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17 pages, 9409 KiB  
Article
Experimental Study and Optimization Analysis of Operating Conditions on Photo-Thermochemical Cycle of Water Splitting for Hydrogen Production Based on CeO2 Catalyst
by Zhiyin Zhang, Huimin Hu, Jie Yang, Zhengguang He, Kai Yan, Tianyu Liu and Chang Wen
Energies 2024, 17(24), 6314; https://doi.org/10.3390/en17246314 (registering DOI) - 14 Dec 2024
Abstract
The photo-thermochemical cycle (PTC) for water splitting offers a sustainable method for hydrogen production by efficiently utilizing solar energy. This study explored the use of CeO2 as a catalyst in the PTC system to enhance hydrogen yield. A nanostructured CeO2 catalyst [...] Read more.
The photo-thermochemical cycle (PTC) for water splitting offers a sustainable method for hydrogen production by efficiently utilizing solar energy. This study explored the use of CeO2 as a catalyst in the PTC system to enhance hydrogen yield. A nanostructured CeO2 catalyst was synthesized via the sol-gel method, achieving an H2 yield of 8.35 μmol g−1 h−1. Stability tests over five cycles showed consistent yields between 7.22 and 8.35 μmol g−1 h−1. Analysis revealed that oxygen vacancies (VOs) increased after the photoreaction and depleted during the thermal reaction, which aligns with the expected PTC mechanism for hydrogen production. Single-factor experiments highlighted that photoreaction duration mainly influenced VOs generation, while thermal duration and temperature impacted VOs consumption and intermediate reaction rates. A response surface methodology (RSM) model predicted optimal conditions for maximum H2 yield (8.85 μmol g−1 h−1) with a photoreaction duration of 46.6 min, thermal duration of 45.4 min, and thermal temperature of 547.2 °C. Full article
(This article belongs to the Special Issue Advances in Hydrogen Production and Hydrogen Storage)
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Figure 1
<p>Schematic diagram of PTC system.</p>
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<p>XRD patterns of as-prepared CeO<sub>2</sub>.</p>
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<p>TEM images of as-prepared CeO<sub>2</sub>.</p>
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<p>EPR spectra of CeO<sub>2</sub> before photoreaction, after photoreaction and after thermal reaction.</p>
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<p>H<sub>2</sub> yields from PTC reactions during five cycles.</p>
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<p>XRD patterns of CeO<sub>2</sub> catalyst before and after PTC reaction of the five cycles.</p>
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<p>H<sub>2</sub> yields in single-factor PTC reactions with different conditions: (<b>a</b>) photoreaction duration; (<b>b</b>) thermal reaction duration; and (<b>c</b>) thermal reaction temperature.</p>
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<p>In situ infrared results of CeO<sub>2</sub> catalyst during thermal reaction.</p>
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<p>EPR spectra of CeO<sub>2</sub> during thermal reaction.</p>
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<p>(<b>a</b>) Residual fitting distribution. (<b>b</b>) Comparison between model predicted values and actual values.</p>
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<p>Response surface of hydrogen production rate. (<b>a</b>) Response surfaces of A and B at fixed C (500 °C). (<b>b</b>) Response surfaces of A and C at fixed B (40 min). (<b>c</b>) Response surfaces of B and C at fixed A (40 min).</p>
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<p>Conceptual framework of the Box–Behnken design.</p>
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<p>XPS spectra of CeO<sub>2</sub> during thermal reaction: (<b>a</b>) Ce, 3d; (<b>b</b>) O, 1s.</p>
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19 pages, 1382 KiB  
Review
Graphene-Based Nanostructured Cathodes for Polymer Electrolyte Membrane Fuel Cells with Increased Resource
by Adriana Marinoiu, Mihaela Iordache, Elena Simona Borta and Anisoara Oubraham
C 2024, 10(4), 105; https://doi.org/10.3390/c10040105 (registering DOI) - 14 Dec 2024
Abstract
Pt on carbon black (Pt/C) has been widely used as a catalyst for both ORR and hydrogen oxidation reaction (HOR), but its stability is compromised due to carbon corrosion and catalyst poisoning, leading to low Pt utilization. To address this issue, this study [...] Read more.
Pt on carbon black (Pt/C) has been widely used as a catalyst for both ORR and hydrogen oxidation reaction (HOR), but its stability is compromised due to carbon corrosion and catalyst poisoning, leading to low Pt utilization. To address this issue, this study suggests replacing carbon black with graphene in the catalyst layer. The importance of this work lies in the detailed examination of novel electrocatalysts with high electrocatalytic activity for large-scale power generation. In this paper, we discuss the use of regulatory techniques like structure tuning and composition optimization to construct nanocatalysts impregnated with noble and non-noble metals on graphene supports. Finally, it highlights the limitations and advantages of these nanocatalysts along with some future perspectives. Our objective is that this summary will help in the research and rational design of graphene-based nanostructures for efficient ORR electrocatalysis. The results of this study showed that the performances of graphene-based catalysts show high electrochemical active surface areas for Pt-Fe/GNPs and Pt-Ni/GNPs catalysts (132 and 136 m2 g−1, respectively) at 100 operating cycles. Also, high current densities and power densities were observed for Pt3-Ni/G and Pt-Co/G catalysts used at the cathode. The values for current density were 1.590 and 1.779 A cm−2, respectively, while the corresponding values for power density were 0.57 and 0.785 W cm−2. Full article
(This article belongs to the Topic Application of Graphene-Based Materials, 2nd Edition)
22 pages, 8100 KiB  
Article
Optically Controlled Drug Delivery Through Microscale Brain–Machine Interfaces Using Integrated Upconverting Nanoparticles
by Levente Víg, Anita Zátonyi, Bence Csernyus, Ágoston C. Horváth, Márton Bojtár, Péter Kele, Miklós Madarász, Balázs Rózsa, Péter Fürjes, Petra Hermann, Orsolya Hakkel, László Péter and Zoltán Fekete
Sensors 2024, 24(24), 7987; https://doi.org/10.3390/s24247987 (registering DOI) - 14 Dec 2024
Viewed by 132
Abstract
The aim of this work is to incorporate lanthanide-cored upconversion nanoparticles (UCNP) into the surface of microengineered biomedical implants to create a spatially controlled and optically releasable model drug delivery device in an integrated fashion. Our approach enables silicone-based microelectrocorticography (ECoG) implants holding [...] Read more.
The aim of this work is to incorporate lanthanide-cored upconversion nanoparticles (UCNP) into the surface of microengineered biomedical implants to create a spatially controlled and optically releasable model drug delivery device in an integrated fashion. Our approach enables silicone-based microelectrocorticography (ECoG) implants holding platinum/iridium recording sites to serve as a stable host of UCNPs. Nanoparticles excitable in the near-infrared (lower energy) regime and emitting visible (higher energy) light are utilized in a study. With the upconverted higher energy photons, we demonstrate the induction of photochemical (cleaving) reactions that enable the local release of specific dyes as a model system near the implant. The modified ECoG electrodes can be implanted in brain tissue to act as an uncaging system that releases small amounts of substance while simultaneously measuring the evoked neural response upon light activation. In this paper, several technological challenges like the surface modification of UCNPs, the immobilization of particles on the implantable platform, and measuring the stability of integrated UCNPs in in vitro and in vivo conditions are addressed in detail. Besides the chemical, mechanical, and optical characterization of the ready-to-use devices, the effect of nanoparticles on the original electrophysiological function is also evaluated. The results confirm that silicone-based brain–machine interfaces can be efficiently complemented with UCNPs to facilitate local model drug release. Full article
(This article belongs to the Special Issue Sensing Technologies in Neuroscience and Brain Research)
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<p>Schematic representation of the surface modification steps.</p>
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<p>Uncaging (photocleavage) mechanism after NIR light exposure of the UCNPs.</p>
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<p>The molecular structure of TetPPG-Rhod, the click and the uncaging process [<a href="#B44-sensors-24-07987" class="html-bibr">44</a>]. NMR spectrum of the dye system can be found in the <a href="#app1-sensors-24-07987" class="html-app">Supporting Information</a> of the cited article.</p>
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<p>Contact angle of the modified silicone (PDMS) model substrate. (<b>a</b>) Bare substrate, (<b>b</b>) plasma treated substrate, (<b>c</b>) NPTES-treated substrate, (<b>d</b>) BCN-NHS-modified substrate (scalebars indicate 1 mm).</p>
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<p>FTIR spectra recorded after each modification step of a PDMS disk. (<b>a</b>) Bare substrate, (<b>b</b>) plasma-treated substrate, (<b>c</b>) NPTES-treated substrate.</p>
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<p>SEM images of the UCNP-ECoG system. (<b>a</b>) The whole probe surface with numbered recording sites, (<b>b</b>) a closer look at recording site 9 at larger magnification, (<b>c</b>) UCNP coverage on the substrate surface near site 4, (<b>d</b>) particles detected with Matlab, near site 4 (white scalebars show 1 mm, 50 µm and 2 µm, respectively).</p>
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<p>EIS measurements of the ECoG systems, represented on Bode plots. (<b>a</b>) Resistance (magnitude) of the unmodified and UCNP-modified ECoGs, (<b>b</b>) reactance (phase angle) of the unmodified and UCNP-modified ECoGs.</p>
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<p>Fluorescence spectroscopy measurements of the ECoG systems. (<b>a</b>) RFI (relative fluorescent intensity) changes due to the IR laser irradiation, (<b>b</b>) Observing the effect of natural light vs. IR laser light on the system.</p>
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<p>Averages of the image histograms of 2P images taken on sample regions of unmodified PDMS discs and a fully modified UCNP-ECoG device with different light intensities. The histograms of UCNP devices (orange, 1.72 mW; red, 8.6 mW) show increased fluorescence on these images, suggesting successful uncaging.</p>
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<p>Sample in vivo electrophysiological recording with a UCNP-modified ECoG device from a ketamine–xylazine anesthetized mouse, showing characteristic oscillations evoked by the anesthesia. The 8 traces are simultaneous recordings from the 8 channels of the device. The signal is low pass filtered to below 150 Hz. 50 Hz line-frequency noise was band-stop filtered.</p>
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11 pages, 3414 KiB  
Article
Study on the Explosion Mechanism of Low-Concentration Gas and Coal Dust
by Li Liu, Xinyi Mao, Yongheng Jing, Yao Tang and Le Sun
Fire 2024, 7(12), 475; https://doi.org/10.3390/fire7120475 (registering DOI) - 13 Dec 2024
Viewed by 182
Abstract
In coal mines, the mixture of coal dust and gas is more ignitable than gas alone, posing a high explosion risk to workers. Using the explosion tube, this study examines the explosion propagation characteristics and flame temperature of low-concentration gas and coal dust [...] Read more.
In coal mines, the mixture of coal dust and gas is more ignitable than gas alone, posing a high explosion risk to workers. Using the explosion tube, this study examines the explosion propagation characteristics and flame temperature of low-concentration gas and coal dust mixtures with various particle sizes. The CPD model and Chemkin-Pro 19.2 simulate the reaction kinetics of these explosions. Findings show that when the gas concentration is below its explosive limit, coal dust addition lowers the gas’s explosive threshold, potentially causing an explosion. Coal particle size significantly affects explosion propagation dynamics, with smaller particles producing faster flame velocities and higher temperatures. Due to their larger surface area, smaller particles absorb heat faster and undergo thermal decomposition, releasing combustible gases that intensify the explosion flame. The predicted yield of light gases from both coal types exceeds 40 wt% daf, raising combustible gas concentrations in the system. When accumulated reaction heat elevates the gas concentration to its explosive limit, an explosion occurs. These results are crucial for preventing gas and coal dust explosion accidents in coal mines. Full article
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<p>Changes in flame propagation velocity and flame temperature in coal-dust mixture explosions at 2 vol% Gas (200 μm, 560 g/m<sup>3</sup> Dongtan coal).</p>
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<p>(<b>a</b>,<b>c</b>) Flame propagation distance and (<b>b</b>,<b>d</b>) velocity for gas-coal dust combustion (2 vol% Gas and 560 g/m<sup>3</sup> coal dust).</p>
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<p>Variation of mean flame propagation velocity for mixed combustion of 2 vol% (<b>a</b>) Dafosi coal (<b>b</b>) Dongtan coal.</p>
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<p>Variation of flame temperature with coal particle size in gas and coal dust explosions (2 vol% gas and 560 g/m<sup>3</sup> coal dust).</p>
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<p>Predicted yield of light gases in coal volatiles by CPD model calculated.</p>
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<p>Evolution of key species and flame temperature with flame propagation distance in gas and coal dust combustion.</p>
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<p>Laminar combustion velocity for coal combustion at the coal dust concentration of 560 g/m<sup>3</sup> and the gas concentration of 2 vol%.</p>
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<p>Mechanism of coal dust explosion under low concentration gas conditions.</p>
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13 pages, 3051 KiB  
Article
Innovative One-Step Sustainable Process to Produce Simonkolleite Nanoparticles
by Valeria Daniele, Claudia Mondelli, Laura Turilli and Giuliana Taglieri
Nanomaterials 2024, 14(24), 2005; https://doi.org/10.3390/nano14242005 - 13 Dec 2024
Viewed by 289
Abstract
The aim of the present paper is to propose an innovative, one-step and sustainable process allowing us to obtain almost 10 kg/week of pure and crystalline simonkolleite nanoparticles (SK NPs) in only 8 min of reaction, working in water, under ambient conditions of [...] Read more.
The aim of the present paper is to propose an innovative, one-step and sustainable process allowing us to obtain almost 10 kg/week of pure and crystalline simonkolleite nanoparticles (SK NPs) in only 8 min of reaction, working in water, under ambient conditions of pressure/temperature, guaranteeing at the same time low environmental impact and a high yield of NP production. In addition, the obtained NPs can also act as ZnO precursors at ambient temperature, and this result supports the sustainability of the process considering that, generally, the production of ZnO from SK occurred via annealing at high temperatures. The SK NPs appeared pure and crystalline, characterized by a highly uniform hexagonal lamellar feature. Each lamella is composed of an ordered assembly of very small monodispersed primary NPs, with a size in the range 3–8 nm. The SK NPs exhibited a surface area of up to 41 m2/g, the highest value recorded in the literature, revealing that pore size distribution mainly peaked between 3 and 20 nm. Full article
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Figure 1
<p>Kinetics of ion exchange process in terms of CC versus time, referring to syntheses performed at ambient temperature (T = 25 °C). Five resin/ZnCl<sub>2</sub> ratios were considered, corresponding to 0.8:1 (<span class="html-italic">0.8R</span> sample), 1:1 (<span class="html-italic">1R</span> sample), 1.5:1 (<span class="html-italic">1.5R</span> sample), 2:1 (<span class="html-italic">2R</span> sample), and 3:1 (3<span class="html-italic">R</span> sample).</p>
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<p>XRD analyses performed at different times from the beginning of the synthesis process by varying the resin/ZnCl<sub>2</sub> (R) ratios. (<b>a</b>) <span class="html-italic">0.8R</span> sample; (<b>b</b>) <span class="html-italic">1R</span> sample; (<b>c</b>) <span class="html-italic">1.5R</span> sample; (<b>d</b>) <span class="html-italic">2R</span> sample; (<b>e</b>) <span class="html-italic">3R</span> sample; (<b>f</b>) a comparison between the samples at the end of the synthesis process (t = 8 min) by varying the <span class="html-italic">R</span> ratio.</p>
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<p>The kinetics of the ion exchange process, in terms of the CC versus time, referring to the syntheses performed with the 3<span class="html-italic">R</span> ratio by varying the temperature conditions.</p>
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<p>The XRD analyses performed on the samples obtained by using the <span class="html-italic">3R</span> ratio but varying the synthesis temperature. (<b>a</b>) T = 8 °C (<span class="html-italic">3R_T 8 °C</span> sample); (<b>b</b>) T = 18 °C (<span class="html-italic">3R_T 18 °C</span> sample); (<b>c</b>) T = 45 °C (<span class="html-italic">3R_T 45 °C</span> sample).</p>
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<p>A typical infrared attenuated total reflection spectrum of the synthesized simonkolleite NPs.</p>
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<p>TEM images of the SK samples obtained by using the 3<span class="html-italic">R</span> ratio but varying the synthesis temperature. (<b>a</b>–<b>c</b>) The <span class="html-italic">3R_T 8 °C</span> sample; (<b>d</b>–<b>f</b>); the <span class="html-italic">3R_T 18 °C</span> sample; (<b>g</b>–<b>i</b>) the <span class="html-italic">3R</span> sample; (<b>j</b>–<b>l</b>) the <span class="html-italic">3R_T 45 °C</span> sample. The inset reported in (<b>c</b>,<b>f</b>,<b>j</b>,<b>l</b>) refers to the particles’ size distribution.</p>
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<p>N<sub>2</sub> absorption/desorption isotherms and pore size distribution of SK samples obtained by varying synthesis temperature. (<b>a</b>,<b>b</b>) <span class="html-italic">3R_T 8 °C</span> sample; (<b>c</b>,<b>d</b>); <span class="html-italic">3R_T 18 °C</span> sample; (<b>e</b>,<b>f</b>) <span class="html-italic">3R</span> sample; (<b>g</b>,<b>h</b>) <span class="html-italic">3R_T 45 °C</span> sample.</p>
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16 pages, 5915 KiB  
Article
Hierarchically Porous Carbon Microspheres Coated with MnO2 Nanosheets as the Sulfur Host for High-Loading Lithium–Sulfur Batteries
by Liqin Dai, Zonglin Yi, Lijing Xie, Fangyuan Su, Xiaoqian Guo, Zhenbing Wang, Jiayao Cheng and Chengmeng Chen
Molecules 2024, 29(24), 5881; https://doi.org/10.3390/molecules29245881 - 13 Dec 2024
Viewed by 244
Abstract
Lithium–sulfur (Li–S) batteries have emerged as a promising candidate for next-generation high-energy rechargeable lithium batteries, but their practical application is impeded by the sluggish redox kinetics and low sulfur loading. Here, we report the in situ growth of δ-MnO2 nanosheets onto hierarchical [...] Read more.
Lithium–sulfur (Li–S) batteries have emerged as a promising candidate for next-generation high-energy rechargeable lithium batteries, but their practical application is impeded by the sluggish redox kinetics and low sulfur loading. Here, we report the in situ growth of δ-MnO2 nanosheets onto hierarchical porous carbon microspheres (HPCs) to form an HPCs/S@MnO2 composite for advanced lithium–sulfur batteries. The delicately designed hybrid architecture can effectively confine LiPSs and obtain high sulfur loading up to 10 mg cm−2, in which the inner carbon microspheres with a large pore volume and large specific surface area can encapsulate high sulfur content, and the outer MnO2 nanosheets, as a catalytic layer, can improve the conversion reaction of LiPSs and suppress the shuttle effect. The thick HPCs/S@MnO2 electrode with 7 mg cm−2 sulfur loading delivers an areal capacity of 4.0 mAh cm−2 at 0.1 C and provides stable cycling stability with a low-capacity decay rate of 0.063 % per cycle after 200 cycles at 0.1 C. Furthermore, a Li–S pouch cell with a capacity of 2.5 A h is fabricated and demonstrates high cycling stability. This work offers a feasible method to build advanced sulfur electrodes with high areal loading and sheds light on their commercial application in high-performance Li–S batteries. Full article
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Figure 1
<p>(<b>a</b>) Schematic illustration of the synthesis of HPCs/S@MnO<sub>2</sub> composite and the corresponding SEM images of (<b>b</b>,<b>e</b>) HPCs, (<b>c</b>,<b>f</b>) HPCs/S, and (<b>d</b>,<b>g</b>) HPCs/S@MnO<sub>2</sub> composites.</p>
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<p>(<b>a</b>,<b>b</b>) TEM images of HPCs/S@MnO<sub>2</sub> at different magnifications. (<b>c</b>) SAED pattern. (<b>d</b>,<b>e</b>) HRTEM images of the MnO<sub>2</sub> nanosheets. (<b>f</b>) HAADF–STEM image of HPCs/S@MnO<sub>2</sub> and the corresponding EDS mapping of C (<b>g</b>), S (<b>h</b>), Mn (<b>i</b>), and O (<b>j</b>) elements in the HPCs/S@MnO<sub>2.</sub></p>
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<p>(<b>a</b>) XRD patterns of δ-MnO<sub>2</sub>, sublimed sulfur, HPCs/S, and HPCs/S@MnO<sub>2</sub> (* denotes the characteristic peak of δ-MnO<sub>2</sub>.) (<b>b</b>) The N<sub>2</sub> adsorption–desorption isotherms of HPCs, HPCs/S, and HPCs/S@MnO<sub>2</sub>. (<b>c</b>) The corresponding pore size distributions (inset: the magnified pore size distribution curve of the HPCs/S@MnO<sub>2</sub> (blue line) and HPCs/S (red line)) and (<b>d</b>) the TG curves of HPCs/S and HPCs/S@MnO<sub>2</sub>.</p>
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<p>XPS spectra of HPCs/S@MnO<sub>2</sub>. (<b>a</b>) C 1s, (<b>b</b>) Mn 2p, (<b>c</b>) S 2p, (<b>d</b>) O 1s.</p>
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<p>(<b>a</b>) Rate performances of HPCs/S and HPCs/S@MnO<sub>2</sub> electrodes. (<b>b</b>) Cycling performances of HPCs/S and HPCs/S@MnO<sub>2</sub> electrodes with mass loading of 4.0 mg cm<sup>−2</sup> at 0.1 C. (<b>c</b>) Cycling performance of the HPCs/S@MnO<sub>2</sub> electrodes with mass loading of 7.0 mg cm<sup>−2</sup> at 0.1 C and 0.5 C. (<b>d</b>) Charging/discharging curves of the HPCs/S@MnO<sub>2</sub> with mass loading of 7.0 mg cm<sup>−2</sup> at 0.1 C. (<b>e</b>) Cycling performance of pouch type cell. (<b>f</b>) Digital graphical photo of pouch cell in working state.</p>
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<p>SEM images of original electrode of (<b>a</b>) HPCs/S, (<b>b</b>) HPCs/S@MnO<sub>2</sub> and cycled electrode of (<b>c</b>) HPCs/S, (<b>d</b>) HPCs/S@MnO<sub>2</sub>; the SEM images and higher magnification of cycled lithium anode (<b>e</b>,<b>g</b>) HPCs/S cell and (<b>f</b>,<b>h</b>) HPCs/S@MnO<sub>2</sub> cell (inset: photograph of the corresponding cycled lithium anode).</p>
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<p>EIS results of fresh and cycled HPCs/S and HPCs/S@MnO<sub>2</sub> cell (<b>a</b>) and DRT calculated from EIS measurements (<b>b</b>).</p>
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<p>(<b>a</b>) Theoretical structures of HPCs and MnO<sub>2</sub>. DFT calculation optimized geometric configurations and binding energies for the adsorption of polysulfides onto the HPCs (<b>b</b>) and MnO<sub>2</sub> (<b>c</b>).</p>
Full article ">Scheme 1
<p>Schematic illustration of polysulfide adsorption via HPCs/S (<b>a</b>) and HPCs/S@MnO<sub>2</sub> (<b>b</b>); Schematic diagrams of morphologies of HPCs/S (<b>c</b>) and HPCs/S@MnO<sub>2</sub> cathode (<b>d</b>) after discharging.</p>
Full article ">
16 pages, 7565 KiB  
Article
Preparation of the New Magnetic Nanoadsorbent Fe3O4@SiO2-yl-VP and Study on the Adsorption Properties of Hg (II) and Pb (II) in Water
by Dun Chen, Jianxin Chen, Wanyong Zhou and Amatjan Sawut
Magnetochemistry 2024, 10(12), 105; https://doi.org/10.3390/magnetochemistry10120105 - 13 Dec 2024
Viewed by 449
Abstract
This article reports the preparation of a novel functionalized magnetic nanoadsorbent through an addition reaction between Fe3O4 nanoparticles coated with allyl silica gel and 4-pyridinyl ethylene. A detailed characterization of Fe3O4@SiO2-yl-VP was conducted. Among [...] Read more.
This article reports the preparation of a novel functionalized magnetic nanoadsorbent through an addition reaction between Fe3O4 nanoparticles coated with allyl silica gel and 4-pyridinyl ethylene. A detailed characterization of Fe3O4@SiO2-yl-VP was conducted. Among them, in the infrared spectrum, we can easily see that the absorption peak of the C=C stretching vibration at 1660 cm−1 in the raw material disappears after the addition reaction, indicating the successful grafting of polymer on the surface of silica gel. The appearance of N element in the EDS spectrum also proves the successful completion of the addition reaction and the successful synthesis of Fe3O4@SiO2-yl-VP. At pH = 5 and pH = 7, it only takes half an hour for Fe3O4@SiO2-yl-VP to achieve maximum adsorption capacities of 85.06 and 73.78 mg/g for Hg (II) and Pb (II), respectively. The adsorption process conforms to the Langmuir model and the pseudo-first- and pseudo-second-order kinetic models and can be reused 11 times, demonstrating excellent reusability. Full article
(This article belongs to the Special Issue Applications of Magnetic Materials in Water Treatment)
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<p>Diagram of application and detection methods of magnetic nanoadsorbents.</p>
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<p>Structural diagrams of different magnetic nanoadsorbents.</p>
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<p>The FT-IR spectra of Fe<sub>3</sub>O<sub>4</sub>, Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub>-yl and Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub>-yl-VP.</p>
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<p>EDS spectra of Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub>-yl-VP (<b>a</b>), Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub>-yl-VP adsorbing mercury ions (<b>b</b>) and lead ion (<b>c</b>).</p>
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<p>XRD pattern of Fe<sub>3</sub>O<sub>4</sub>, Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub>-yl, and Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub>-yl-VP.</p>
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<p>The magnetic hysteresis curves of Fe<sub>3</sub>O<sub>4</sub>, Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub>-yl, and Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub>-yl-VP.</p>
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<p>TG curves of Fe<sub>3</sub>O<sub>4</sub>, Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub>-yl, and Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub>-yl-VP.</p>
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<p>SEM image of Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub>-yl-VP.</p>
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<p>TEM image of Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub>-yl-VP.</p>
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<p>The effect of initial concentration on the adsorption quantity.</p>
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<p>Adsorption isotherms of Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub>-yl-VP for Hg (II) and Pb (II).</p>
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<p>The effect of pH on the removal efficiency of Hg (II) and Pb (II) ions using Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub>-yl-VP.</p>
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<p>Adsorption kinetic curves of Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub>-yl-VP for Hg (II) and Pb (II).</p>
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<p>The effect of reused times on the adsorption capacities.</p>
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<p>The synthetic route of Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub>-yl-VP.</p>
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28 pages, 12281 KiB  
Article
Electrochemical Mineralization of Chloroquine in a Filter-Press-Type Flow Reactor in Batch Recirculation Mode Equipped with Two Boron-Doped Diamond Electrodes: Parametric Optimization, Total Operating Cost, Phytotoxicity Test, and Life Cycle Assessment
by Alejandro Regalado-Méndez, Juliana Zavaleta-Avendaño, Claudia Alanis-Ramírez, Deysi Amado-Piña, Armado Ramírez Serrano and Ever Peralta-Reyes
Catalysts 2024, 14(12), 918; https://doi.org/10.3390/catal14120918 - 12 Dec 2024
Viewed by 437
Abstract
This study investigated the electro-mineralization of chloroquine (CQ) in a filter-press-type flow reactor using two BDD electrodes operating in batch recirculation mode. The optimal operating parameters were established using response surface methodology (RSM) and central composite rotatable design (CCRD) with three parameters: current [...] Read more.
This study investigated the electro-mineralization of chloroquine (CQ) in a filter-press-type flow reactor using two BDD electrodes operating in batch recirculation mode. The optimal operating parameters were established using response surface methodology (RSM) and central composite rotatable design (CCRD) with three parameters: current density (j), initial pH (pH0), and volumetric flow rate (Q), with the mineralization efficiency of (CQ) and specific energy consumption (SEC) as responses. Optimal operating parameters were j = 155.0 mA/cm2, pH0 = 9.75, and Q = 0.84 L/min within a reaction time of 9 h, leading to a maximum mineralization efficiency of CQ of 52.59% and a specific energy consumption of 15.73 kW/mg TOC, with a total operating cost of USD 0.18 per liter. Additionally, an ultra-high-performance chromatography study identified three by-products (4-amino-7-choloroquinoline, formic acid, and acid acetic) of CQ degradation. Furthermore, the phytotoxicity test indicates that the electrochemical wastewater proposed decreased the effluent’s phytotoxicity, and an increase in the percentage of Vigna radiata germination was observed. The carbon footprint of optimized electrochemical mineralization of chloroquine is 2.48 kg CO2 eq., representing a 48% reduction in cumulative energy demand (CED) when the source of energy is a mixture of fossil fuels (50%), wind (25%), and photovoltaic (25%) energy. Full article
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<p>Cyclic voltammogram for a solution containing 150 mg/L CQ in a 0.1 M Na<sub>2</sub>SO<sub>4</sub> solution at the BDD anode: at different potential scan rates of 50, 100, and 200 mV/s, 1 atm, and <span class="html-italic">T</span> of 25 °C.</p>
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<p>(<b>a</b>) Comparison of modeled and experimental TOC removal efficiency (<span class="html-italic">η<sub>TOC</sub></span>); (<b>b</b>) comparison of modeled and experimental specific energy consumption (<span class="html-italic">η<sub>SEC</sub></span>).</p>
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<p>(<b>a</b>) Perturbation diagram for <math display="inline"><semantics> <mrow> <msub> <mi>η</mi> <mrow> <mi>T</mi> <mi>O</mi> <mi>C</mi> </mrow> </msub> </mrow> </semantics></math>; (<b>b</b>) perturbation diagram for <math display="inline"><semantics> <mrow> <msub> <mi>η</mi> <mrow> <mi>S</mi> <mi>E</mi> <mi>C</mi> </mrow> </msub> </mrow> </semantics></math>; (<b>c</b>) Spearman’s rho graphic; and (<b>d</b>) Pareto diagram for both responses (<math display="inline"><semantics> <mrow> <msub> <mi>η</mi> <mrow> <mi>T</mi> <mi>O</mi> <mi>C</mi> </mrow> </msub> </mrow> </semantics></math> and <math display="inline"><semantics> <mrow> <msub> <mi>η</mi> <mrow> <mi>S</mi> <mi>E</mi> <mi>C</mi> </mrow> </msub> </mrow> </semantics></math>).</p>
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<p>Optimization ramps for initial pH (<span class="html-italic">A</span>), current density (<span class="html-italic">B</span>), and volumetric flow rate (<span class="html-italic">C</span>).</p>
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<p>(<b>a</b>) Surface graphic of <math display="inline"><semantics> <mrow> <msub> <mi>η</mi> <mrow> <mi>T</mi> <mi>O</mi> <mi>C</mi> </mrow> </msub> </mrow> </semantics></math> as a function of <span class="html-italic">B</span> and <span class="html-italic">A</span>; (<b>b</b>) surface graphic of <math display="inline"><semantics> <mrow> <msub> <mi>η</mi> <mrow> <mi>S</mi> <mi>E</mi> <mi>C</mi> </mrow> </msub> </mrow> </semantics></math> as a function of <span class="html-italic">B</span> and <span class="html-italic">A</span>; (<b>c</b>) surface graphic of <math display="inline"><semantics> <mrow> <msub> <mi>η</mi> <mrow> <mi>T</mi> <mi>O</mi> <mi>C</mi> </mrow> </msub> </mrow> </semantics></math> as a function of <span class="html-italic">C</span> and <span class="html-italic">A</span>; (<b>d</b>) surface graphic <math display="inline"><semantics> <mrow> <msub> <mi>η</mi> <mrow> <mi>S</mi> <mi>E</mi> <mi>C</mi> </mrow> </msub> </mrow> </semantics></math> as a function of <span class="html-italic">C</span> and <span class="html-italic">A</span>; (<b>e</b>) surface graphic of <math display="inline"><semantics> <mrow> <msub> <mi>η</mi> <mrow> <mi>T</mi> <mi>O</mi> <mi>C</mi> </mrow> </msub> </mrow> </semantics></math> as function of <span class="html-italic">C</span> and <span class="html-italic">B</span>; (<b>f</b>) surface graphic of <math display="inline"><semantics> <mrow> <msub> <mi>η</mi> <mrow> <mi>S</mi> <mi>E</mi> <mi>C</mi> </mrow> </msub> </mrow> </semantics></math> as a function of <span class="html-italic">C</span> and <span class="html-italic">B</span>; (<b>g</b>) desirability bar chart diagram; (<b>h</b>) operational region plot for the three design operating variables’ process (pH<sub>0</sub>, <span class="html-italic">j</span>, and <span class="html-italic">j</span>) and two responses’ constraints <math display="inline"><semantics> <mrow> <msub> <mi>η</mi> <mrow> <mi>T</mi> <mi>O</mi> <mi>C</mi> </mrow> </msub> </mrow> </semantics></math> and <math display="inline"><semantics> <mrow> <msub> <mi>η</mi> <mrow> <mi>S</mi> <mi>E</mi> <mi>C</mi> </mrow> </msub> </mrow> </semantics></math> with the volumetric flow rate at optimal level (<span class="html-italic">Q</span> = 0.84 L/min).</p>
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<p>(<b>a</b>) Surface graphic of <math display="inline"><semantics> <mrow> <msub> <mi>η</mi> <mrow> <mi>T</mi> <mi>O</mi> <mi>C</mi> </mrow> </msub> </mrow> </semantics></math> as a function of <span class="html-italic">B</span> and <span class="html-italic">A</span>; (<b>b</b>) surface graphic of <math display="inline"><semantics> <mrow> <msub> <mi>η</mi> <mrow> <mi>S</mi> <mi>E</mi> <mi>C</mi> </mrow> </msub> </mrow> </semantics></math> as a function of <span class="html-italic">B</span> and <span class="html-italic">A</span>; (<b>c</b>) surface graphic of <math display="inline"><semantics> <mrow> <msub> <mi>η</mi> <mrow> <mi>T</mi> <mi>O</mi> <mi>C</mi> </mrow> </msub> </mrow> </semantics></math> as a function of <span class="html-italic">C</span> and <span class="html-italic">A</span>; (<b>d</b>) surface graphic <math display="inline"><semantics> <mrow> <msub> <mi>η</mi> <mrow> <mi>S</mi> <mi>E</mi> <mi>C</mi> </mrow> </msub> </mrow> </semantics></math> as a function of <span class="html-italic">C</span> and <span class="html-italic">A</span>; (<b>e</b>) surface graphic of <math display="inline"><semantics> <mrow> <msub> <mi>η</mi> <mrow> <mi>T</mi> <mi>O</mi> <mi>C</mi> </mrow> </msub> </mrow> </semantics></math> as function of <span class="html-italic">C</span> and <span class="html-italic">B</span>; (<b>f</b>) surface graphic of <math display="inline"><semantics> <mrow> <msub> <mi>η</mi> <mrow> <mi>S</mi> <mi>E</mi> <mi>C</mi> </mrow> </msub> </mrow> </semantics></math> as a function of <span class="html-italic">C</span> and <span class="html-italic">B</span>; (<b>g</b>) desirability bar chart diagram; (<b>h</b>) operational region plot for the three design operating variables’ process (pH<sub>0</sub>, <span class="html-italic">j</span>, and <span class="html-italic">j</span>) and two responses’ constraints <math display="inline"><semantics> <mrow> <msub> <mi>η</mi> <mrow> <mi>T</mi> <mi>O</mi> <mi>C</mi> </mrow> </msub> </mrow> </semantics></math> and <math display="inline"><semantics> <mrow> <msub> <mi>η</mi> <mrow> <mi>S</mi> <mi>E</mi> <mi>C</mi> </mrow> </msub> </mrow> </semantics></math> with the volumetric flow rate at optimal level (<span class="html-italic">Q</span> = 0.84 L/min).</p>
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<p>(<b>a</b>) Concentration profile of CQ and by-products as a function of time determined by UHPLC; (<b>b</b>) kinetic analysis for the pseudo-zero-order model for CQ removal; and (<b>c</b>) kinetic analysis for the pseudo-zero-order model for TOC removal. Performed under optimal operating parameters: <span class="html-italic">T</span> = 25 °C, pH<sub>0</sub> = 9.75, <span class="html-italic">j</span> = 155 mA/cm<sup>2</sup>, and <span class="html-italic">Q</span> = 0.84 L/min within 9.0 h of electrolysis time.</p>
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<p>Growth of <span class="html-italic">Vigna radiata</span> in (<b>a</b>) tap water; (<b>b</b>) distilled water; (<b>c</b>) electrolyte support (Na<sub>2</sub>SO<sub>4</sub> at 0.1 M); (<b>d</b>) solution containing CQ (50 mg/L); and (<b>e</b>) wastewater treated on BDD anode. The electrochemical mineralization of the solution containing CQ was performed under optimal operating parameters: <span class="html-italic">T</span> = 25 °C, pH<sub>0</sub> = 9.75, <span class="html-italic">j</span> = 155 mA/cm<sup>2</sup>, and <span class="html-italic">Q</span> = 0.84 L/min within 9.0 h of electrolysis time.</p>
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<p>Contribution analysis based on ReCiPe midpoint method via characterization per functional unit for the electrooxidation process of chloroquine.</p>
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<p>Effects of electricity consumption for scenarios S0, S1, S2 and S3, using fossil fuels and renewable sources (photovoltaic and wind turbine) on % of environmental impacts: CED, GWP, Tec, and HncT.</p>
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<p>Electrochemical plant set-up.</p>
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<p>System boundary of the electrochemical degradation of chloroquine in terms of material and energy consumption.</p>
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14 pages, 5880 KiB  
Article
Functional Mechanical Behavior and Biocompatible Characteristics of Graphene-Coated Cardiovascular Stents
by Łukasz Wasyluk, Dariusz Hreniak, Vitalii Boiko, Beata Sobieszczańska, Emanuela Bologna, Massimiliano Zingales, Robert Pasławski, Jacek Arkowski, Przemysław Sareło and Magdalena Wawrzyńska
Int. J. Mol. Sci. 2024, 25(24), 13345; https://doi.org/10.3390/ijms252413345 - 12 Dec 2024
Viewed by 282
Abstract
Percutaneous Coronary Intervention (PCI) is a treatment method that involves reopening narrowed arteries with a balloon catheter that delivers a cylindrical, mesh-shaped implant device to the site of the stenosis. Currently, by applying a coating to a bare metal stent (BMS) surface to [...] Read more.
Percutaneous Coronary Intervention (PCI) is a treatment method that involves reopening narrowed arteries with a balloon catheter that delivers a cylindrical, mesh-shaped implant device to the site of the stenosis. Currently, by applying a coating to a bare metal stent (BMS) surface to improve biocompatibility, the main risks after PCI, such as restenosis and thrombosis, are reduced while maintaining the basic requirements for the mechanical behavior of the stent itself. In this work, for the first time, the development and optimization process of the spatial structure of the Co-Cr stent (L-605) with a graphene-based coating using cold-wall chemical vapor deposition (CW-CVD) to ensure uniform coverage of the implant was attempted. The CW-CVD process allows the coating of 3D structures, minimizing thermal stress on the surrounding equipment and allowing the deposition of coatings on temperature-sensitive materials. It produces uniform and high-purity films with control over the thickness and composition. The reduced heating of the chamber walls minimizes unwanted reactions, leading to fewer impurities in the final coating. The graphene layers obtained using Raman spectroscopy at different parameters of the CW-CVD process were verified, their properties were investigated, and the functional mechanical behavior of the studied graphene-covered stent was confirmed. In vitro, graphene-coated stents promoted rapid endothelial cell repopulation, an advantage over gold-standard drug-eluting stents delaying re-endothelialization. Also, full-range biocompatibility studies on potential allergic, irritation, toxicological, and pyrogenic reactions of new material in vivo on small animal models demonstrated excellent biocompatibility of the graphene-coated stents. Full article
(This article belongs to the Special Issue Biofunctional Coatings for Medical Applications)
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Figure 1
<p>Raman spectra (λ<sub>ex</sub>—514 nm) of the cardiovascular stents before (black line) and after CW-CVD (red, green, and blue line) with different deposition temperatures (700 °C, 900 °C, and 1100 °C, respectively).</p>
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<p>SEM images of a cardiovascular stent (<b>a</b>) before and (<b>b</b>) after CW-CVD. (<b>c</b>) The stent fracture after crimping. (<b>d</b>–<b>f</b>) Images of critical areas for properly crimped and expanded stent. The scale bar is presented in the appropriate image.</p>
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<p>(<b>a</b>) The radial force measurement device. (<b>b</b>) The values of the obtained radial forces of graphene-coated stent (GC-stent) and uncoated stent (BM-stent). The <span class="html-italic">p</span>-value according to the non-parametric Mann–Whitney U test.</p>
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<p>(<b>a</b>) The coronary stents used in the test and the BOSE 9400 MAPS system. (<b>b</b>) The macro-photography of the bare metal stent. (<b>c</b>) The macro-photography of the graphene-coated stent. (<b>d</b>) Time evolution of the stent diameter for the reference and graphene-coated stents and (<b>e</b>) pressure-diameter elastic behavior of the stent in the cyclic load-unload test for the reference and graphene-coated stents. The response to cyclic loading confirms that graphene-coated stents are just as safe as uncoated stents, which have been used clinically for many years. The mechanical properties of graphene-coated stents are similar to those of other coatings. The main advantage of graphene coating is increased biocompatibility.</p>
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<p>(<b>a</b>) HUVEC cell proliferation on bare metal (BM) stents and graphene-coated (GC) bare metal stents after 72 h quantified in the WST-1 assay. * <span class="html-italic">p</span> &lt; 0.001. (<b>b</b>) The proliferation of HUVEC cells on bare metal (BM) stent and graphene-coated bare metal (GC) stent after 72 h. Cells were visualized by staining the cell’s actin cytoskeleton with phalloidin-FITC and the cell’s nuclei with DAPI. Magnification 400×.</p>
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<p>Photographic documentation of the allergy and skin irritation tests performed, where (<b>a</b>) the method of applying the tested graphene-coated samples on the shaved skin of a guinea pig during the GPMT test is presented. The tested implant was placed on the skin of a rabbit similarly during the Rabbit Skin Primary Irritation Test. (<b>b</b>) The site after applying the graphene-coated stent and after a 14-day break and re-applying of the stent. The site was assessed using the Magnusson and Kligman scale in the GPMT test. (<b>c</b>) The site after 72 h where the graphene-coated stent was applied and subjected to erythema and edema assessments on a scale of 0 to 4 in the Rabbit Skin Primary Irritation Test.</p>
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<p>Photographic documentation (<b>a</b>–<b>c</b>) of individual stages of intraperitoneal insertion of the tested graphene-coated stents. (<b>d</b>) The autopsy did not show any symptoms of reaction to the tested material. The implanted material samples were loose in the peritoneal cavity and could be easily removed.</p>
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<p>The histopathological microscope images show no organ changes following the introduction of graphene-coated stents: chronic response study. No changes were observed in (<b>a</b>) lungs, (<b>b</b>) heart, (<b>c</b>) kidneys, and (<b>d</b>) liver. The results do not differ from typical images characteristic of healthy organs. Below, histopathological images of the skin after (<b>e</b>) 24 h, (<b>f</b>) 48 h, and (<b>g</b>) 72 h, respectively, are shown in the skin irritation tests. The tests were performed on the White New Zealand rabbit. The scale shown in the images indicates 400 μm.</p>
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23 pages, 1240 KiB  
Review
Improving Phosphate Acquisition from Soil via Higher Plants While Approaching Peak Phosphorus Worldwide: A Critical Review of Current Concepts and Misconceptions
by Jörg Gerke
Plants 2024, 13(24), 3478; https://doi.org/10.3390/plants13243478 - 12 Dec 2024
Viewed by 287
Abstract
Phosphate (P) is the plant macronutrient with, by far, the lowest solubility in soil. In soils with low P availability, the soil solution concentrations are low, often below 2 [µmol P/L]. Under these conditions, the diffusive P flux, the dominant P transport mechanism [...] Read more.
Phosphate (P) is the plant macronutrient with, by far, the lowest solubility in soil. In soils with low P availability, the soil solution concentrations are low, often below 2 [µmol P/L]. Under these conditions, the diffusive P flux, the dominant P transport mechanism to plant roots, is severely restricted. Phosphate is sorbed into various soil solids, Fe/Al oxides, clay minerals and, sometimes overlooked, humic Fe/Al surfaces. The immobilization of P in soil is often the result of the diffusion of P into the internal surfaces of oxides or humic substances. This slow reaction between soil and P further reduces the availability of P in soil, leading to P fixation. The solubilization of soil P by root-released carboxylates is a promising way to increase the acquisition and uptake of P from P-fixing soils. Citrate and, sometimes, oxalate are effective with respect to additional P solubilization or P mobilization, which may help increase the diffusive P flux into the roots by increasing the P solution concentrations in the rhizosphere. The mobilization of humic-associated P by carboxylates may be an effective way to improve soil P solubility. Not only orthophosphate anions are mobilized by root-released carboxylates, but also higher phosphorylated inositol phosphates, as the main part of P esters in soil are mobilized by carboxylates. Because of the rather strong bonding of higher phosphorylated inositol phosphates to the soil solid phase, the mobilization step by carboxylates appears to be essential for plants to acquire inositol-P. The ecological relevance of P mobilization by carboxylates and its effect on the uptake of P by crops and grassland species are, at best, partially understood. Plant species which form cluster roots such as white lupin (Lupinus albus L.) or yellow lupin (Lupinus luteus L.) release high rates of carboxylates, mainly citrate from these root clusters. These plant species acquire fixed or low available P which is accessible to plants at rates which do not satisfy their P demand without P mobilization. And white lupin and yellow lupin make soil P available to other plants in mixed cropping systems or for subsequent plant species in crop rotations. The mobilization of P by carboxylates is probably also important for legume/grass mixtures for forage production. Species such as alfalfa, red clover or white clover release carboxylates. The extent of P mobilization and P uptake from mobilized P by legume/grass mixtures deserves further research. In particular, which plant species mostly benefit from P mobilization by legume-released carboxylates is unknown. Organic farming systems require such legume/grass mixtures for the introduction of nitrogen (N) by forage legumes into their farming system. For this agricultural system, the mobilization of soil P by carboxylates and its impact on P uptake of the mixtures are an important research task. Full article
(This article belongs to the Section Plant Nutrition)
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Figure 1
<p>Adsorption–desorption hysteresis of soil phosphate. Note that to achieve a definite P solution concentration, the P coverage of the soil solid phase must be much higher during desorption (Psd) compared to adsorption (Psa).</p>
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<p>Principal slow reaction between added phosphate and soil.</p>
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<p>Phosphate at the soil solid phase, P transfer into the soil solution and immobilization reactions affecting soil P availability. P<sub>i</sub>—orthophosphate; P<sub>o</sub>—phosphate ester, solu.—species in solution.</p>
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18 pages, 3479 KiB  
Article
Generation of Charges During the Synthesis of Nanopowders of Doped Cerium Dioxide in Combustion Reactions
by Alexander Ostroushko, Olga Russkikh, Tatiyana Zhulanova, Anastasia Permyakova and Elena Filonova
Materials 2024, 17(24), 6066; https://doi.org/10.3390/ma17246066 - 12 Dec 2024
Viewed by 253
Abstract
The development and characterization of synthesis techniques for oxide materials based on ceria is a subject of extensive study with the objective of their wide-ranging applications in pursuit of sustainable development. The present study demonstrates the feasibility of controlled synthesis of Ce1−x [...] Read more.
The development and characterization of synthesis techniques for oxide materials based on ceria is a subject of extensive study with the objective of their wide-ranging applications in pursuit of sustainable development. The present study demonstrates the feasibility of controlled synthesis of Ce1−xMxO2−δ (M = Fe, Ni, Co, Mn, Cu, Ag, Sm, Cs, x = 0.0–0.3) in combustion reactions from precursors comprising glycine, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, and cellulose as organic components. Controlled synthesis is achieved by varying the composition of the precursor, the type of organic component, and the amount of organic component, which allows for the influence of the generation of high-density electrical charges and outgassing during synthesis. The intensity of charge generation is quantified by measuring the value of the precursor–ground potential difference. It has been demonstrated that an increase in the intensity of charge generation results in a more developed morphology, which is essential for the practical implementation of ceria as a catalyst to enhance contact with gases and solid particles. The maximum value of the potential difference, equal to 68 V, is obtained during the synthesis of Ce0.7Ni0.3O2−δ with polyvinyl alcohol in stoichiometric relations, which corresponds to a specific surface area of 21.7 m2 g−1. A correlation is established between the intensity of gas release for systems with different organic components, the intensity of charge generation, morphology, and the value of the specific surface area of the samples. Full article
(This article belongs to the Special Issue Advanced Materials – Microstructure, Manufacturing and Analysis)
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<p>SEM images of oxide materials synthesized from precursors containing polyvinyl alcohol at different amounts relative to the stoichiometric (<span class="html-italic">φ</span>) for the combustion reaction, bulk composition: Ce<sub>0.9</sub>Ag<sub>0.1</sub>O<sub>2−δ</sub> (<span class="html-italic">φ</span> = 1) (<b>а</b>); Ce<sub>0.9</sub>Ag<sub>0.1</sub>O<sub>2−δ</sub> (<span class="html-italic">φ</span> = 2) (<b>b</b>); Ce<sub>0.9</sub>Cu<sub>0.1</sub>O<sub>2−δ</sub> (<span class="html-italic">φ</span> = 1) (<b>c</b>); Ce<sub>0.9</sub>Ni<sub>0.1</sub>O<sub>2−δ</sub> (<span class="html-italic">φ</span> = 1) (<b>d</b>); Ce<sub>0.9</sub>Fe<sub>0.1</sub>O<sub>2−δ</sub> (<span class="html-italic">φ</span> = 1) (<b>e</b>).</p>
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<p>SEM images with EDX analysis for Ce<sub>0.9</sub>Ag<sub>0.1</sub>O<sub>2−δ</sub> (<b>а</b>) and Ce<sub>0.9</sub>Ni<sub>0.1</sub>O<sub>2−δ</sub> (<b>b</b>) synthesized from precursors containing polyvinyl alcohol (<span class="html-italic">φ</span> = 1) (purple indicates the region where the second phase of NiO is absent).</p>
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<p>Examples of XRD of single-phase samples (<b>a</b>) and two-phase samples (<b>b</b>).</p>
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<p>Maximum potential difference (<b>a</b>,<b>b</b>) and maximum temperature (<b>c</b>,<b>d</b>) obtained during the synthesis of the complex oxide material Ce<sub>1−x</sub>M<sub>x</sub>O<sub>2−δ</sub> (bulk composition) from precursors containing polyvinyl alcohol with <span class="html-italic">φ</span> = 1 (<b>a</b>,<b>c</b>) and with <span class="html-italic">φ</span> = 2 (<b>b</b>,<b>d</b>). The diagrams show the doping elements, M = Fe, Mn, Ni, Ag, Cs, and their mole fractions (0.1; 0.3).</p>
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<p>Maximum precursor–ground potential difference (<b>a</b>) and maximum temperature (<b>b</b>) obtained during the synthesis of the complex oxide material Ce<sub>1−x</sub>M<sub>x</sub>O<sub>2−δ</sub> (bulk composition) from precursors containing polyvinylpyrrolidone with <span class="html-italic">φ</span> = 1.</p>
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<p>Maximum precursor–ground potential difference (<b>a</b>) and maximum temperature (<b>b</b>) obtained during the synthesis of the complex oxide material Ce<sub>0.9</sub>Fe<sub>0.1</sub>O<sub>2−δ</sub> from precursors containing glycine (Gly), polyvinyl alcohol (PVA), polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), cellulose (C), polyacrylamide (PAA) with <span class="html-italic">φ</span> = 1.</p>
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<p>Maximum precursor–ground potential difference (<b>a</b>) and maximum temperature (<b>b</b>) obtained during the synthesis of the complex oxide material Ce<sub>0.9</sub>Ni<sub>0.1</sub>O<sub>2−δ</sub> from precursors containing glycine (Gly), polyvinyl alcohol (PVA), polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), cellulose (C), polyacrylamide (PAA) with <span class="html-italic">φ</span> = 1.</p>
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<p>Concentration profiles of the release of CO (<b>a</b>) and NO (<b>b</b>) during the synthesis of Ce<sub>0.9</sub>Ni<sub>0.1</sub>O<sub>2−δ</sub> (bulk composition) from precursors containing polyvinylpyrrolidone (PVP) with <span class="html-italic">φ</span> = 1, polyvinyl alcohol (PVA) with <span class="html-italic">φ</span> = 1, polyethylene glycol (PEG) with <span class="html-italic">φ</span> = 1, 2, cellulose (C) with <span class="html-italic">φ</span> = 1, 2; CO, NO, NO<sub>2</sub> (<b>c</b>) during the synthesis of Ce<sub>0.7</sub>Ni<sub>0.3</sub>O<sub>2</sub> (bulk composition) from a precursor containing polyvinylpyrrolidone with <span class="html-italic">φ</span> = 1.</p>
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<p>Maximum concentration of CO (<b>a</b>) NO (<b>b</b>) during the synthesis of materials with bulk composition Ce<sub>1−x</sub>M<sub>x</sub>O<sub>2−δ</sub> obtained from precursors containing polyvinyl alcohol with <span class="html-italic">φ</span> = 1. The diagrams show the doping elements, M = Fe, Mn, Ni, Ag, Cs, and their mole fractions (0.1; 0.3).</p>
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<p>The precursor–ground potential difference and the concentration of gases released during the synthesis of the complex oxide Ce<sub>0.9</sub>Cs<sub>0.1</sub>O<sub>2−δ</sub> from a precursor containing polyvinyl alcohol with <span class="html-italic">φ</span> = 1 (the data here are given without considering the blank experiment).</p>
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11 pages, 1527 KiB  
Article
Enhancement of the Thermostability of Microbacterium Esterase by Combinatorial Rational Design
by Wenyu Peng, Xiaomei Wu, Baodi Ma and Yi Xu
Molecules 2024, 29(24), 5839; https://doi.org/10.3390/molecules29245839 - 11 Dec 2024
Viewed by 232
Abstract
The esterase EstSIT01 from Microbacterium can catalyze the asymmetric hydrolysis of meso-dimethyl ester to produce the crucial chiral intermediate (4S, 5R)-hemimethyl ester for d-biotin synthesis. Despite its high yields and stereoselectivity, the low thermostability of EstSIT01 limits [...] Read more.
The esterase EstSIT01 from Microbacterium can catalyze the asymmetric hydrolysis of meso-dimethyl ester to produce the crucial chiral intermediate (4S, 5R)-hemimethyl ester for d-biotin synthesis. Despite its high yields and stereoselectivity, the low thermostability of EstSIT01 limits its practical application. Herein, two kinds of rational strategies were combined to enhance the thermostability of EstSIT01. Based on the Surface Residue Substitution (SRS) method, two variants (G215A and G316A) with improved thermostability and one mutant (G293A) with superior activity were identified from nine candidates. According to the Consensus Mutation method, two mutants (E301P and A332P) with enhanced thermostability were identified from six candidates. However, the combined mutation failed to yield mutants surpassing the best single mutant, E301P, in terms of thermostability. The combined mutant E301P/G215A and E301P/G215A/G293A exhibited a slight enhancement in enzyme activity relative to E301P, while also exhibiting improved thermostability compared to the wild-type EstSIT01. Compared with the wild-type esterase, the thermal inactivation half-lives (t1/2) of mutant E301P were enhanced 1.4-fold, 2.4-fold and 1.8-fold at 45 °C, 55 °C, and 65 °C, respectively. The optimal reaction temperature and pH for mutant E301P remained consistent with those of the wild type, at 40 °C and 10.0, respectively. The Km of E301P was 0.22 ± 0.03 mM and the kcat was 5.1 ± 0.28 s−1. Further analysis indicated that the free energies of G215A, G293A and E301P were decreased by 0.91, 0.308 and 1.1049 kcal/mol, respectively, compared to the wild-type EstSIT01. The interaction analysis revealed that the substitution of glutamic acid with proline at position 301 enhanced the hydrophobic interactions within the protein. The decreased free energies and the increased hydrophobic interactions were well correlated with the enhanced stability in these mutants. Full article
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<p>Enzymatic asymmetric hydrolysis of <span class="html-italic">meso</span>-diester for the production of (4<span class="html-italic">S</span>, 5<span class="html-italic">R</span>)-hemiester.</p>
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<p>Distribution of the potential mutated residues in the structure of EstSIT01. (<b>a</b>) Glycine (green sticks) on the surface of EstSIT01 predicted by GETAREA. (<b>b</b>) Six potential mutations (blue sticks) determined by consensus analysis.</p>
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<p>Characteristics of EstSIT01 and its variant E301P. (<b>a</b>) Effect of temperature on activity. The activities of wild-type EstSIT01 and the E301P mutant were evaluated across a range of temperatures from 30 °C to 70 °C in PBS (50 mM, pH 8.0). The maximum activities were defined as 100%, with wild-type EstSIT01 achieving 8.5 U/mg and E301P achieving 5.9 U/mg. (<b>b</b>) Thermal stability. Thermal stability was assessed by measuring the residual activity after incubating the wild-type EstSIT01 and E301P mutant at various temperatures (30 °C to 70 °C) for 60 min. The initial activity was set at 100% for both enzymes. (<b>c</b>) Effect of pH on activity. The effect of pH on enzyme activity was studied at 55 °C using different buffers: PBS for pH 6.0 to 8.0, Tris-HCl for pH 8.0 to 9.0, and Gly-NaOH for pH 9.0 to 11.0. Relative activity was expressed as a percentage of the maximum activity for each enzyme. (<b>d</b>) pH stability. pH stability was determined by monitoring residual activity after incubating the enzymes in various buffers at 55 °C for 1 h. The initial activity at each pH value was defined as 100%.</p>
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<p>Structures of EstSIT01 (purple) and its mutants (green). (<b>a</b>) The structure of wild-type EstSIT01; (<b>b</b>) the E301P mutant formed hydrophobic interaction of Pro 301 with both Gln 300 and Gln 305; (<b>c</b>) WT exhibited hydrophobic interaction of Glu 301 with Val 271.</p>
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19 pages, 2651 KiB  
Article
Cationic/Anionic Poly(p-Phenylene Oxide) Membranes: Preparation and Electrodialysis Performance for Nickel Recovery from Industrial Effluents
by Fabrício Wilbert, Joana Farias Corte, Felipe Tiago do Nascimento, Vanusca Dalosto Jahno, Marco Antônio Siqueira Rodrigues, Fabrício Celso, Salatiel W. da Silva and Andrea Moura Bernardes
Membranes 2024, 14(12), 268; https://doi.org/10.3390/membranes14120268 - 11 Dec 2024
Viewed by 352
Abstract
Electrodialysis (ED) has already been applied to recover nickel in galvanizing processes, allowing nickel recovery and the production of a treated effluent with demineralized water quality. However, the growth in ED use is still limited by the production and commercialization of ion-selective membranes, [...] Read more.
Electrodialysis (ED) has already been applied to recover nickel in galvanizing processes, allowing nickel recovery and the production of a treated effluent with demineralized water quality. However, the growth in ED use is still limited by the production and commercialization of ion-selective membranes, currently limited to a few large companies. Therefore, this paper presents the development of homogeneous cationic and anionic membranes made from poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) for ED use. Cationic membranes were prepared by the sulfonation reaction of PPO under different experimental conditions (PPO:H2SO4 molar ratio and reaction time). Anionic membranes were prepared by the bromination reaction of PPO, followed by the amination reaction. The membranes were characterized for their chemical and electrochemical properties, including ion exchange capacity, conductivity, thermal stability, and surface morphology. The optimal conditions for cationic membrane sulfonation were achieved with a 1:4.4 PPO:H2SO4 molar ratio, and a reaction time of 0.5 h. For anionic membranes, the best results were obtained with bromination, with a PPO:NBS (N-Bromosuccinimide) molar ratio of 1:0.5, followed by 14 days of amination. Overall, 91.8% chloride, 90.9% sulfate, and 85.5% nickel ion extraction was achieved, highlighting PPO as a promising polymer for the development of anionic and cationic ion-selective membranes for ED. Full article
(This article belongs to the Special Issue Research on Electrodialytic Processes)
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<p>Electrodialysis bench system used for nickel wastewater treatment.</p>
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<p>SEM surface images of the cationic membranes HDX 100 and CATPPO-1.</p>
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<p>SEM surface images of the anionic membranes HDX200 and ANIPPO-1.</p>
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<p>Current–voltage curves of CATPPO-1 membrane in sodium sulfate solution (<b>a</b>) or nickel industrial effluent (<b>b</b>) and of HDX100 membrane in sodium sulfate solution (<b>c</b>) or nickel industrial effluent (<b>d</b>).</p>
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<p>Current–voltage curves of CATPPO-1 membrane in sodium sulfate solution (<b>a</b>) or nickel industrial effluent (<b>b</b>) and of HDX100 membrane in sodium sulfate solution (<b>c</b>) or nickel industrial effluent (<b>d</b>).</p>
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<p>Current–voltage curves of ANIPPO-1 membrane in sodium sulfate solution (<b>a</b>) or nickel industrial effluent (<b>b</b>) and of HDX200 membrane in sodium sulfate solution (<b>c</b>) or nickel industrial effluent (<b>d</b>).</p>
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<p>Current–voltage curves of ANIPPO-1 membrane in sodium sulfate solution (<b>a</b>) or nickel industrial effluent (<b>b</b>) and of HDX200 membrane in sodium sulfate solution (<b>c</b>) or nickel industrial effluent (<b>d</b>).</p>
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19 pages, 5820 KiB  
Article
Studying the Effect of Reducing Agents on the Properties of Gold Nanoparticles and Their Integration into Hyaluronic Acid Hydrogels
by Elżbieta Adamska, Agata Kowalska, Anna Wcisło, Katarzyna Zima and Beata Grobelna
Molecules 2024, 29(24), 5837; https://doi.org/10.3390/molecules29245837 - 11 Dec 2024
Viewed by 308
Abstract
Gold nanoparticles (Au NPs) are a promising target for research due to their small size and the resulting plasmonic properties, which depend, among other things, on the chosen reducer. This is important because removing excess substrate from the reaction mixture is problematic. However, [...] Read more.
Gold nanoparticles (Au NPs) are a promising target for research due to their small size and the resulting plasmonic properties, which depend, among other things, on the chosen reducer. This is important because removing excess substrate from the reaction mixture is problematic. However, Au NPs are an excellent component of various materials, enriching them with their unique features. One example is hydrogels, which provide a good, easily modifiable base for multiple applications such as cosmetics. For this purpose, various compounds, including hyaluronic acid (HA) and its derivatives, are distinguished by their high water-binding capacity and many characteristics resulting from their natural origin in organisms, including biocompatibility, biodegradability, and tissue regeneration. In this work Au NPs were synthesized using a green chemistry method, either by using onion extract as a reductant or chemically reducing them with sodium citrate. A complete characterization of the nanoparticles was carried out using the following methods: Fourier-Transform Infrared Spectroscopy (FT-IR), Electrophoretic (ELS), and Dynamic Light Scattering (DLS) as well as Transmission Electron Microscope (TEM) and Scanning Electron Microscope (SEM). Their antioxidant activity was also tested using the 2,2-diphenyl-1-picrylhydrazyl radical (DPPH). The results showed that the synthesized nanoparticles enrich the hydrogels with antioxidant properties and new surface properties (depending on the reducing agent, they can be more hydrophilic or hydrophobic). Preliminary observations indicated low cytotoxicity of the nanomaterials in both liquid form and as a hydrogel component, as well as their lack of penetration through pig skin. The cosmetic properties of hydrogel masks were also confirmed, such as increasing skin hydration. Full article
(This article belongs to the Special Issue Synthesis of Nanomaterials and Their Applications in Biomedicine)
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<p>HPLC-UV chromatograms of onion extract acquired at 254 nm. Peak identification: 1—Gallic acid, 2—Myricetin, 3—Catechin, 4—Caffeic acid, 5—Quercetin, 6—Rutin.</p>
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<p>Synthesized colloids of Au NPs obtained with the reducer (<b>a</b>) onion extract; (<b>b</b>) sodium citrate.</p>
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<p>TEM images and diagrams of the particle diameter for Au NPs obtained using the reducer (<b>a</b>) onion extract; (<b>b</b>) sodium citrate on two scales: 50 and 200 nm.</p>
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<p>FT-IR spectra for Au NPs obtained using the reducer (<b>a</b>) onion extract, and (<b>b</b>) sodium citrate.</p>
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<p>DPPH radical scavenging activity of reducer and Au NPs obtained using onion extract ((<b>left</b>) diagram) and sodium citrate ((<b>right</b>) diagram) after 15 min, 1 h, and 1, 2, 3, 6, 7 days. Results are expressed in terms of mean ± SEM (<span class="html-italic">n</span> = 3).</p>
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<p>TEM images for hydrogel masks: (<b>a</b>) control and obtained using the reducer; (<b>b</b>) onion extract; (<b>c</b>) sodium citrate on a scale of 200 nm.</p>
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<p>SEM images for hydrogel masks: (<b>a</b>) control and obtained using the reducer; (<b>b</b>) onion extract; (<b>c</b>) sodium citrate with smaller (<b>left</b>) and larger (<b>right</b>) zoom.</p>
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<p>Water contact angle measurement results for: Au NPs obtained using the reducer (<b>a</b>) onion extract; (<b>b</b>) sodium citrate; (<b>c</b>) hydrogel mask (control, without NPs); (<b>d</b>) hydrogel mask Au NPs obtained using the onion extract; (<b>e</b>) hydrogel mask Au NPs obtained using the sodium citrate.</p>
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<p>Average results of (<b>a</b>) skin hydration level, (<b>b</b>) oil level, and (<b>c</b>) transepidermal water loss (TEWL), were obtained for the skin before, after 1 min, 15 min, and 1 week after applying a hydrogel mask (control, without NPs).</p>
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<p>The viability of the HaCaT epidermal cell line evaluated by the MTT assay after 24, 48, and 72 h of exposure to lower concentrations of (<b>a</b>) hydrogel citrate Au NPs, (<b>b</b>) hydrogel onion Au NPs, (<b>c</b>) liquid citrate Au NPs, and (<b>d</b>) liquid onion Au NPs. Data are expressed as mean values ± SD from three independent experiments. * <span class="html-italic">p</span> &lt; 0.05; ** <span class="html-italic">p</span> &lt; 0.01; *** <span class="html-italic">p</span> &lt; 0.001; **** <span class="html-italic">p</span> &lt; 0.0001 versus negative control (CTRL−). The positive control (CTRL+) was water for the liquid formulations or hydrogel without Au NPs for the hydrogel formulations.</p>
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<p>The viability of the HaCaT epidermal cell line evaluated by the MTT test after 24 h of exposure to high concentrations of (<b>a</b>) Au NPs citrate and (<b>b</b>) Au NPs onion. Data are expressed as mean values ± SD from three separate experiments. * <span class="html-italic">p</span> &lt; 0.05; ** <span class="html-italic">p</span> &lt; 0.01; **** <span class="html-italic">p</span> &lt; 0.0001 versus negative control (CTRL−). The positive control (CTRL+) was water for the liquid formulations.</p>
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<p>The IC<sub>50</sub> values calculated by a nonlinear regression analysis for HaCaT (<b>a</b>) Au NPs citrate; (<b>b</b>) Au NPs onion after 24 h of exposure to high concentrations. Data are expressed as means ± SD for three separate experiments. R<sup>2</sup>—coefficient of determination.</p>
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<p>Absorption spectra for Au NPs obtained using the reducer: (<b>a</b>) onion extract; (<b>b</b>) sodium citrate. 1—for the receiving solution from the Franz diffusion chamber and 2—for the solution of nanoparticles used as an ingredient in the hydrogel mask (initial).</p>
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<p>Scheme for obtaining HA-based hydrogels with Au NPs.</p>
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32 pages, 8473 KiB  
Review
Application of Defect Engineering via ALD in Supercapacitors
by Tiange Gao, Xiaoyang Xiao, Zhenliang Dong, Xilong Lu, Liwen Mao, Jinzheng Wang, Yiming Liu, Qingmin Hu and Jiaqiang Xu
Batteries 2024, 10(12), 438; https://doi.org/10.3390/batteries10120438 - 10 Dec 2024
Viewed by 385
Abstract
Supercapacitors are a kind of energy storage device that lie between traditional capacitors and batteries, characterized by high power density, long cycle life, and rapid charging and discharging capabilities. The energy storage mechanism of supercapacitors mainly includes electrical double-layer capacitance and pseudocapacitance. In [...] Read more.
Supercapacitors are a kind of energy storage device that lie between traditional capacitors and batteries, characterized by high power density, long cycle life, and rapid charging and discharging capabilities. The energy storage mechanism of supercapacitors mainly includes electrical double-layer capacitance and pseudocapacitance. In addition to constructing multi-level pore structures to increase the specific surface area of electrode materials, defect engineering is essential for enhancing electrochemical active sites and achieving additional extrinsic pseudocapacitance. Therefore, developing a simple and efficient method for defect engineering is essential. Atomic layer deposition (ALD) technology enables precise control over thin film thickness at the atomic level through layer-by-layer deposition. This capability allows the intentional introduction of defects, such as vacancies, heteroatom doping, or misalignment, at specific sites within the material. The ALD process can regulate the defects in materials without altering the overall structure, thereby optimizing both the electrochemical and physical properties of the materials. Its self-limiting surface reaction mechanism also ensures that defects and doping sites are introduced uniformly across the material surface. This uniform defect distribution is particularly profitable for high surface area electrodes in supercapacitor applications, as it promotes consistent performance across the entire electrode. This review systematically summarizes the latest advancements in defect engineering via ALD technology in supercapacitors, including the enhancement of conductivity and the increase of active sites in supercapacitor electrode materials through ALD, thereby improving specific capacitance and energy density of the supercapacitor device. Furthermore, we discuss the underlying mechanisms, advantages, and future directions for ALD in this field. Full article
(This article belongs to the Special Issue High-Performance Super-capacitors: Preparation and Application)
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<p>(<b>a</b>) Graphical illustration portraying the requisites for green supercapacitors and aspects associated with their development. Reproduced with permission. Copyright 2024, Elsevier Publishing [<a href="#B4-batteries-10-00438" class="html-bibr">4</a>]. (<b>b</b>) Ragone plot illustrating the performances of specific power vs. specific energy for different electrical energy-storage technologies. Schematics of charge-storage mechanisms for (<b>c</b>) an EDLC. Reproduced with permission. Copyright 2018, ACS Publishing [<a href="#B10-batteries-10-00438" class="html-bibr">10</a>]. (<b>d</b>–<b>f</b>) Different types of pseudocapacitive electrodes: (<b>d</b>) underpotential deposition, (<b>e</b>) redox pseudocapacitor, and (<b>f</b>) ion intercalation pseudocapacitor. Reproduced with permission. Copyright 2014 Royal Society of Chemistry [<a href="#B11-batteries-10-00438" class="html-bibr">11</a>].</p>
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<p>Schematic of ALD of tin nitride (SnN<sub>x</sub>) process using TDMASn and NH<sub>3</sub> precursors as an example. Reproduced with permission. Copyright 2023, Wiley-VCH [<a href="#B55-batteries-10-00438" class="html-bibr">55</a>].</p>
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<p>(<b>a</b>) Schematic outline of the corrosion protection of Al substrate achieved by optimized ALD TiOx protection layers; (<b>b</b>) O/Ti ratios for the ALD recipes; (<b>c</b>) polarization curves. Reproduced with permission. Copyright 2024, ACS Publishing [<a href="#B81-batteries-10-00438" class="html-bibr">81</a>]. (<b>d</b>) ALD deposition process of ZnO; (<b>e</b>) XPS survey spectra of ZnO films; (<b>f</b>) atomic structure of oxygen-deficient ZnO surface; (<b>g</b>) gas sensing test; (<b>h</b>) surface reaction mechanism. Reproduced with permission. Copyright 2021, Elsevier Publishing [<a href="#B83-batteries-10-00438" class="html-bibr">83</a>].</p>
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<p>(<b>a</b>) Schematic diagram of the formation process of confined samples; (<b>b</b>) the schematic illustration for proposed sensing mechanism; (<b>c</b>) sensing performance. Reproduced with permission. Copyright 2024, Elsevier Publishing [<a href="#B86-batteries-10-00438" class="html-bibr">86</a>]. (<b>d</b>) Illustration of intergranular contact regions and relation between ALD ZnO thickness and length of space-charge layer; (<b>e</b>,<b>f</b>) TEM and HRTEM images. XPS survey spectra of (<b>g</b>) ZnO films and (<b>h</b>) ZnCo50 film; (<b>i</b>,<b>j</b>) gas sensing test. Reproduced with permission. Copyright 2023, Spinger Nature Publishing [<a href="#B87-batteries-10-00438" class="html-bibr">87</a>].</p>
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<p>(<b>a</b>) Synthesis route of SnO<sub>2</sub> porous nanorods; (<b>b</b>) the scheme of detection of VOCs and the sensing performance; (<b>c</b>,<b>d</b>) XPS survey; (<b>e</b>) the adsorption of acetone molecules; (<b>f</b>) the response transient. Reproduced with permission. Copyright 2024, Elsevier Publishing [<a href="#B95-batteries-10-00438" class="html-bibr">95</a>]. (<b>g</b>) Schematic illustration of the fabrication of NiSnNC samples; (<b>h</b>) TEM and HRTEM images; (<b>i</b>–<b>k</b>) XPS survey spectra of O-NiSnNCs, I-NiSnNCs, and B-NiSnNCs. (<b>l</b>) The funnelling effects of the hydrogen concentration effects during the sensing performance. Reproduced with permission. Copyright 2022, RSC Publishing [<a href="#B96-batteries-10-00438" class="html-bibr">96</a>].</p>
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<p>(<b>a</b>–<b>d</b>) Schematic illustration of the principle of modulating the valence state of the Ni element using ALD; (<b>e</b>) schematic NiO<sub>x</sub> lattice structure with Ni vacancy defects; (<b>f</b>) surface O/Ni ratio, Ni<sup>3+</sup>/Ni<sup>2+</sup> ratio, and C content of different NiO<sub>x</sub>; (<b>g</b>) schematic stack of the p-i-n structured PSCs; (<b>h</b>) PCE histograms of 20 devices. Reproduced with permission. Copyright 2024, ACS Publishing [<a href="#B106-batteries-10-00438" class="html-bibr">106</a>].</p>
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<p>(<b>a</b>) Mechanism of the electrocatalytic oxidation of catechol to o-benzoquinone; (<b>b</b>) STEM-HAADF images; (<b>c</b>) SECM images of electrocatalytic oxidation acquired via substrate generation/tip collection (SG/TC) mode for blank and 80 cycle Al<sub>2</sub>O<sub>3</sub>-coated 3D-printed nanocarbon electrodes; (<b>d</b>,<b>e</b>) electrochemical characterization. Reproduced with permission. Copyright 2021, ACS Publishing [<a href="#B117-batteries-10-00438" class="html-bibr">117</a>].</p>
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<p>(<b>a</b>–<b>c</b>) Schematic representation of the fabrication steps involved in the production of WO<sub>3</sub>-MoO<sub>3</sub> electrodes; (<b>d</b>) thickness vs. ALD cycle number; (<b>e</b>) wafer scale spectroscopic ellipsometry measurements; (<b>f</b>) to-view and (<b>g</b>) cross-sectional FE-SEM images of the WO<sub>3</sub>-MoO<sub>3</sub> film; (<b>h</b>,<b>i</b>) electrochemical characterization. Reproduced with permission. Copyright 2024, Elsevier Publishing [<a href="#B143-batteries-10-00438" class="html-bibr">143</a>]. (<b>j</b>) Schematic illustration of 2D SnO<sub>2</sub>-ZnO heterojunction electrodes; (<b>k</b>) TEM images; (<b>l</b>) long-term cycle test of 2D SnO<sub>2</sub>-ZnO heterojunction electrodes; (<b>m</b>) film thickness vs. ALD cycle number monitored by an in situ sensing electrode for SnO<sub>2</sub> and ZnO. Reproduced with permission. Copyright 2023, ACS Publishing [<a href="#B144-batteries-10-00438" class="html-bibr">144</a>]. (<b>n</b>) Schematic illustration of 2D SnO<sub>2</sub>-In<sub>2</sub>O<sub>3</sub> electrodes; (<b>o</b>) film thickness vs. ALD cycle number for SnO<sub>2</sub> and In<sub>2</sub>O<sub>3</sub>; (<b>p</b>) long-term cycle test. Reproduced with permission. Copyright 2022, Elsevier Publishing [<a href="#B145-batteries-10-00438" class="html-bibr">145</a>].</p>
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<p>(<b>a</b>) Schematic representation of the synthesis of MoS<sub>2</sub>-coated Co<sub>3</sub>O<sub>4</sub> and NiCo<sub>2</sub>O<sub>4</sub> nanostructures; (<b>b</b>,<b>c</b>) FESEM images of Co<sub>3</sub>O<sub>4</sub>-MoS<sub>2</sub> and NiCo<sub>2</sub>O<sub>4</sub>-MoS<sub>2</sub>; (<b>d</b>–<b>g</b>) electrochemical behaviors of NiCo<sub>2</sub>O<sub>4</sub>-MoS<sub>2</sub>. Reproduced with permission. Copyright 2022, Elsevier Publishing [<a href="#B158-batteries-10-00438" class="html-bibr">158</a>].</p>
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<p>(<b>a</b>) Schematic illustration of TiO<sub>2</sub>NP-WO<sub>3</sub> film; (<b>b</b>) optical image of the samples; (<b>c</b>) high-resolution optical image of the samples; (<b>d</b>) AFM image; (<b>e</b>) 2D WO<sub>3</sub> film and (<b>f</b>) 2D TiO<sub>2</sub>NP-WO<sub>3</sub> film after post-annealing; (<b>g</b>) size distribution histogram of TiO<sub>2</sub> nanoparticles; (<b>h</b>–<b>k</b>) electrochemical behaviors. Reproduced with permission. Copyright 2017, Elsevier Publishing [<a href="#B166-batteries-10-00438" class="html-bibr">166</a>].</p>
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<p>(<b>a</b>) Schematic presentation for TiN-CNT architecture; (<b>b</b>) conceptual illustration of increasing capacitance through increased surface area and the pseudo capacitive effect; (<b>c</b>) SEM image of uncycled ALD TiN coated onto vertically aligned CNT forest; (<b>d</b>) close-up SEM image of uncycled ALD TiN-coated CNTs; (<b>e</b>) TEM image of single multiwalled carbon nanotube; (<b>f</b>) TEM image of ALD TiN-coated multiwalled carbon nanotube; (<b>g</b>) XPS characterization of ALD TiN; (<b>h</b>–<b>j</b>) electrochemical behaviors of ALD TiN-CNTs. Reproduced with permission. Copyright 2016, Elsevier Publishing [<a href="#B80-batteries-10-00438" class="html-bibr">80</a>].</p>
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<p>(<b>a</b>) Illustration for the function of oxygen plasma and Al<sub>2</sub>O<sub>3</sub> ALD coating on the AC electrode. SEM image: (<b>b</b>) bare AC; (<b>c</b>) oxygen-plasma treatment at 5 min (OP-5); (<b>d</b>) oxygen-plasma treatment at 15 min (OP-15); (<b>e</b>) oxygen-plasma treatment at 30 min (OP-30). (<b>f</b>) Raman spectra; (<b>g</b>–<b>i</b>) Electrochemical behaviors. TEM image of fresh electrode: (<b>j</b>) bare AC; (<b>k</b>) OP-15; (<b>l</b>) ALD-OP15; (<b>m</b>) OP15-ALD. Reproduced with permission. Copyright 2024, Frontiers Publishing [<a href="#B214-batteries-10-00438" class="html-bibr">214</a>].</p>
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<p>(<b>a</b>) Schematic of fabrication process of rGO/RuO<sub>2</sub>; (<b>b</b>) average size dependence of RuO<sub>2</sub> nanoparticles on number of ALD cycles; (<b>c</b>,<b>d</b>) SEM images of (<b>c</b>) carbon fiber and (<b>d</b>) carbon fiber covered with rGO; (<b>e</b>–<b>h</b>) STEM images of (<b>e</b>) rGO, (<b>f</b>) rGO/RuO<sub>2</sub>-15, (<b>g</b>) rGO/RuO<sub>2</sub>-20, and (<b>h</b>) rGO/RuO<sub>2</sub>-30; (<b>i</b>–<b>l</b>) electrochemical behaviors. Reproduced with permission. Copyright 2015, ACS Publishing [<a href="#B229-batteries-10-00438" class="html-bibr">229</a>].</p>
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