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Photochem, Volume 4, Issue 3 (September 2024) – 8 articles

Cover Story (view full-size image): Single-walled carbon nanotube (SWCNT) electrodes are increasingly being recognized as promising alternatives to traditional metal electrodes in perovskite solar cells. Typically, strong acidic p-dopants are used to enhance the electrical properties of p-type semiconductors, but these can damage perovskite crystals, complicating their direct application. In contrast, 2,2,2-trifluoroethanol, with much weaker acidity, allows for direct doping. Repeated re-doping with this substance results in a gradual decrease in power conversion efficiency from 14.1% to 8.6% after 260 days, yet the cells maintain high stability even when stored in ambient conditions without encapsulation, demonstrating significant promise for future use. View this paper
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16 pages, 4098 KiB  
Article
Cyanobacterial Pigments as Natural Photosensitizers for Dye-Sensitized Solar Cells
by Tatiana Montagni, Mauricio Ávila, Sofía Fernández, Sylvia Bonilla and María Fernanda Cerdá
Photochem 2024, 4(3), 388-403; https://doi.org/10.3390/photochem4030024 - 12 Sep 2024
Cited by 1 | Viewed by 701
Abstract
Three filamentous freshwater cyanobacterial strains were grown at high light intensity to produce lipidic dyes composed of xanthophylls, carotenes, and chlorophyll a. The properties of the pigments were evaluated as suitable natural compounds to be applied in dye-sensitized solar cells (DSSC). The assembled [...] Read more.
Three filamentous freshwater cyanobacterial strains were grown at high light intensity to produce lipidic dyes composed of xanthophylls, carotenes, and chlorophyll a. The properties of the pigments were evaluated as suitable natural compounds to be applied in dye-sensitized solar cells (DSSC). The assembled DSSC were characterized using the density current vs. potential profiles and electrochemical impedance spectroscopy. With an efficiency of 0.127%, our results are higher than those previously reported using similarly structured compounds from natural sources such as algae and cyanobacteria, among others. The best efficiencies were probably related to myxoxanthophyll-like derivates and aphanizophyll are carotenoids with many hydroxyl groups being able to interact with the semiconductor surface. The stability of the bonding between the dyes and the titanium oxide of the photoelectrode is crucial to ensuring the acceptable performance of the DSSC, which was successfully achieved in our experiments with carotenoids with many hydroxyl groups. Our results point to cyanobacterial pigments as a promising source of natural dyes for use in solar cells. Full article
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11 pages, 1629 KiB  
Article
Riboflavin as a Coloring Agent of Tablets Affects the Photostability of Manidipine after the Change of Dosage Forms
by Kohei Kawabata, Minami Tsukimori, Kyoka Hirai, Shiori Akimoto, Naoto Uramaru, Masanori Inagaki and Hiroyuki Nishi
Photochem 2024, 4(3), 377-387; https://doi.org/10.3390/photochem4030023 - 10 Sep 2024
Viewed by 413
Abstract
Manidipine (MP) is widely used for reducing high blood pressure. Calslot® (CALS) tablets, which are the original MP medicines, and their generic medicines have been used for patients in clinical situations. The authors hypothesized that the photodegradability of MP drug substance in [...] Read more.
Manidipine (MP) is widely used for reducing high blood pressure. Calslot® (CALS) tablets, which are the original MP medicines, and their generic medicines have been used for patients in clinical situations. The authors hypothesized that the photodegradability of MP drug substance in CALS tablets might be enhanced when the tablets were photo-exposed after the change of the dosage form by the presence of riboflavin (RF), which is utilized as a coloring agent and a well-known photosensitizer. The present study clarified that RF enhanced the photodegradation of MP when the powders and the suspensions of CALS tablets were ultraviolet light (UV) irradiated. The addition of RF to the suspension of MP standard substances also promoted MP photodegradation along with the increase of the generation rate of its main photoproduct, benzophenone. Finally, the authors performed the photostabilization of MP suspensions based on the addition of quercetin (QU), which is one of polyphenols and has both the antioxidative potency and the UV filtering potency. It is summarized that QU has a protective potency for MP’s own photodegradation, and it partially suppresses the photocatalytic effect of RF. Further studies focused on the photochemical behaviors of utilized additives for medicines are needed for their safe use. Full article
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16 pages, 5464 KiB  
Article
Photo-Activated Carbon Dots as Catalysts in Knoevenagel Condensation: An Advance in the Synthetic Field
by Cinzia Michenzi, Francesca Scaramuzzo, Chiara Salvitti, Federico Pepi, Anna Troiani and Isabella Chiarotto
Photochem 2024, 4(3), 361-376; https://doi.org/10.3390/photochem4030022 - 27 Aug 2024
Viewed by 1338
Abstract
Photoinduced chemical reactions and the development of new materials represent a current and significant topic. We present a sustainable and eco-friendly approach to the Knoevenagel condensation reaction involving carbonyl and active methylene compounds. Our method utilizes photo-activated carbon dots (CDs) derived from 5-hydroxymethylfurfural [...] Read more.
Photoinduced chemical reactions and the development of new materials represent a current and significant topic. We present a sustainable and eco-friendly approach to the Knoevenagel condensation reaction involving carbonyl and active methylene compounds. Our method utilizes photo-activated carbon dots (CDs) derived from 5-hydroxymethylfurfural (5HMF) within an aqueous medium and does not require acidic, basic, or thermal conditions. This protocol operates effectively with aromatic, aliphatic, and heteroaromatic aldehydes and ketones. The 5HMF-derived-CDs can be reused four times without significant loss of activity. Moreover, this methodology is suitable for scaling up reactions, thereby highlighting its potential for industrial applications. Full article
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15 pages, 2224 KiB  
Article
Concurrent Photooxidation and Photoreduction of Catechols and Para-Quinones by Chlorophyll Metabolites
by Katherine Phan, Emily E. Lessard, Joseph A. Reed, Meredith G. Warsen, Soren Zimmer and Lisa M. Landino
Photochem 2024, 4(3), 346-360; https://doi.org/10.3390/photochem4030021 - 15 Aug 2024
Viewed by 1212
Abstract
Photosynthesis is initiated when the sun’s light induces electron transfer from chlorophyll to plastoquinone, a para-quinone. While photosynthesis occurs in the intact chloroplasts of living plants, similar photochemical reactions between dietary chlorophyll metabolites and quinones are likely and may affect health outcomes. Herein, [...] Read more.
Photosynthesis is initiated when the sun’s light induces electron transfer from chlorophyll to plastoquinone, a para-quinone. While photosynthesis occurs in the intact chloroplasts of living plants, similar photochemical reactions between dietary chlorophyll metabolites and quinones are likely and may affect health outcomes. Herein, we continue our studies of the direct photoreduction of para-quinones and ortho-quinones that were generated by the photo-oxidation of catechols. Chlorophyll metabolites, including pheophorbide A, chlorin e6, and pyropheophorbide A, as well as methylene blue were employed as photosensitizers. We detected hydrogen peroxide using horseradish peroxidase following the photo-oxidation of the catechol dopamine, even in the presence of EDTA, a tertiary amine electron donor. Under ambient oxygen, hydrogen peroxide was also detected after the photoreduction of several para-quinones, including 2,3-dimethoxy-5-methyl-p-benzoquinone (CoQ0), methoxy-benzoquinone, and methyl-benzoquinone. The combinations of methylene blue and EDTA or pheophorbide A and triethanolamine as the electron donor in 20% dimethylformamide were optimized for photoreduction of the para-quinones. Chlorin e6 and pyropheophorbide A were less effective for the photoreduction of CoQ0 but were equivalent to pheophorbide A for generating hydrogen peroxide in photo-oxidation reactions with photosensitizers, oxygen, and triethanolamine. We employed dinitrophenylhydrazine to generate intensely colored adducts of methoxy-benzoquinone, methyl-benzoquinone, and 1,4-benzoquinone. Full article
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12 pages, 2156 KiB  
Article
Optimization of CdSe Thin-Film Photoelectrochemical Cells: Effects of NaOH/Na2S/S Redox Couple Concentration and Activity on Cell Efficiency
by Ahed H. Zyoud
Photochem 2024, 4(3), 334-345; https://doi.org/10.3390/photochem4030020 - 10 Aug 2024
Cited by 1 | Viewed by 1089
Abstract
This study investigates the relationships among redox couple activity, electrolyte concentration, and efficiency in CdSe thin-film photoelectrochemical solar cells. A CdSe photo-electrode was prepared using the electro-depositing technique to produce well-staged layering of CdSe, followed by chemical bath deposition to produce a layer [...] Read more.
This study investigates the relationships among redox couple activity, electrolyte concentration, and efficiency in CdSe thin-film photoelectrochemical solar cells. A CdSe photo-electrode was prepared using the electro-depositing technique to produce well-staged layering of CdSe, followed by chemical bath deposition to produce a layer with an acceptable thickness to absorb enough photons to create a suitable amount of photocurrent. The CdSe photo-electrochemical cell was tested under various concentrations of a NaOH/Na2S/S electrolyte solution. The results showed that the activity of the redox couple greatly affected the efficiencies of the solar cells. Correlation plots between ionic strength and PEC efficiency with the Debye–Hückel equation yielded an R² value of 0.96, while those between ionic strength and photocurrent density had an R² value of 0.92. The correlation between concentration and PEC efficiency was much weaker. This paper highlights how optimal ionic activity increases the performance of photoelectrochemical solar cells, which consequently improves the conversion efficiency of solar energy. Full article
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15 pages, 4087 KiB  
Article
Facile Doping of 2,2,2-Trifluoroethanol to Single-Walled Carbon Nanotubes Electrodes for Durable Perovskite Solar Cells
by Naoki Ueoka, Achmad Syarif Hidayat, Hisayoshi Oshima, Yoshimasa Hijikata and Yutaka Matsuo
Photochem 2024, 4(3), 319-333; https://doi.org/10.3390/photochem4030019 - 14 Jul 2024
Viewed by 893
Abstract
Perovskite solar cells with an indium tin oxide (ITO)/SnO2/CH3NH3PbI3/Spiro-OMeTAD/2,2,2-trifluoroethanol (TFE) doped single-walled carbon nanotube (SWCNT) structure were developed by dropping TFE onto SWCNTs, which replaced the metal back electrode, and a conversion efficiency of 14.1% [...] Read more.
Perovskite solar cells with an indium tin oxide (ITO)/SnO2/CH3NH3PbI3/Spiro-OMeTAD/2,2,2-trifluoroethanol (TFE) doped single-walled carbon nanotube (SWCNT) structure were developed by dropping TFE onto SWCNTs, which replaced the metal back electrode, and a conversion efficiency of 14.1% was achieved. Traditionally, acidic doping of the back electrode, SWCNT, has been challenging due to the potential damage it may cause to the perovskite layer. However, TFE has facilitated easy doping of SWCNT as the back electrode. The sheet resistance of the SWCNTs decreased and their ionization potential shifted to deeper levels, resulting in improved hole transport properties with a lower barrier to carrier transport. Furthermore, the Seebeck coefficient (S) increased from 34.5 μV/K to 73.1 μV/K when TFE was dropped instead of EtOH, indicating an enhancement in the behavior of p-type charge carriers. It was observed that hydrophilic substances adhered less to the SWCNT surface, and the formation of PbI2 was suppressed. These effects resulted in higher conversion efficiency and improved solar cell performance. Furthermore, the decrease in conversion efficiency after 260 days was suppressed, showing improved durability. The study suggests that combining SWCNTs and TFEs improves solar cell performance and stability. Full article
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17 pages, 5713 KiB  
Article
Synthesis of Metallic and Metal Oxide Nanoparticles Using Homopolymers as Solid Templates: Luminescent Properties of the Eu+3 Nanoparticle Products
by María Ángeles Cortés, Carlos Díaz, Raquel de la Campa, Alejandro Presa-Soto and María Luisa Valenzuela
Photochem 2024, 4(3), 302-318; https://doi.org/10.3390/photochem4030018 - 14 Jul 2024
Viewed by 726
Abstract
Starting from poly(4-vinylpyridine) ((P4VP)n), poly(2-vinylpyridine) ((P2VP)n), and [N=P(O2CH2CF3)]m-b-P2VP20 block copolymers, a series of metal-containing homopolymers, (P4VP)n⊕MXm, (P2VP)n⊕MXm, and [N=P(O2 [...] Read more.
Starting from poly(4-vinylpyridine) ((P4VP)n), poly(2-vinylpyridine) ((P2VP)n), and [N=P(O2CH2CF3)]m-b-P2VP20 block copolymers, a series of metal-containing homopolymers, (P4VP)n⊕MXm, (P2VP)n⊕MXm, and [N=P(O2CH2CF3)]m-b-P2VP20]⊕MXm MXm = PtCl2, ZnCl2, and Eu(NO3)3, have been successfully prepared by using a direct and simple solution methodology. Solid-state pyrolysis of the prepared metal-containing polymeric precursors led to the formation of a variety of different metallic and metal oxide nanoparticles (Pt, ZnO, Eu2O3, and EuPO4) depending on the composition and nature of the polymeric template precursor. Thus, whereas Eu2O3 nanostructures were obtained from europium-containing homopolymers ((P4VP)n⊕MXm and (P2VP)n⊕MXm), EuPO4 nanostructures were achieved using phosphorus-containing block copolymer precursors, [N=P(O2CH2CF3)]m-b-P2VP20]⊕MXm with MXm = Eu(NO3)3. Importantly, and although both Eu2O3 and EuPO4 nanostructures exhibited a strong luminescence emission, these were strongly influenced by the nature and composition of the macromolecular metal-containing polymer template. Thus, for P2VP europium-containing homopolymers ((P4VP)n⊕MXm and (P2VP)n⊕MXm), the highest emission intensity corresponded to the lowest-molecular-weight homopolymer template, [P4VP(Eu(NO3)3]6000, whereas the opposite behavior was observed when block copolymer precursors, [N=P(O2CH2CF3)]m-b-P2VP20]⊕MXm MXm= Eu(NO3)3, were used (highest emission intensity corresponded to [N=P(O2CH2CF3)]100-b-[P2VP(Eu(NO3)3)x]20). The intensity ratio of the emission transitions: 5D07F2/5D07F1, suggested a different symmetry around the Eu3+ ions depending on the nature of the polymeric precursor, which also influenced the sizes of the prepared Pt°, ZnO, Eu2O3, and EuPO4 nanostructures. Full article
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17 pages, 1708 KiB  
Systematic Review
A Systematic Review of Heterogeneous Catalysis Applied to the Treatment of Pharmaceutical Wastewater: Operational Conditions and Statistical Analysis
by Raqueline Caldas do Nascimento, Arthur Cahino, Larissa Granjeiro Lucena, Inalmar D. Barbosa Segundo, Jonathan Cawettiere Espíndola and Elisângela M. R. Rocha
Photochem 2024, 4(3), 285-301; https://doi.org/10.3390/photochem4030017 - 29 Jun 2024
Viewed by 699
Abstract
The use of heterogeneous photocatalysis has garnered significant attention, mainly due to its remarkable efficacy in degrading recalcitrant compounds. The main objective of this research was to investigate this process applied to pharmaceutical treatment. For that, an analysis of a Final Bibliographic Portfolio [...] Read more.
The use of heterogeneous photocatalysis has garnered significant attention, mainly due to its remarkable efficacy in degrading recalcitrant compounds. The main objective of this research was to investigate this process applied to pharmaceutical treatment. For that, an analysis of a Final Bibliographic Portfolio (FBP), using the systematic review of the PRISMA and the ProKnow-C method, and a meta-analysis study in a historical series from 2010 to 2020, were performed for scientific works published in indexed journals from the Scopus and Web of Science databases and fully available in English. The works were filtered after a careful reading of the titles, followed by the exclusion of repeated documents and those that were not aligned with the research from 3498 articles, 40 of which were chosen to compose the FBP that addressed the classes of antibiotics, antihypertensives, analgesics, and anti-inflammatory drugs after scientific recognition and exclusion due to not fitting into one of the four FBP structured stages: (1) identification, (2) triage, (3) eligibility, and (4) inclusion. The following gaps were highlighted: (i) a limited number of studies working with interactions of the interfering variables; (ii) a large number of experiments not considering the natural constituents of wastewater; (iii) the use of drug concentrations high above the values found in aquatic matrices; (iv) little applicability of the process at the real scale. In this meta-analysis study, operational parameter optimization was fundamental to guarantee degradation efficiencies above 80% with a variety of pharmaceutical pollutants, the main representatives studied of which were tetracycline, nimesulide, diclofenac, ibuprofen, and atenolol. However, there is still a need to determine the best conditions for this technique when using real effluents, which have the utmost importance for the process on a large scale. Full article
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