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21 pages, 13175 KiB  
Article
Simulation and Discussion on Strength Mechanism of Trimodal Grain-Structured CNT/Al Composites Using Strain Gradient Theory
by Sijie Wang, Qianduo Zhuang, Weijie Liu, Xijin Liu, Houssem Badreddine, Farhad Saba, Zhiqiang Li and Zhenming Yue
J. Compos. Sci. 2024, 8(12), 490; https://doi.org/10.3390/jcs8120490 (registering DOI) - 22 Nov 2024
Abstract
The trimodal grain-structured (TGS) carbon nanotube-reinforced aluminum matrix composites (CNT/Al) exhibit better strength–ductility synergy compared to bimodal grain-structured (BGS) composites. The addition of fine grain (FG) to the TGS composites effectively facilitates strain hardening and reduces strain/stress concentrations. In order to address the [...] Read more.
The trimodal grain-structured (TGS) carbon nanotube-reinforced aluminum matrix composites (CNT/Al) exhibit better strength–ductility synergy compared to bimodal grain-structured (BGS) composites. The addition of fine grain (FG) to the TGS composites effectively facilitates strain hardening and reduces strain/stress concentrations. In order to address the strain incompatibility in TGS composites, a significant accumulation of geometrically necessary dislocations (GNDs) occurs at the hetero-zone boundaries. This accumulation serves as the key factor in generating additional strengthening and work hardening. By utilizing a multi-mechanism strain gradient model, a quantitative analysis of the contributions made by Hall–Petch, Taylor, and back stress strengthening was conducted. Furthermore, effects of each domain volume fraction on the GND density at the boundaries between heterogeneous domains were carefully and extensively investigated and compared. It is found that the strengthening effect of back stress significantly surpasses that of the Hall–Petch and Taylor strengthening accounting. Compared to BGS composites, the TGS composites are more effective in facilitating strain hardening and reducing strain/stress concentrations, which may lead to a better balance between strength and ductility. Full article
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Figure 1

Figure 1
<p>Schematic diagram of manufacturing process of TGS composites.</p>
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<p>Multi-scale characterization of the TGS composites: (<b>a</b>) low power and (<b>c</b>) high resolution EBSD maps; (<b>b</b>) single tensile curve of composites with different grain structures; and (<b>d</b>) grain size distribution of the TGS composites [<a href="#B7-jcs-08-00490" class="html-bibr">7</a>].</p>
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<p>Illustration of the origin of (<b>a</b>) <math display="inline"><semantics> <mrow> <msubsup> <mrow> <mi>σ</mi> </mrow> <mrow> <mi mathvariant="normal">B</mi> <mi mathvariant="normal">a</mi> <mi mathvariant="normal">c</mi> <mi mathvariant="normal">k</mi> </mrow> <mrow> <mi mathvariant="normal">g</mi> <mi mathvariant="normal">r</mi> <mi mathvariant="normal">a</mi> </mrow> </msubsup> </mrow> </semantics></math> and (<b>b</b>) <math display="inline"><semantics> <mrow> <msubsup> <mrow> <mi>σ</mi> </mrow> <mrow> <mi mathvariant="normal">B</mi> <mi mathvariant="normal">a</mi> <mi mathvariant="normal">c</mi> <mi mathvariant="normal">k</mi> </mrow> <mrow> <mi mathvariant="normal">s</mi> <mi mathvariant="normal">a</mi> <mi mathvariant="normal">m</mi> </mrow> </msubsup> </mrow> </semantics></math>.</p>
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<p>Information transition relationship of multi-scale FEA method.</p>
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<p>(<b>a</b>) The 2D periodic structure; (<b>b</b>) periodic boundary conditions; (<b>c</b>) KAM diagram of TGS; and (<b>d</b>) UFG-CG, CG-FG, and FG-UFG boundary path setting and RVE unidirectional stretching periodic boundary conditions in the TGS composite RVE [<a href="#B46-jcs-08-00490" class="html-bibr">46</a>].</p>
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<p>Comparison of numerical and experimental (<b>a</b>) true stress–strain and (<b>b</b>) back stress plastic strain curves. The experimental results come from our previous study [<a href="#B7-jcs-08-00490" class="html-bibr">7</a>].</p>
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<p>(<b>a</b>) <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>P</mi> </mrow> <mrow> <mi mathvariant="normal">C</mi> <mi mathvariant="normal">G</mi> </mrow> </msub> </mrow> </semantics></math> = 0.1, (<b>b</b>) <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>P</mi> </mrow> <mrow> <mi mathvariant="normal">C</mi> <mi mathvariant="normal">G</mi> </mrow> </msub> </mrow> </semantics></math> = 0.2, (<b>c</b>) <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>P</mi> </mrow> <mrow> <mi mathvariant="normal">C</mi> <mi mathvariant="normal">G</mi> </mrow> </msub> </mrow> </semantics></math> = 0.3, (<b>d</b>) <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>P</mi> </mrow> <mrow> <mi mathvariant="normal">C</mi> <mi mathvariant="normal">G</mi> </mrow> </msub> </mrow> </semantics></math> = 0.4, and (<b>e</b>) <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>P</mi> </mrow> <mrow> <mi mathvariant="normal">C</mi> <mi mathvariant="normal">G</mi> </mrow> </msub> </mrow> </semantics></math> = 0.50; the comparison of simulated and experimental stress–strain curves of different volume fractions of <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>P</mi> </mrow> <mrow> <mi mathvariant="normal">U</mi> <mi mathvariant="normal">F</mi> <mi mathvariant="normal">G</mi> </mrow> </msub> </mrow> </semantics></math> and <math display="inline"><semantics> <mrow> <msub> <mrow> <mi>P</mi> </mrow> <mrow> <mi mathvariant="normal">F</mi> <mi mathvariant="normal">G</mi> </mrow> </msub> </mrow> </semantics></math>.</p>
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<p>(<b>a</b>) Stress distribution and (<b>b</b>) strain distribution (ε = 8%).</p>
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<p>(<b>a</b>) Stress standard deviation with each volume fraction (ε = 8%). (<b>b</b>) Strain standard deviation with each volume fraction (ε = 8%).</p>
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<p>(<b>a</b>) Standard deviation of statistical storage dislocations with different volume fractions (ε = 8%) and (<b>b</b>) statistical storage dislocations with each volume fraction (ε = 8%).</p>
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<p>(<b>a</b>) Distribution of density of GNDs of sample level in different volume fractions (ε = 8%). (<b>b</b>) Distribution of density of GNDs of grain level in different volume fractions (ε = 8%). (<b>c</b>) Distribution of total GND density in different volume fractions (ε = 8%).</p>
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<p>(<b>a</b>) Distribution of standard deviations of density of GNDs of sample level with strain variation (ε = 8%). (<b>b</b>) Distribution of standard deviations of density of GNDs of grain level with strain variation (ε = 8%). (<b>c</b>) Distribution of standard deviations of density of total GNDs with strain variation (ε = 8%). (<b>d</b>) Density of GNDs of grain level in UFG, FG, and CG with strain variation (ε = 8%).</p>
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<p>(<b>a</b>–<b>c</b>) GND density maps of various boundary regions in different volume fractions (ε = 2%); (<b>d</b>–<b>f</b>) GND density maps of various boundary regions in different volume fractions (ε = 5%); and (<b>g</b>–<b>i</b>) GND density maps of various boundary regions in different volume fractions (ε = 8%).</p>
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<p>Comparison of the density of UFG and CG boundary dislocations with the same volume fraction in different strains.</p>
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<p>(<b>a</b>) The rainbow of back stress of the sample level (ε = 8%). (<b>b</b>) The rainbow of back stress of the grain level (ε = 8%).</p>
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<p>(<b>a</b>) The deviation of back stress of the sample level (ε = 8%). (<b>b</b>) The deviation of back stress of the grain level (ε = 8%).</p>
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<p>Comparison of the numerical and experimental true stress–strain curves. (<math display="inline"><semantics> <mrow> <msub> <mrow> <mi>σ</mi> </mrow> <mrow> <mi mathvariant="normal">T</mi> </mrow> </msub> <mo> </mo> </mrow> </semantics></math> is the extra stress from the Taylor hardening; <math display="inline"><semantics> <mrow> <msub> <mrow> <mi mathvariant="sans-serif">σ</mi> </mrow> <mrow> <mi mathvariant="normal">H</mi> <mi mathvariant="normal">P</mi> </mrow> </msub> </mrow> </semantics></math> is the extra stress from the GB hardening effect).</p>
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18 pages, 1592 KiB  
Article
Form-Stable Phase-Change Materials Using Chemical Vapor Deposition-Derived Porous Supports: Carbon Nanotube/Diatomite Hybrid Powder and Carbon Nanotube Sponges
by Francesca Romana Lamastra, Mario Bragaglia, Lorenzo Paleari, Francesca Nanni, Francesco Fabborcino and Manuela Scarselli
Materials 2024, 17(23), 5721; https://doi.org/10.3390/ma17235721 (registering DOI) - 22 Nov 2024
Abstract
In this work, two types of chemical vapor deposition (CVD)-derived porous supporting materials consisting of CNTs–decorated diatomite (CNT/DE) and CNT sponges (CNS) were developed to prepare novel form-stable phase-change material (PCM) composites by impregnation, using polyethylene glycol (PEG) as the PCM. The CNT/DE [...] Read more.
In this work, two types of chemical vapor deposition (CVD)-derived porous supporting materials consisting of CNTs–decorated diatomite (CNT/DE) and CNT sponges (CNS) were developed to prepare novel form-stable phase-change material (PCM) composites by impregnation, using polyethylene glycol (PEG) as the PCM. The CNT/DE support matrix showed highly entangled nanotubes (the weight ratio of CNTs to DE was 0.16) over and inside the porous structure of diatomite, giving the hybrid matrix an electrical response. The CNS that resulted was mainly composed of bent and interconnected CNTs forming a three-dimensional highly porous structure. XPS and FTIR results revealed that CNTs in both the supporting materials have a moderate amount of oxygen-containing functional groups. Both hosts allow for high PEG loading (about 75 wt%) without showing any PCM leakage during melting. Both form-stable PCM composites showed high thermal reliability upon a hundred melting–solidification DSC cycles (PEG/CNT/DE latent heat is 86 ± 4 J/g and PEG/CNS latent heat is 100 ± 2 J/g; melting temperature 34 °C). An analytical model was used to evaluate the passive cooling performance of the systems, simulating the thermal behaviour of a building wall containing the confined PCM in the hosts, resulting in a reduction in required cooling power of about 10%. The overall results suggest that the developed form-stable PCM composites could be considered promising additive materials for the production of building envelopes with thermal energy storage capability. Full article
19 pages, 1903 KiB  
Review
A Survey on the Sustainability of Traditional and Emerging Materials for Next-Generation EV Motors
by Francesco Lucchini, Riccardo Torchio and Nicola Bianchi
Energies 2024, 17(23), 5861; https://doi.org/10.3390/en17235861 - 22 Nov 2024
Abstract
The transportation sector is experiencing a profound shift, driven by the urgent need to reduce greenhouse gas (GHG) emissions from internal combustion engine vehicles (ICEVs). As electric vehicle (EV) adoption accelerates, the sustainability of the materials used in their production, particularly in electric [...] Read more.
The transportation sector is experiencing a profound shift, driven by the urgent need to reduce greenhouse gas (GHG) emissions from internal combustion engine vehicles (ICEVs). As electric vehicle (EV) adoption accelerates, the sustainability of the materials used in their production, particularly in electric motors, is becoming a critical focus. This paper examines the sustainability of both traditional and emerging materials used in EV traction motors, with an emphasis on permanent magnet synchronous motors (PMSMs), which remain the dominant technology in the industry. Key challenges include the environmental and supply-chain concerns associated with rare earth elements (REEs) used in permanent magnets, as well as the sustainability of copper windings. Automakers are exploring alternatives such as REE-free permanent magnets, soft magnetic composites (SMCs) for reduced losses in the core, and carbon nanotube (CNT) windings for superior electrical, thermal, and mechanical properties. The topic of materials for EV traction motors is discussed in the literature; however, the focus on environmental, social, and economic sustainability is often lacking. This paper fills the gap by connecting the technological aspects with sustainability considerations, offering insights into the future configuration of EV motors. Full article
(This article belongs to the Special Issue Energy, Electrical and Power Engineering: 3rd Edition)
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<p>Forecasting global electric car sales over the next 20 years. Reproduced from BloombergNEF’s Electric Vehicle Outlook 2019 [<a href="#B4-energies-17-05861" class="html-bibr">4</a>].</p>
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<p>Comparative life-cycle <math display="inline"><semantics> <msub> <mi>CO</mi> <mn>2</mn> </msub> </semantics></math> emissions for EVs and ICEVs. Reproduced from [<a href="#B13-energies-17-05861" class="html-bibr">13</a>].</p>
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<p>Schematics of electric motors. (<b>a</b>) PMSM. (<b>b</b>) SRM. (<b>c</b>) IM. (<b>d</b>) PMaSynRM.</p>
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<p>Timeline of materials for PMs and their maximum energy product [<a href="#B47-energies-17-05861" class="html-bibr">47</a>].</p>
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<p>Distribution of global rare earth mine production in 2023. Data adapted from [<a href="#B55-energies-17-05861" class="html-bibr">55</a>].</p>
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<p>Potential recycling supply ratio for Nd and Dy. Data adapted from [<a href="#B66-energies-17-05861" class="html-bibr">66</a>].</p>
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<p>Global price of aluminum and copper from 2000 to today. Data adapted from [<a href="#B78-energies-17-05861" class="html-bibr">78</a>].</p>
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<p>Distribution of global copper mine production in 2023. Data adapted from [<a href="#B82-energies-17-05861" class="html-bibr">82</a>].</p>
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<p>Structure of steel and amorphous metal [<a href="#B103-energies-17-05861" class="html-bibr">103</a>].</p>
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13 pages, 3472 KiB  
Article
Fabrication of Pb-Containing PtAu Nanoflowers via Galvanic Replacement Method for Electrocatalytical Oxidation of Methanol
by Zhao Huang, Zhirou Zhang, Long Chao and Xueen Jia
Molecules 2024, 29(23), 5492; https://doi.org/10.3390/molecules29235492 - 21 Nov 2024
Viewed by 214
Abstract
A Pb-containing PtAu nanoflower electrocatalyst was deposited on the cathode via galvanic replacement reaction in a double-cabin galvanic cell (DCGC) with a Cu plate as the anode, a multiwalled carbon nanotube (MWCNT) modified glassy carbon electrode (GCE) as the cathode, 0.1 M HClO [...] Read more.
A Pb-containing PtAu nanoflower electrocatalyst was deposited on the cathode via galvanic replacement reaction in a double-cabin galvanic cell (DCGC) with a Cu plate as the anode, a multiwalled carbon nanotube (MWCNT) modified glassy carbon electrode (GCE) as the cathode, 0.1 M HClO4 aqueous solution as the anolyte, and Pb2+-containing Pt4+ salt and Au3+ salt mixed aqueous solution as the catholyte, respectively, and the electrocatalytic performance of the modified electrode toward methanol oxidation in the alkaline medium was investigated. Electrochemical studies reveal that the stripping of bulk Cu can induce underpotential deposition (UPD) of Pb on Pt during the galvanic replacement reaction, which affects the morphology and composition of Pb-containing PtAu nanoparticles. Under the optimal experimental conditions, a Pb-Pt3Au1/MWCNTs/GCE shows the highest activity and the best stability toward electrocatalytic oxidation of methanol in the alkaline medium, and the Pt active area-normalized specific electrocatalytic activity of Pb-Pt3Au1/MWCNTs/GCE is as high as 59.8 mA cmPt−2. We believe that the method presented here of depositing highly active noble metal nanostructures by galvanic replacement reaction in a DCGC device is expected to be widely applied in the preparation of nanomaterials for their study in fuel cells and electrocatalysis. Full article
(This article belongs to the Special Issue Carbon-Based Electrochemical Materials for Energy Storage)
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Figure 1
<p>Simultaneous responses of <span class="html-italic">i</span><sub>cell</sub> and <span class="html-italic">E</span><sub>cathode</sub> in the DCGC with a Cu plate as the anode, 0.1 M HClO<sub>4</sub> as the anolyte (stationary), and the MWCNTs/GCE as the cathode, while the catholyte (stationary) was 3.0 mM H<sub>2</sub>PtCl<sub>6</sub> + 1.0 mM HAuCl<sub>4</sub> + 5.0 mM Pb(ClO<sub>4</sub>)<sub>2</sub> + 0.1 M HClO<sub>4</sub> aqueous solution (a), for the deposition of Pb-Pt<sub>3</sub>Au<sub>1</sub>) and 3.0 mM H<sub>2</sub>PtCl<sub>6</sub> + 1.0 mM HAuCl<sub>4</sub> + 0.1 M HClO<sub>4</sub> aqueous solution (b), for deposition of Pt<sub>3</sub>Au<sub>1</sub>), respectively. Short-circuit discharging of the DCGC (connecting the anode and cathode by a conducting Cu wire) was from 30 to 270 s.</p>
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<p>SEM of Pt<sub>3</sub>Au<sub>1</sub>/MWCNTs/GCE (<b>A</b>,<b>B</b>) and Pb-Pt<sub>3</sub>Au<sub>1</sub>/MWCNTs/GCE (<b>C</b>,<b>D</b>).</p>
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<p>EDS spectra of Pt<sub>3</sub>Au<sub>1</sub>/MWCNTs/GCE (<b>A</b>) and Pb-Pt<sub>3</sub>Au<sub>1</sub>/MWCNTs/GCE (<b>B</b>), respectively.</p>
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<p>Cyclic voltammograms of Pt<sub>pla</sub>/Au (<b>A</b>) and bare Au (<b>B</b>) in 3.0 mM Pb(ClO<sub>4</sub>)<sub>2</sub> + 0.1 M HClO<sub>4</sub> aqueous solution, respectively. Scan rate: 20 mV s<sup>−1</sup>.</p>
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<p>Cyclic voltammograms of Pb-Pt<sub>3</sub>Au<sub>1</sub>/MWCNTs/GCE (a), Pt<sub>3</sub>Au<sub>1</sub>/MWCNTs/GCE (b), and Pb-Pt/MWCNTs/GCE (c) in 1.0 M KOH aqueous solution (<b>A</b>) and 1.0 M CH<sub>3</sub>OH + 1.0 M KOH aqueous solution (<b>B</b>,<b>C</b>), respectively. Currents in plans (<b>A</b>–<b>C</b>) are normalized to geometric area (<b>A</b>,<b>B</b>) and Pt active area (<b>C</b>), respectively. The inset in plan (<b>A</b>) is the CV of Pb-Au/MWCNTs/GCE in 1.0 M KOH aqueous solution. Scan rate: 50 mV s<sup>−1</sup>.</p>
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<p>Cyclic voltammograms of Pb-Pt<sub>3</sub>Au<sub>0.5</sub>/MWCNTs/GCE (a), Pb-Pt<sub>3</sub>Au<sub>1</sub>/MWCNTs/GCE (b), Pb-Pt<sub>3</sub>Au<sub>3</sub>/MWCNTs/GCE (c), Pb-Pt<sub>3</sub>Au<sub>5</sub>/MWCNTs/GCE (d), and Pb-Pt<sub>3</sub>Au<sub>7</sub>/MWCNTs/GCE (e) in 1.0 M KOH aqueous solution (<b>A</b>) and 1.0 M CH<sub>3</sub>OH + 1.0 M KOH aqueous solution (<b>B</b>,<b>C</b>), respectively. Currents in plans (<b>A</b>–<b>C</b>) are normalized to geometric area (<b>A</b>,<b>B</b>) and Pt active area (<b>C</b>), respectively. Scan rate: 50 mV s<sup>−1</sup>.</p>
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<p>The <span class="html-italic">i</span>-t curves at −0.25 V of Pb-Pt<sub>3</sub>Au<sub>0.5</sub>/MWCNTs/GCE (a), Pb-Pt<sub>3</sub>Au<sub>1</sub>/MWCNTs/GCE (b), Pt<sub>3</sub>Au<sub>1</sub>/MWCNTs/GCE (c), Pb-Pt/MWCNTs/GCE (d) (<b>A</b>) and Pb-Pt<sub>3</sub>Au<sub>3</sub>/MWCNTs/GCE (e), Pb-Pt<sub>3</sub>Au<sub>5</sub>/MWCNTs/GCE (f), and Pb-Pt<sub>3</sub>Au<sub>7</sub>/MWCNTs/GCE (g) (<b>B</b>) in 1.0 M CH<sub>3</sub>OH + 1.0 M KOH aqueous solution, respectively. Currents are normalized to Pt active area.</p>
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<p>Schematic diagram of the total experimental setup. GCE: glassy carbon electrode. IE: indicator electrode.</p>
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23 pages, 5362 KiB  
Review
Superior Ceramics: Graphene and Carbon Nanotube (CNT) Reinforcements
by Katalin Balázsi, Alaa Almansoori and Csaba Balázsi
Ceramics 2024, 7(4), 1758-1778; https://doi.org/10.3390/ceramics7040112 - 20 Nov 2024
Viewed by 182
Abstract
Carbon nanotube (CNT)/graphene ceramic composites with outstanding properties are expected to replace a number of components currently used in the automotive and aerospace industries in the future. Consequently, this area of research has progressed significantly. This review paper, therefore, delves into the enhancement [...] Read more.
Carbon nanotube (CNT)/graphene ceramic composites with outstanding properties are expected to replace a number of components currently used in the automotive and aerospace industries in the future. Consequently, this area of research has progressed significantly. This review paper, therefore, delves into the enhancement of ceramic properties through the integration of graphene and CNTs. These reinforcements are known to mitigate the inherent brittleness of ceramics, thereby unlocking their potential for applications in sectors requiring high mechanical reliability, such as the aerospace, automotive, and biomedical industries. By summarizing recent research, this paper outlines various preparation methods, including ball milling, heat pressing and spark plasma sintering, and discusses how these techniques contribute to improved mechanical and thermal performance. This review emphasizes the critical role of graphene and CNT ratios, sizes, and their synergistic effects in enhancing fracture toughness, machinability, and overall structural integrity. Thus, this paper provides a comprehensive overview of the current research in this area and discusses the potential of these technologies. Full article
(This article belongs to the Special Issue Advances in Ceramics, 2nd Edition)
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Graphical abstract

Graphical abstract
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<p>Research progress on ceramic composite materials and their applications.</p>
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<p>An illustration of how a 2D graphene sheet is rolled to form CNT structures (zigzag, armchair and chiral nanotubes).</p>
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<p>SEM images of Al<sub>2</sub>O<sub>3</sub> composite fracture surfaces reinforced with CNTs and graphene (GNP), showing the reduction in the grain size of Al<sub>2</sub>O<sub>3</sub> (<b>a</b>–<b>c</b>) and increasing the fracture toughness, together with reducing the hardness of the Al<sub>2</sub>O<sub>3</sub> composite (<b>d</b>,<b>e</b>), respectively. Adapted with permission from [<a href="#B57-ceramics-07-00112" class="html-bibr">57</a>], Elsevier, 2018.</p>
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<p>The toughening mechanism of CNT bridging using high-magnification TEM images on the fracture surfaces of the Al<sub>2</sub>O<sub>3</sub>-graphene (GNP) and -CNT composite (<b>a</b>–<b>c</b>) and the fracture toughness and flexural strength of the Al<sub>2</sub>O<sub>3</sub> composite at different graphene and CNT ratios (<b>d</b>). Adapted with permission from [<a href="#B86-ceramics-07-00112" class="html-bibr">86</a>], Elsevier, 2015.</p>
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<p>SEM and EDS profiles of the fracture of Graphene/CNT-reinforced Al<sub>2</sub>O<sub>3</sub>-TiC ceramic composite with the following contents: (<b>a</b>,<b>b</b>) 0.5 wt.% MWCNTs/0.5 wt.% Graphenes; (<b>c</b>,<b>d</b>) 0.7 wt.% MWCNTs/0.3 wt.% Graphenes and (<b>e</b>,<b>f</b>) 0.8 wt.% MWCNTs/0.2 wt.% Graphenes. Reproduced with permission from [<a href="#B68-ceramics-07-00112" class="html-bibr">68</a>], Elsevier, 2020.</p>
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<p>TEM images of the Graphenes/Al<sub>2</sub>O<sub>3</sub> interface. The interface between the outer graphene (GNP) layer and the ceramic matrix may have hindered the crack propagation. Reproduced with permission from [<a href="#B88-ceramics-07-00112" class="html-bibr">88</a>], IOP Publishing, 1990.</p>
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<p>Comparison of the wear coefficients for Si<sub>3</sub>N<sub>4</sub> ceramic reinforced by MLG and SiC ceramic fabricated by HIP and SPS (v = 20 and 200 mm/s sliding speeds). Reproduced with permission from [<a href="#B79-ceramics-07-00112" class="html-bibr">79</a>], Elsevier, 2016.</p>
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<p>Illustrates the correlation and trends between the graphene content, density, and Vickers hardness of composites: (<b>a</b>,<b>b</b>) show that the Vickers hardness decreases with increasing graphene content, while it increases with increasing density [<a href="#B100-ceramics-07-00112" class="html-bibr">100</a>]. Reproduced from [<a href="#B100-ceramics-07-00112" class="html-bibr">100</a>], Elsevier, 2024.</p>
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11 pages, 2461 KiB  
Article
Enhancing the Non-Isothermal Crystallization Kinetics of Polylactic Acid by Incorporating a Novel Nucleating Agent
by Ruijie Jin, Zehong Chen, Yidan Ouyang, Xintu Lin, Xin Dai, Shangxi Zhang, Ruilan Xu, Zhengbao Wang and Yong Peng
Polymers 2024, 16(22), 3204; https://doi.org/10.3390/polym16223204 - 19 Nov 2024
Viewed by 280
Abstract
Polylactic acid (PLA) is a widely recognized biodegradable polymer. However, the slow crystallization rate of PLA restricts its practical applications. In this study, camphor leaf biochar decorated with multi-walled carbon nanotubes (C@MWCNTs) was prepared using the strong adhesive properties of polydopamine, and PLA/C@MWCNTs [...] Read more.
Polylactic acid (PLA) is a widely recognized biodegradable polymer. However, the slow crystallization rate of PLA restricts its practical applications. In this study, camphor leaf biochar decorated with multi-walled carbon nanotubes (C@MWCNTs) was prepared using the strong adhesive properties of polydopamine, and PLA/C@MWCNTs composites were fabricated via the casting solution method. The influence of C@MWCNTs as a novel nucleating agent on the melt behavior and non-isothermal crystallization behavior of PLA was investigated using differential scanning calorimetry (DSC). The crystallization kinetic parameters were obtained through the Jeziorny, Ozawa, and Mo methods, and the crystallization activation energy of the PLA/C@MWCNTs composites was calculated by the Kissinger method. The results show that the PLA/C@MWCNTs composites exhibit higher crystallinity and crystallization temperatures than those of PLA. Non-isothermal crystallization kinetic analysis reveals that the Mo method better describes the non-isothermal crystallization kinetics of both PLA and PLA/C@MWCNTs composites. In addition, it was found that C@MWCNTs, despite increasing the crystallization activation energy, can act as an efficient nucleating agent to increase the crystallization rate of PLA. These experimental results provide valuable insights for enhancing the slow crystallization rates associated with PLA. Full article
(This article belongs to the Special Issue Additive Agents for Polymer Functionalization Modification)
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<p>Cooling curve (<b>a</b>) and second heating curve (<b>b</b>) of PLA with different C@MWCNTs contents.</p>
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<p>Plots of cooling rate versus (<b>a</b>) t<sub>1/2</sub> value and (<b>b</b>) onset temperature for PLA/C@MWCNTs composites.</p>
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<p>Plots of <math display="inline"><semantics> <mrow> <mrow> <mrow> <mi mathvariant="normal">log</mi> </mrow> <mo>⁡</mo> <mrow> <mfenced open="[" close="]" separators="|"> <mrow> <mo>−</mo> <mrow> <mrow> <mi mathvariant="normal">ln</mi> </mrow> <mo>⁡</mo> <mrow> <mfenced separators="|"> <mrow> <msub> <mrow> <mn>1</mn> <mo>−</mo> <mi mathvariant="normal">X</mi> </mrow> <mrow> <mi mathvariant="normal">t</mi> </mrow> </msub> </mrow> </mfenced> </mrow> </mrow> </mrow> </mfenced> </mrow> </mrow> </mrow> </semantics></math> as function of log t for (<b>a</b>) PLA, (<b>b</b>) PLA/0.1%C@MWCNTs, and (<b>c</b>) PLA/0.3%C@MWCNTs composites.</p>
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<p>Plots of <math display="inline"><semantics> <mrow> <mrow> <mrow> <mi mathvariant="normal">log</mi> </mrow> <mo>⁡</mo> <mrow> <mfenced open="[" close="]" separators="|"> <mrow> <mo>−</mo> <mrow> <mrow> <mi mathvariant="normal">ln</mi> </mrow> <mo>⁡</mo> <mrow> <mfenced separators="|"> <mrow> <msub> <mrow> <mn>1</mn> <mo>−</mo> <mi mathvariant="normal">X</mi> </mrow> <mrow> <mi mathvariant="normal">t</mi> </mrow> </msub> </mrow> </mfenced> </mrow> </mrow> </mrow> </mfenced> </mrow> </mrow> </mrow> </semantics></math> as function of <math display="inline"><semantics> <mrow> <mrow> <mrow> <mi mathvariant="normal">log</mi> </mrow> <mo>⁡</mo> <mrow> <mi mathvariant="sans-serif">β</mi> </mrow> </mrow> </mrow> </semantics></math> for (<b>a</b>) PLA, (<b>b</b>) PLA/0.1%C@MWCNTs, and (<b>c</b>) PLA/0.3%C@MWCNTs composites.</p>
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<p>Plots of <math display="inline"><semantics> <mrow> <mrow> <mrow> <mi mathvariant="normal">log</mi> </mrow> <mo>⁡</mo> <mrow> <mi mathvariant="sans-serif">β</mi> </mrow> </mrow> </mrow> </semantics></math> versus <math display="inline"><semantics> <mrow> <mrow> <mrow> <mi mathvariant="normal">log</mi> </mrow> <mo>⁡</mo> <mrow> <mi mathvariant="normal">t</mi> </mrow> </mrow> </mrow> </semantics></math> for non-isothermal crystallization of (<b>a</b>) PLA, (<b>b</b>) PLA/0.1%C@MWCNTs, and (<b>c</b>) PLA/0.3%C@MWCNTs composites.</p>
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<p>Plots of <math display="inline"><semantics> <mrow> <mi mathvariant="normal">l</mi> <mi mathvariant="normal">n</mi> <mo>(</mo> <mi mathvariant="sans-serif">β</mi> <mo>/</mo> <msubsup> <mrow> <mi mathvariant="normal">T</mi> </mrow> <mrow> <mi mathvariant="normal">p</mi> </mrow> <mrow> <mn>2</mn> </mrow> </msubsup> <mo>)</mo> </mrow> </semantics></math> versus <math display="inline"><semantics> <mrow> <mrow> <mrow> <mn>1</mn> </mrow> <mo>/</mo> <mrow> <msub> <mrow> <mi mathvariant="normal">T</mi> </mrow> <mrow> <mi mathvariant="normal">p</mi> </mrow> </msub> </mrow> </mrow> </mrow> </semantics></math> for PLA /C@MWCNTs composites.</p>
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<p>Preparation process of PLA/C@MWCNTs composites.</p>
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17 pages, 3318 KiB  
Article
Carbon Nanotube–Phenyl Modified g-C3N4: A Visible Light Driven Efficient Charge Transfer System for Photocatalytic Degradation of Rhodamine B
by Sahar Aghapour Ghourichay, Samira Agbolaghi, Riccardo Corpino and Pier Carlo Ricci
Molecules 2024, 29(22), 5439; https://doi.org/10.3390/molecules29225439 - 18 Nov 2024
Viewed by 297
Abstract
In this study, we report the synthesis and characterization of a novel photocatalyst composite composed of functionalized carbon nanotubes (f-CNT) and phenyl-modified graphitic carbon nitride (PhCN). The incorporation of the phenyl group extends the absorption range into the visible spectrum compared to pure [...] Read more.
In this study, we report the synthesis and characterization of a novel photocatalyst composite composed of functionalized carbon nanotubes (f-CNT) and phenyl-modified graphitic carbon nitride (PhCN). The incorporation of the phenyl group extends the absorption range into the visible spectrum compared to pure g-C3N4. Additionally, the formation of the heterostructure in the f-CNT/PhCN composite exhibits improved charge transfer efficiency, facilitating the separation and transfer of photogenerated electron-hole pairs and reducing recombination rates. The photocatalytic performance of this composite was evaluated by the degradation of Rhodamine B (RhB) under visible light irradiation. The f-CNT/PhCN composite exhibits remarkable efficiency in degrading RhB, achieving 60% degradation after 4 h, and 100% after 24 h under low-power white LED excitation. This represents a substantial improvement over the non-functionalized CNT/PhCN composite, which shows much lower performance. In contrast, pure PhCN demonstrates very little activity. Structural and optical properties were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), Raman spectroscopy, and UV–Vis spectroscopy. Time-resolved photoluminescence measurements were used to study the behavior of photoexcited carriers, confirming that the composite improves charge transfer efficiency for photogenerated carriers by approximately 30%. The results indicate that the functionalization of CNTs significantly enhances the photocatalytic properties of the composite, making f-CNT/PhCN a promising candidate for environmental remediation applications, particularly in the degradation of organic pollutants in wastewater. Full article
(This article belongs to the Section Physical Chemistry)
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<p>Raman spectra of CNT-COOH, f-CNT, and f-CNT/PhCN. The asterisks (*) indicate the Raman peaks of PhCN.</p>
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<p>XRD patterns for (<b>a</b>) PhCN, f-CNT/PhCN, inset normalized area of PhCN diffraction peak and (<b>b</b>) f-CNT, f-CNT/PhCN.</p>
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<p>TEM images of (<b>a</b>) f-CNT, (<b>b</b>) PhCN, and (<b>c</b>) f-CNT/PhCN.</p>
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<p>Absorption spectra of PhCN and f-CNT/PhCN.</p>
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<p>Time-resolved measurement for PhCN and f-CNT/PhCN: ((<b>a</b>,<b>c</b>) 3D profiles for f-CNT/PhCN and PhCN), (<b>b</b>) photoluminescence intensity versus time delay. The blue and red line represent the numerical fit. (<b>d</b>) Photoluminescence intensity versus wavelength.</p>
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<p>Evaluation of the photocatalytic activity. (<b>A</b>) Photocatalytic degradation of pure PhCN, CNT/PhCN and f-CNT/PhCN. (<b>B</b>) Absorption spectrum of RhB solution with f-CNT/PhCN. (<b>C</b>) Repeatability test of f-CNT/PhCN evaluated after four hours.</p>
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<p>Scheme of the mechanism of f-CNT/PhCN for RhB degradation.</p>
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13 pages, 3286 KiB  
Article
Improving the NO2 Gas Sensing Performances at Room Temperature Based on TiO2 NTs/rGO Heterojunction Nanocomposites
by Yan Ling, Yunjiang Yu, Canxin Tian and Changwei Zou
Nanomaterials 2024, 14(22), 1844; https://doi.org/10.3390/nano14221844 - 18 Nov 2024
Viewed by 445
Abstract
The development of energy-efficient, sensitive, and reliable gas sensors for monitoring NO2 concentrations has garnered considerable attention in recent years. In this manuscript, TiO2 nanotube arrays/reduced graphene oxide nanocomposites with varying rGO contents (TiO2 NTs/rGO) were synthesized via a two-step [...] Read more.
The development of energy-efficient, sensitive, and reliable gas sensors for monitoring NO2 concentrations has garnered considerable attention in recent years. In this manuscript, TiO2 nanotube arrays/reduced graphene oxide nanocomposites with varying rGO contents (TiO2 NTs/rGO) were synthesized via a two-step method for room temperature NO2 gas detection. From SEM and TEM images, it is evident that the rGO sheets not only partially surround the TiO2 nanotubes but also establish interconnection bridges between adjacent nanotubes, which is anticipated to enhance electron–hole separation by facilitating electron transfer. The optimized TiO2 NTs/rGO sensor demonstrated a sensitive response of 19.1 to 1 ppm of NO2, a 5.26-fold improvement over the undoped TiO2 sensor. Additionally, rGO doping significantly enhanced the sensor’s response/recovery times, reducing them from 24 s/42 s to 18 s/33 s with just 1 wt.% rGO. These enhancements are attributed to the increased specific surface area, higher concentration of chemisorbed oxygen species, and the formation of p-n heterojunctions between TiO2 and rGO within the nanocomposites. This study provides valuable insights for the development of TiO2/graphene-based gas sensors for detecting oxidizing gases at room temperature. Full article
(This article belongs to the Special Issue Design and Applications of Heterogeneous Nanostructured Materials)
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<p>Schematic of synthesis process (<b>a</b>) and photograph of NO<sub>2</sub> detection testing system (<b>b</b>).</p>
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<p>XRD patterns of TiO<sub>2</sub> NTs/rGO nanocomposites grown with different rGO contents.</p>
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<p>SEM images of TiO<sub>2</sub> NTs/rGO nanocomposites with rGO contents of 0 wt.% (<b>a</b>), 0.5 wt.% (<b>b</b>), 1 wt.% (<b>c</b>), and 3 wt.% (<b>d</b>), respectively. Inset of <a href="#nanomaterials-14-01844-f003" class="html-fig">Figure 3</a>d shows the EDX spectrum of TiO<sub>2</sub> NTs/rGO nanocomposites with rGO contents of 3 wt.%. The red circles in <a href="#nanomaterials-14-01844-f003" class="html-fig">Figure 3</a>d illustrate the structure of rGO surrounding the TiO<sub>2</sub> nanotubes.</p>
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<p>TEM (<b>a</b>,<b>b</b>) and high-resolution TEM (<b>c</b>,<b>d</b>) images of TiO<sub>2</sub> nanotubes (<b>a</b>,<b>c</b>) and TiO<sub>2</sub> NTs/rGO nanocomposites (<b>b</b>,<b>d</b>) with rGO contents of 1 wt.%.</p>
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<p>Raman spectra of TiO2 NTs/rGO nanocomposites with different rGO contents.</p>
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<p>XPS spectra of TiO<sub>2</sub> NTs/rGO nanocomposite with rGO contents of 1 wt.%. (<b>a</b>) Full scan. (<b>b</b>) Ti 2p. (<b>c</b>) C 1s. (<b>d</b>) O 1s.</p>
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<p>The response value of the sensor based on TiO<sub>2</sub> NTs/rGO composites vs. NO<sub>2</sub> concentration at room temperature.</p>
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<p>The dynamic response transients of the sensor based on TiO<sub>2</sub> NTs/rGO nanocomposites to 20 ppm NO<sub>2</sub> at room temperature.</p>
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<p>Response of the sensor based on TiO<sub>2</sub> NTs/rGO nanocomposites to 50 ppm of C<sub>2</sub>H<sub>5</sub>OH, CH<sub>3</sub>OH, H<sub>2</sub>, NH<sub>3</sub>, H<sub>2</sub>S, and NO<sub>2</sub> at room temperature.</p>
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<p>Long-term stability of the sensor based on TiO<sub>2</sub> NTs and TiO<sub>2</sub> NTs/rGO nanocomposites to 1 ppm of NO<sub>2</sub> at room temperature.</p>
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<p>I-V curves of the sensor based on TiO<sub>2</sub> NTs/rGO nanocomposites with different rGO contents.</p>
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<p>Energy band diagrams for TiO<sub>2</sub> NTs, rGO and TiO<sub>2</sub> NTs/rGO heterostructure, where E<sub>VB</sub>, E<sub>F</sub>, E<sub>CB</sub>, E<sub>vac</sub> represent valence band, Fermi level, conduction band, and vacuum level, respectively. (<b>a</b>) The energy band diagrams for TiO<sub>2</sub> nanotubes, rGO, and their corresponding TiO<sub>2</sub> NTs/rGO nanocomposites. (<b>b</b>) Schematic illustration of electron transfer and sensing mechanism of TiO<sub>2</sub> NTs/rGO nanocomposites.</p>
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18 pages, 711 KiB  
Review
Proposed Mechanisms of Cell Therapy for Alzheimer’s Disease
by Ekaterina Belousova, Diana Salikhova, Yaroslav Maksimov, Vladimir Nebogatikov, Anastasiya Sudina, Dmitry Goldshtein and Aleksey Ustyugov
Int. J. Mol. Sci. 2024, 25(22), 12378; https://doi.org/10.3390/ijms252212378 - 18 Nov 2024
Viewed by 225
Abstract
Alzheimer’s disease is a progressive neurodegenerative disorder characterized by mitochondria dysfunction, accumulation of beta-amyloid plaques, and hyperphosphorylated tau tangles in the brain leading to memory loss and cognitive deficits. There is currently no cure for this condition, but the potential of stem cells [...] Read more.
Alzheimer’s disease is a progressive neurodegenerative disorder characterized by mitochondria dysfunction, accumulation of beta-amyloid plaques, and hyperphosphorylated tau tangles in the brain leading to memory loss and cognitive deficits. There is currently no cure for this condition, but the potential of stem cells for the therapy of neurodegenerative pathologies is actively being researched. This review discusses preclinical and clinical studies that have used mouse models and human patients to investigate the use of novel types of stem cell treatment approaches. The findings provide valuable insights into the applications of stem cell-based therapies and include the use of neural, glial, mesenchymal, embryonic, and induced pluripotent stem cells. We cover current studies on stem cell replacement therapy where cells can functionally integrate into neural networks, replace damaged neurons, and strengthen impaired synaptic circuits in the brain. We address the paracrine action of stem cells acting via secreted factors to induce neuroregeneration and modify inflammatory responses. We focus on the neuroprotective functions of exosomes as well as their neurogenic and synaptogenic effects. We look into the shuttling of mitochondria through tunneling nanotubes that enables the transfer of healthy mitochondria by restoring the normal functioning of damaged cells, improving their metabolism, and reducing the level of apoptosis. Full article
(This article belongs to the Special Issue From Molecular Insights to Novel Therapies: Neurological Diseases)
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<p>Stem cell strategies for Alzheimer’s disease and proposed mechanisms of stem cell therapy. Mesenchymal stem cells (MSCs), neural stem cells (NSCs), glial progenitor cells (GPCs), neural progenitor cells (NPCs), embryonic stem cells (ESCs), and induced pluripotent stem cells (iPSCs) participate in various types of cell processing affecting cell replacement and are involved in paracrine action via secreted factors and exosomes, as well as the transfer of mitochondria through tunneling nanotube (TNT) pathway.</p>
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1 pages, 138 KiB  
Correction
Correction: Wang et al. Multi-Walled Carbon Nanotubes Accelerate Leukaemia Development in a Mouse Model. Toxics 2024, 12, 646
by Qingqing Wang, Jingdan Han, Mujia Wei, Huikai Miao, Min Zhang, Biao Wu, Yao Chen, Yanwen Zheng, Robert Peter Gale and Bin Yin
Toxics 2024, 12(11), 823; https://doi.org/10.3390/toxics12110823 - 18 Nov 2024
Viewed by 192
Abstract
At the request of the authors, Haiyan Xu has been removed from the original publication [...] Full article
13 pages, 7273 KiB  
Article
Catalytic Methane Decomposition on In Situ Reduced FeCo Alloy Catalysts Derived from Layered Double Hydroxides
by Dianfeng Cao, Yuwen Li, Chao Lv, Yongtao An, Jiangfeng Song, Mingcan Li and Xin Zhang
Nanomaterials 2024, 14(22), 1831; https://doi.org/10.3390/nano14221831 - 15 Nov 2024
Viewed by 325
Abstract
Catalytic methane decomposition (CMD) reaction is considered a promising process for converting greenhouse gas CH4 into hydrogen and high-value-added carbon materials. In this work, a series of Al2O3-supported FeCo alloy catalysts were successfully prepared in the CMD process. [...] Read more.
Catalytic methane decomposition (CMD) reaction is considered a promising process for converting greenhouse gas CH4 into hydrogen and high-value-added carbon materials. In this work, a series of Al2O3-supported FeCo alloy catalysts were successfully prepared in the CMD process. Compared to the pre-reduced catalysts, the in situ reduced FeCo alloy catalysts showed higher methane conversion rates, with the highest reaching 83% at 700 °C, due to the finer active nanoparticle size and greater exposure of active site. Furthermore, the time-on-stream tests demonstrated that the catalytic activity of in situ reduced FeCo alloy catalysts could remain above 92.3% of the highest catalytic activity after 10 h. In addition, TEM analyses of the carbon products from the CMD in situ reduced catalysts revealed the production of carbon nanofibers and nanotubes several microns in length after the reaction. This indicates that the in situ reduced FeCo alloy catalysts more effectively promoted the growth of carbon nanofibers. These results could provide a viable strategy for future methane decomposition development aimed at producing hydrogen and high-value carbon. Full article
(This article belongs to the Special Issue Nanomaterials for Sustainable Green Energy)
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<p>(<b>a</b>) XRD patterns of FeCoAl-LDH-<span class="html-italic">x</span> and (<b>b</b>) XRD patterns of FeCo/Al<sub>2</sub>O<sub>3</sub>-<span class="html-italic">x</span>.</p>
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<p>TEM images of (<b>a</b>–<b>c</b>) FeCoAl-LDH-<span class="html-italic">x</span> (<span class="html-italic">x</span> = 1–3). (<b>d</b>–<b>f</b>) TEM images of FeCo/Al<sub>2</sub>O<sub>3</sub>-<span class="html-italic">x</span> (<span class="html-italic">x</span> = 1–3). (<b>g</b>–<b>i</b>) Statistical distribution graphs of the particle size of FeCo/Al<sub>2</sub>O<sub>3</sub>-<span class="html-italic">x</span> (<span class="html-italic">x</span> = 1–3).</p>
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<p>(<b>a</b>) TG analysis of the FeCoAl-LDH-<span class="html-italic">x</span>, (<b>b</b>) the differential curves of TG about FeCoAl-LDH-<span class="html-italic">x</span>, (<b>c</b>) TG analysis of the FeCo/Al<sub>2</sub>O<sub>3</sub>-<span class="html-italic">x</span>, and (<b>d</b>) the differential curves of TG about FeCo/Al<sub>2</sub>O<sub>3</sub>-<span class="html-italic">x</span>.</p>
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<p>The relationship between methane conversion and temperature in the TPSR test at 5 °C/min to 800 °C for (<b>a</b>) FeCoAl-LDH-<span class="html-italic">x</span> and (<b>b</b>) FeCo/Al<sub>2</sub>O<sub>3</sub>-<span class="html-italic">x</span>, and the relationship between methane conversion and temperature in the TOS test at 5 °C/min to 700 °C for insulation of (<b>c</b>) FeCoAl-LDH-<span class="html-italic">x</span> and (<b>d</b>) FeCo/Al<sub>2</sub>O<sub>3</sub>-<span class="html-italic">x</span>.</p>
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<p>XRD patterns of methane decomposition reaction products catalyzed by (<b>a</b>) FeCoAl-LDH-<span class="html-italic">x</span> and (<b>b</b>) FeCo/Al<sub>2</sub>O<sub>3</sub>-<span class="html-italic">x</span>.</p>
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<p>TEM images of carbon products created by (<b>a</b>,<b>b</b>) FeCoAl-LDH-1, (<b>c</b>,<b>d</b>) FeCoAl-LDH-2, (<b>e</b>,<b>f</b>) and FeCoAl-LDH-3.</p>
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<p>TEM images of TG products created by (<b>a</b>) FeCo/Al<sub>2</sub>O<sub>3</sub>-1, (<b>b</b>) FeCo/Al<sub>2</sub>O<sub>3</sub>-2, and (<b>c</b>) FeCo/Al<sub>2</sub>O<sub>3</sub>-3.</p>
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<p>Raman spectra of (<b>a</b>) spent FeCoAl-LDHs-<span class="html-italic">x</span> (<span class="html-italic">x</span> = 1–3) and (<b>b</b>) FeCo/Al<sub>2</sub>O<sub>3</sub>-<span class="html-italic">x</span> (<span class="html-italic">x</span> = 1–3) catalysts after TG.</p>
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13 pages, 3048 KiB  
Article
Thermal Quenching of Intrinsic Photoluminescence in Amorphous and Monoclinic HfO2 Nanotubes
by Artem Shilov, Sergey Savchenko, Alexander Vokhmintsev, Kanat Zhusupov and Ilya Weinstein
Materials 2024, 17(22), 5587; https://doi.org/10.3390/ma17225587 - 15 Nov 2024
Viewed by 275
Abstract
Nanotubular hafnia arrays hold significant promise for advanced opto- and nanoelectronic applications. However, the known studies concern mostly the luminescent properties of doped HfO2-based nanostructures, while the optical properties of nominally pure hafnia with optically active centers of intrinsic origin are [...] Read more.
Nanotubular hafnia arrays hold significant promise for advanced opto- and nanoelectronic applications. However, the known studies concern mostly the luminescent properties of doped HfO2-based nanostructures, while the optical properties of nominally pure hafnia with optically active centers of intrinsic origin are far from being sufficiently investigated. In this work, for the first time we have conducted research on the wide-range temperature effects in the photoluminescence processes of anion-defective hafnia nanotubes with an amorphous and monoclinic structure, synthesized by the electrochemical oxidation method. It is shown that the spectral parameters, such as the position of the maximum and half-width of the band, remain almost unchanged in the range of 7–296 K. The experimental data obtained for the photoluminescence temperature quenching are quantitatively analyzed under the assumption made for two independent channels of non-radiative relaxation of excitations with calculating the appropriate energies of activation barriers—9 and 39 meV for amorphous hafnia nanotubes, 15 and 141 meV for monoclinic ones. The similar temperature behavior of photoluminescence spectra indicates close values of short-range order parameters in the local atomic surrounding of the active emission centers in hafnium dioxide with amorphous and monoclinic structure. Anion vacancies VO and VO2 appeared in the positions of three-coordinated oxygen and could be the main contributors to the spectral features of emission response and observed thermally stimulated processes. The recognized and clarified mechanisms occurring during thermal quenching of photoluminescence could be useful for the development of light-emitting devices and thermo-optical sensors with functional media based on oxygen-deficient hafnia nanotubes. Full article
(This article belongs to the Special Issue Advances in Luminescent Materials)
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<p>Scanning electron microscope (SEM) (<b>a</b>,<b>b</b>) and transmission electron microscope (TEM) (<b>c</b>,<b>d</b>) images obtained for the monoclinic HfO<sub>2</sub> nanotubes under study. The value marked in (<b>d</b>) corresponds to the interplanar distance <math display="inline"><semantics> <mrow> <mover accent="true"> <mn>1</mn> <mo>¯</mo> </mover> <mn>11</mn> </mrow> </semantics></math>.</p>
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<p>Photoluminescence (PL) spectra of amorphous (<b>top</b>) and monoclinic (<b>bottom</b>) hafnia nanotubes measured at different temperatures.</p>
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<p>Temperature dependencies of the experimental values of the maximum position E<sub>max</sub> (blue color) and half-width FWHM (green color) of the measured PL bands. The circles indicate data for amorphous NTs, triangles—for monoclinic NTs. The dashed lines show the averaged values of E<sub>max</sub> and FWHM in the temperature range of 7–296 K.</p>
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<p>PL spectra of amorphous (<b>left</b>, circles) and monoclinic (<b>right</b>, triangles) nanotubes measured at a temperature of 10 K, with decomposition into Gaussian components (red lines).</p>
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<p>Dependence <span class="html-italic">I</span>(<span class="html-italic">T</span>) for amorphous (<b>top</b>) and monoclinic (<b>bottom</b>) NTs. The red and blue lines, see insets, are linear approximations.</p>
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11 pages, 4468 KiB  
Article
Kinetics of Thermal Decomposition of Carbon Nanotubes Decorated with Magnetite Nanoparticles
by Rubén H. Olcay, Elia G. Palacios, Iván A. Reyes, Laura García-Hernández, Pedro A. Ramírez-Ortega, Sayra Ordoñez, Julio C. Juárez, Martín Reyes, Juan-Carlos González-Islas and Mizraim U. Flores
C 2024, 10(4), 96; https://doi.org/10.3390/c10040096 - 15 Nov 2024
Viewed by 348
Abstract
Magnetite nanoparticles were synthesized using the green chemistry technique; ferric chloride was used as a precursor agent and Moringa oleifera extract was used as a stabilizer agent. A black powder, characteristic of magnetite, was obtained. X-ray diffraction was performed on the synthesis product [...] Read more.
Magnetite nanoparticles were synthesized using the green chemistry technique; ferric chloride was used as a precursor agent and Moringa oleifera extract was used as a stabilizer agent. A black powder, characteristic of magnetite, was obtained. X-ray diffraction was performed on the synthesis product and identified as magnetite (Fe3O4). Scanning electron microscopy characterization shows that nanoparticles have a spherical morphology, with sizes ranging from 15 nm to 35 nm. The synthesis of carbon nanotubes was carried out by the pyrolytic chemical deposition technique, from which multiwalled carbon nanotubes were obtained with diameters of 15–35 nm and of varied length. The decoration was carried out using the wet and sonification technique, where a non-homogeneous coating was obtained around the nanotubes. The thermal decomposition for both decorated and undecorated nanotubes presents two mass losses but with different slopes, where the activation energy for the decorated carbon nanotubes was 79.54 kJ/mol, which shows that the decoration gives more stability to the nanotubes since the activation energy of the undecorated nanotubes is 25.74 kJ/mol. Full article
(This article belongs to the Collection Novel Applications of Carbon Nanotube-Based Materials)
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<p>X-ray diffraction spectrum of carbon nanotubes.</p>
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<p>X-ray diffraction spectrum of magnetite particles.</p>
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<p>SEM images of (<b>a</b>) the nanoparticles with diameters of 30 nanoparticles with diameters of 30 nm; (<b>b</b>) carbon nanotubes with diameters of 25 nm; (<b>c</b>) carbon nanotubes decorated with the magnetite nanoparticles viewed at 50,000X; (<b>d</b>) carbon nanotubes decorated with the magnetite nanoparticles viewed at 100,000X.</p>
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<p>X-ray diffraction spectrum of carbon nanotubes decorated with magnetite nanoparticles.</p>
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<p>(<b>a</b>) Differential thermogravimetric analysis of carbon nanotubes; (<b>b</b>) differential thermogravimetric analysis of magnetite nanoparticles; (<b>c</b>) differential thermogravimetric analysis of carbon nanotubes decorated with magnetite nanoparticles.</p>
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<p>Kinetic analysis of thermal decomposition of carbon nanotubes. (<b>a</b>) First-stage mass loss isotherms; (<b>b</b>) calculation of the first-stage activation energy; (<b>c</b>) second-stage mass loss isotherms; (<b>d</b>) calculation of the second-stage activation energy.</p>
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<p>Kinetic analysis of thermal decomposition of carbon nanotubes decorated with magnetite nanoparticles. (<b>a</b>) First-stage mass loss isotherms of carbon nanotubes decorated with magnetite nanoparticles; (<b>b</b>) calculation of the first-stage activation energy of carbon nanotubes decorated with magnetite nanoparticles; (<b>c</b>) second-stage mass loss isotherms of carbon nanotubes decorated with magnetite nanoparticles; (<b>d</b>) calculation of the second-stage activation energy of carbon nanotubes decorated with magnetite nanoparticles.</p>
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<p>Methodology for the synthesis of carbon nanotubes.</p>
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27 pages, 7765 KiB  
Article
Carbon Nanotubes in Cement—A New Approach for Building Composites and Its Influence on Environmental Effect of Material
by Teobald Kupka, Natalina Makieieva, Paweł Świsłowski, Małgorzata Rajfur, Artur Małolepszy, Leszek Stobiński, Stefania Grzeszczyk, Krystian Jurowski, Adam Sudoł, Roman Wrzalik, Oimahmad Rahmonov and Krzysztof Ejsmont
Molecules 2024, 29(22), 5379; https://doi.org/10.3390/molecules29225379 - 14 Nov 2024
Viewed by 516
Abstract
An addition of carbon nanostructures to cement paste is problematic due to the difficulties in obtaining homogenous mixtures. The paper reports on a more effective way of mixing carboxylated multi-walled carbon nanotubes (MWCNT-COOH) in cement pastes. The additional biological impact of the studied [...] Read more.
An addition of carbon nanostructures to cement paste is problematic due to the difficulties in obtaining homogenous mixtures. The paper reports on a more effective way of mixing carboxylated multi-walled carbon nanotubes (MWCNT-COOH) in cement pastes. The additional biological impact of the studied nanomodified cement was analyzed in the case of two moss species’ vitality. The applied approach of obtaining a homogeneous mixture is based on intense mechanochemical mixing of MWCNT-COOH together with polycarboxylate superplasticizer (SP). As a result, a more homogenous suspension of MWCNT-COOH within a liquid superplasticizer, suitable for addition to hydrophilic cement paste, was obtained. FT-IR/Raman spectroscopy was used for materials’ characterization. To explain the mixing process at the molecular level, systematic theoretical studies using density functional theory (DFT) were performed. The structures, interaction energies and IR/Raman vibrational spectra of model carboxylic acids, mixed with functionalized SWCNTs as simplified models of real MWCNTs, were obtained. Due to the controversial opinions on the environmental hazards of carbon nanostructures, additional in vivo studies were performed. In this case, effects of cement modified by the addition of small amounts of MWCNT-COOH with SP in comparison to the composite without carbon nanostructures and control subsoil on the vitality of mosses Polytrichum formosum and Pseudoscleropodium purum were studied. Full article
(This article belongs to the Special Issue Feature Papers in Applied Chemistry: 3rd Edition)
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<p>Schematic diagram explaining the interaction between polar groups of superplasticizer and carbon nanotubes, partly covered with carboxylic (and some hydroxyl) groups. Left, middle and right schemes show three stages of interaction between superplasticizer and carbon nanotube.</p>
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<p>Selected fragments of the ATR spectrum of superplasticizer (SP) with peaks labeled. Partly overlapped peaks are clearly visible.</p>
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<p>Selected fragments of the FT-IR spectrum of superplasticizer with peaks labeled.</p>
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<p>Carbonyl region fragment of FT-IR spectrum of (<b>A</b>) neat SP and (<b>B</b>) SP containing 3% MWCNT and the result of line fitting is also shown.</p>
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<p>The Raman spectra of (<b>A</b>) neat superplasticizer and (<b>B</b>) SP + 3% MWCNTs.</p>
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<p>BLYPD3BJ- and BLYP-optimized structures of (<b>A</b>) <span class="html-italic">trans</span>-formic acid dimers and “mixed dimer HCOOH⋯OOCH” (<b>B</b>) (interatomic distances are in Å).</p>
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<p>Side (<b>A</b>) and top (<b>B</b>) view of BLYPD3BJ/aug-cc-pVTZ structure of calcium (neutral complex) and sodium formate ((<b>C</b>,<b>D</b>), total charge = −1).</p>
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<p>B3LYPD3BJ/aug-cc-pVTZ structure of calcium formate with (<b>A</b>) two and (<b>B</b>) three water molecules (aug-cc-pVTZ-X2C basis set for calcium).</p>
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<p>BLYPD3BJ/aug-cc-pVTZ structure of mixed sodium formate salt.</p>
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<p>Fully optimized linear ae CCSD(T)/aug-cc-pVTZ structure of Ca(OH)<sub>2</sub>.</p>
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<p>Optimized models of superplasticizer building blocks: (<b>A</b>) Acid, (<b>B</b>) Salt (or a carboxylate anion) and (<b>C</b>) Ester.</p>
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<p>(<b>A</b>) Optimized B3LYPD3BJ/6-311++G** structure of model fragment of zigzag (5,0) SWCNT-COOH composed of five “belts” and the predicted (<b>B</b>) IR and (<b>C</b>) Raman spectra.</p>
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<p>Optimized B3LYP/6-31+G* structure of model fragment of zigzag (5,0) SWCNT-COOH interacting with HCOOH.</p>
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<p>Comparison of photosynthetic activity between individual samples in the species <span class="html-italic">Polytrichum formosum</span> (Pf) and in the species <span class="html-italic">Pseudoscleropodium purum</span> (Pp).</p>
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<p>TEM image of (<b>A</b>) bundled MWCNTs and (<b>B</b>) enlarged fragment of MWCNT.</p>
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<p>Observed patterns for metal carboxylates: (<b>A</b>) ionic systems and (<b>B</b>–<b>D</b>) with more covalent and coordinated character.</p>
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18 pages, 5175 KiB  
Article
Co-Activating Lattice Oxygen of TiO2-NT and SnO2 Nanoparticles on Superhydrophilic Graphite Felt for Boosting Electrocatalytic Oxidation of Glyphosate
by Wenyan He, Sheng Bai, Kaijie Ye, Siyan Xu, Yinuo Dan, Moli Chen and Kuo Fang
Nanomaterials 2024, 14(22), 1824; https://doi.org/10.3390/nano14221824 - 14 Nov 2024
Viewed by 299
Abstract
Glyphosate (GH) wastewater potentially poses hazards to human health and the aquatic environment, due to its persistence and toxicity. A highly superhydrophilic and stable graphite felt (GF)/polydopamine (PDA)/titanium dioxide nanotubes (TiO2-NT)/SnO2/Ru anode was fabricated and characterized for the degradation [...] Read more.
Glyphosate (GH) wastewater potentially poses hazards to human health and the aquatic environment, due to its persistence and toxicity. A highly superhydrophilic and stable graphite felt (GF)/polydopamine (PDA)/titanium dioxide nanotubes (TiO2-NT)/SnO2/Ru anode was fabricated and characterized for the degradation of glyphosate wastewater. Compared to control anodes, the GF/PDA/TiO2-NT/SnO2/Ru anode exhibited the highest removal efficiency (near to 100%) and a yield of phosphate ions of 76.51%, with the lowest energy consumption (0.088 Wh/L) for degrading 0.59 mM glyphosate (GH) at 7 mA/cm2 in 30 min. The exceptional activity of the anode may be attributed to the co-activation of lattice oxygen in TiO2-NT and SnO2 by coupled Ru, resulting in a significant amount of •O2 and oxygen vacancies as active sites for glyphosate degradation. After electrolysis, small molecular acids and inorganic ions were obtained, with hydroxylation and dephosphorization as the main degradation pathways. Eight cycles of experiments confirmed that Ru doping prominently enhanced the stability of the GF/PDA/TiO2-NT/SnO2/Ru anode due to its high oxygenophilicity and electron-rich ability, which promoted the generation and utilization efficiency of active free radicals and defects-associated oxygen. Therefore, this study introduces an effective strategy for efficiently co-activating lattice oxygen in SnO2 and TiO2-NT on graphite felt to eliminate persistent organophosphorus pesticides. Full article
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<p>Schematic diagram for preparation different electrodes.</p>
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<p>SEM images of (<b>a</b>) GF/PDA/TiO<sub>2</sub>-NT/SnO<sub>2</sub>/Ru, (<b>b</b>) GF/PDA/TiO<sub>2</sub>-NT/SnO<sub>2</sub>, (<b>c</b>) GF/PDA/TiO<sub>2</sub>-NT/Ru, (<b>d</b>) GF/PDA/TiO<sub>2</sub>-NT. (<b>e</b>) XRD patterns and (<b>f</b>) water contact angle of the four electrodes.</p>
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<p>(<b>a</b>) A full-scale XPS spectrum of GF/PDA/TiO<sub>2</sub>-NT/SnO<sub>2</sub>/Ru. XPS spectra of (<b>b</b>) Sn 3d, (<b>c</b>) C 1s and Ru 3d, (<b>d</b>) Ti 2p and O 1s of (<b>e</b>) GF/PDA/TiO<sub>2</sub>-NT/SnO<sub>2</sub>/Ru, (<b>f</b>) GF/PDA/TiO<sub>2</sub>-NT/SnO<sub>2</sub>, (<b>g</b>) GF/PDA/TiO<sub>2</sub>-NT/Ru, (<b>h</b>) GF/PDA/TiO<sub>2</sub>-NT.</p>
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<p>Effects of (<b>a</b>) pH, (<b>b</b>) initial concentration of glyphosate, (<b>c</b>) current density, (<b>d</b>) Ru loading on the glyphosate degradation efficiency of GF/PDA/TiO<sub>2</sub>-NT/SnO<sub>2</sub>/Ru electrode.</p>
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<p>(<b>a</b>) Degradation efficiency, (<b>b</b>) TOC removal rate, (<b>c</b>) production rate of PO<sub>4</sub><sup>3−</sup>, (<b>d</b>) energy consumption on GF/PDA/TiO<sub>2</sub>-NT, GF/PDA/TiO<sub>2</sub>-NT/Ru, GF/PDA/TiO<sub>2</sub>-NT/SnO<sub>2</sub>, GF/PDA/TiO<sub>2</sub>-NT/SnO<sub>2</sub>/Ru electrodes. (<b>e</b>) Recycle experiments of glyphosate degradation, (<b>f</b>) accelerated lifetime test of GF/PDA/TiO<sub>2</sub>-NT/SnO<sub>2</sub>, GF/PDA/TiO<sub>2</sub>-NT/SnO<sub>2</sub>/Ru electrodes.</p>
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<p>Electrochemical characterization of the four electrodes: (<b>a</b>) EIS curves, (<b>b</b>) LSV curves, (<b>c</b>) Tafel plots, (<b>d</b>) CV, (<b>e</b>) C<sub>dl</sub> of GF/PDA/TiO<sub>2</sub>-NT/SnO<sub>2</sub>, GF/PDA/TiO<sub>2</sub>-NT/SnO<sub>2</sub>/Ru electrodes.</p>
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<p>(<b>a</b>) EPR tests for •OH and (<b>c</b>) •O<sub>2</sub><sup>−</sup> on different electrode; (<b>b</b>) •OH quenching experiments and (<b>d</b>) •O<sub>2</sub><sup>−</sup> quenching experiments on different electrodes.</p>
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<p>Comparison of XPS spectra of (<b>a</b>) C 1s and Ru 3d, (<b>b</b>) Sn 3d; (<b>c</b>) Ti 2p, (<b>d</b>) O 1s of GF/PDA/TiO<sub>2</sub>-NT/SnO<sub>2</sub>/Ru electrodes before and after electrolysis.</p>
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<p>Schematic diagram of the glyphosate degradation on GF/PDA/TiO<sub>2</sub>-NT/SnO<sub>2</sub>/Ru anode in electrocatalytic oxidation process.</p>
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