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17 pages, 6521 KiB  
Article
Rational Fabrication of Ag2S/g-C3N4 Heterojunction for Photocatalytic Degradation of Rhodamine B Dye Under Natural Solar Radiation
by Ali Alsalme, Ahmed Najm, Nagy N. Mohammed, M. F. Abdel Messih, Ayman Sultan and Mohamed Abdelhay Ahmed
Catalysts 2024, 14(12), 914; https://doi.org/10.3390/catal14120914 - 11 Dec 2024
Viewed by 484
Abstract
Near-infrared light-triggered photocatalytic water treatment has attracted significant attention in recent years. In this novel research, rational sonochemical fabrication of Ag2S/g-C3N4 nanocomposites with various compositions of Ag2S (0–25) wt% was carried out to eliminate hazardous rhodamine [...] Read more.
Near-infrared light-triggered photocatalytic water treatment has attracted significant attention in recent years. In this novel research, rational sonochemical fabrication of Ag2S/g-C3N4 nanocomposites with various compositions of Ag2S (0–25) wt% was carried out to eliminate hazardous rhodamine B dye in a cationic organic pollutant model. g-C3N4 sheets were synthesized via controlled thermal annealing of microcrystalline urea. However, black Ag2S nanoparticles were synthesized through a precipitation-assisted sonochemical route. The chemical interactions between various compositions of Ag2S and g-C3N4 were carried out in an ultrasonic bath with a power of 300 W. XRD, PL, DRS, SEM, HRTEM, mapping, BET, and SAED analysis were used to estimate the crystalline, optical, nanostructure, and textural properties of the solid specimens. The coexistence of the diffraction peaks of g-C3N4 and Ag2S implied the successful production of Ag2S/g-C3N4 heterojunctions. The band gap energy of g-C3N4 was exceptionally reduced from 2.81 to 1.5 eV with the introduction of 25 wt% of Ag2S nanoparticles, implying the strong absorbability of the nanocomposites to natural solar radiation. The PL signal intensity of Ag2S/g-C3N4 was reduced by 40% compared with pristine g-C3N4, implying that Ag2S enhanced the electron–hole transportation and separation. The rate of the photocatalytic degradation of rhodamine B molecules was gradually increased with the introduction of Ag2S on the g-C3N4 surface and reached a maximum for nanocomposites containing 25 wt% Ag2S. The radical trapping experiments demonstrated the principal importance of reactive oxygen species and hot holes in destroying rhodamine B under natural solar radiation. The charge transportation between Ag2S and g-C3N4 semiconductors proceeded through the type I straddling scheme. The enriched photocatalytic activity of Ag2S/g-C3N4 nanocomposites resulted from an exceptional reduction in band gap energy and controlling the electron–hole separation rate with the introduction of Ag2S as an efficient photothermal photocatalyst. The novel as-synthesized nanocomposites are considered a promising photocatalyst for destroying various types of organic pollutants under low-cost sunlight radiation. Full article
(This article belongs to the Section Photocatalysis)
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<p>XRD of g-C<sub>3</sub>N<sub>4</sub>, Ag<sub>2</sub>S, and CNAgS25 nanocomposites.</p>
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<p>N<sub>2</sub>-adsorption isotherm of (<b>a</b>) g-C<sub>3</sub>N<sub>4</sub> and (<b>b</b>) CNAgS25.</p>
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<p>(<b>a</b>) SEM of CNAgS25, (<b>b</b>) mapping of CNAgS25, (<b>c</b>) mapping of C, (<b>d</b>) mapping of (N), (<b>e</b>) mapping of Ag, (<b>f</b>) mapping of S, (<b>g</b>) EDX of CNAgS25.</p>
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<p>(<b>a</b>) TEM of CNAgS25, (<b>b</b>) HRTEM of CNAgS25 and (<b>c</b>) SAED of CNAgS25.</p>
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<p>(<b>a</b>) TEM of CNAgS25, (<b>b</b>) HRTEM of CNAgS25 and (<b>c</b>) SAED of CNAgS25.</p>
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<p>(<b>a</b>) DRS of g-C<sub>3</sub>N<sub>4</sub>, Ag<sub>2</sub>S, CNAgS15, and CNAgS25. (<b>b</b>) Tauc plot of g-C<sub>3</sub>N<sub>4</sub>, Ag2S, CNAgS15, and CNAgS25.</p>
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<p>PL analysis of g-C<sub>3</sub>N<sub>4</sub>, NAgS15, and CNAgS25.</p>
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<p>The absorption spectrum for photocatalytic degradation of rhodamine B over the surfaces of g-C3N4, CNAg10, CNAg15, and CNAg25.</p>
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<p>(<b>a</b>) The variations in the amount of RhB removed (%) under dark and light reactions with the illumination time over the surfaces of g-C<sub>3</sub>N<sub>4</sub>, CNAg10, CNAg15, and CNAg25. (<b>b</b>) The kinetic first-order plot for photocatalytic degradation of RhB dye over the surfaces of g-C<sub>3</sub>N<sub>4</sub>, CNAg10, CNAg15, and CNAg25.</p>
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<p>Photocatalytic degradation of rhodamine B (2 × 10<sup>−5</sup> M) over CNAgS25 nanocomposite in the presence of 2 × 10<sup>−5</sup> M of the following scavengers: (<b>a</b>) benzoquinone, (<b>b</b>) ammonium oxalate, and (<b>c</b>) isopropanol. (<b>d</b>) PL spectrum of terephthalic acid 2 × 10<sup>−4</sup> M over CNAgS25 nanocomposite at 325 nm excitation wavelength.</p>
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<p>Photocatalytic degradation of rhodamine B (2 × 10<sup>−5</sup> M) over CNAgS25 nanocomposite in the presence of 2 × 10<sup>−5</sup> M of the following scavengers: (<b>a</b>) benzoquinone, (<b>b</b>) ammonium oxalate, and (<b>c</b>) isopropanol. (<b>d</b>) PL spectrum of terephthalic acid 2 × 10<sup>−4</sup> M over CNAgS25 nanocomposite at 325 nm excitation wavelength.</p>
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<p>Regeneration of CNAgS25 for five consecutive cycles for removal of RhB dye over CNAgS25 nanocomposite.</p>
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<p>A scheme for electron transportation between g-C<sub>3</sub>N<sub>4</sub> and Ag<sub>2</sub>S semiconductors.</p>
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<p>Scheme for synthesis of (<b>a</b>) g-C<sub>3</sub>N<sub>4</sub>, (<b>b</b>) Ag<sub>2</sub>S and (<b>c</b>) Ag<sub>2</sub>S/g-C<sub>3</sub>N<sub>4</sub> heterojunction.</p>
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7 pages, 1202 KiB  
Proceeding Paper
Optimizing Germanium-Selective Functionalization on Patterned SiGe Substrates with Thiol-Based Molecules: The Critical Role of Oxygen-Free Conditions
by Alessia Arrigoni, Federico Turco, Benedetta Maria Squeo, Sonia Freddi, Monica Bollani, Tersilla Virgili, Andrea Chiappini, Laura Pasquardini and Mariacecilia Pasini
Chem. Proc. 2024, 16(1), 21; https://doi.org/10.3390/ecsoc-28-20193 - 9 Dec 2024
Viewed by 169
Abstract
Germanium offers attractive optical properties despite being an indirect bandgap semiconductor, and new Ge-based devices are being optimized for sensing and photonics applications. In particular, considering the use of Ge as a sensor, improving its selectivity via organic grafting offers new alternatives that [...] Read more.
Germanium offers attractive optical properties despite being an indirect bandgap semiconductor, and new Ge-based devices are being optimized for sensing and photonics applications. In particular, considering the use of Ge as a sensor, improving its selectivity via organic grafting offers new alternatives that are still under investigation. In this work, we focus on the selective functionalization of germanium in SiGe-patterned alloys using a custom thiol-based luminescent molecule, namely 6-[2,7-bis[5-(5-hexyl-2-thienyl)-2-thienyl]-9-(6-sulfanylhexyl)fluoren-9-yl]hexane-1-thiol. The process selectively targets regions with Ge, while leaving Si-rich areas uncovered. Moreover, this study emphasizes the importance of an oxygen-free environment, as performing the functionalization in an inert atmosphere significantly improves surface coverage. Full article
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<p>Chemical structure of the grafted molecule.</p>
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<p>Fluorescence microscopy images of SiGe samples functionalized in (<b>1</b>) air, two different sample regions (<b>a</b>,<b>b</b>) and (<b>2</b>) under inert conditions, two different sample regions (<b>c</b>,<b>d</b>). Samples are irradiated by UV light.</p>
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<p>Reaction scheme for the synthesis of Bis-TTF.</p>
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32 pages, 6022 KiB  
Article
Combination of Biochar and Advanced Oxidation Processes for the Sustainable Elimination of Pharmaceuticals in Water
by Carolina Gallego-Ramírez, Edwin Chica and Ainhoa Rubio-Clemente
Sustainability 2024, 16(23), 10761; https://doi.org/10.3390/su162310761 - 8 Dec 2024
Viewed by 522
Abstract
The presence of pharmaceuticals in aquatic ecosystems is an issue of increasing concern. Regardless of the low concentration of pharmaceuticals in water, they can have a toxic effect on both humans and aquatic organisms. Advanced oxidation processes (AOPs) have been described as a [...] Read more.
The presence of pharmaceuticals in aquatic ecosystems is an issue of increasing concern. Regardless of the low concentration of pharmaceuticals in water, they can have a toxic effect on both humans and aquatic organisms. Advanced oxidation processes (AOPs) have been described as a promising technique for eliminating pharmaceuticals due to their high efficiency. However, the cost associated with the application of these processes and their high reagents and energy requirements have affected the implementation of AOPs at large scales. Biochar has been suggested to be used as a catalyst in AOPs to overcome these limitations. Biochar is considered as an alternative heterogeneous catalyst thanks to its physicochemical characteristics like its specific surface area, porous structure, oxygen-containing functional groups, electrical conductivity, persistent free radicals (PFRs), modifiable properties, and structure defects. This carbonaceous material presents the capacity to activate oxidizing agents leading to the formation of radical species, which are needed to degrade pharmaceuticals. Additionally, AOP/biochar systems can destroy pharmaceutical molecules following a non-radical pathway. To enhance biochar catalytic performance, modifications have been suggested such as iron (Fe) impregnation, heteroatom doping, and supporting semiconductors on the biochar surface. Although biochar has been efficiently used in combination with several AOPs for the mineralization of pharmaceuticals from water, further research must be conducted to evaluate different regeneration techniques to increase biochar’s sustainable applicability and reduce the operational cost of the combined process. Moreover, operational conditions influencing the combined system are required to be evaluated to discern their effect and find conditions that maximize the degradation of pharmaceuticals by AOP/biochar systems. Full article
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<p>Distribution of pharmaceuticals in the environment.</p>
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<p>Number of publications on the elimination of pharmaceuticals in water with biochar/advanced oxidation process (AOP) according to the Scopus database. Keywords: [TITLE–KEY-ABS (“advanced oxidation process” OR “advanced oxidation technologies” AND biochar AND pharmaceuticals AND water)].</p>
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<p>Flow chart of the solvothermal method for the supporting of titanium dioxide (TiO<sub>2</sub>) on biochar.</p>
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22 pages, 7309 KiB  
Article
Mechanism Analysis of Bubble Discharge Within Silicone Gels Under Pulsed Electric Field
by Dongxin He, Zhe Zhang, Guangzhu Wang, Keming Liu, Haochen Wang, Zhe Xu, Gilbert Teyssedre and Yuantao Zhang
Gels 2024, 10(12), 799; https://doi.org/10.3390/gels10120799 - 6 Dec 2024
Viewed by 312
Abstract
Silicone gel, used in the packaging of high-voltage, high-power semiconductor devices, generates bubbles during the packaging process, which accelerates the degradation of its insulation properties. This paper establishes a testing platform for electrical treeing in silicone gel under pulsed electric fields, investigating the [...] Read more.
Silicone gel, used in the packaging of high-voltage, high-power semiconductor devices, generates bubbles during the packaging process, which accelerates the degradation of its insulation properties. This paper establishes a testing platform for electrical treeing in silicone gel under pulsed electric fields, investigating the effect of pulse voltage amplitude on bubble development and studying the initiation and growth of electrical treeing in a silicone gel with different pulse edge times. The relationship between bubbles and electrical treeing in silicone gel materials is discussed. A two-dimensional plasma simulation model for bubble discharge in silicone gel under pulsed electric fields is developed, analyzing the internal electric field distortion caused by the response times of different ions and electrons. Additionally, the discharge current and its effects on silicone gel under pulsed electric fields are examined. By studying the influence of different pulse edge times, repetition frequencies, and temperatures on discharge current magnitude and ozone generation rates, the impact of electrical breakdown and chemical corrosion on the degradation of organic silicone gel under various operating conditions is analyzed. This study explores the macroscopic and microscopic mechanisms of dielectric performance degradation in organic silicone gel under pulsed electric fields, providing a basis for research on high-performance packaging materials and the development of high-voltage, high-power semiconductor devices. Full article
(This article belongs to the Special Issue Polymer-Based Dielectric Gels)
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<p>The variation law of bubble shape near the needle tip with the amplitude of pulse voltage.</p>
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<p>Dynamic process of electrical tree generation in silicone gel.</p>
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<p>(<b>a</b>) A schematic diagram of stress on bubbles in silicone gel; (<b>b</b>) a schematic diagram of bubble expansion inducing the internal electrical treeing process in silicone gel.</p>
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<p>The variation pattern of electrical treeing inception voltage in silicone gel with pulsed electric field edge time.</p>
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<p>Morphology of electrical tree branches under pulse electric fields with different edge times.</p>
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<p>Spatial and temporal evolution of (<b>a</b>–<b>c</b>) electron density (<b>d</b>–<b>f</b>) and positive ion density during discharge.</p>
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<p>Evolution of surface charges.</p>
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<p>Spatial and temporal evolution of electrical field intensity during discharge.</p>
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<p>(<b>a</b>) Average reaction rate of oxygen atoms and ozone molecules in air gap over 1.5 cycles; (<b>b</b>) average chemical reaction rate of ozone generation.</p>
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<p>Variation in total number of oxygen atoms and ozone molecules in air gap with time.</p>
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<p>Discharge results within half a cycle for edge times of 50 ns and 200 ns. (<b>a</b>) Discharge current; (<b>b</b>) breakdown voltage.</p>
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<p>Variation in discharge current and breakdown voltage with pulse edge time. (<b>a</b>) Discharge current; (<b>b</b>) breakdown voltage.</p>
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<p>Variation in number of ozone molecules with pulse edge time.</p>
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<p>Results within half a cycle for repetition frequencies of 5 kHz and 20 kHz. (<b>a</b>) Discharge current; (<b>b</b>) breakdown voltage.</p>
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<p>Variation in discharge current and breakdown voltage with pulse edge time. (<b>a</b>) Discharge current; (<b>b</b>) breakdown voltage.</p>
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<p>Variation in the number of ozone molecules with pulse repetition frequency.</p>
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<p>Discharge results in half a cycle for temperatures of 300 K and 450 K. (<b>a</b>) Discharge current; (<b>b</b>) breakdown voltage.</p>
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<p>Variation in discharge current and breakdown voltage with temperature. (<b>a</b>) Discharge current; (<b>b</b>) breakdown voltage.</p>
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<p>Variation in ozone molecule number with temperature.</p>
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<p>(<b>a</b>) Chemical equation for silicone hydrogenation reaction. (<b>b</b>) Silicone gel crosslinking system.</p>
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<p>Silicone gel electric tree mold.</p>
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<p>Silicone gel electrical treeing test platform under pulsed electric field.</p>
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<p>Geometry of simulation model.</p>
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27 pages, 5067 KiB  
Review
Materials Nanoarchitectonics for Advanced Devices
by Katsuhiko Ariga
Materials 2024, 17(23), 5918; https://doi.org/10.3390/ma17235918 - 3 Dec 2024
Viewed by 589
Abstract
Advances in nanotechnology have made it possible to observe and evaluate structures down to the atomic and molecular level. The next step in the development of functional materials is to apply the knowledge of nanotechnology to materials sciences. This is the role of [...] Read more.
Advances in nanotechnology have made it possible to observe and evaluate structures down to the atomic and molecular level. The next step in the development of functional materials is to apply the knowledge of nanotechnology to materials sciences. This is the role of nanoarchitectonics, which is a concept of post-nanotechnology. Nanoarchitectonics is defined as a methodology to create functional materials using nanounits such as atoms, molecules, and nanomaterials as building blocks. Nanoarchitectonics is very general and is not limited to materials or applications, and thus nanoarchitecture is applied in many fields. In particular, in the evolution from nanotechnology to nanoarchitecture, it is useful to consider the contribution of nanoarchitecture in device applications. There may be a solution to the widely recognized problem of integrating top-down and bottom-up approaches in the design of functional systems. With this in mind, this review discusses examples of nanoarchitectonics in developments of advanced devices. Some recent examples are introduced through broadly dividing them into organic molecular nanoarchitectonics and inorganic materials nanoarchitectonics. Examples of organic molecular nanoarchitecture include a variety of control structural elements, such as π-conjugated structures, chemical structures of complex ligands, steric hindrance effects, molecular stacking, isomerization and color changes due to external stimuli, selective control of redox reactions, and doping control of organic semiconductors by electron transfer reactions. Supramolecular chemical processes such as association and intercalation of organic molecules are also important in controlling device properties. The nanoarchitectonics of inorganic materials often allows for control of size, dimension, and shape, and their associated physical properties can also be controlled. In addition, there are specific groups of materials that are suitable for practical use, such as nanoparticles and graphene. Therefore, nanoarchitecture of inorganic materials also has a more practical aspect. Based on these aspects, this review finally considers the future of materials nanoarchitectonics for further advanced devices. Full article
(This article belongs to the Section Materials Chemistry)
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Graphical abstract
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<p>Nanoarchitectonics as the concept of constructing functional material systems from the fundamental building blocks of atoms, molecules, and nanomaterials (from the <b>top</b>) and device nanoarchitectonics as the convergence of the top-down and bottom-up approaches (<b>bottom</b>) [<a href="#B54-materials-17-05918" class="html-bibr">54</a>,<a href="#B95-materials-17-05918" class="html-bibr">95</a>].</p>
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<p>Nanoarchitectonics of introducing azulene into linear π-extended polycyclic aromatic hydrocarbons where the gap between HOMO and LUMO can be reduced to a level comparable to that of [n]acene. Reprinted with permission from [<a href="#B225-materials-17-05918" class="html-bibr">225</a>]. Copyright 2023 Oxford University Press.</p>
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<p>n-type exciplex host partners based on quinoline-modified phenanthroline derivatives with estimation of HOMO and LUMO, where the calculated triplet energy values were markedly larger, indicating effective confinement of triplet excitons in the emitter. Reprinted with permission from [<a href="#B226-materials-17-05918" class="html-bibr">226</a>]. Copyright 2023 Oxford University Press.</p>
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<p>A mononuclear Al complex with a β-diketone ligand with excellent thermally activated delayed fluorescence properties. DFT calculations demonstrated that metal complexation could generate a distinctive electronic structure, which could markedly enhance the optical functions of the original diketone ligand. Reprinted with permission from [<a href="#B227-materials-17-05918" class="html-bibr">227</a>]. Copyright 2023 Oxford University Press.</p>
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<p>Nanoarchitectonics of ultrathin 2D organic nanosheets with denser molecular packing: (<b>top</b>) the component molecule with the orthogonal spirofluorene exanthene scaffold; (<b>bottom</b>) the formation of ultrathin 2D organic nanosheets with its AFM image and its molecular-packing model. Reprinted with permission from [<a href="#B228-materials-17-05918" class="html-bibr">228</a>]. Copyright 2023 Wiley-VCH.</p>
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<p>Polyvinyl spiropyran-grafted polydopamine-encapsulated structures for transient digital memristors where black phosphorus quantum dots functionalized with photochromic polyvinyl spiropyran-grafted polydopamine are employed in the construction. Reprinted with permission from [<a href="#B229-materials-17-05918" class="html-bibr">229</a>]. Copyright 2024 Oxford University Press.</p>
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<p>An energy cycle based on a highly selective redox reaction between lactate and pyruvate obtained from biomass resources: (<b>A</b>) a lactic acid electrosynthesis cell (LAEC); (<b>B</b>) a direct lactic acid fuel cell (DLAFC). Reprinted with permission from [<a href="#B231-materials-17-05918" class="html-bibr">231</a>]. Copyright 2023 Oxford University Press.</p>
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<p>A novel coupling between proton-coupled electron transfer reactions and polymer organic semiconductors: (<b>top</b>) doping mechanism; (<b>bottom</b>) chemical structures. Reprinted with permission from [<a href="#B232-materials-17-05918" class="html-bibr">232</a>]. Copyright 2023 Springer-Nature.</p>
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<p>GaS nanosheet devices comprising varying thicknesses and their photoresponsive devices. Reproduced under terms of the CC-BY license [<a href="#B233-materials-17-05918" class="html-bibr">233</a>]. Copyright 2023 MDPI.</p>
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<p>A cadmium-free red-emitting quantum dot enabled by incorporating copper into a silver indium gallium sulfide/gallium sulfide (Ag-In-Ga-S/Ga-S) core/shell quantum dot as quantum dot-LED devices. Reprinted with permission from [<a href="#B234-materials-17-05918" class="html-bibr">234</a>]. Copyright 2023 Oxford University Press.</p>
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<p>Caffeine–methylammonium lead iodide perovskite solar cell device where the introduction of caffeine into methylammonium lead iodide results in the production of a highly efficient and stable caffeine-based additive methylammonium lead iodide perovskite solar cell device. Reprinted with permission from [<a href="#B235-materials-17-05918" class="html-bibr">235</a>]. Copyright 2023 Springer-Nature.</p>
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<p>Fabricated a bilayer composite comprising uniformly incorporated polyaniline nanorods within a 3D mesoporous matrix of natural wood where the numerous aligned wood microchannels facilitate constant and rapid water transport at the air–water interface, driven by capillary forces. Reprinted with permission from [<a href="#B236-materials-17-05918" class="html-bibr">236</a>]. Copyright 2023 Oxford University Press.</p>
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<p>A remote health monitoring system based on a telemedicine platform for remote health assessment by an integrated nanoarchitectonics approach in which the electrodes of the stretchable asymmetric supercapacitor and strain sensor were composed of a composite of FePS<sub>3</sub> and reduced graphene oxide coated on a stretchable fabric. Reproduced under terms of the CC-BY license [<a href="#B237-materials-17-05918" class="html-bibr">237</a>]. Copyright 2022 Springer-Nature.</p>
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27 pages, 2052 KiB  
Review
Photocatalytic Composites Based on Biochar for Antibiotic and Dye Removal in Water Treatment
by Amra Bratovčić and Vesna Tomašić
Processes 2024, 12(12), 2746; https://doi.org/10.3390/pr12122746 - 3 Dec 2024
Viewed by 887
Abstract
Many semiconductor photocatalysts are characterized by high photostability and non-toxicity but suffer from the limited excitation in the UV part of the spectrum and the fast recombination of the photogenerated electron–hole pairs. To improve the above properties, biochar-supported composite photocatalysts have recently attracted [...] Read more.
Many semiconductor photocatalysts are characterized by high photostability and non-toxicity but suffer from the limited excitation in the UV part of the spectrum and the fast recombination of the photogenerated electron–hole pairs. To improve the above properties, biochar-supported composite photocatalysts have recently attracted much attention. Compared with the pure photocatalyst, the biochar-enriched catalyst has superior specific surface area and high porosity, catalytic efficiency, stability, and recoverability. Biochar can be obtained from various carbon-rich plant or animal wastes by different thermochemical processes such as pyrolysis, hydrothermal carbonization, torrefaction, and gasification. The main features of biochar are its low price, non-toxicity, and the large number of surface functional groups. This paper systematically presents the latest research results on the method of preparation of various composites in terms of the choice of photoactive species and the source of biomass, their physico-chemical properties, the mechanism of the photocatalytic activity, and degradation efficiency in the treatment of organic contaminants (dyes and antibiotics) in an aquatic environment. Particular emphasis is placed on understanding the role of biochar in improving the photocatalytic activity of photoactive species. Full article
(This article belongs to the Special Issue Treatment and Remediation of Organic and Inorganic Pollutants)
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<p>Classification of biomass sources based on the initial moisture content and categorization of thermochemical processes based on the aggregate state of the target product.</p>
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<p>Advantages of biochar in photocatalysis.</p>
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<p>Schematic illustration of the catalytic degradation of organic pollutant.</p>
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24 pages, 9019 KiB  
Article
The Synthesis, Characterization, and Theoretical Study of Ruthenium (II) Polypyridyl Oligomer Hybrid Structures with Reduced Graphene Oxide for Enhanced Optoelectronic Applications
by Alexander Schultheiss, Jamel White, Khoa Le, Nicole Boone, Ufana Riaz and Darlene K. Taylor
Int. J. Mol. Sci. 2024, 25(23), 12989; https://doi.org/10.3390/ijms252312989 - 3 Dec 2024
Viewed by 326
Abstract
π-conjugated polymers are arguably one of the most exciting classes of materials and have attracted substantial attention due to their unique optical and electronic properties. The introduction of transition metals into conjugated polymers tunes the optoelectronic properties of these metallopolymers, which may improve [...] Read more.
π-conjugated polymers are arguably one of the most exciting classes of materials and have attracted substantial attention due to their unique optical and electronic properties. The introduction of transition metals into conjugated polymers tunes the optoelectronic properties of these metallopolymers, which may improve their performance in device applications. Graphene and reduced graphene oxide (RGO) derivatives are interesting materials with a unique structure and outstanding properties. The present work reports an investigation of three hybrid RGO and π-conjugated oligomers that contain ruthenium polypyridyl chromophores serving as models to provide molecular-level insight for the corresponding transition-metal-containing conjugated polymers. Full article
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Graphical abstract
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<p>UV–visible spectra of (<b>a</b>) C989Ru, A1, a mixture of A1 + C989Ru, and A1[Ru(bpy)<sub>2</sub>]<sup>2+</sup>; (<b>b</b>) C989Ru, A2, a mixture of A<sup>2+</sup> C989Ru, and A2[Ru(bpy)<sub>2</sub>]<sup>2+</sup>. Note the red arrows draw attention to the peaks of interest.</p>
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<p>Absorbance and emission spectra of (<b>a</b>) A1[Ru(bpy)<sub>2</sub>]<sup>2+</sup> and (<b>b</b>) A2[Ru(bpy)<sub>2</sub>]<sup>2+</sup>.</p>
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<p>Cyclic voltammetry of (<b>a</b>) A1[Ru(bpy)<sub>2</sub>]<sup>2+</sup> and (<b>b</b>) A2[Ru(bpy)<sub>2</sub>]<sup>2+</sup> at a scan rate of 100 mV/s. The arrows displayed in the figure draw attention to the redox peaks discussed in the text.</p>
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<p>(<b>a</b>) Fluorescence emission quenching of A1[Ru(bpy)<sub>2</sub>]<sup>2+</sup> by RGO. (<b>b</b>) Transient absorption spectrum of A2[Ru(bpy)<sub>2</sub>]<sup>2+</sup> at 50 ns, 2 us, and 10 us. (<b>c</b>) Time-dependent emission decay for A2[Ru(bpy)<sub>2</sub>]<sup>2+</sup> at 630 nm and bleaching at 470 nm.</p>
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<p>(<b>a</b>) Fluorescence emission quenching of A1[Ru(bpy)<sub>2</sub>]<sup>2+</sup> by RGO. (<b>b</b>) Transient absorption spectrum of A2[Ru(bpy)<sub>2</sub>]<sup>2+</sup> at 50 ns, 2 us, and 10 us. (<b>c</b>) Time-dependent emission decay for A2[Ru(bpy)<sub>2</sub>]<sup>2+</sup> at 630 nm and bleaching at 470 nm.</p>
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<p>Raman spectra of GO, RGO, and RGO-A2[Ru(bpy)<sub>2</sub>]<sup>2+</sup>.</p>
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<p>Scanning electron microscope (SEM) images of RGO and RGO-A2[Ru(bpy)<sub>2</sub>]<sup>2+</sup>. Note the increased surface roughness observed in RGO-A2[Ru(bpy)<sub>2</sub>]<sup>2+</sup> due to the formation of a thin film of the oligomer material that is covalently attached to the RGO surface.</p>
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<p>X-ray photoelectron spectroscopy (XPS) spectrum of RGO-A2[Ru(bpy)<sub>2</sub>]<sup>2+</sup>.</p>
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<p>Relaxed geometries of A1 monomer backbone with HOMO orbitals followed by the LUMO orbitals for each: (<b>a</b>,<b>b</b>) FHI-aims HF; (<b>c</b>,<b>d</b>) FHI-aims PBE/PBE0. (<b>e</b>) Shows the color scale and values for the orbitals in eVs. Relaxed geometries of C989Ru chromophore with HOMO orbitals followed by the LUMO orbitals for each: (<b>f</b>,<b>g</b>) Gaussian via HF. Relaxed geometries of A1[Ru]bpy monomer with HOMO orbitals followed by the LUMO orbitals for each: (<b>h</b>,<b>i</b>) FHI-aims via PBE/PBE0 (<b>j</b>,<b>k</b>); FHI-aims (PBE/PBE0) with van der Waals force considerations.</p>
Full article ">Figure 8 Cont.
<p>Relaxed geometries of A1 monomer backbone with HOMO orbitals followed by the LUMO orbitals for each: (<b>a</b>,<b>b</b>) FHI-aims HF; (<b>c</b>,<b>d</b>) FHI-aims PBE/PBE0. (<b>e</b>) Shows the color scale and values for the orbitals in eVs. Relaxed geometries of C989Ru chromophore with HOMO orbitals followed by the LUMO orbitals for each: (<b>f</b>,<b>g</b>) Gaussian via HF. Relaxed geometries of A1[Ru]bpy monomer with HOMO orbitals followed by the LUMO orbitals for each: (<b>h</b>,<b>i</b>) FHI-aims via PBE/PBE0 (<b>j</b>,<b>k</b>); FHI-aims (PBE/PBE0) with van der Waals force considerations.</p>
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<p>Relaxed geometries of A1 monomer backbone with HOMO orbitals followed by the LUMO orbitals for each: (<b>a</b>,<b>b</b>) FHI-aims HF; (<b>c</b>,<b>d</b>) FHI-aims PBE/PBE0. (<b>e</b>) Shows the color scale and values for the orbitals in eVs. Relaxed geometries of C989Ru chromophore with HOMO orbitals followed by the LUMO orbitals for each: (<b>f</b>,<b>g</b>) Gaussian via HF. Relaxed geometries of A1[Ru]bpy monomer with HOMO orbitals followed by the LUMO orbitals for each: (<b>h</b>,<b>i</b>) FHI-aims via PBE/PBE0 (<b>j</b>,<b>k</b>); FHI-aims (PBE/PBE0) with van der Waals force considerations.</p>
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<p>(<b>a</b>) Extrapolated data of A1[Ru]bpy<sup>2+</sup> per unit length. Blue graph includes van der Waals considerations, while the red graph does not. (<b>b</b>) EDX data reveal the element concentration of A1[Ru] powder.</p>
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<p>Geometric conformation of [A1[Ru]bpy<sup>2+</sup>]2Cl<sup>−</sup> for the (<b>a</b>) monomer, (<b>b</b>) dimer, and (<b>c</b>) trimer.</p>
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<p>Extrapolated bandgaps of [A1[Ru]bpy<sup>2+</sup>]<sub>2</sub>Cl<sup>−</sup> where the diamonds represent the three data points obtained from theoretical calculations. The circle signifies the bandgap of P3HT (2.2 eV) for comparison purposes.</p>
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<p>Reaction scheme for A1[Ru(bpy)<sub>2</sub>]<sup>2+</sup>.</p>
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<p>Reaction scheme for A1[Ru(bpy)<sub>2</sub>]<sup>2+</sup>.</p>
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<p>Reaction scheme for A1[Ru(bpy)<sub>2</sub>]<sup>2+</sup>.</p>
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<p>Reaction scheme for A2[Ru(bpy)<sub>2</sub>]<sup>2+</sup>.</p>
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<p>Reaction scheme for A2[Ru(bpy)<sub>2</sub>]<sup>2+</sup>.</p>
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<p>Reaction scheme for grafting A2[Ru(bpy)<sub>2</sub>]<sup>2+</sup> to RGO.</p>
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13 pages, 4524 KiB  
Article
Self-Powered Photodetectors with High Stability Based on Se Paper/P3HT:Graphene Heterojunction
by Xuewei Yu, Yuxin Huang, Pengfan Li, Shiliang Feng, Xi Wan, Yanfeng Jiang and Pingping Yu
Nanomaterials 2024, 14(23), 1923; https://doi.org/10.3390/nano14231923 - 29 Nov 2024
Viewed by 447
Abstract
Photodetectors based on selenium (Se) have attracted significant attention because of their outstanding optoelectronic characteristics, including their rapid reactivity and high photoconductivity. However, the poor responsivity of pure Se limits their further development. In this study, a novel Se-P/P3HT:G photodetector was designed and [...] Read more.
Photodetectors based on selenium (Se) have attracted significant attention because of their outstanding optoelectronic characteristics, including their rapid reactivity and high photoconductivity. However, the poor responsivity of pure Se limits their further development. In this study, a novel Se-P/P3HT:G photodetector was designed and fabricated by combining an organic semiconductor made of poly-3-hexylthiophene mixed with graphene (P3HT:G) with self-supporting Se paper (Se-P) via spin-coating process. The device possesses a dark current of around 4.23 × 10−12 A and self-powered characteristics at 300–900 nm. At zero bias voltage and 548 nm illumination, the Se-P/P3HT:G photodetector demonstrates a maximum photocurrent of 1.35 × 10−9 A (745% higher than that of Se-P at 0.1 V), a quick response time (16.2/27.6 ms), an on/off ratio of 292, and a maximum detectivity and responsivity of 6.47 × 1011 Jones and 34 mA W−1, respectively. Moreover, Se-P/P3HT:G exhibits superior environmental stability. After one month, the photocurrent value of the Se-P/P3HT:G device held steady at 91.4% of its initial value, and even following pre-treatment at 140 °C, the on/off ratio still remained 17 (at a retention rate of about 5.9%). The excellent thermal stability, environmental reliability, and optoelectronic performance of this heterojunction structure offer a useful pathway for the future advancement of high-performance optoelectronic devices. Full article
(This article belongs to the Special Issue Graphene and 2D Material-Based Photodetectors)
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<p>Schematic illustration of the fabrication process for Se-P/P3HT:G heterojunction photodetectors.</p>
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<p>(<b>a</b>) Photograph of Se-P, and SEM images of Se-P at low (<b>b</b>) and high (<b>c</b>) magnification. A SEM image of Se-P/P3HT:G (<b>d</b>), SEM images of a graphene nanoflake (<b>e</b>), and P3HT (<b>f</b>) in the Se-P/P3HT:G heterojunction.</p>
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<p>(<b>a</b>) XRD patterns of Se-P, graphene, and Se-P/P3HT:G; (<b>b</b>) Raman spectra of Se-P, Graphene, P3HT, and Se-P/P3HT:G; (<b>c</b>) UV-vis absorption spectra of P3HT, graphene, P3HT:G, Se-P, and Se-P/P3HT:G; and (<b>d</b>) Eg of Se-P and P3HT:G.</p>
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<p>Se-P I-V curves (<b>a</b>) and I-t curves (<b>b</b>) at various wavelengths; Se-P/P3HT I-V curves (<b>c</b>) and I-t curves (<b>d</b>) at various wavelengths; and Se-P/P3HT:G I-V curves (<b>e</b>) and I-t curves (<b>f</b>) at various wavelengths.</p>
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<p>Rise/fall times of the Se-P at 548 nm (1.31 mW cm<sup>−2</sup>) under 0.1 V (<b>a</b>) and Se-P/P3HT (<b>b</b>) and Se-P/P3HT:G (<b>c</b>) at 548 nm and 0 V bias in a single cycle. Responsivity (<b>d</b>), specific detectivity (<b>e</b>), and external quantum efficiency (<b>f</b>) of Se-P, Se-P/P3HT, and Se-P/P3HT:G versus the wavelength range of 348–876 nm at 0 V bias.</p>
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<p>UPS spectra of Se-P (<b>a</b>,<b>b</b>) P3HT:G. Energy band diagrams of Se-P/P3HT (<b>c</b>) and Se-P/P3HT:G (<b>d</b>) before contact and without light illumination. Energy band diagrams of Se-P/P3HT (<b>e</b>) and Se-P/P3HT:G (<b>f</b>) after contact under light illumination.</p>
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<p>At 548 nm and 0 V bias, I-t curves (<b>a</b>) of Se-P/P3HT:G device left for 1 day, 1 week, and 1 month and I-t curves (<b>b</b>) of Se-P/P3HT:G device after treatment at 0 °C, 25 °C, 70 °C, 100 °C, and 140 °C, respectively.</p>
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14 pages, 3443 KiB  
Article
Menthol-Induced Chirality in Semiconductor Nanostructures: Chiroptical Properties of Atomically Thin 2D CdSe Nanoplatelets Capped with Enantiomeric L-(−)/D-(+)-Menthyl Thioglycolates
by Maria Yu. Skrypnik, Daria A. Kurtina, Sofia P. Karamysheva, Evgeniia A. Stepanidenko, Irina S. Vasil’eva, Shuai Chang, Alexander I. Lebedev and Roman B. Vasiliev
Nanomaterials 2024, 14(23), 1921; https://doi.org/10.3390/nano14231921 - 28 Nov 2024
Viewed by 675
Abstract
Semiconductor colloidal nanostructures capped with chiral organic molecules are a research hotspot due to their wide range of important implications for photonic and spintronic applications. However, to date, the study of chiral ligands has been limited almost exclusively to naturally occurring chiral amino [...] Read more.
Semiconductor colloidal nanostructures capped with chiral organic molecules are a research hotspot due to their wide range of important implications for photonic and spintronic applications. However, to date, the study of chiral ligands has been limited almost exclusively to naturally occurring chiral amino and hydroxy acids, which typically contain only one stereocenter. Here, we show the pronounced induction of chirality in atomically thin CdSe nanoplatelets (NPLs) by capping them with enantiopure menthol derivatives as multi-stereocenter molecules. L-(−)/D-(+)-menthyl thioglycolate, easily synthesized from L-(−)/D-(+)-menthol, is attached to Cd-rich (001) basal planes of 2- and 3-monolayer (ML) CdSe NPLs. We show the appearance of narrow sign-alternating bands in the circular dichroism (CD) spectra of 2 ML NPLs corresponding to heavy-hole (HH) and light-hole (LH) excitons with maximal dissymmetry g-factor up to 2.5 × 10−4. The most intense CD bands correspond to the lower-energy HH exciton, and in comparison with the N-acetyl-L-Cysteine ligand, the CD bands for L-(−)-menthyl thioglycolate have the opposite sign. The CD measurements are complemented with magnetic CD measurements and first-principles modeling. The obtained results may be of interest for designing new chiral semiconductor nanostructures and improving understanding of their chiroptical properties. Full article
(This article belongs to the Special Issue Nano Surface Engineering)
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<p>(<b>a</b>) Scheme of synthesis of chiral ester from menthol and thioglycolic acid. (<b>b</b>) Structural formulas of mirror stereoisomers of L-(−)/D-(+)-menthyl thioglycolate. (<b>c</b>) Scheme of attachment of chiral ester to basal planes of CdSe nanoplatelets due to formation of cadmium–sulfur bond. Note the nonpolar outer surface of the obtained nanoplatelets, caused by cyclohexane fragments of the ester.</p>
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<p>(<b>a</b>) FTIR spectra of the initial reagents, TGA (green line) and L-menthol (grey line), and spectrum of the synthesized ester menthylTG sample (blue line). (<b>b</b>) FTIR spectra of menthylTG-capped CdSe2ML_menthylTG (blue line) sample. Black line shows the FTIR spectrum of the initial OA-capped CdSe2ML_OA sample. Positions of the main vibration bands are marked by black vertical lines. The spectra are offset for clarity. Typical absorbance spectra of (<b>c</b>) CdSe2ML_OA NPLs (black solid line) and (<b>d</b>) the same sample after ligand exchange with menthylTG (CdSe2ML_menthylTG, blue line) and thioglycolic acid (CdSe2ML_TGA, green line) ligands. (<b>e</b>) Modification of absorbance spectra during the ligand exchange at different times. Black arrows show changes in the intensity of bands during the ligand exchange.</p>
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<p>TEM images of the transformation of as-synthesized scroll-like CdSe2ML_OA NPLs covered with oleic acid ligands (<b>a</b>) to flat CdSe2ML_menthylTG NPLs after ligand exchange with L-menthylTG (<b>b</b>). Insets: enlarged images of NPL ensembles.</p>
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<p>(<b>a</b>) CD spectra of 2 ML CdSe NPLs coated with L-(−)-menthyl thioglycolate (blue line), D-(+)-menthyl thioglycolate (red line), and achiral TGA ligands (grey line). (<b>b</b>) Comparison of CD spectra of CdSe3ML_L-MenthyTG (green line) and CdSe2ML_L-MenthyTG (blue line) samples emphasizing the effect of thickness. The CD spectrum of free L-MenthyTG (black line) is shown for comparison. (<b>c</b>) Decomposition of the CD spectrum of 2 ML CdSe NPLs coated with L-(−)-menthyl thioglycolate into the sum of Lorentz lines. Empty circles are experimental data, dashed green lines are Lorentz profiles, and the red line is the sum of Lorentz profiles. (<b>d</b>) Comparison of CD spectra of 2 ML CdSe NPLs coated with L-(−)-menthyl thioglycolate (blue line) and L-acetylcysteine (red line). All panels show the corresponding absorption spectra at the top.</p>
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<p>DFT models of the crystal structure of 2 ML CdSe NPLs coated with (<b>a</b>) L-(−)-menthyl thioglycolate, in a [110] orientation, (<b>b</b>) L-(−)-menthyl thioglycolate, in a [001] orientation, and (<b>c</b>) thioglycolic acid, in [110] orientation. Atoms are marked: Cd—green, Se—purple, S—yellow, O—red.</p>
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<p>MCD spectra of 2 ML CdSe NPL samples coated with (<b>a</b>) L-(−)-menthyl thioglycolate and (<b>b</b>) TGA ligands. The spectra were recorded from NPL dispersions in (<b>a</b>) THF and (<b>b</b>) methanol. The measurements were performed in magnetic fields up to ±1.5 T. The spectra were recorded with an interval of 0.5 T.</p>
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15 pages, 10219 KiB  
Article
Effect of Alkyl Side Chain Length on Electrical Performance of Ion-Gel-Gated OFETs Based on Difluorobenzothiadiazole-Based D-A Copolymers
by Han Zhou, Zaitian Cheng, Guoxing Pan, Lin Hu and Fapei Zhang
Polymers 2024, 16(23), 3287; https://doi.org/10.3390/polym16233287 - 26 Nov 2024
Viewed by 384
Abstract
The performance of organic field-effect transistors (OFETs) is highly dependent on the dielectric–semiconductor interface, especially in ion-gel-gated OFETs, where a significantly high carrier density is induced at the interface at a low gate voltage. This study investigates how altering the alkyl side chain [...] Read more.
The performance of organic field-effect transistors (OFETs) is highly dependent on the dielectric–semiconductor interface, especially in ion-gel-gated OFETs, where a significantly high carrier density is induced at the interface at a low gate voltage. This study investigates how altering the alkyl side chain length of donor–acceptor (D-A) copolymers impacts the electrical performance of ion-gel-gated OFETs. Two difluorobenzothiadiazole-based D-A copolymers, PffBT4T-2OD and PffBT4T-2DT, are compared, where the latter features longer alkyl side chains. Although PffBT4T-2DT shows a 2.4-fold enhancement of charge mobility in the SiO2-gated OFETs compared to its counterpart due to higher crystallinity in the film, PffBT4T-2OD outperforms PffBT4T-2DT in the ion-gel-gated OFETs, manifested by an extraordinarily high mobility of 17.7 cm2/V s. The smoother surface morphology, as well as stronger interfacial interaction between the ion-gel dielectric and PffBT4T-2OD, enhances interfacial charge accumulation, which leads to higher mobility. Furthermore, PffBT4T-2OD is blended with a polymeric elastomer SEBS to achieve ion-gel-gated flexible OFETs. The blend devices exhibit high mobility of 8.6 cm2/V s and high stretchability, retaining 45% of initial mobility under 100% tensile strain. This study demonstrates the importance of optimizing the chain structure of polymer semiconductors and the semiconductor–dielectric interface to develop low-voltage and high-performance flexible OFETs for wearable electronics applications. Full article
(This article belongs to the Section Polymer Chemistry)
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<p>(<b>a</b>) Chemical structure of PffBT4T-2OD and PffBT4T-2DT. (<b>b</b>) The normalized UV-visible absorption spectra of the PffBT4T-2OD and PffBT4T-2DT film.</p>
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<p>(<b>a</b>,<b>b</b>) Two-dimensional GIXRD patterns of the PffBT4T-2OD film (<b>a</b>) and PffBT4T-2DT film (<b>b</b>), respectively; (<b>c</b>,<b>d</b>) Cross-section profiles along the <span class="html-italic">q<sub>xy</sub></span> (<b>c</b>) and <span class="html-italic">q<sub>z</sub></span> (<b>d</b>) directions of the GIXRD patterns shown in (<b>a</b>,<b>b</b>).</p>
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<p>(<b>a</b>) The molecular structure of [EMIM]<sup>+</sup>[TFSI]<sup>−</sup> and P(VDF-HFP). (<b>b</b>) The photograph of prepared ion-gel films. (<b>c</b>) The specific capacitance–frequency curve of ion-gel film. The inset shows the schematic of an Au/ion-gel/Au capacitor structure.</p>
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<p>(<b>a</b>,<b>b</b>) Typical transfer curves of the ion-gel-gated OFETs (W = 2 mm/L = 50 μm) based on PffBT4T-2OD films (<b>a</b>) and PffBT4T-2DT films (<b>b</b>). The inset of (<b>a</b>) illustrates the schematic of ion-gel-gated OFETs on the TG/BC structure. (<b>c</b>,<b>d</b>) Corresponding output curves of the ion-gel-gated OFETs of PffBT4T-2OD films (<b>c</b>) and PffBT4T-2DT films (<b>d</b>), respectively.</p>
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<p>AFM height images (<b>a</b>,<b>b</b>) and phase images (<b>c</b>,<b>d</b>) of PffBT4T-2OD films (<b>a</b>,<b>c</b>) and PffBT4T-2DT films (<b>b</b>,<b>d</b>) in tapping mode.</p>
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<p>(<b>a</b>) Photograph illustration of stretching polymer films at the strain of 25%, 50%, and 100%. (<b>b</b>,<b>c</b>) OM images of the stretched PffBT4T-2OD films (<b>b</b>) and blended films (PffBT4T-2DT/SEBS = 7:3) (<b>c</b>) under various strains, where the white arrow denotes the strain direction.</p>
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<p>Typical transfer curves of the ion-gated OFETs based on pure PffBT4T-2OD films (<b>a</b>,<b>c</b>) and PffBT4T-2OD/SEBS (7:3) blend films (<b>b</b>,<b>d</b>) before tensile strain (<b>a</b>,<b>b</b>) and under the strain of 100% (<b>c</b>,<b>d</b>), respectively. The strain direction is parallel to the direction of channel current. The channel length (L) and channel width (W) are 200 μm and 2 mm, respectively.</p>
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24 pages, 7104 KiB  
Review
Recent Advances in Metal Oxide Semiconductor Heterojunctions for the Detection of Volatile Organic Compounds
by Shengming Zhang, Heng Zhang, Haiyu Yao, Peijie Wang, Min Zhu, Xuerong Shi and Shusheng Xu
Chemosensors 2024, 12(12), 244; https://doi.org/10.3390/chemosensors12120244 - 22 Nov 2024
Viewed by 814
Abstract
The efficient detection of volatile organic compounds (VOCs) is critically important in the domains of environmental protection, healthcare, and industrial safety. The development of metal oxide semiconductor (MOS) heterojunction gas-sensing materials is considered one of the most effective strategies to enhance sensor performance. [...] Read more.
The efficient detection of volatile organic compounds (VOCs) is critically important in the domains of environmental protection, healthcare, and industrial safety. The development of metal oxide semiconductor (MOS) heterojunction gas-sensing materials is considered one of the most effective strategies to enhance sensor performance. This review summarizes and discusses the types of heterojunctions and their working principles, enhancement strategies, preparation methodologies, and applications in acetone and ethanol detection. To address the constraints pertaining to low sensitivity, sluggish response/recovery times, and elevated operating temperatures that are inherent in VOC sensors, several improvement methods are proposed, including doping with metals like Ag and Pd, incorporating additives such as MXene and polyoxometalates, optimizing morphologies through a fine design, and self-doping via oxygen vacancies. Furthermore, this work provides insights into the challenges faced by MOSs heterojunction-based gas sensors and outlines future research directions in this field. This review will contribute to foundational theories to overcome existing bottlenecks in MOS heterojunction technology while promoting its large-scale application in disease screening or agricultural food quality assessments. Full article
(This article belongs to the Special Issue Functional Nanomaterial-Based Gas Sensors and Humidity Sensors)
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<p>Illustration of three types of heterojunction.</p>
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<p>Illustration of strategies for promoting the sensing performance of MOS heterojunctions.</p>
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<p>Illustrations of preparation methods for MOSs heterojunction materials.</p>
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<p>(<b>a</b>) The TEM image of hierarchical Fe<sub>2</sub>O<sub>3</sub>-Co<sub>3</sub>O<sub>4</sub> heterojunction; (<b>b</b>) the contents of oxygen species based on the analysis of X-ray photoelectron spectroscopy (XPS); (<b>c</b>) the dynamic dot-line pattern of three sensors; (<b>d</b>) the selectivity of all gas sensors’ exposure to 100 ppm of different gases [<a href="#B86-chemosensors-12-00244" class="html-bibr">86</a>]. Reprinted with permission from Elsevier, copyright 2024.</p>
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<p>Schematic illustration of the synthetic process of the ZIF-67-derived oxide cage/nanofiber Co<sub>3</sub>O<sub>4</sub>/In<sub>2</sub>O<sub>3</sub> heterostructure for acetone gas sensing [<a href="#B55-chemosensors-12-00244" class="html-bibr">55</a>]. Reprinted with permission from [<a href="#B56-chemosensors-12-00244" class="html-bibr">56</a>]. Copyright {2024} American Chemical Society.</p>
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<p>(<b>a</b>) Illustration of the preparation process for the Ag-NiO/SnO<sub>2</sub> nanotubes (NTs); (<b>b</b>) scanning electron microscope (SEM) image; (<b>c</b>) transmission electron microscope (TEM) image; and (<b>d</b>) the diagram of the energy band structure of the Ag-NiO/SnO<sub>2</sub> NTs [<a href="#B87-chemosensors-12-00244" class="html-bibr">87</a>]. Reprinted with permission from Elsevier, copyright 2024. (<b>e</b>) Synthetic scheme of ZnO-CuO core–hollow cube nanostructures [<a href="#B90-chemosensors-12-00244" class="html-bibr">90</a>]. Reprinted with permission from [<a href="#B91-chemosensors-12-00244" class="html-bibr">91</a>]. Copyright {2020} American Chemical Society.</p>
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<p>(<b>a</b>) Preparation of the p-type CuO/TiO<sub>2</sub>/MXene gas-sensitive sensor; (<b>b</b>) energy band diagram of the gas-sensitive sensor in four different situations [<a href="#B102-chemosensors-12-00244" class="html-bibr">102</a>]. Reprinted with permission from [<a href="#B104-chemosensors-12-00244" class="html-bibr">104</a>]. Copyright {2024} American Chemical Society.</p>
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<p>(<b>a</b>) Schematic illustration of the formation process of the 3% Fe<sub>2</sub>O<sub>3</sub>-loaded ultrathin nanosheet assembled hollowed-out hierarchical NiO nanorods (Fe<sub>2</sub>O<sub>3</sub>@NiO); (<b>b</b>) SEM and TEM images of Fe<sub>2</sub>O<sub>3</sub>@NiO; (<b>c</b>) response of the Fe<sub>2</sub>O<sub>3</sub>@NiO to 10 ppm ethanol at different operating temperatures and 80% RH; (<b>d</b>) response of the Fe<sub>2</sub>O<sub>3</sub>@NiO at 150 °C to 10 ppm of different target gases under different humidity conditions [<a href="#B98-chemosensors-12-00244" class="html-bibr">98</a>]. Reprinted with permission from [<a href="#B99-chemosensors-12-00244" class="html-bibr">99</a>]. Copyright {2023} American Chemical Society.</p>
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<p>(<b>a</b>) The schematic illustration of the construction and engineering of SnO<sub>2</sub>-ZnO based on MOF precursor and corresponding TEM and HRTEM images [<a href="#B115-chemosensors-12-00244" class="html-bibr">115</a>]. Reprinted with permission from Elsevier, copyright 2023.; (<b>b</b>) SEM image of ZnO-SnO<sub>2</sub> heterojunction IOPBs; and (<b>c</b>) the response at 260 °C to 10, 20, 50, 80, and 100 ppm acetone [<a href="#B69-chemosensors-12-00244" class="html-bibr">69</a>]. Reprinted with permission from Elsevier, copyright 2024.</p>
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<p>Schematic diagram of gas molecular adsorption, electron transfer, and energy band structure for the In<sub>2</sub>O<sub>3</sub>-ZnO material in (<b>a</b>) air and (<b>b</b>) ethanol [<a href="#B50-chemosensors-12-00244" class="html-bibr">50</a>]. Reprinted with permission from Elsevier, copyright 2023.</p>
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<p>(<b>a</b>) SEM image of Zn<sub>2</sub>SnO<sub>4</sub>/CdSnO<sub>3</sub>; (<b>b</b>) EPR spectra of CdSnO<sub>3</sub>, Zn<sub>2</sub>SnO<sub>4</sub>, and Zn<sub>2</sub>SnO<sub>4</sub>/CdSnO<sub>3</sub>; (<b>c</b>) schematic diagram of the energy band structure and ethanol gas sensing process of CdSnO<sub>3</sub>/Zn<sub>2</sub>SnO<sub>4</sub> heterostructure [<a href="#B57-chemosensors-12-00244" class="html-bibr">57</a>]. Reprinted with permission from Elsevier, copyright 2024.</p>
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<p>(<b>a</b>) Schematic illustration of the fabrication process of In<sub>2</sub>O<sub>3</sub>@PW<sub>12</sub>@SnO<sub>2</sub> NFs [<a href="#B97-chemosensors-12-00244" class="html-bibr">97</a>]; (<b>b</b>) TEM image of In@3%P@Sn NFs after calcination and selectivity pattern of the gas sensors based on In@3%P@Sn [<a href="#B97-chemosensors-12-00244" class="html-bibr">97</a>]; (<b>c</b>) transient responses of different concentrations of ethanol at the optimal operating temperature [<a href="#B97-chemosensors-12-00244" class="html-bibr">97</a>]. Reprinted with permission from Elsevier, copyright 2024.</p>
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<p>(<b>a</b>) Formation process schematic for SnO<sub>2</sub>/ZnO/Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub> MXene nanocomposites; (<b>b</b>) the curves for dynamic response and recovery of SnO<sub>2</sub>/ZnO/Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub> MXene at 120 °C to 100 ppm ethanol [<a href="#B103-chemosensors-12-00244" class="html-bibr">103</a>]; (<b>c</b>) SnO<sub>2</sub>/ZnO/Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub> MXene responses to various gases (100 ppm) at 120 °C [<a href="#B103-chemosensors-12-00244" class="html-bibr">103</a>]; (<b>d</b>) electron transfer of ZnO, SnO<sub>2</sub>, and Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub> MXene in air and ethanol [<a href="#B103-chemosensors-12-00244" class="html-bibr">103</a>]. Reprinted with permission from Elsevier, copyright 2024.</p>
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37 pages, 8367 KiB  
Review
Advances in Surface-Enhanced Raman Spectroscopy for Urinary Metabolite Analysis: Exploiting Noble Metal Nanohybrids
by Ningbin Zhao, Peizheng Shi, Zengxian Wang, Zhuang Sun, Kaiqiang Sun, Chen Ye, Li Fu and Cheng-Te Lin
Biosensors 2024, 14(12), 564; https://doi.org/10.3390/bios14120564 - 21 Nov 2024
Viewed by 504
Abstract
This review examines recent advances in surface-enhanced Raman spectroscopy (SERS) for urinary metabolite analysis, focusing on the development and application of noble metal nanohybrids. We explore the diverse range of hybrid materials, including carbon-based, metal–organic-framework (MOF), silicon-based, semiconductor, and polymer-based systems, which have [...] Read more.
This review examines recent advances in surface-enhanced Raman spectroscopy (SERS) for urinary metabolite analysis, focusing on the development and application of noble metal nanohybrids. We explore the diverse range of hybrid materials, including carbon-based, metal–organic-framework (MOF), silicon-based, semiconductor, and polymer-based systems, which have significantly improved SERS performance for detecting key urinary biomarkers. The principles underlying SERS enhancement in these nanohybrids are discussed, elucidating both electromagnetic and chemical enhancement mechanisms. We analyze various fabrication methods that enable precise control over nanostructure morphology, composition, and surface chemistry. The review critically evaluates the analytical performance of different hybrid systems for detecting specific urinary metabolites, considering factors such as sensitivity, selectivity, and stability. We address the analytical challenges associated with SERS-based urinary metabolite analysis, including sample preparation, matrix effects, and data interpretation. Innovative solutions, such as the integration of SERS with microfluidic devices and the application of machine learning algorithms for spectral analysis, are highlighted. The potential of these advanced SERS platforms for point-of-care diagnostics and personalized medicine is discussed, along with future perspectives on wearable SERS sensors and multi-modal analysis techniques. This comprehensive overview provides insights into the current state and future directions of SERS technology for urinary metabolite detection, emphasizing its potential to revolutionize non-invasive health monitoring and disease diagnosis. Full article
(This article belongs to the Special Issue Feature Paper in Biosensor and Bioelectronic Devices 2024)
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<p>Schematic diagram of EM (<b>A</b>) and CM (<b>B</b>).</p>
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<p>TEM images of monodispersed gold nanostars (<b>A</b>), gold nanorods (<b>B</b>), gold nano-bipyramids (<b>C</b>), spherical gold nanoparticles (<b>D</b>), gold nanocubes (<b>E</b>), and gold nanotriangles (<b>F</b>). Reprinted with permission from refs. [<a href="#B28-biosensors-14-00564" class="html-bibr">28</a>,<a href="#B29-biosensors-14-00564" class="html-bibr">29</a>,<a href="#B30-biosensors-14-00564" class="html-bibr">30</a>,<a href="#B31-biosensors-14-00564" class="html-bibr">31</a>,<a href="#B32-biosensors-14-00564" class="html-bibr">32</a>]. Copyright Elsevier and ACS.</p>
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<p>Correlation of SERS intensity and scattering resonance. Gold nanoparticle faceting and impact on SERS enhancement. Reprinted with permission from ref. [<a href="#B35-biosensors-14-00564" class="html-bibr">35</a>]. Copyright 2016 ACS.</p>
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<p>AFM images of the surface of Ag substrate before and after irradiating by femtosecond laser. Reprinted with permission from ref. [<a href="#B44-biosensors-14-00564" class="html-bibr">44</a>]. Copyright 2011 Elsevier.</p>
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<p>SEM image of the created Si nanopillars and the AgNPs formed on the Si nanopillars. Reprinted with permission from ref. [<a href="#B51-biosensors-14-00564" class="html-bibr">51</a>]. Copyright 2017 ACS.</p>
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<p>Synthetic route for antibody-modified Fe<sub>3</sub>O<sub>4</sub>@Ag magnetic tags and schematic diagram of the magnetic SERS Strip for detecting two respiratory viruses. Reprinted with permission from ref. [<a href="#B52-biosensors-14-00564" class="html-bibr">52</a>]. Copyright 2019 ACS.</p>
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<p>Schematic representation of Au@MIP fabrication process. Reprinted with permission from ref. [<a href="#B53-biosensors-14-00564" class="html-bibr">53</a>]. Copyright 2020 ACS.</p>
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<p>Energy-level diagrams illustrating the electronic transitions. The calculated band structures of MoS<sub>2</sub> a and MoS<sub>x</sub>O<sub>y</sub> taking Fermi level as the reference. Schematic energy-level diagrams of R6G on c MoS<sub>x</sub>O<sub>y</sub> and d MoS<sub>2</sub> and MoO<sub>3</sub> with respect to the vacuum level. Reprinted with permission from ref. [<a href="#B56-biosensors-14-00564" class="html-bibr">56</a>]. Copyright 2017 Nature.</p>
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<p>The proposed mechanisms of the CT process in the Ag–rGO system and SiO<sub>2</sub>–Ag–rGO system combined with 4-MBA molecules. Reprinted with permission from ref. [<a href="#B62-biosensors-14-00564" class="html-bibr">62</a>]. Copyright 2021 ACS.</p>
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<p>Schematic illustration of the one-pot synthesis of AuNPLs on CNT sheet (<b>A</b>) and the synthetic procedure of Au/AgNP/crossed CNT substrate (<b>B</b>). Reprinted with permission from refs. [<a href="#B66-biosensors-14-00564" class="html-bibr">66</a>,<a href="#B67-biosensors-14-00564" class="html-bibr">67</a>]. Copyright 2017 ACS and 2021 MDPI.</p>
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<p>Illustration of the preparation of 2D Ni-MOF-Au@AgNPs composite. Reprinted with permission from ref. [<a href="#B73-biosensors-14-00564" class="html-bibr">73</a>]. Copyright 2022 Elsevier.</p>
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<p>Optical image of the Ag/pSi SERS substrate (<b>a</b>) and SERS mapping (<b>b</b>) for 10<sup>−5</sup> M R6G on the area (<b>A</b>). Schematics of the Galvanic replacement reaction of silver dendritic nanoforests on silicon (Ag-DNFs/Si) (<b>B</b>). Reprinted with permission from refs. [<a href="#B76-biosensors-14-00564" class="html-bibr">76</a>,<a href="#B78-biosensors-14-00564" class="html-bibr">78</a>]. Copyright 2019 Elsevier and 2020 MDPI.</p>
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<p>Top-view FESEM images for TiO2-NTFs exposed for different times to UVC radiation: 5 (<b>a</b>), 15 (<b>b</b>), 30 (<b>c</b>) and 60 min (<b>d</b>); with pre-immersion treatment in 50 mM AgNO<sub>3</sub> (<b>A</b>). Schematic diagram for the synthesis of HGNs and HGNs-MBA@ZnS with well-controlled core morphology and tshell (<b>B</b>). Reprinted with permission from ref. [<a href="#B80-biosensors-14-00564" class="html-bibr">80</a>,<a href="#B81-biosensors-14-00564" class="html-bibr">81</a>]. Copyright 2024 Elsevier.</p>
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<p>The schematic representation showing the fabrication of polymer/Ag core-shell microspheres and SERS application (<b>A</b>). Schematic diagram of the fabrication SERS-active substrate. (<b>B</b>): preparation of AuNPLs capture probe (<b>I</b>), preparation of PLA fiber flexible substrate (<b>II</b>), preparation of SERS nanotags (<b>III</b>). Reprinted with permission from refs. [<a href="#B85-biosensors-14-00564" class="html-bibr">85</a>,<a href="#B86-biosensors-14-00564" class="html-bibr">86</a>]. Copyright 2022 Elsevier and 2024 Elsevier.</p>
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<p>Schematic diagrams of AgNPs@mrGO SERS-active substrate. Reprinted with permission from ref. [<a href="#B90-biosensors-14-00564" class="html-bibr">90</a>]. Copyright 2020 Elsevier.</p>
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<p>Principle of AuCOF preparation and aptamer-regulated AuCOF catalyzed RRS/SERS coupled dual-mode assay for small molecule (<b>A</b>). Synthesis of bovine serum albumin (BSA)-modified silver nanoparticles capped with 4-mercaptopyridine (AgNP-MPy), microcapsules containing BSA-modified MPy-AgNPs, and the urea sensing hydrogel (<b>B</b>). Reprinted with permission from refs. [<a href="#B100-biosensors-14-00564" class="html-bibr">100</a>,<a href="#B103-biosensors-14-00564" class="html-bibr">103</a>]. Copyright 2020 Elsevier and 2019 MDPI.</p>
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<p>Schematic representation of the SGNS@MPA synthesis and microplate-based SERS detection platform for creatinine detection in human saliva. Reprinted with permission from ref. [<a href="#B113-biosensors-14-00564" class="html-bibr">113</a>]. Copyright 2024 Elsevier.</p>
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<p>Schematic illustration of the preparation process for the AgNPs/MIL-101 (Fe) hybrid structure (<b>A</b>) and schematic diagram of the detection of DA based on SERS (<b>B</b>). Reprinted with permission from ref. [<a href="#B122-biosensors-14-00564" class="html-bibr">122</a>]. Copyright 2015 ACS.</p>
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16 pages, 1831 KiB  
Article
Expedient Synthesis of Substituted Thieno[3,2-b]thiophenes and Selenopheno[3,2-b]selenophenes Through Cascade Cyclization of Alkynyl Diol Derivatives
by Yingqi Feng, Xuelin Zhang, Ziqing He, Miaoshan Zhao, Lu Chen, Yibiao Li and Xiai Luo
Molecules 2024, 29(23), 5507; https://doi.org/10.3390/molecules29235507 - 21 Nov 2024
Viewed by 416
Abstract
Thieno[3,2-b]thiophenes are used as key components in optoelectronic materials, porous hydrogen-storage hosts, organic solar cells, and polymer semiconductors. A step-efficient synthetic protocol was proposed herein for obtaining multisubstituted thieno[3,2-b]thiophene and selenopheno[3,2-b]selenophenes in moderate to good yields via [...] Read more.
Thieno[3,2-b]thiophenes are used as key components in optoelectronic materials, porous hydrogen-storage hosts, organic solar cells, and polymer semiconductors. A step-efficient synthetic protocol was proposed herein for obtaining multisubstituted thieno[3,2-b]thiophene and selenopheno[3,2-b]selenophenes in moderate to good yields via the bisulfur/biselenium cyclization of alkynyl diols with I2/Na2S2O3 or selenium. Using this strategy, substitution patterns were obtained for backbone modification in functional materials. Full article
(This article belongs to the Special Issue Recent Advances in Domino Reactions)
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<p>Previous methods for synthesis of thieno[3,2-<span class="html-italic">b</span>]thiophene (<b>a</b>,<b>b</b>) and sulfur cyclization hypothesis (<b>c</b>).</p>
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<p>Substrate scope of alkynyl diol derivatives. Reaction condition: alkynyl diol <b>1</b> (0.5 mmol), Na<sub>2</sub>S<sub>2</sub>O<sub>3</sub> (1.0 mmol), I<sub>2</sub> (0.5 mmol), and NMP (2 mL) stirred at 140 °C for 8 h in a sealed tube under an air atmosphere. Isolated yields.</p>
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<p>Synthesis of selenopheno[3,2-<span class="html-italic">b</span>]selenophenes. (<b>a</b>) Synthesis of 3,6-dimethylselenopheno[3,2-<span class="html-italic">b</span>]selenophene <b>3a</b>. (<b>b</b>) Synthesi of 2,3,5,6-tetramethylselenopheno[3,2-<span class="html-italic">b</span>]selenophene <b>3b</b>.</p>
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<p>Synthetic modifications of thienothiophene <b>2a</b>.</p>
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<p>Control experiments. (<b>a</b>) Intermediate detection reaction. (<b>b</b>) Iodination of 2,5-dimethylhex-3-yne-2,5-diol. (<b>c</b>) Sulfur cyclization of 1,4-diiodobut-2-yne. (<b>d</b>) Sulfur cyclization of 2,5-dimethylhexa-1,5-dien-3-yne. (<b>e</b>) Redox reaction of Na<sub>2</sub>S<sub>2</sub>O<sub>3</sub> with I<sub>2.</sub> (<b>f</b>) Na<sub>2</sub>S<sub>4</sub>O<sub>6</sub> reaction with 2,5-dimethylhex-3-yne-2,5-diol give thieno[3,2-<span class="html-italic">b</span>]thiophene. (<b>g</b>) Sulfur cyclization of phenylacetylene with Na<sub>2</sub>S<sub>4</sub>O<sub>6.</sub> (<b>h</b>) Deuteration experiments. (<b>i</b>) Radical inhibition reaction. (<b>j</b>) Proposed reaction mechanism for synthesis of <b>5d</b>.</p>
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<p>Proposed reaction mechanism.</p>
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15 pages, 4009 KiB  
Article
Nanostructure-Dependent Electrical Conductivity Model Within the Framework of the Generalized Effective Medium Theory Applied to Poly(3-hexyl)thiophene Thin Films
by Henryk Bednarski, Ayman A. A. Ismail, Marcin Godzierz, Andrzej Marcinkowski, Muhammad Raheel Khan, Bożena Jarząbek, Barbara Hajduk and Pallavi Kumari
Polymers 2024, 16(22), 3227; https://doi.org/10.3390/polym16223227 - 20 Nov 2024
Viewed by 584
Abstract
One of the key parameters characterizing the microstructure of a layer is its degree of order. It can be determined from optical studies or X-ray diffraction. However, both of these methods applied to the same layer may give different results because, for example, [...] Read more.
One of the key parameters characterizing the microstructure of a layer is its degree of order. It can be determined from optical studies or X-ray diffraction. However, both of these methods applied to the same layer may give different results because, for example, aggregates may contribute to the amorphous background in XRD studies, while in optical studies, they may already show order. Because we are usually interested in the optical and/or electrical properties of the layers, which in turn are closely related to their dielectric properties, determining the optical order of the layers is particularly important. In this work, the microstructure, optical properties and electrical conductivity of poly(3-hexyl)thiophene layers were investigated, and a model describing the electrical conductivity of these layers was proposed. The model is based on the generalized theory of the effective medium and uses the equation from the percolation theory of electrical conductivity for the effective medium of a mixture of two materials. The results indicate a key role of the aggregate size and limited conductivity of charge carriers, mainly due to structural imperfections that manifest themselves as an increase in the number of localized states visible in the subgap absorption near the optical absorption edge. The critical value of the order parameter and the corresponding values of the Urbach energy, excitonic linewidth and band gap energy are determined. Full article
(This article belongs to the Special Issue Polymer Thin Films: Synthesis, Characterization and Applications)
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<p>XRD patterns of P3HT thin films deposited from 20 mg/mL solution concentration with indicated spin-coating rates.</p>
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<p>XRD patterns of P3HT thin films deposited from 40 mg/mL solution concentration with indicated spin-coating rates.</p>
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<p>The neat area of (100) peak as a function spin-coating rate for P3HT thin films deposited from 20 and 40 mg/mL solution concentration.</p>
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<p>Three-dimensional surface AFM images of P3HT films deposited with spin-coating rates: (<b>a</b>) 750 rpm from 20 mg/mL solution; (<b>b</b>) 4500 rpm from 20 mg/mL solution; (<b>c</b>) 1250 rpm from 40 mg/mL solution; (<b>d</b>) 7000 rpm from 40 mg/mL solution.</p>
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<p>Thickness of the films determined in AFM and ellipsometry studies as a function of ω<sup>−1/2</sup>.</p>
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<p>Example analysis of the absorption spectrum for a 342 nm thick layer to determine the values of (<b>a</b>) the band gap energy Eg; (<b>b</b>) the Urbach energy Eu.</p>
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<p>Dependences of (<b>a</b>) the energy gap Eg; (<b>b</b>) the Urbach energy Eu on the spin-coating rate.</p>
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<p>The band gap energy Eg is a function of the Urbach energy Eu.</p>
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<p>Example analysis of the absorption spectrum for a 342 nm thick P3HT film to determine the values of the exciton bandwidth W and the exciton linewidth σ.</p>
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<p>Dependences of the exciton linewidth σ. on the Urbach energy.</p>
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<p>Band gap energy as a function of the exciton linewidth s.</p>
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<p>Conductivity of P3HT films as a function of the order parameter.</p>
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13 pages, 5392 KiB  
Article
Exploring Light Stability and Trapping Mechanisms in Organic Thin-Film Transistors for High-Brightness MicroLED Integration
by Chia-Hung Tsai, Yang-En Wu, Chuan-Wei Kuo, Ting-Chang Chang, Li-Yin Chen, Fang-Chung Chen and Hao-Chung Kuo
Materials 2024, 17(22), 5643; https://doi.org/10.3390/ma17225643 - 19 Nov 2024
Viewed by 504
Abstract
Organic thin-film transistors (OTFTs), benefiting from a low-temperature process (≤120 °C), offer a promising approach for the monolithic integration of MicroLED structures through organic-last integration. Previous research has demonstrated that small-molecule/polymer binder-based organic semiconductor deposition, utilizing the vertical phase separation mechanism, can achieve [...] Read more.
Organic thin-film transistors (OTFTs), benefiting from a low-temperature process (≤120 °C), offer a promising approach for the monolithic integration of MicroLED structures through organic-last integration. Previous research has demonstrated that small-molecule/polymer binder-based organic semiconductor deposition, utilizing the vertical phase separation mechanism, can achieve good device uniformity while preserving high field-effect carrier mobility. However, the stability of OTFTs under light exposure at the device level remains underexplored. This study investigates the effects of various light irradiation conditions on OTFTs and delves into the underlying mechanisms of the light-trapping effect. Based on these findings, we propose an optimal OTFT design tailored for driving MicroLED displays at high operational brightness, ensuring both performance and stability. Full article
(This article belongs to the Special Issue Advanced Materials for Organic Semiconductors and Their Applications)
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<p>Monolithic MicroLED driven by OTFTs.</p>
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<p>Cross-sectional image of monolithic MicroLED: (<b>a</b>) relative position of OTFTs and MicroLED, and (<b>b</b>) FIB image.</p>
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<p>Five-mask organic TFTs’ process flow.</p>
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<p>(<b>a</b>) The transmission spectra of the TG metal structured with a 50 nm Au layer. The thin layer of TG metal is semi-transparent in light transmission across the visible spectrum, particularly between 400 nm and 700 nm. (<b>b</b>) A schematic of the device structure, indicating the path of blue light with an energy range of 2.7 eV as it penetrates the TG layer and reaches the organic semiconductor (OSC) layer, where exciton generation and dissociation can occur.</p>
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<p>OTFT device under varying conditions of light exposure. The test process sequence consists of three steps, beginning with an initial transfer characteristic (ID-VG) electrical test conducted in a dark environment to establish the baseline performance characteristics of the device. The middle panel illustrates the device being exposed to blue light with an intensity of 8000 nits for a light-doping period. Following the light exposure, the device was again tested in a dark environment to assess any changes in its electrical properties post-illumination.</p>
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<p>(<b>a</b>) Energy band diagram during light exposure with a positive gate voltage (VG) applied. (<b>b</b>) ID-VG curve, indicating VG forward sweep (+30 V to −30 V). (<b>c</b>) Energy band diagram during light exposure with a negative VG applied. (<b>d</b>) ID-VG curve, indicating VG reverse sweep (−30 V to +30 V).</p>
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<p>The structural differences between the original top gate (TG) design and the modified TG design with the inclusion of a light-blocking layer. These comparisons are made across four critical layers of the OTFT.</p>
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<p>Comparison of the ID-VG of OTFT devices under two different designs: (<b>a</b>) TG-only and (<b>b</b>) TG with light-blocking layer. The measurements were taken both in the dark (black lines) and under illumination (red lines), with VG sweeping in forward and reverse directions. This comparison highlights the impact of the light-blocking layer on device performance, pink color represents the gate contact, which serves as the light-blocking layer, while brown color represents the TG.</p>
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<p>The ID-VG curve of the OTFT device under different VD conditions (−0.1 V, −5 V, −10 V, and −15 V), measured both in the dark (black curves) and under light exposure (blue curves).</p>
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<p>The testing procedure for the TG with light-blocking layer device, including the sequence of tests performed under different conditions.</p>
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