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17 pages, 3924 KiB  
Article
Green Fabrication of Zinc-Based Metal–Organic Frameworks@Bacterial Cellulose Aerogels via In Situ Mineralization for Wastewater Treatment
by Xinru Liu, Jie Gu, Yongqi Cao, Liping Tan and Tongjun Liu
Molecules 2025, 30(5), 982; https://doi.org/10.3390/molecules30050982 - 20 Feb 2025
Viewed by 442
Abstract
Compared to conventional adsorbents, zinc-based metal–organic frameworks (MOFs) such as zeolite imidazolium skeleton-8 (ZIF-8) exhibit enhanced thermal, chemical, and structural stability. Nonetheless, their powdered form results in limited dispersibility in aqueous solutions and a tendency to aggregate, which significantly restricts their utility in [...] Read more.
Compared to conventional adsorbents, zinc-based metal–organic frameworks (MOFs) such as zeolite imidazolium skeleton-8 (ZIF-8) exhibit enhanced thermal, chemical, and structural stability. Nonetheless, their powdered form results in limited dispersibility in aqueous solutions and a tendency to aggregate, which significantly restricts their utility in adsorption applications. This study reports a green composite aerogel through the in situ mineralization of ZIF-8 onto bacterial cellulose (BC) for the effective removal of toxic metal ions (Cu2+) and Congo red (CR) from wastewater. The ZIF@BC composite aerogel was characterized using scanning electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, X-ray diffraction, X-ray photoelectron spectroscopy, and specific surface area analysis. The findings indicated that the ZIF-8 produced were evenly distributed across the BC nanonetwork, facilitating effective adsorption of CR and Cu2+. The maximum adsorption capacities of the ZIF@BC aerogels were determined to be 397.55 mg/g for CR and 424.80 mg/g for Cu2+, as per the Langmuir isotherm. Furthermore, the ZIF-8@BC aerogels demonstrated excellent selectivity and reusability, particularly for CR adsorption. The proposed mechanism for the interaction between the composite aerogel and CR and Cu2+ involves electrostatic interactions, hydrogen bonding, π-π bonding, coordination bonding, ion exchange, microchemical precipitation, and pore diffusion. This research offers significant promise for the utilization of MOF powders and highlights substantial industrial potential. Full article
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<p>SEM images of (<b>a</b>) BC; (<b>b</b>) ZIF-8@BC-1; (<b>c</b>) ZIF-8@BC-2; (<b>d</b>) ZIF-8@BC-3; (<b>e</b>) ZIF-8@BC-4; (<b>f</b>) ZIF-8@BC-5; (<b>g</b>) Photo of ZIF-8@BC-4 placed on foxtail grass; (<b>h</b>) Element C; (<b>i</b>) Element O; (<b>j</b>) Element N; (<b>k</b>) Element Zn of energy spectrum analysis for the ZIF-8@BC-4 aerogel.</p>
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<p>The obtained (<b>a</b>) XRD and (<b>b</b>) FTIR spectra, along with (<b>c</b>) TGA results, as well as (<b>d</b>) N<sub>2</sub> adsorption–desorption isotherms of BC and ZIF-8@BC-X.</p>
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<p>(<b>a</b>) Influence of BC and ZIF-8@BC-X on the adsorption effect of CR and Cu<sup>2+</sup>; (<b>b</b>) Impact of pH value on the adsorption efficiency of CR and Cu<sup>2+</sup> by ZIF-8@BC-4; (<b>c</b>) Impact of coexisting anions on the adsorption efficiency of CR by ZIF-8@BC-4; (<b>d</b>) Recycling test of ZIF-8@BC-4 for CR.</p>
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<p>The Freundlich and Langmuir models for the adsorption of ZIF-8@BC-4 for (<b>a</b>) CR and (<b>b</b>) Cu<sup>2+</sup>; (<b>c</b>) PFO kinetic model of CR adsorption on ZIF-8@BC-4; (<b>d</b>) PSO kinetic model of CR adsorption on ZIF-8@BC-4; (<b>e</b>) PFO kinetic model of Cu<sup>2+</sup> adsorption on ZIF-8@BC-4; (<b>f</b>) PSO kinetic model of Cu<sup>2+</sup> adsorption on ZIF-8@BC-4.</p>
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<p>FTIR spectra of ZIF-8@BC-4 prior to and following the adsorption of CR (<b>a</b>) and Cu<sup>2+</sup> (<b>b</b>); XRD patterns of ZIF-8@BC-4 before and after the adsorption of CR (<b>c</b>) and Cu<sup>2+</sup> (<b>d</b>).</p>
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<p>XPS analysis. (<b>a</b>) Full spectrum of ZIF-8@BC-4 prior to and following adsorption of CR and Cu<sup>2+</sup>; Zn 2p (<b>b</b>), Cu 2p (<b>c</b>), C 1s (<b>d</b>), N 1s (<b>e</b>), and O 1s (<b>f</b>) before adsorption of CR and Cu<sup>2+</sup> for ZIF-8@BC-4.</p>
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15 pages, 2862 KiB  
Article
Natural Molecule-Derived Nanogels from Hematoxylin and l-lysine for Biomedical Use with Antimicrobial Properties
by Mehtap Sahiner, Zhi Tian, Diane Allen-Gipson, Aydin K. Sunol and Nurettin Sahiner
Int. J. Mol. Sci. 2025, 26(1), 138; https://doi.org/10.3390/ijms26010138 - 27 Dec 2024
Cited by 1 | Viewed by 727
Abstract
Hematoxylin (HT) is a natural staining dye used in histopathology, often combined with Eosin for H&E staining. A poly(hematoxylin-co-l-lysine) (p(HT-co-l)) nanonetwork was synthesized through a one-step Mannich condensation reaction using formaldehyde as a linking agent. The resulting p(HT-co-l [...] Read more.
Hematoxylin (HT) is a natural staining dye used in histopathology, often combined with Eosin for H&E staining. A poly(hematoxylin-co-l-lysine) (p(HT-co-l)) nanonetwork was synthesized through a one-step Mannich condensation reaction using formaldehyde as a linking agent. The resulting p(HT-co-l) nanogels had an average size of about 200 nm and exhibited a smooth surface and desirable functional groups such as -OH, -NH2, and -COOH, as recognized by FT-IR analysis. The isoelectric point (IEP) of the p(HT-co-l) nanogel was determined as pH 7.9, close to physiological environments, despite HT being acidic IEP at pH 1.7 and l-lysine being basic IPE at pH 8.7. The time-dependent swelling studies of p(HT-co-l) nanogels were carried out using dynamic light scattering (DLS) in different salt solutions, e.g., MgCl2, KNO3, KCl, PBS, and DI water environments revealed that nanogels have high swelling ability depending on the medium, e.g., >10-fold in a saline solution compared to distilled water within 1.5 h. Hydrolytic degradation studies in PBS demonstrated a linear release profile up to 125 h at 37.5 °C. The p(HT-co-l) nanogels also demonstrated significant antimicrobial and antifungal activities against E. coli (ATCC 8739), S. aureus (ATCC 6538), and C. albicans (ATCC 10231). Furthermore, biocompatibility tests indicated that p(HT-co-l) nanogels are more biocompatible than HT alone, as tested with human Nuli-1 bronchial epithelial cells. Full article
(This article belongs to the Special Issue Phenolic Compounds in Human Diseases)
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<p>Illustration of the suggested mechanism for p(HT-co-<span class="html-small-caps">l</span>) nanogels formation and the corresponding SEM images of p(HT-co-<span class="html-small-caps">l</span>) nanogels.</p>
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<p>(<b>A</b>) FT-IR spectrum of <span class="html-small-caps">l</span>-lysine, HT, and p(HT-co-<span class="html-small-caps">l</span>) nanogels, (<b>B</b>) thermal degradation profile of L, HT, and p(HT-co-<span class="html-small-caps">l</span>) nanogels, and (<b>C</b>) size distribution of p(HT-co-<span class="html-small-caps">l</span>) nanogels in 10 mM KNO<sub>3</sub> solution.</p>
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<p>(<b>A</b>) Zeta potential versus solution pH values of p(HT-co-<span class="html-small-caps">l</span>), lysine, and HT and (<b>B</b>) the comparison of the UV-Vis spectrum of HT and p(HT-co-<span class="html-small-caps">l</span>) in deionized water at 50 and 1000 ppm concentration range.</p>
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<p>The change in size of p(HT-co-<span class="html-small-caps">l</span>) nanogels (<b>A</b>) at different temperatures and (<b>B</b>) at different pHs via DLS measurements.</p>
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<p>(<b>A</b>) The swelling of p(HT-co-<span class="html-small-caps">l</span>) nanogel in 10 mM different salt solutions for up to 90 min and (<b>B</b>) HT release in PBS solution at 37.5 °C.</p>
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<p>(<b>A</b>) p(HT-co-<span class="html-small-caps">l</span>) nanogels for 20 h and then 62.5 µg/mL, 125 µg/mL, 250 µg/mL, 500 µg/mL, and 1000 µg/mL of p(HT-co-<span class="html-small-caps">l</span>), (<b>B</b>) Cell cytotoxicity assay of p(HT-co-<span class="html-small-caps">l</span>) and HT for 20 h at the concentration of 125 µg/mL of HT-L or HT were added to each well, respectively. (<b>C</b>) The cell viability of Nuli-1 cells treated with various amounts of p(HT-co-<span class="html-small-caps">l</span>) nanogels for 72 h, and (<b>D</b>) The Cell viability of Nuli-1 cells treated with media, p(HT-co-<span class="html-small-caps">l</span>), and HT molecules at 125 µg/mL concentration for 72 h.</p>
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12 pages, 4612 KiB  
Article
Molecular Beam Epitaxial Growth and Optical Properties of InN Nanostructures on Large Lattice-Mismatched Substrates
by Rongtao Nie, Yifan Hu, Guoguang Wu, Yapeng Li, Yutong Chen, Haoxin Nie, Xiaoqiu Wang, Mengmeng Ren, Guoxing Li, Yuantao Zhang and Baolin Zhang
Materials 2024, 17(24), 6181; https://doi.org/10.3390/ma17246181 - 18 Dec 2024
Viewed by 537
Abstract
Narrow-gap InN is a desirable candidate for near-infrared (NIR) optical communication applications. However, the absence of lattice-matched substrates impedes the fabrication of high-quality InN. In this paper, we employed Molecular Beam Epitaxy (MBE) to grow nanostructured InN with distinct growth mechanisms. Morphological and [...] Read more.
Narrow-gap InN is a desirable candidate for near-infrared (NIR) optical communication applications. However, the absence of lattice-matched substrates impedes the fabrication of high-quality InN. In this paper, we employed Molecular Beam Epitaxy (MBE) to grow nanostructured InN with distinct growth mechanisms. Morphological and quality analysis showed that the liquid phase epitaxial (LPE) growth of hexagonal InN nanopillar could be realized by depositing molten In layer on large lattice-mismatched sapphire substrate; nevertheless, InN nanonetworks were formed on nitrided sapphire and GaN substrates through the vapor-solid process under the same conditions. The supersaturated precipitation of InN grains from the molten In layer effectively reduced the defects caused by lattice mismatch and suppressed the introduction of non-stoichiometric metal In in the epitaxial InN. Photoluminescence and electrical characterizations demonstrated that high-carrier concentration InN prepared by vapor-solid mechanism showed much stronger band-filling effect at room temperature, which significantly shifted its PL peak to higher energy. LPE InN displayed the strongest PL intensity and the smallest wavelength shift with increasing temperature from 10 K to 300 K. These results showed enhanced optical properties of InN nanostructures prepared on large lattice mismatch substrates, which will play a crucial role in near-infrared optoelectronic devices. Full article
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<p>Three different sets of substrate treatment and epitaxy methods. The top left inset illustrates the growth of InN on nitrided sapphire substrate, the top right inset depicts the growth of InN on sapphire substrate with pre-deposited molten In layer, and the bottom inset presents the direct growth of InN on GaN substrate.</p>
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<p>RHEED patterns of (<b>a</b>) nitrided C-face sapphire substrate. (<b>b</b>) GaN substrate. (<b>c</b>) Sapphire substrate pre-deposited with around 40 nm molten metal In. (<b>d</b>) Sample A: InN grew on a nitrided sapphire substrate. (<b>e</b>) Sample B: InN grown directly on GaN substrate. (<b>f</b>) Sample C: InN grown on sapphire substrate with pre-deposited In metal.</p>
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<p>SEM images showing surface and cross-sectional view of sample A (<b>a</b>), sample B (<b>b</b>), and sample C (<b>c</b>).</p>
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<p>(<b>a</b>) Normalized XRD patterns of samples A, B, and C and pickled sample C; (<b>b</b>) XRD patterns with logarithmic vertical scaling; (<b>c</b>) the normalized ω scans of InN (002) derived from different growth methods.</p>
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<p>The In 3d<sub>5/2</sub> (<b>a</b>,<b>c</b>,<b>e</b>) and N 1s (<b>b</b>,<b>d</b>,<b>f</b>) XPS core-level photoemission peaks of samples A, B, and C.</p>
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<p>Growth mechanism schematic diagram of InN on sapphire with pre-deposited molten In layer.</p>
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<p>Room-temperature PL spectra of samples A, B, and C, alongside carrier concentrations derived from the Hall measurements.</p>
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<p>Temperature-dependent PL spectra of samples A (<b>a</b>), B (<b>b</b>), and C (<b>c</b>) at 10–280 k. The black dashed line shows the shift of the split peaks caused by the band-filling effect. The red dashed line is the split-peak shift caused by bandgap contraction.</p>
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<p>The energy band diagrams of samples A (<b>a</b>), B (<b>b</b>), and C (<b>c</b>) with the increase in temperature. (I) Band-filling effect. (II) Band-to-band radiative recombination.</p>
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14 pages, 2284 KiB  
Article
Preamble-Based Noncoherent Synchronization in Molecular Communication: A Machine Learning Approach
by Seok-Hwan Moon, Pankaj Singh and Sung-Yoon Jung
Appl. Sci. 2024, 14(23), 10779; https://doi.org/10.3390/app142310779 - 21 Nov 2024
Viewed by 619
Abstract
In the field of wireless communication, there is growing interest in molecular communication (MC), which integrates nano-, bio-, and communication technologies. Inspired by nature, MC uses molecules to transmit data, especially in environments where EM waves struggle to penetrate. In MC, signals can [...] Read more.
In the field of wireless communication, there is growing interest in molecular communication (MC), which integrates nano-, bio-, and communication technologies. Inspired by nature, MC uses molecules to transmit data, especially in environments where EM waves struggle to penetrate. In MC, signals can be distinguished based on molecular concentration, known as concentrated-encoded molecular communication (CEMC). These molecules diffuse through an MC channel and are received via ligand–receptor binding mechanisms. Synchronization in CEMC is critical for minimizing errors and enhancing communication performance. This study introduces a novel preamble-based noncoherent synchronization method, specifically designed for resource-constrained environments like nanonetworks. The method’s simple, low-complexity structure makes it suitable for nanomachines, while machine learning (ML) techniques are used to improve synchronization accuracy by adapting to the nonlinear characteristics of the channel. The proposed approach leverages ML to achieve robust performance. Simulation results demonstrate a synchronization probability of 0.8 for a transmitter-receiver distance of 1 cm, given a molecular collection time duration four times the pulse duration. These results confirm the significant benefits of integrating ML, showcasing improved synchronization probability and reduced mean square error. The findings contribute to the advancement of efficient and practical MC systems, offering insights into synchronization and error reduction in complex environments. Full article
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<p>Block diagram of preamble-based synchronization in MC system.</p>
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<p>Pulse-based preamble signal structure [<a href="#B18-applsci-14-10779" class="html-bibr">18</a>].</p>
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<p>Sliding window-based noncoherent molecular synchronization approach (<math display="inline"><semantics> <msub> <mi>N</mi> <mi>p</mi> </msub> </semantics></math> = 4, <math display="inline"><semantics> <mrow> <mi>N</mi> <mo>=</mo> <mn>2</mn> </mrow> </semantics></math>). For simplicity, we assume <math display="inline"><semantics> <mrow> <msub> <mi>T</mi> <mrow> <mi>t</mi> <mi>x</mi> </mrow> </msub> <mo>/</mo> <msub> <mi>N</mi> <mrow> <mi>i</mi> <mi>n</mi> <mi>t</mi> </mrow> </msub> <mo>=</mo> <mi>m</mi> <mo>.</mo> <msub> <mi>T</mi> <mi>p</mi> </msub> </mrow> </semantics></math> and <math display="inline"><semantics> <mrow> <msub> <mi>T</mi> <mi>s</mi> </msub> <mo>/</mo> <mi>m</mi> <mo>.</mo> <msub> <mi>T</mi> <mi>p</mi> </msub> <mo>=</mo> <mi>l</mi> </mrow> </semantics></math>, where <span class="html-italic">m</span> and <span class="html-italic">l</span> are integers [<a href="#B18-applsci-14-10779" class="html-bibr">18</a>].</p>
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<p>Machine learning model [<a href="#B28-applsci-14-10779" class="html-bibr">28</a>].</p>
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<p>Synchronization probability with distance for different SCW widths prior to training.</p>
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<p>Average normalized mean square error with distance for different SCW widths prior to training.</p>
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<p>Train and validation accuracy based data.</p>
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<p>Synchronization probability with distance for different SCW widths after training.</p>
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<p>Average normalized mean square error with distance for different SCW widths after training.</p>
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16 pages, 5414 KiB  
Article
3D NiCoW Metallic Compound Nano-Network Structure Catalytic Material for Urea Oxidation
by Zuoyuan Liang, Lang Yao, Yipeng Zhang, Sirong Li and Xuechun Xiao
Nanomaterials 2024, 14(22), 1793; https://doi.org/10.3390/nano14221793 - 7 Nov 2024
Viewed by 994
Abstract
Urea shows promise as an alternative substrate to water oxidation in electrolyzers, and replacing OER with the Urea Oxidation Reaction (UOR, theoretical potential of 0.37 V vs. RHE) can significantly increase hydrogen production efficiency. Additionally, the decomposition of urea can help reduce environmental [...] Read more.
Urea shows promise as an alternative substrate to water oxidation in electrolyzers, and replacing OER with the Urea Oxidation Reaction (UOR, theoretical potential of 0.37 V vs. RHE) can significantly increase hydrogen production efficiency. Additionally, the decomposition of urea can help reduce environmental pollution. This paper improves the inherent activity of catalytic materials through morphology and electronic modulation by incorporating tungsten (W), which accelerates electron transfer, enhances the electronic structure of neighboring atoms to create a synergistic effect, and regulates the adsorption process of active sites and intermediates. NiCoW catalytic materials with an ultra-thin nanosheet structure were prepared using an ultrasonic-assisted NaBH4 reduction method. The results show that during the OER process, NiCoW catalytic materials have a potential of only 1.53 V at a current density of 10 mA/cm2, while the UOR process under the same conditions requires a lower potential of 1.31 V, demonstrating superior catalytic performance. In a mixed electrolyte of 1 M KOH and 0.5 M urea, overall water splitting also shows excellent performance. Therefore, the designed NiCoW electrocatalyst, with its high catalytic activity, provides valuable insights for enhancing the efficiency of water electrolysis for hydrogen production and holds practical research significance. Full article
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<p>The preparation process of NiCoW.</p>
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<p>XRD patterns of (<b>a</b>) NiCo-2 catalyst and (<b>b</b>) NiCoW catalyst.</p>
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<p>SEM images of NiCo-2 at (<b>a</b>) low and (<b>b</b>) high magnification. (<b>c</b>–<b>f</b>) Elemental mapping images of NiCo-2.</p>
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<p>(<b>a</b>) SEM images of NiCoW, (<b>b</b>) TEM images of NiCoW, and (<b>c</b>) HRTEM images of porous NiCoW, (<b>d</b>) SAED pattern of NiCoW and (<b>e</b>–<b>h</b>) elemental mapping images of NiCoW.</p>
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<p>XPS spectrum of NiCoW and NiCo-2 catalysts: (<b>a</b>) full spectrum, (<b>b</b>) Ni 2p, (<b>c</b>) Co 2p, (<b>d</b>) W 4f, (<b>e</b>) C 1s, (<b>f</b>) O 1s.</p>
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<p>(<b>a</b>) N<sub>2</sub> adsorption and desorption isotherm curve of the NiCo-2 catalyst, (<b>b</b>) N<sub>2</sub> adsorption and desorption isotherm curve of the NiCoW catalyst.</p>
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<p>(<b>a</b>) Polarization curves of NiCo-1, NiCo-2, and NiCoW catalysts for 1 M KOH electrolyte. (<b>b</b>) Tafel slopes of NiCo-1, NiCo-2, and NiCoW catalysts. (<b>c</b>) Nyquist plots of NiCo-1, NiCo-2, and NiCoW catalysts. (<b>d</b>) The histogram of overpotentials at 10 and 100 mA cm<sup>−2</sup>.</p>
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<p>(<b>a</b>–<b>c</b>) Typical CV curves of 1.0 M KOH; scan rates range from 20 to 100 mV s<sup>−1</sup>. (<b>d</b>) C<sub>dl</sub> of NiCoW, NiCo-1, and NiCo-2 catalysts. The different colors of the curves in the figure mean that we performed the CV cycles at different sweep speeds.</p>
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<p>(<b>a</b>) Polarization curves of NiCo-1, NiCo-2, and NiCoW catalysts for 1 M KOH electrolyte with and without 0.5 M urea. (<b>b</b>) Tafel slopes of NiCo-1, NiCo-2, and NiCoW catalysts. (<b>c</b>) Nyquist plots of NiCo-1, NiCo-2, and NiCoW catalysts. (<b>d</b>) The histogram of potentials at 10 and 100 mA cm<sup>−2</sup>.</p>
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<p>(<b>a</b>–<b>c</b>) Typical CV curves of 1.0 M KOH + 0.5 M urea, scan rates range from 20 to 100 mV s<sup>−1</sup>. (<b>d</b>) C<sub>dl</sub> of NiCoW, NiCo-1, and NiCo-2 catalysts. The different colors of the curves in the figure mean that we performed the CV cycles at different sweep speeds.</p>
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<p>(<b>a</b>) LSV curves of NiCoW before and after repeated 3000 CV tests. (<b>b</b>) Schematic presentation of overall water-splitting performance. In an electrochemical cell, a two-electrode system is required for measuring complete water solution, in which the green wire connects the working electrode, the anode, and the white and red wire connects the other electrode, the cathode. (<b>c</b>) LSV of NiCoW overall water-splitting and (<b>d</b>) i-t curve of NiCoW overall water-splitting.</p>
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<p>Mechanisms corresponding to OER (<b>a</b>) and UOR (<b>b</b>) processes.</p>
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12 pages, 3438 KiB  
Article
Size Effect of Graphite Nanosheet-Induced Anti-Corrosion of Hydrophobic Epoxy Coatings
by Kuilin Lv, Yiwang Bao, Huachao Ma, Xiaogen Liu, Ying Zhu and Detian Wan
Coatings 2024, 14(6), 769; https://doi.org/10.3390/coatings14060769 - 18 Jun 2024
Cited by 4 | Viewed by 1496
Abstract
In order to broaden the selectivity of graphite nanosheet additives on epoxy resin-based coatings and verify the size effect, this work aims to dope graphite nanosheets of different sizes into the three-dimensional structure produced by cross-linking and curing epoxy resin and polyamide resin. [...] Read more.
In order to broaden the selectivity of graphite nanosheet additives on epoxy resin-based coatings and verify the size effect, this work aims to dope graphite nanosheets of different sizes into the three-dimensional structure produced by cross-linking and curing epoxy resin and polyamide resin. In addition, a micro-nano level secondary structure and a surface with special roughness are constructed to obtain the composite epoxy hydrophobic coating. The influence of the size effect of graphite nanosheets on the hydrophobic performance and corrosion resistance of the coating is summarized as well. Among them, the optimized doping size (2.2 μm) of graphite nanosheets in the epoxy coating showed the largest impedance arc of 2.58 × 108 Ω cm2, which could form an excellent nano-network covering the micropores to impede the diffusion of corrosive medium. Through simulation calculation analysis, we also found that the edge site of graphene is more effective in capturing H2O and O2; therefore, a smaller size of graphene with a large edge can be more favorable. This work will be used as a reference for the industrial application of graphite anti-corrosive coating. Full article
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<p>The surface SEM of EG<sub>1000</sub> (<b>a</b>), EG<sub>3000</sub> (<b>b</b>), EG<sub>5000</sub> (<b>c</b>), and EG<sub>8000</sub> (<b>d</b>); the red frame represents the field of vision, and the blue frame represents the graphene nanosheet.</p>
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<p>HRTEM image of EG<sub>1000</sub> (<b>a</b>), EG<sub>3000</sub> (<b>b</b>), EG<sub>5000</sub> (<b>c</b>), and EG<sub>8000</sub> (<b>d</b>). Size statistics of EG<sub>8000</sub> (<b>e</b>), EG<sub>5000</sub> (<b>f</b>), EG<sub>3000</sub> (<b>g</b>), and EG<sub>1000</sub> (<b>h</b>).</p>
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<p>(<b>a</b>,<b>b</b>) Raman spectra of G, EG<sub>1000</sub>, EG<sub>3000</sub>, EG<sub>5000</sub>, and EG<sub>8000</sub>, respectively. (<b>c</b>) FTIR spectra of G, EG<sub>1000</sub>, EG<sub>3000</sub>, EG<sub>5000</sub>, and EG<sub>8000</sub>, respectively.</p>
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<p>(<b>a</b>) Water contact angle of EG<sub>x</sub>/C<sub>1</sub>P<sub>0.2</sub>EP coatings with different storage times. (<b>b</b>) Water contact angle of EG<sub>5000</sub>/C<sub>1</sub>P<sub>0.2</sub>EP with different EG<sub>5000</sub> contents.</p>
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<p>Nyquist plots of the EG<sub>1000</sub>/C<sub>1</sub>P<sub>0.2</sub>EP, EG<sub>3000</sub>/C<sub>1</sub>P<sub>0.2</sub>EP, EG<sub>5000</sub>/C<sub>1</sub>P<sub>0.2</sub>EP, and EG<sub>8000</sub>/C<sub>1</sub>P<sub>0.2</sub>EP coatings after 7 d (<b>a</b>), 30 d (<b>b</b>), and 60 d (<b>c</b>) of immersion, respectively.</p>
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<p>Nyquist plots of EG<sub>5000</sub>/C<sub>1</sub>P<sub>0.2</sub>EP with different EG<sub>5000</sub> addition amounts after 7 d (<b>a</b>), 30 d (<b>b</b>), and 60 d (<b>c</b>) of immersion.</p>
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<p>(<b>a</b>) Bode modulus plots of EG<sub>5000</sub>/C<sub>1</sub>P<sub>0.2</sub>EP after 7 d, 14 d, 30 d, and 60 d of immersion. (<b>b</b>) The polarization curve of EG<sub>1000</sub>/C<sub>1</sub>P<sub>0.2</sub>EP, EG<sub>3000</sub>/C<sub>1</sub>P<sub>0.2</sub>EP, EG<sub>5000</sub>/C<sub>1</sub>P<sub>0.2</sub>EP and EG<sub>8000</sub>/C<sub>1</sub>P<sub>0.2</sub>EP after 60 d of neutral salt spray test.</p>
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<p>The adsorption structures and energies of O<sub>2</sub> and H<sub>2</sub>O at varying sites on single layers of graphite sheet.</p>
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<p>The adsorption energies of O<sub>2</sub> and H<sub>2</sub>O at varying sites on single and double layers of graphite sheet as well as EGx/C<sub>1</sub>P<sub>0.2</sub>EP.</p>
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13 pages, 6110 KiB  
Article
Nanohydroxyapatite/Peptide Composite Coatings on Pure Titanium Surfaces with Nanonetwork Structures Using Oyster Shells
by Kuan-Hsiang Hsieh, Hsueh-Chuan Hsu, Yu-Lin Kao, Shih-Ching Wu, Tzu-Yen Yang and Wen-Fu Ho
Nanomaterials 2024, 14(7), 577; https://doi.org/10.3390/nano14070577 - 26 Mar 2024
Cited by 3 | Viewed by 1221
Abstract
Titanium and its alloys are extensively applied in artificial tooth roots because of their excellent corrosion resistance, high specific strength, and low elastic modulus. However, because of their biological inertness, their surface needs to be modified to improve the osteointegration of titanium implants. [...] Read more.
Titanium and its alloys are extensively applied in artificial tooth roots because of their excellent corrosion resistance, high specific strength, and low elastic modulus. However, because of their biological inertness, their surface needs to be modified to improve the osteointegration of titanium implants. The preparation of biologically active calcium–phosphorus coatings on the surface of an implant is one effective method for enhancing the likelihood of bone integration. In this study, osteoinductive peptides were extracted from oyster shells by using acetic acid. Two peptide-containing hydroxyapatite (HA) composite coatings were then prepared: one coating was prepared by hydrothermally synthesizing an HA coating in the presence of peptides (HA/P/M), and the other coating was prepared by hydrothermally synthesizing HA and then immersing the hydrothermally synthesized HA in a peptide solution (HA/P/S). Characterization results indicated that the composite HA coatings containing oyster shell-based peptides were successfully prepared on the alkali-treated pure titanium surfaces. The HA/P/M and HA/P/S composite coatings were found to exhibit excellent hydrophilicity. Protein adsorption tests confirmed that the HA/P/M and HA/P/S coatings had an approximately 2.3 times higher concentration of adsorbed proteins than the pure HA coating. Full article
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<p>SEM images of pure titanium (<b>a</b>) after alkali treatment and with (<b>b</b>) an HA coating prepared through hydrothermal treatment; (<b>c</b>) an HA/peptide composite coating prepared through hydrothermal treatment (HA/P/M); and (<b>d</b>) an HA/peptide composite coating prepared through hydrothermal and subsequent soaking treatment (HA/P/S).</p>
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<p>XRD patterns of pure titanium after alkali treatment and various types of surface-coating treatment.</p>
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<p>(<b>a</b>) FTIR spectrum of peptides extracted from oyster shells, and (<b>b</b>) FTIR–attenuated total reflectance spectra of HA/P/S and HA/P/M composite coatings prepared on pure titanium surfaces.</p>
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<p>XPS survey spectra of HA/P/S and HA/P/M composite coatings prepared on pure titanium surfaces.</p>
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<p>High-resolution XPS spectra of HA/P/M composite coating on a pure titanium surface.</p>
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<p>Contact angles of the surfaces of pure titanium after alkali treatment and various types of surface coating treatment. Statistical significance (**) was set at a <span class="html-italic">p</span>-value of less than 0.01.</p>
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<p>Protein adsorption capacities of the surfaces of pure titanium after alkali treatment and various types of surface coating treatment. The samples were cultured for 24 h in MEM containing 1% FBS. Statistical significance (**) was set at a <span class="html-italic">p</span>-value of less than 0.01.</p>
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15 pages, 5407 KiB  
Article
Construction of Nanofibrillar Networked Wood Aerogels Derived from Typical Softwood and Hardwood: A Comparative Study on the In Situ Formation Mechanism of Nanofibrillar Networks
by Wenjing Yan, Yan Qing, Zhihan Li, Lei Li, Sha Luo, Ying Wu, Deng Chen, Yiqiang Wu and Cuihua Tian
Molecules 2024, 29(5), 938; https://doi.org/10.3390/molecules29050938 - 21 Feb 2024
Cited by 1 | Viewed by 1288
Abstract
The construction of networks within natural wood (NW) lumens to produce porous wood aerogels (WAs) with fascinating characteristics of being lightweight, flexible, and porous is significant for the high value-added utilization of wood. Nonetheless, how wood species affect the structure and properties of [...] Read more.
The construction of networks within natural wood (NW) lumens to produce porous wood aerogels (WAs) with fascinating characteristics of being lightweight, flexible, and porous is significant for the high value-added utilization of wood. Nonetheless, how wood species affect the structure and properties of WAs has not been comprehensively investigated. Herein, typical softwood of fir and hardwoods of poplar and balsa are employed to fabricate WAs with abundant nanofibrillar networks using the method of lignin removal and nanofibril’s in situ regeneration. Benefiting from the avoidance of xylem ray restriction and the exposure of the cellulose framework, hardwood has a stronger tendency to form nanofibrillar networks compared to softwood. Specifically, a larger and more evenly distributed network structure is displayed in the lumens of balsa WAs (WA-3) with a low density (59 kg m−3), a high porosity (96%), and high compressive properties (strain = 40%; maximum stress = 0.42 MPa; height retention = 100%) because of the unique structure and properties of WA-3. Comparatively, the specific surface area (SSA) exhibits 25-, 27-, and 34-fold increments in the cases of fir WAs (WA-1), poplar WAs (WA-2), and WA-3. The formation of nanofibrillar networks depends on the low-density and thin cell walls of hardwood. This work offers a foundation for investigating the formation mechanisms of nanonetworks and for expanding the potential applications of WAs. Full article
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Graphical abstract

Graphical abstract
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<p>Schematics of the preparation of fir, poplar, and balsa wood aerogels (WAs). The left diagram shows the sequential steps involved in the production of WAs using wood materials sourced from three species, each with a different density and cell wall thickness. The upper-right corner visually represents the mechanical strength characteristics of the three WAs, whereas the lower-right corner provides a visual representation of the formation of nanofibrillar network structures.</p>
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<p>Morphology and structure of various wood samples. SEM images of the cross-sections of (<b>a1</b>) NW-1, (<b>a2</b>) DW-1, (<b>a3</b>) WA-1, (<b>b1</b>) NW-2, (<b>b2</b>) DW-2, (<b>b3</b>) WA-2, (<b>c1</b>) NW-3, (<b>c2</b>) DW-3, and (<b>c3</b>) WA-3, as well as the surfaces along the fiber direction of (<b>a4</b>) WA-1, (<b>b4</b>) WA-2, and (<b>c4</b>) WA-3. (<b>d</b>) Nitrogen physisorption isotherms and (<b>e</b>) an image of the pore size distributions of NW-3, WA-1, WA-2, and WA-3.</p>
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<p>Chemical characteristics of various wood samples. (<b>a</b>) Cellulose, hemicellulose, and lignin contents of NW-1, NW-2, NW-3, DW-1, DW-2, and DW-3. (<b>b</b>) Weights and densities of NW-1, NW-2, NW-3, WA-1, WA-2, and WA-3. (<b>c</b>) Fourier transform infrared spectra of NW-3, WA-1, WA-2, and WA-3. (<b>d</b>) TG and (<b>e</b>) DTG curves of NW-1, NW-2, NW-3, WA-1, WA-2, and WA-3. (<b>f</b>) X-ray diffraction spectra of NW-3, WA-1, WA-2, and WA-3. (<b>g</b>) Schematic of the TEMPO-NaClO<sub>2</sub>-NaClO-mediated oxidation system acting on the cellulose chain. (<b>h</b>) Polarizing microscopic image of NW-3 and WA-3.</p>
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<p>Mechanical compressibility and fatigue resistance of the NW-3 and WAs. Stress–strain curves of (<b>a</b>) WA-1, (<b>b</b>) WA-2, and (<b>c</b>) WA-3 under compression of cross, radial, and tangential sections. Stress–strain curves of (<b>d</b>) NW-3 and (<b>e</b>) WA-3 under compression at maximum strain values of 10%, 20%, 30%, and 40%. Stress–strain curves of (<b>f</b>) NW-3, (<b>g</b>) WA-1, (<b>h</b>) WA-2, and (<b>i</b>) WA-3 under cyclic compression at a maximum strain of 40%. (<b>j</b>) Photographs of WA-3 showing its reversible compressibility along the layer stacking direction.</p>
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<p>The cell wall thickness of WAs and their response to transverse compression. Schematics of (<b>a</b>) NW-1 and WA-1, (<b>b</b>) NW-2 and WA-2, (<b>c</b>) NW-3 and WA-3, (<b>d</b>) the cell walls of WA-1, WA-2, and WA-3 under transverse compression.</p>
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<p>(<b>a</b>) Low- and (<b>b</b>,<b>c</b>) high-magnification SEM images of the cross-sections of WA-3. SEM images of (<b>d</b>) a single cell of WA-3, (<b>e</b>) nanofibrillar networks in WA-3 cell wall, (<b>f</b>) interwoven networks in the cell lumen, and (<b>g</b>) nanofibers of network structure. (<b>h</b>) Confocal Raman spectroscopy and images of NW-3 and WA-3.</p>
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25 pages, 5539 KiB  
Article
Effects of a Nanonetwork-Structured Soil Conditioner on Microbial Community Structure
by Jingjing Cao, Pan Zhao, Dongfang Wang, Yonglong Zhao, Zhiqin Wang and Naiqin Zhong
Biology 2023, 12(5), 668; https://doi.org/10.3390/biology12050668 - 28 Apr 2023
Cited by 7 | Viewed by 2702
Abstract
Fertilizer application can increase yields, but nutrient runoff may cause environmental pollution and affect soil quality. A network-structured nanocomposite used as a soil conditioner is beneficial to crops and soil. However, the relationship between the soil conditioner and soil microbes is unclear. We [...] Read more.
Fertilizer application can increase yields, but nutrient runoff may cause environmental pollution and affect soil quality. A network-structured nanocomposite used as a soil conditioner is beneficial to crops and soil. However, the relationship between the soil conditioner and soil microbes is unclear. We evaluated the soil conditioner’s impact on nutrient loss, pepper growth, soil improvement, and, especially, microbial community structure. High-throughput sequencing was applied to study the microbial communities. The microbial community structures of the soil conditioner treatment and the CK were significantly different, including in diversity and richness. The predominant bacterial phyla were Pseudomonadota, Actinomycetota, and Bacteroidota. Acidobacteriota and Chloroflexi were found in significantly higher numbers in the soil conditioner treatment. Ascomycota was the dominant fungal phylum. The Mortierellomycota phylum was found in significantly lower numbers in the CK. The bacteria and fungi at the genus level were positively correlated with the available K, available N, and pH, but were negatively correlated with the available P. Our results showed that the loss of nutrients controlled by the soil conditioner increased available N, which improved soil properties. Therefore, the microorganisms in the improved soil were changed. This study provides a correlation between improvements in microorganisms and the network-structured soil conditioner, which can promote plant growth and soil improvement. Full article
(This article belongs to the Section Microbiology)
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<p>Leaching assay. (<b>A</b>) Schematic diagram of the leaching system. (<b>B</b>) Influence of the amount of SC on the leaching loss of urea from soil. Notes: ATP: attapulgite; PAM: polyacrylamide; U: urea. Asterisks indicate statistically significant differences, as determined by Student’s <span class="html-italic">t</span>-test (*** <span class="html-italic">p</span> &lt; 0.001).</p>
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<p>The microstructure of the SC as revealed by SEM with different magnifications: (<b>A</b>,<b>B</b>) attapulgite; (<b>C</b>,<b>D</b>) SC.</p>
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<p>Interaction analyses of the SC system. (<b>A</b>) FTIR spectra of attapulgite. (<b>B</b>) XRD patterns of attapulgite, polyacrylamide, and SC. (<b>C</b>–<b>E</b>) TGA (black line) and DTA (blue line) curves of attapulgite, polyacrylamide, and SC. (<b>F</b>) N<sub>2</sub> adsorption–desorption isotherms of SC. (Inset) Pore size distribution of SC. Notes: ATP: attapulgite; PAM: polyacrylamide; U: urea; FTIR: Fourier transform infrared spectrometer; XRD: X-ray diffractometer; TGA: thermal gravimetric analysis; DTA: differential thermal analysis.</p>
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<p>Effects of SC on plant growth. (<b>A</b>–<b>D</b>) Plant height, SPAD, and fruit length and weight when treated with different amounts of SC. Asterisks indicate statistically significant differences, as determined by Student’s <span class="html-italic">t</span>-test (** <span class="html-italic">p</span> &lt; 0.01).</p>
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<p>The OTUs between CK and SC3, displayed in a Venn diagram. (<b>A</b>) Bacteria, (<b>B</b>) fungi. The overlapping part shows the common OTU numbers.</p>
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<p>Composition and relative abundance of bacterial communities. (<b>A</b>) UPGMA clustering analysis showed the top 10 relative abundance levels of the bacterial community in each sample at the phylum level. (<b>B</b>) Clustering heat map of the relative abundance levels of the top 35 bacteria at the genus level in each sample. The “Z” value corresponding to the heat map is described by the color intensity from 2 to −2. The color gradient shifted from blue to red (from low to high abundance). CK1-CK3 represent the 3 replicates of soil without soil conditioner; SC31-SC33 represent the 3 replicates of soil with 400 kg ha<sup>−1</sup> soil conditioner.</p>
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<p>LEfSe analysis of the difference in bacterial abundance between CK and SC3. (<b>A</b>) LDA score between CK and SC3. The column length indicates the effect size of the bacterial lineages. (<b>B</b>) The cladogram of bacterial communities with differences between CK and SC3. The proportion of bacterial abundance is indicated by the circle’s diameter. Red and green nodes: bacterial taxa that play a vital role in CK and SC3, respectively. Yellow: nonsignificant.</p>
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<p>Composition and relative abundance of fungal communities. (<b>A</b>) UPGMA clustering analysis: the top 10 relative abundance levels in each sample at the phylum level. (<b>B</b>) Clustering heat map of the relative abundance of the top 35 fungi at the genus level in each sample. The corresponding value of the heat map is the “Z” value, depicted by the color intensity, ranging from 2 to −2. The gradient of color shifts from blue (low abundance) to red (high abundance). CK1-CK3 represent the 3 replicates of soil without soil conditioner; SC31-SC33 represent the 3 replicates of soil with 400 kg ha<sup>−1</sup> soil conditioner.</p>
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<p>LEfSe analysis of fungal abundance between CK and SC3. (<b>A</b>) LDA score between CK and SC3. The column length indicates the effect size of the bacterial lineages. (<b>B</b>) The cladogram of fungal communities with differences between CK and SC3. The proportion of bacterial abundance is indicated by the circle’s diameter. Red and green nodes: fungal taxa that play a vital role in CK and SC3, respectively. Yellow: nonsignificant.</p>
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<p>Redundancy analysis (RDA) of microbial genera and soil physical and chemical properties. (<b>A</b>,<b>B</b>) RDA of bacterial and fungal communities and environmental variables. The arrow length in the RDA plot corresponds to the strength of the correlation between a variable and the community structure. CK1-CK3 represent the 3 replicates of soil without soil conditioner; SC31-SC33 represent the 3 replicates of soil with 400 kg ha<sup>−1</sup> soil conditioner.</p>
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<p>The heatmap of Spearman’s rank correlation. (<b>A</b>,<b>B</b>) The correlation between the richness of bacterial and fungal genera and environmental factors, where the “r” value is between −1 and 1, r &lt; 0 is a negative correlation, and r &gt; 0 is a positive correlation. Asterisks indicate statistically significant differences, as determined by Student’s <span class="html-italic">t</span>-test (* <span class="html-italic">p</span> &lt; 0.05, ** <span class="html-italic">p</span> &lt; 0.01). The gradient of color shifts from blue to red (from low to high abundance).</p>
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<p>Clustering heat map of the functional pathway analyses. (<b>A</b>) The relative abundance of KEGG (level-2) pathways for bacterial communities of all samples. The KEGG pathways are indicated by a gradient of color from blue (low abundance) to red (high abundance). The corresponding value of the heat map is the “Z” value. (<b>B</b>) The relative abundance of predicted fungal functions. The corresponding value of the heat map is the “Z” value when the relative abundance was normalized. The gradient of color shifts from blue (low abundance) to red (high abundance). CK1-CK3 represent the 3 replicates of soil without soil conditioner; SC31-SC33 represent the 3 replicates of soil with 400 kg ha<sup>−1</sup> soil conditioner.</p>
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11 pages, 6845 KiB  
Article
Densification of Two Forms of Nanostructured TATB under Uniaxial Die Pressures: A USAXS–SAXS Study
by Yan Zhou, Jing Shi, Mark Julian Henderson, Xiuhong Li, Feng Tian, Xiaohui Duan, Qiang Tian and László Almásy
Nanomaterials 2023, 13(5), 869; https://doi.org/10.3390/nano13050869 - 26 Feb 2023
Cited by 1 | Viewed by 1894
Abstract
Sequential ultra-small-angle and small-angle and X-ray scattering (USAXS and SAXS) measurements of hierarchical microstructure of a common energetic material, the high explosive 2,4,6-Triamino-1,3,5-trinitrobenzene (TATB), were performed to follow the microstructure evolution upon applied pressure. The pellets were prepared by two different routes—die pressed [...] Read more.
Sequential ultra-small-angle and small-angle and X-ray scattering (USAXS and SAXS) measurements of hierarchical microstructure of a common energetic material, the high explosive 2,4,6-Triamino-1,3,5-trinitrobenzene (TATB), were performed to follow the microstructure evolution upon applied pressure. The pellets were prepared by two different routes—die pressed from a nanoparticle form and a nano-network form of TATB powder. The derived structural parameters, such as void size, porosity, and the interface area, reflected the response of TATB under compaction. Three populations of voids were observed in the probed q range from 0.007 to 7 nm−1. The inter-granular voids with size larger than 50 nm were sensitive to low pressures and had a smooth interface with the TATB matrix. The inter-granular voids with size of ~10 nm exhibited a less volume-filling ratio at high pressures (>15 kN) as indicated by a decrease of the volume fractal exponent. The response of these structural parameters to external pressures implied that the main densification mechanisms under die compaction were the flow, fracture, and plastic deformation of the TATB granules. Compared to the nanoparticle TATB, the applied pressure strongly influenced the nano-network TATB due to its more uniform structure. The findings and research methods of this work provide insights into the structural evolution of TATB during densification. Full article
(This article belongs to the Special Issue Functionalization Chemistry in Porous Nanomaterials)
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<p>SEM micrographs of the initial TATB powders: (<b>a</b>) Nano-particle form; (<b>b</b>) Nano-networks form (<b>b</b>).</p>
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<p>USAXS–SAXS data obtained from NPD (<b>a</b>) and NND (<b>b</b>). The curves are shifted vertically by factors of 4, 16, 64, 256, and 1024 for clarity (continuous black lines are the fits to a two-level Guinier–Porod model).</p>
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<p>Kratky plot of the USAXS–SAXS data obtained from NPD and NND samples die pressed at 30 kN.</p>
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<p><span class="html-italic">Iq</span><sup>4</sup>-<span class="html-italic">q</span> representations of the USAXS–SAXS data obtained from the NPD (<b>a</b>) and NND (<b>b</b>).</p>
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<p>Fractal exponent derived from USAXS–SAXS data obtained from NPD and NND samples.</p>
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<p>Porosities of NPD (<b>a</b>) and NND (<b>b</b>) as a function of density.</p>
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<p>SEM images of the cross-section of NPD (<b>a</b>) and NND (<b>b</b>) die pressed at 1 kN, 10 kN, and 30 kN.</p>
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18 pages, 18690 KiB  
Article
Doping of Transparent Electrode Based on Oriented Networks of Nickel in Poly(3,4-Ethylenedioxythiophene) Polystyrene Sulfonate Matrix with P-Toluenesulfonic Acid
by Irek R. Nizameev, Guliya R. Nizameeva and Marsil K. Kadirov
Nanomaterials 2023, 13(5), 831; https://doi.org/10.3390/nano13050831 - 23 Feb 2023
Cited by 3 | Viewed by 1921
Abstract
This work aimed to obtain an optically transparent electrode based on the oriented nanonetworks of nickel in poly(3,4-ethylenedioxythiophene) polystyrene sulfonate matrix. Optically transparent electrodes are used in many modern devices. Therefore, the search for new inexpensive and environmentally friendly materials for them remains [...] Read more.
This work aimed to obtain an optically transparent electrode based on the oriented nanonetworks of nickel in poly(3,4-ethylenedioxythiophene) polystyrene sulfonate matrix. Optically transparent electrodes are used in many modern devices. Therefore, the search for new inexpensive and environmentally friendly materials for them remains an urgent task. We have previously developed a material for optically transparent electrodes based on oriented platinum nanonetworks. This technique was upgraded to obtain a cheaper option from oriented nickel networks. The study was carried out to find the optimal electrical conductivity and optical transparency values of the developed coating, and the dependence of these values on the amount of nickel used was investigated. The figure of merit (FoM) was used as a criterion for the quality of the material in terms of finding the optimal characteristics. It was shown that doping PEDOT: PSS with p-toluenesulfonic acid in the design of an optically transparent electroconductive composite coating based on oriented nickel networks in a polymer matrix is expedient. It was found that the addition of p-toluenesulfonic acid to an aqueous dispersion of PEDOT: PSS with a concentration of 0.5% led to an eight-fold decrease in the surface resistance of the resulting coating. Full article
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<p>Optical images of coatings with nickel networks on the surface of a glass substrate with different densities: 0.6 μg/cm<sup>2</sup> (<b>A</b>), 31 μg/cm<sup>2</sup> (<b>B</b>), 62 μg/cm<sup>2</sup> (<b>C</b>), and 311 μg/cm<sup>2</sup> (<b>D</b>).</p>
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<p>Dependence of the transparency coefficient at a wavelength of 550 nm on the deposited nickel amount on a glass substrate (<b>A</b>); dependence of the surface resistance on the amount of deposited nickel on the glass surface (<b>B</b>).</p>
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<p>AFM images of the surface of the obtained coatings {Ni + PEDOT:PSS + PTSA}: the concentration of PTSA in the aqueous dispersion was 0.75 wt.% (<b>A</b>,<b>D</b>) and 1.00 wt.% (<b>B</b>,<b>E</b>); pristine PEDOT: PSS (<b>C</b>,<b>F</b>).</p>
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<p>Topographic histograms corresponding to PTSA concentration in the aqueous dispersion of 0.75 wt.% (<b>A</b>) and 1.00 wt.% (<b>B</b>); pristine PEDOT: PSS (<b>C</b>).</p>
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<p>Images of the resulting coating surface {Ni + PEDOT: PSS + PTSA} (PTSA concentration in the aqueous dispersion is 0.75 wt.%): images obtained with an optical microscope (<b>A</b>) and a scanning electron microscope (<b>B</b>).</p>
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<p>Dependence of the surface resistance of the resulting layer on the concentration of PTSA in an aqueous dispersion of PEDOT: PSS (<b>A</b>); dependence of the transparency coefficient of the modified {Ni + PEDOT: PSS + PTSA} coating on a glass substrate at a wavelength of 550 nm on the concentrations of PTSA in the initial aqueous dispersion of PEDOT: PSS (<b>B</b>).</p>
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<p>Temperature dependence of the surface resistance value of the developed coating.</p>
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<p>The stability of the obtained material’s parameters (PTSA concentration of 0.5 wt.%): surface resistance (<b>A</b>) and transparency coefficient at 550 nm (<b>B</b>).</p>
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12 pages, 5766 KiB  
Article
High Temperature-Resistant Transparent Conductive Films for Photoelectrochemical Devices Based on W/Ag Composite Nanonetworks
by Menghan Liu, Peiling Ren, Hu Qiao, Miaomiao Zhang, Wenxuan Wu, Baoping Li, Hongjun Wang, Daobin Luo, Jianke Liu and Youqing Wang
Nanomaterials 2023, 13(4), 708; https://doi.org/10.3390/nano13040708 - 12 Feb 2023
Cited by 1 | Viewed by 1767
Abstract
The traditional Ag nanowire preparation means that it cannot meet the demanding requirements of photoelectrochemical devices due to the undesirable conductivity, difficulty in compounding, and poor heat resistance. Here, we prepared an Ag nanonetwork with superior properties using a special template method based [...] Read more.
The traditional Ag nanowire preparation means that it cannot meet the demanding requirements of photoelectrochemical devices due to the undesirable conductivity, difficulty in compounding, and poor heat resistance. Here, we prepared an Ag nanonetwork with superior properties using a special template method based on electrospinning technology. The transparent conductive films based on Ag nanonetworks have good transmittance in a wide range from ultraviolet to visible. It is important that the films have high operability and are easy to be compounded with other materials. After compounding with high-melting-point W metal, the heat-resistance temperature of the W/Ag composite transparent conductive films is increased by 100 °C to 460 °C, and the light transmission and electrical conductivity of the films are not significantly affected. All experimental phenomena in the study are analyzed theoretically. This research can provide an important idea for the metal nanowire electrode, which is difficult to be applied to the photoelectrochemical devices. Full article
(This article belongs to the Special Issue Nanomaterials for Novel Photoelectrochemical Devices)
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<p>Schematic diagram of the experimental flow for the preparation of W/Ag (or Ag/W) composite nanonetwork TCFs.</p>
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<p>(<b>a</b>) Thin Ag film attached to the collection ring. (<b>b</b>) The AgTCF obtained by transferring AgNWs to a quartz substrate. (<b>c</b>) FESEM image of Ag nanonetworks. (<b>d</b>) FESEM morphology of single AgNW.</p>
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<p>(<b>a</b>) Relation diagram of sheet resistance and transmittance of AgTCFs. (<b>b</b>) Transmittance curves of different TCFs.</p>
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<p>(<b>a</b>–<b>d</b>) Micrograph of AgNW films treated at different temperatures. (<b>e</b>) The FESEM morphology of AgNW films treated at 380 °C. (<b>f</b>) Relation diagram of temperature and sheet resistance of AgNWs. Where T% is the transmittance.</p>
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<p>(<b>a</b>) Sheet resistance of Ag/WTCFs treated at different temperatures. (<b>b</b>) Sheet resistance of W/AgTCFs treated at different temperatures. (<b>c</b>) Test for heat resistance of W/AgTCFs at different W sputtering time (2, 3, 4, 5 and 6 min, respectively). Where T% is the transmittance. (<b>d</b>) Transmittance curves of AgNWs and W/AgNWs (without substrates). The inset is a SEM image of W/AgNWs. (<b>e</b>) Relation diagram of sheet resistance and transmittance of AgTCF and W/AgTCF.</p>
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<p>(<b>a</b>–<b>f</b>) The micrograph of melting state of W/AgNWs at different temperatures. (<b>g</b>–<b>i</b>) The SEM images of melting state of W/AgNWs at different temperatures.</p>
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<p>Schematic diagram of the melting processes and structures of different films.</p>
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14 pages, 2567 KiB  
Article
Mechanical Properties of a Bone-like Bioceramic–Epoxy-Based Composite Material with Nanocellulose Fibers
by Young-Seong Kim, Jin Woo Baek, Zhengyun Jin, Hee Chang Jeon, Min-Woo Han and Joong Yeon Lim
Materials 2023, 16(2), 739; https://doi.org/10.3390/ma16020739 - 12 Jan 2023
Cited by 3 | Viewed by 2596
Abstract
Several composite materials are being investigated as reinforcement fillers for surgery simulations. This study presents an artificial composite material with properties similar to those of the human bone, which may be used in surgery simulations. Moreover, considering the potential toxicity of debris generated [...] Read more.
Several composite materials are being investigated as reinforcement fillers for surgery simulations. This study presents an artificial composite material with properties similar to those of the human bone, which may be used in surgery simulations. Moreover, considering the potential toxicity of debris generated during sawing, a safe epoxy-based composite material was synthesized using cellulose nanocrystals (CNCs) and bioceramics (i.e., hydroxyapatite, Yttria stabilized zirconia oxide, Zirconia oxide), which were used to mimic the stiffness of human bone. To examine the change in mechanical properties according to the composition, 1, 3, and 5 wt% of CNCs were mixed with 5 wt% of the bioceramics. When CNCs were added at 1 wt%, there was a confirmed change in the non-linear stiffness and ductility. The CNC-added specimen fractured when forming a nano-network around the local CNCs during curing. In contrast, the specimen without CNCs was more densely structured, and combined to form a network of all specimens such that a plastic region could exist. Thus, this study successfully manufactured a material that could mimic longitudinal and transverse characteristics similar to those of real human bone, as well as exhibit mechanical properties such as strength and stiffness. Bioceramics are harmless to the human body, and can be used by controlling the added quantity of CNCs. We expect that this material will be suitable for use in surgery simulations. Full article
(This article belongs to the Section Advanced Composites)
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<p>Synthesis of composite material.</p>
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<p>Results of the compression test on different types of bioceramic–epoxy composite materials. (<b>A</b>) Compressive strength. (<b>B</b>) Compressive elastic modulus.</p>
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<p>Results of the tensile test of different types of bioceramic–epoxy composite materials. (<b>A</b>) Tensile strength. (<b>B</b>) Elastic modulus. (<b>C</b>) Toughness. (<b>D</b>) Elongation.</p>
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<p>Scanning electron microscopy (SEM) images. (<b>A</b>) HAP–epoxy composite materials. (<b>B</b>) An enlarged image of (<b>A</b>). (<b>C</b>) The particle size of HAP–epoxy composite materials after sawing. (<b>D</b>) HAP–epoxy composite with CNC. (<b>E</b>) An enlarged image of (<b>D</b>). (<b>F</b>) The particle size of HAP–epoxy composite with CNC after sawing. (<b>C</b>,<b>F</b>) are statistics of particle size from SEM images with a total area of 0.0439 mm<sup>2</sup>.</p>
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<p>(<b>A</b>) Comparison of compressive strength vs. strain changes according to CNC weight percentage in each bioceramic–epoxy composite material. (<b>B</b>) Compressive strength vs. strain in HAP–epoxy composite material as function of CNC content. (<b>C</b>) Compressive strength vs. strain in YZO–epoxy composite material as a function of CNC content. (<b>D</b>) Compressive strength vs. strain in ZO–epoxy composite material as a function of CNC content.</p>
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<p>(<b>A</b>) Comparison of tensile strength change according to CNC weight percentage in each bioceramic–epoxy composite material. (<b>B</b>) Tensile strength vs. strain in HAP–epoxy composite material as a function of CNC content. (<b>C</b>) Tensile strength vs. strain in YZO–epoxy composite material as a function of CNC content. (<b>D</b>) Tensile strength vs. strain in ZO–epoxy composite material as a function of CNC content.</p>
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14 pages, 5913 KiB  
Article
The Thermoelectric Properties of Spongy PEDOT Films and 3D-Nanonetworks by Electropolymerization
by Cristina V. Manzano, Olga Caballero-Calero, Aída Serrano, Pedro M. Resende and Marisol Martín-González
Nanomaterials 2022, 12(24), 4430; https://doi.org/10.3390/nano12244430 - 12 Dec 2022
Cited by 3 | Viewed by 1817
Abstract
Recently, polymers have been attracted great attention because of their thermoelectric materials’ excellent mechanical properties, specifically their cost-effectiveness and scalability at the industrial level. In this study, the electropolymerization conditions (applied potential and deposition time) of PEDOT films were investigated to improve their [...] Read more.
Recently, polymers have been attracted great attention because of their thermoelectric materials’ excellent mechanical properties, specifically their cost-effectiveness and scalability at the industrial level. In this study, the electropolymerization conditions (applied potential and deposition time) of PEDOT films were investigated to improve their thermoelectric properties. The morphology and Raman spectroscopy of the PEDOT films were analyzed according to their applied potential and deposition time. The best thermoelectric properties were found in films grown at 1.3 V for 10 min, with an electrical conductivity of 158 ± 8 S/cm, a Seebeck coefficient of 33 ± 1 µV/K, and a power factor of 17 ± 2 µW/K·m2. This power factor value is three times higher than the value reported in the literature for electropolymerized PEDOT films in acetonitrile using lithium perchlorate as a counter-ion. The thermal conductivity was found to be (1.3 ± 0.3) × 10−1 W/m·K. The highest figure of merit obtained at room temperature was (3.9 ± 1.0) × 10−2 using lithium perchlorate as a counter-ion. In addition, three-dimensional (3D) PEDOT nanonetworks were electropolymerized inside 3D anodic aluminum oxide (3D AAO), obtaining lower values in their thermoelectric properties. Full article
(This article belongs to the Special Issue New Challenges in Nanofilm and Nanowire Characterization)
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<p>Cyclic voltammetry in acetonitrile of 0.01 M EDOT and 0.1 M LiClO<sub>4</sub> with a scan rate of 0.01 V/s and at room temperature.</p>
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<p>FE-SEM images of PEDOT films for different electropolymerization conditions, at (<b>A</b>) 1.3 V for 5 min, (<b>B</b>) 1.3 V for 10 min, (<b>C</b>) 1.3 V for 15 min, (<b>D</b>) 1.4 V for 5 min, (<b>E</b>) 1.4 V for 10 min, and (<b>F</b>) 1.4 V for 15 min.</p>
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<p>Raman spectra of the PEDOT films grown by electropolymerization under different oxidation potentials, i.e., 1.3 and 1.4 V, and electropolymerization times, i.e., 5, 10, and 15 min. Raman spectra were normalized to the band corresponding to the symmetric C<sub>α</sub> = C<sub>β</sub> (-O) stretching at 1445 cm<sup>−1</sup>.</p>
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<p>Thermoelectric properties: (<b>A</b>) the electrical conductivity, (<b>B</b>) the Seebeck coefficient, and (<b>C</b>) the power factor of PEDOT films grown at different potentials and deposition times.</p>
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<p>(<b>A</b>) benzoid structure and (<b>B</b>) quinoid structure.</p>
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<p>(<b>A</b>) FE-SEM of 3D PEDOT nanostructures inside AAO, (<b>B</b>) detail of the FE-SEM images of the transversal channels of the 3D PEDOT nanostructures inside AAO, and (<b>C</b>) freestanding 3D PEDOT nanostructures where the air gaps are controlled inside the PEDOT film.</p>
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13 pages, 3554 KiB  
Article
3D Carbon Nanonetwork Coated Composite Electrode with Multi-Heteroatom Doping for High-Rate Vanadium Redox Flow Batteries
by Wei Ling, Xiongwei Wu and Funian Mo
Polymers 2022, 14(23), 5269; https://doi.org/10.3390/polym14235269 - 2 Dec 2022
Cited by 4 | Viewed by 1990
Abstract
With the advantages of benign mechanical property, electrochemical stability, and low cost, graphite fibers (GFs) have been widely used as electrodes for vanadium redox flow batteries (VRFBs). However, GFs usually possess inferior electrochemical activity and ion diffusion kinetics for electrode reaction, vastly limiting [...] Read more.
With the advantages of benign mechanical property, electrochemical stability, and low cost, graphite fibers (GFs) have been widely used as electrodes for vanadium redox flow batteries (VRFBs). However, GFs usually possess inferior electrochemical activity and ion diffusion kinetics for electrode reaction, vastly limiting their application in VRFBs. Here, a 3D carbon nanonetwork coated GFs with multi-heteroatom doping was constructed for application in VRFBs via low temperature polymerization between linear polymer monomer and phytic acid, and subsequent carbonization (900 °C) on the GFs (GF@PCNs-900). Benefiting from the 3D structural features and multi-heteroatom doping (O, N and P), the composite electrode displayed sufficient diffusion of vanadium ions, rapid electron conduction, and highly enhanced electrochemical activity of reactive site on the electrodes. As a result, the GF@PCNs-900 delivered a high discharge capacity of 21 Ah L−1 and energy efficiency of above 70% with extraordinary stability during 200 cycles at 200 mA cm−2. Even at a huge current density of 400 mA cm−2, the GF@PCNs-900 still maintained a discharge capacity of 5.0 Ah L−1, indicating an excellent rate of performance for VRFBs. Such design strategy opens up a clear view for further development of energy storage field. Full article
(This article belongs to the Special Issue Polymer Based Electronic Devices and Sensors II)
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<p>(<b>a</b>) The preparation process of GF@PCNs electrode, (<b>b</b>) Schematic diagram of cross-linking reaction on the surface of GF@PCNs.</p>
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<p>The SEM images of GF@PCNs electrode with various carbonized temperatures, (<b>a</b>) without carbonized process, (<b>b</b>) 800 °C, (<b>c</b>) 900 °C and (<b>d</b>) 1000 °C.</p>
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<p>CV curves of GF@PCNs-800, GF@PCNs-900 and GF@PCNs-1000.</p>
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<p>The SEM images of the (<b>a</b>) GF, (<b>b</b>) GF@CG-900, (<b>c</b>) GF@PCNs-900 and (<b>d</b>) the morphology and (<b>e</b>) element distribution of GF@PCNs-900.</p>
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<p>(<b>a</b>) XRD and (<b>b</b>) Raman spectrums of GF, GF@CG-900 and GF@PCNs-900.</p>
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<p>(<b>a</b>) XPS survey, (<b>b</b>) High-resolution XPS O 1s and (<b>c</b>) N 1s spectrum of the GF, GF@CG-900 and GF@PCNs900, (<b>d</b>) High-resolution XPS P 2p spectrum of GF@PCNs.</p>
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<p>CV curves of GF, GF@CG-900 and GF@PCNs-900 at a scan rate of 10 mV s<sup>−1</sup>.</p>
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<p>Multi-sweep tests of (<b>a</b>) GF, (<b>b</b>) GF@CG-900, (<b>c</b>) GF@PCNs-900 at various rate of 5, 8, 10, 12 and 15 mV/s, (<b>d</b>) the relationship curve between the square root of scan rate and peak current density, (<b>e</b>) the relationship between the peak current ratio and scan rate, (<b>f</b>) the Nyquist plots of the GF, GF@CG-900 and GF@PCNs-900.</p>
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<p>(<b>a</b>) Charge-discharge curve of the GF and GF@PCNs, (<b>b</b>) voltage efficiency, (<b>c</b>) energy efficiency, (<b>d</b>) discharge specific capacity and (<b>e</b>) cycling performances of GF@PCNs electrodes at 200 mA cm<sup>−2</sup>.</p>
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