of makin showing the strongest inhibitory activity. Therefore, local citrus species from Aceh are potential sources of beneficial compounds with possible health preventive effects.

ZnO Nanostructures for Dye-Sensitized Solar Cells Using the TEMPO+ /TEMPO Redox Mediator and Ruthenium(II) Photosensitizers with 1,2,3-Triazole-Derived Ligands.

A series of thiocyanate-free bis(tridentate) ruthenium(II) complexes incorporating 1,2,3-triazole-derived NNN-, NCN-, and CNC-coordinating ligands has been employed for sensitizing ZnO photoanodes for dye-sensitized solar cells (DSSCs). Additionally, the first use of the TEMPO+ /TEMPO (2,2,6,6-tetramethyl-piperidine-1-oxyl) redox mediator as a surrogate for the I3 - /I- redox couple in ZnO nanostructured DSSCs is presented. Compared with I3 - /I- -based electrolytes, shorter charge lifetimes and diffusion lengths were determined for the TEMPO+ /TEMPO-based electrolyte. Nonetheless, similar power conversion efficiencies (PCEs) were achieved with both electrolytes for the RuNCN and RuCNC complexes, whereas higher PCEs are enabled by the iodine-free electrolyte in case of RuNNN. The combination of the molecular sensitizers and the TEMPO-based electrolyte exhibits relatively high external quantum efficiency (EQE) and promising PCEs, ranging from 4.48 to 1.47 %, which are-in part-comparable to that of ZnO-DSSCs with the benchmark N749 black dye. The TEMPO-based electrolyte also exhibits less absorption compared with its I3 - /I- counterpart, a favorable feature for enhancing the light harvesting ability of the photoanode. Furthermore, the results show the effect of the dye-sensitization procedure on the PCE values: The use of ethanol as the solvent compared with methanol increases the DSSC's efficiency, which is attributed to improved chemisorption of the sensitizer onto the ZnO surface.