SciCombinator

Discover the most talked about and latest scientific content & concepts.

Concept: Phthalocyanine

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In contrast to pristine zinc phthalocyanine (1), zinc phthalocyanine based oPPV-oligomers (2-4) of different chain lengths interact tightly and reversibly with graphite, affording stable and finely dispersed suspensions of mono- to few-layer graphene-nanographene (NG)-that are photoactive. The p-type character of the oPPV backbones and the increasing length of the oPPV backbones facilitate the overall π-π interactions with the graphene layers. In NG/2, NG/3, and NG/4 hybrids, strong electronic coupling between the individual components gives rise to charge transfer from the photoexcited zinc phthalocyanines to NG to form hundreds of picoseconds lived charge transfer states. The resulting features, namely photo- and redoxactivity, serve as incentives to construct and to test novel solar cells. Solar cells made out of NG/4 feature stable and repeatable photocurrent generation during several ‘on-off’ cycles of illumination with monochromatic IPCE values of around 1%.

Concepts: Photoelectric effect, Cadmium, Solar cell, Photovoltaics, Length, Photovoltaic module, Band gap, Phthalocyanine

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A biosorbent was developed by simple dried Agaricus bisporus (SDAB) and effectively used for the biosorption of cationic dyes, Crystal Violet and Brilliant Green.

Concepts: Dye, Dyes, Pigment, Mushroom, Triarylmethane dyes, Agaricus bisporus, Phthalocyanine

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Purified laccase from Trametes polyzona WR710-1 was used as biocatalyst for bisphenol A biodegradation and decolorization of synthetic dyes. Degradation of bisphenol A by laccase with or without redox mediator, 1-hydroxybenzotriazole (HBT) was studied. The quantitative analysis by HPLC showed that bisphenol A rapidly oxidized by laccase with HBT. Bisphenol A was completely removed within 3 h and 4-isopropenylphenol was found as the oxidative degradation product from bisphenol A when identified by GC-MS. All synthetic dyes used in this experiment, Bromophenol Blue, Remazol Brilliant Blue R, Methyl Orange, Relative Black 5, Congo Red, and Acridine Orange were decolorized by Trametes laccase and the percentage of decolorization increased when 2 mM HBT was added in the reaction mixture. This is the first report showing that laccase from T. polyzona is an affective enzyme having high potential for environmental detoxification, bisphenol A degradation and synthetic dye decolorization.

Concepts: Enzyme, Redox, Nicotinamide adenine dinucleotide, Dye, Triarylmethane dyes, Azo dyes, Acridine, Phthalocyanine

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Porphyrins, phthalocyanines and subphthalocyanines are three attractive classes of chromophores with intriguing properties making them suitable for the design of artificial photosynthetic systems. The assembly of these components by a supramolecular approach is of particular interest as it provides a facile means to build multi-chromophoric arrays with various architectures and tuneable photophysical properties. In this paper, we show the formation of mixed host-guest supramolecular complexes that consist of a β-cyclodextrin-conjugated subphthalocyanine, a tetrasulfonated porphyrin and a series of silicon(iv) phthalocyanines substituted axially with two β-cyclodextrins via different spacers. We found that the three components form supramolecular complexes held by host-guest interactions in aqueous solution. Upon excitation of the subphthalocyanine part of the complex, the excitation energy is delivered to the phthalocyanine unit via excitation energy transfer and the porphyrin chromophore acts as an energy transfer bridge enabling this process. It was shown that photo-induced charge transfer also takes place. A sequential electron transfer process from the porphyrin unit to the phthalocyanine moiety and subsequently from the subphthalocyanine moiety to the porphyrin unit takes place, and the probability of this process is controlled by the linker between β-cyclodextrin and phthalocyanine. The lifetime of the charge-separated state was found to be 1.7 ns by transient absorption spectroscopy.

Concepts: Electron, Metabolism, Electromagnetic radiation, Chemistry, Supramolecular chemistry, Porphyrin, Macrocycle, Phthalocyanine

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The molecular doping of graphene with π-stacked conjugated molecules has been widely studied during the last 10 years, both experimentally or using first-principle calculations, mainly with strongly acceptor or donor molecules. Macrocyclic metal complexes have been far less studied and their behavior on graphene is less clear-cut. The present density functional theory study of cobalt porphyrin and phthalocyanine adsorbed on monolayer or bilayer graphene allows to compare the outcomes of two models, either a finite-sized flake of graphene or an infinite 2D material using periodic calculations. The electronic structures yielded by both models are compared, with a focus on the density of states around the Fermi level. Apart from the crucial choice of calculation conditions, this investigation also shows that unlike strongly donating or accepting organic dopants, these macrocycles do not induce a significant doping of the graphene sheet and that a finite size model of graphene flake may be confidently used for most modeling purposes. © 2017 Wiley Periodicals, Inc.

Concepts: Condensed matter physics, Chemistry, Computational chemistry, Density functional theory, Model, Porphyrin, Macrocycle, Phthalocyanine

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Phthalocyanines and subphthalocyanines are attracting attention as functional dyes that are applicable to organic solar cells, photodynamic therapy, organic electronic devices, and other applications. However, phthalocyanines are generally difficult to handle due to their strong ability to aggregate, so this property must be controlled for further applications of phthalocyanines. On the other hand, trifluoroethoxy-substituted phthalocyanines are known to suppress aggregation due to repulsion of the trifluoroethoxy group. Furthermore, the electronic characteristics of phthalocyanines are significantly changed by the strong electronegativity of fluorine. Therefore, it is expected that trifluoroethoxy-substituted phthalocyanines can be applied to new industrial fields. This review summarizes the synthesis and application of trifluoroethoxy-substituted phthalocyanine and subphthalocyanine derivatives.

Concepts: Oxygen, Engineering, Solar cell, Photovoltaics, Organic solar cell, Diode, Spreadsheet, Phthalocyanine

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Correction for ‘Sisters together: co-sensitization of near-infrared emission of ytterbium(iii) by BODIPY and porphyrin dyes’ by Hongshan He et al., Chem. Commun., 2017, 53, 10120-10123.

Concepts: Supramolecular chemistry, Phthalocyanine, Mordant

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D-π-A type porphyrin dyes have been widely used for fabricating efficient dye-sensitized solar cells (DSSCs) owing to their strong absorption in the visible region and the ease of modifying their chemical structures and photovoltaic behavior. Based on our previously reported efficient porphyrin dye XW11 which contains a phenothiazine-based elec-tron donor, a π-extending ethynylene unit, and an auxiliary benzothiadiazole acceptor, we herein report the syntheses of novel porphyrin dyes XW26-XW28 by introducing one or two alkyl/alkoxy chains into the auxiliary acceptor. The introduced chains can effectively suppress the dye aggregation. As a result, XW26-XW28 show excellent photovoltages of 700, 701 and 711 mV, respectively, obviously higher than 645 mV obtained for XW11. Nevertheless, the optimized structures of XW26 and XW27 exhibit severe distortion, showing large dihedral angles of 57.2°, and 44.0°, respectively, between the benzothiadiazole and the benzoic acid units, resulting from the steric hindrance between the benzoic acid unit and the neighboring alkyl/alkoxy chain on the benzothiadiazole unit, and thus blue-shifted absorption, decreased photocurrents and low efficiencies of 5.19% and 6.42% were observed for XW26 and XW27, respectively. Interestingly, XW26 exhibits more blue-shifted absorption spectrum relative to XW27, indicating that the steric hindrance of the alkyl/alkoxy chains has a more pronounced effect than the electronic effect. Different from XW26 and XW27, XW28 contains only one alkyl chain neighboring to the ethynylene unit, which does not induce obvious steric hindrance with the benzoic acid unit, and thus the distortion of the molecule is not seriously aggravated as compared with XW11. Hence, its absorption spectrum and photocurrent are similar to those of XW11. As a result, a higher efficiency of 9.12% was achieved for XW28 because of its suppressed dye aggregation and higher photovoltage. It is noteworthy that a high efficiency of 10.14% was successfully achieved for XW28 upon coadsorption with CDCA, which is also higher than the corresponding efficiency obtained for XW11. These results provide a novel approach for developing efficient porphyrin dyes by introducing chains into the suitable position of the auxiliary benzothiadiazolyl moiety to suppress the dye aggregation, without seriously aggravating the distortion of the dye molecules.

Concepts: Protein, Solar cell, Absorption, Photovoltaics, Dye, Suppression, Suppression of dissent, Phthalocyanine

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Dye-sensitized solar cells (DSCs) are a promising source of renewable energy. However, power conversion efficiency (PCE) of devices has been limited largely by the difficulty of producing electricity using photons from the near-infrared (NIR) spectral region. Metal-free organic sensitizers frequently employ strong electron donating or withdrawing moieties to tune the optical band gap to allow the absorption of lower energy wavelengths in charge transfer systems while porphyrins and phthalocyanines use substituents to shift the Soret and Q bands toward lower energy absorption. Very few devices employing precious metal free dyes have been able to achieve panchromatic, NIR photon conversion for electricity generation at wavelengths >750 nm despite a tremendous number of sensitizers published over last 25 years. This minireview seeks to compile a summary of these sensitizers to encourage assimilation, analysis and development of efficient future NIR sensitizers. Herein, we discuss common synthetic strategies, optical properties and electronic properties of the most successful panchromatic organic sensitizers in this regard.

Concepts: Photon, Energy, Quantum mechanics, Light, Electromagnetic radiation, Solar cell, Porphyrin, Phthalocyanine

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Co-sensitization in dye sensitized solar cells (DSSCs) received significant attention for improving the efficiency and stability of renewable energy resources. In this context, ruthenium metal and porphyrin dyes based DSSCs achieved increment in power conversion efficiency (PCE) from 8 - 11% to 11-14% after addition of additives, co-adsorbents and co-sensitizers by reducing the aggregation and charge recombination. Among the three supporting materials, co-sensitizers played major role to enhance the performance and stability of DSSCs which assist in commercialization. In this review, we highlighted the importance of co-sensitizers in photovoltaic performance of ruthenium metal and porphyrin dye based solar cells. Consequently, co-sensitizers are rather important to modulate the PCE of DSSCs and find realistic future practical applications.

Concepts: Energy, Solar cell, Photovoltaics, Energy conversion, Energy conversion efficiency, Renewable energy, Wind power, Phthalocyanine