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29 pages, 10767 KiB  
Review
Emerging Carbon-Based Catalysts for the Oxygen Reduction Reaction: Insights into Mechanisms and Applications
by Jing Guo, Yuqi Yao, Xin Yan, Xue Meng, Qing Wang, Yahui Zhang, Shengxue Yan, Xue Zhao and Shaohua Luo
Inorganics 2024, 12(12), 303; https://doi.org/10.3390/inorganics12120303 - 25 Nov 2024
Viewed by 20
Abstract
The oxygen reduction reaction (ORR), as a key electrode process in fuel cells and metal-air batteries, plays a pivotal role in advancing clean energy technologies. However, the slow kinetics and high overpotential of the ORR significantly limit the efficiency of these energy devices. [...] Read more.
The oxygen reduction reaction (ORR), as a key electrode process in fuel cells and metal-air batteries, plays a pivotal role in advancing clean energy technologies. However, the slow kinetics and high overpotential of the ORR significantly limit the efficiency of these energy devices. Therefore, the development of efficient, stable, and cost-effective ORR catalysts has become a central focus of current research. Carbon-based catalysts, with their excellent conductivity, chemical stability, and tunable structural features, have emerged as promising alternatives to traditional precious metal catalysts. Nevertheless, challenges remain in the design of active sites, the tuning of electronic structures, and the large-scale synthesis of carbon-based catalysts. This review systematically introduces the fundamental mechanisms and key factors influencing the ORR, providing an analysis of the critical variables that affect catalyst performance. Furthermore, it summarizes several common methods for synthesizing carbon-based catalysts, including pyrolysis, deposition, and ball milling. Following this, the review categorizes and discusses the latest advancements in metal-free carbon-based catalysts, single-atom and dual-atom catalysts, as well as metal-based nanoparticle catalysts, with a particular focus on their mechanisms for enhancing the ORR performance. Finally, the current state of research on carbon-based ORR catalysts is summarized, and future development directions are proposed, emphasizing the optimization of active sites, improvements in catalyst stability, and potential strategies for large-scale applications. Full article
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<p>Regulatory strategies of carbon-based catalysts.</p>
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<p>The Wroblowa process of oxygen electrode reactions in alkaline electrolyte.</p>
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<p>Schematic illustration of some common synthetic methods for C@NPMs: (<b>a</b>) pyrolysis; (<b>b</b>) CVD; (<b>c</b>) ALD; (<b>d</b>) ball milling. Copyright 2020, Wiley-VCH [<a href="#B91-inorganics-12-00303" class="html-bibr">91</a>].</p>
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<p>(<b>a</b>) Sketch of the electrocatalyst preparation; (<b>b</b>) Raman spectra of the electrocatalysts [<a href="#B96-inorganics-12-00303" class="html-bibr">96</a>]; (<b>c</b>) DFT pore size-distribution curves reveal the co-existence of micropores and mesopores for corresponding samples; inset figure is nitrogen adsorption–desorption isotherms; (<b>d</b>) XRD patterns of catalysts with or without ammonia chloride and further pyrolysis (PDF: 00-041-1487); (<b>e</b>) N 1s XPS spectra of samples [<a href="#B97-inorganics-12-00303" class="html-bibr">97</a>]; (<b>f</b>) ORR LSVs obtained at 5 mV s<sup>−1</sup> [<a href="#B99-inorganics-12-00303" class="html-bibr">99</a>]; (<b>g</b>) HRTEM micrograph of cc1U; the area marked by the yellow square is shown in (<b>h</b>) [<a href="#B100-inorganics-12-00303" class="html-bibr">100</a>].</p>
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<p>(<b>a</b>) A schematic diagram of nanographene showing armchair and zigzag edges with oxygen-containing groups. (<b>b</b>) The free energies for elementary steps along the reaction coordinate in ORR on the zigzag edge of graphene. (<b>c</b>) Oxygen-reduction voltammogram of GP and GP-BM resulting from ball milling for different durations. Copyright 2011, The Royal Society of Chemistry [<a href="#B104-inorganics-12-00303" class="html-bibr">104</a>]. (<b>d</b>) Schematic representation of the mechanochemical reaction between in situ-generated active carbon species and reactant gases in a sealed ball-mill crusher. Copyright 2013, American Chemical Society [<a href="#B105-inorganics-12-00303" class="html-bibr">105</a>]. (<b>e</b>) HRTEM image of CNC700. (<b>f</b>) Raman spectra. ID/IG is the area ratio of the D peak to the G peak. (<b>g</b>) Schematic structural characters of the carbon nanocages. Copyright 2015, American Chemical Society [<a href="#B103-inorganics-12-00303" class="html-bibr">103</a>].</p>
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<p>(<b>a</b>) Illustration of typical N species in carbon-skeleton charge distribution of (<b>b</b>) CNT and (<b>c</b>) NCNT. Copyright 2010, American Chemical Society [<a href="#B113-inorganics-12-00303" class="html-bibr">113</a>]. (<b>d</b>) The charge-density-difference mappings for various doping structures. Copyright 2022, Wiley-VCH [<a href="#B115-inorganics-12-00303" class="html-bibr">115</a>]. (<b>e</b>) Schematic illustration of the synthesis process. STEM (<b>f</b>) and the corresponding filtered images (<b>g</b>) of NSCA-700-1000. Copyright 2018, Elsevier [<a href="#B116-inorganics-12-00303" class="html-bibr">116</a>].</p>
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<p>(<b>a</b>) Synthesis route of single-atomically dispersed Hf catalyst. (<b>b</b>) Fourier-transformed extended X-ray absorption fine structure (EXAFS) in R-space. (<b>c</b>) In situ electrochemical Raman spectra of s-Hf-N/O-C. Copyright 2024, Wiley-VCH [<a href="#B64-inorganics-12-00303" class="html-bibr">64</a>]. (<b>d</b>) The atomic structures of Fe-N-C with six single Cs. (<b>e</b>) The free-energy diagrams of ORR on Fe-N-C with six C vacancies. (<b>f</b>) The relationship between the adsorption energy of OH* and the ΔG of the potential-determining step on Fe-N-C with six C vacancies. Copyright 2023, Wiley-VCH [<a href="#B20-inorganics-12-00303" class="html-bibr">20</a>]. (<b>g</b>) In situ confinement pyrolysis strategy to synthesize core-shell-structured Co-N-C@surfactants catalysts with increased active-site density. (<b>h</b>) ORR polarization plots. Copyright 2019, The Royal Society of Chemistry [<a href="#B119-inorganics-12-00303" class="html-bibr">119</a>].</p>
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<p>(<b>a</b>) Fe-Fe shell length calculated from operando EXAFS spectra. (<b>b</b>) Fitted average oxidation state of Fe in the planar-like Fe<sub>2</sub>N<sub>6</sub> structure according to operando XANES spectra. (<b>c</b>) Proposed ORR reaction pathways on the planar-like Fe<sub>2</sub>N<sub>6</sub> structure. Copyright 2020, Elsevier [<a href="#B122-inorganics-12-00303" class="html-bibr">122</a>]. (<b>d</b>) The dotted circles show single atoms (red) and dual-atom pairs (yellow). (<b>e</b>) Three-dimensional atom-overlapping Gaussian-function fitting map of the atom pair A<sub>1</sub>-B<sub>1</sub> highlighted in the rectangular dashed box in d. (<b>f</b>) Statistical distribution of the single atoms and dual-atom pairs in d. (<b>g</b>) Schematic illustration of the synthesis of FeCo-N<sub>3</sub>O<sub>3</sub>@C. Copyright 2024, Springer Nature [<a href="#B123-inorganics-12-00303" class="html-bibr">123</a>]. (<b>h</b>) Se K-edge Fourier-transformed EXAFS spectra of Fe<sub>1</sub>Se<sub>1</sub>-NC. (<b>i</b>) Fe K-edge Fourier-transformed EXAFS spectra in the R-space. (<b>j</b>) Fitting curves of the EXAFS of Fe SACs of Fe<sub>1</sub>Se<sub>1</sub>-NC in the R-space. Copyright 2022, Elsevier [<a href="#B124-inorganics-12-00303" class="html-bibr">124</a>].</p>
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<p>(<b>a</b>) The synthesis process of Pd/N-HsGY. Copyright 2021, The Royal Society of Chemistry [<a href="#B126-inorganics-12-00303" class="html-bibr">126</a>]. (<b>b</b>) The free-energy diagram for Pd and PdO nanoparticles during the ORR under acidic condition at the equilibrium potential. (<b>c</b>) The charge densities of HsGY repeating unit. (<b>d</b>) Calculated overpotentials of the ORR for the Pd/HsGY and Pd/N-HsGY system. (<b>e</b>) Powder XRD pattern of 37 wt% FePt/rGO and reference peak positions of the candidate phases. (<b>f</b>) Measured HAADF-STEM image of 37 wt% FePt/rGO (<b>g</b>) ORR polarization curves of NiPt/rGO and CoPt/rGO. Copyright 2020, American Chemical Society [<a href="#B127-inorganics-12-00303" class="html-bibr">127</a>]. (<b>h</b>) SEM images of NC-Co<sub>3</sub>O<sub>4</sub> nanoarrays on carbon cloth. (<b>i</b>,<b>j</b>) Colored STEM HAADF/ABF images (<b>k</b>) FFT image from (<b>j</b>); the reflections from both Co and C are indexed. Copyright 2017, Wiley-VCH [<a href="#B129-inorganics-12-00303" class="html-bibr">129</a>].</p>
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<p>(<b>a</b>) Schematic of the preparation of the bare CD-MOF, M-loaded CD-MOFs, and the M–N–C catalysts. Copyright 2023, Springer Nature [<a href="#B131-inorganics-12-00303" class="html-bibr">131</a>]. (<b>b</b>) Fourier-transform Fe K-edge EXAFS spectra of FeNC, FePNC-N, FePNC, and reference samples. (<b>c</b>) The structural model of FeN<sub>3</sub>P<sub>1</sub> and Fe<sub>2</sub>P atomic clusters. (<b>d</b>) Charge-density-difference diagrams of Feac-FeN<sub>4</sub>, Fe<sub>2</sub>Pac-FeN<sub>4</sub>, FeN<sub>3</sub>P<sub>1</sub>, and Fe<sub>2</sub>Pac-FeN<sub>3</sub>P<sub>1</sub>. Copyright 2023, Wiley-VCH [<a href="#B132-inorganics-12-00303" class="html-bibr">132</a>]. HAADF-STEM images (<b>e</b>), and atomic-resolution (<b>f</b>,<b>g</b>) HAADF-STEM images of L<sub>12</sub>-Pt<sub>3</sub>Co@MnSA-NC. Copyright 2023, American Chemical Society [<a href="#B133-inorganics-12-00303" class="html-bibr">133</a>]. (<b>h</b>) Comparison of E<sub>1/2</sub> between Fe<sub>SAs+NPs</sub>Ce<sub>SAs+Fe-ONPs</sub>/NC and control catalysts. Copyright 2024, Wiley-VCH [<a href="#B134-inorganics-12-00303" class="html-bibr">134</a>].</p>
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17 pages, 3415 KiB  
Article
Study on the Scale-Up Possibility of a Combined Wet Grinding Technique Intended for Oral Administration of Meloxicam Nanosuspension
by Csilla Bartos, Anett Motzwickler-Németh, Dávid Kovács, Katalin Burián and Rita Ambrus
Pharmaceutics 2024, 16(12), 1512; https://doi.org/10.3390/pharmaceutics16121512 - 25 Nov 2024
Viewed by 174
Abstract
Background/Objectives: This article reports on the scalability of a combined wet grinding technique applying planetary ball mill and ZrO2 pearls as the grinding medium. After the determination of the parameters in a laboratory scale, the tenfold scale-up method was set. Meloxicam (MEL) [...] Read more.
Background/Objectives: This article reports on the scalability of a combined wet grinding technique applying planetary ball mill and ZrO2 pearls as the grinding medium. After the determination of the parameters in a laboratory scale, the tenfold scale-up method was set. Meloxicam (MEL) was used as a nonsteroidal anti-inflammatory drug (NSAID) intended for per os delivery. During grinding, the PVA solution was used as a dispersion medium. Methods: The influence of the scaling-up on the particle size, morphology, crystallinity, and intra- and interparticulate phenomena has been studied. Formulation investigations of the milled suspensions were carried out. The dissolution test and the cytotoxicity analyses were accomplished. Results: Submicron MEL particle-containing samples were produced in both grinding scales. After the particle size determination was achieved from the suspensions, the wet milled, dried products were studied. The particle size of the dried products fell into the same range for both scales of milling (the maximum particle size was about 580 nm). There was no significant difference in drug crystallinity after the grindings; 70% of MEL remained crystalline in both cases. A remarkable interaction between the components did not develop as a result of milling. The polarity of the products increased, which resulted in a better dissolution, especially in the case of intestinal fluid (~100% in the first 5 min). The products were not found to be toxic. Conclusions: This research demonstrates that the scaling-up of combined wet grinding technique is feasible by adjusting the milling parameters and the adequate amount of excipient. Full article
(This article belongs to the Special Issue Advances in Oral Administration)
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<p>The picture of the planetary ball mill (<b>A</b>) and the schematic view of the ball mill (<b>B</b>).</p>
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<p>The photo of initial MEL (<b>A</b>), untreated suspended MEL (<b>B</b>), and MEL milled at different scales (<b>C</b>,<b>D</b>).</p>
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<p>SEM pictures of rawMEL (<b>A</b>), of dried untreated suspension of MEL (<b>B</b>), of MEL milled in laboratory scale (<b>C</b>), and of MEL milled at scaled-up conditions (<b>D</b>).</p>
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<p>XRPD patterns of rawMEL, of dried untreated suspension of MEL, and of MEL milled at different scales.</p>
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<p>DSC thermograms of rawMEL, of dried untreated suspension of MEL, and of MEL milled at different scales.</p>
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<p>FTIR spectra of rawMEL, of dried untreated suspension of MEL, and of MEL milled at different scales.</p>
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<p>In vitro dissolution profile of initial and milled suspensions filled into capsules in artificial gastric fluid (<b>A</b>) and in artificial intestinal fluid (<b>B</b>).</p>
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<p>Cytotoxicity of the untreated and milled suspensions as a function of concentration on a Caco-2 cell line.</p>
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18 pages, 1880 KiB  
Article
Effects of Three Modification Methods on the In Vitro Gastrointestinal Digestion and Colonic Fermentation of Dietary Fiber from Lotus Leaves
by Hui Zheng, Yao Xu, Yuhang Wu, Xuantong Huangfu, Wenxiu Chen, Kai He and Yong Yang
Foods 2024, 13(23), 3768; https://doi.org/10.3390/foods13233768 - 24 Nov 2024
Viewed by 385
Abstract
Shear emulsifying (SE), ball milling (BM), and autoclave treatment (AT) were utilized for the modification of lotus leaves, and the effects on in vitro gastrointestinal digestion and colonic fermentation of insoluble dietary fiber (IDF) from lotus leaves were compared. Compared with SEIDF and [...] Read more.
Shear emulsifying (SE), ball milling (BM), and autoclave treatment (AT) were utilized for the modification of lotus leaves, and the effects on in vitro gastrointestinal digestion and colonic fermentation of insoluble dietary fiber (IDF) from lotus leaves were compared. Compared with SEIDF and ATIDF, BMIDF released more polyphenols and exhibited better antioxidant capacity during in vitro gastrointestinal digestion. The IDF of lotus leaves changed the gut microbiota composition during in vitro colonic fermentation. SEIDF was beneficial to the diversity of gut microbiota compared with BMIDF and ATIDF. Among the three IDF groups of lotus leaves, six significant differences of OTUs were all in ATIDF; however there was the highest relative abundance of Escherichia-Shigella in ATIDF. In addition, the concentrations of butyric acid and valeric acid produced by SEIDF were significantly higher than that of BMIDF and ATIDF. Overall, SE modification improved the colonic fermentation characteristics of IDFs in lotus leaves more effectively; while BM modification helped to promote the release of polyphenols from IDFs in lotus leaves during in vitro gastrointestinal digestion. The research lays the foundation for the application of the dietary fiber of lotus leaves as a premium fiber additive in functional food. Full article
(This article belongs to the Special Issue Advanced Research and Development of Carbohydrate from Foods)
19 pages, 2959 KiB  
Article
A Green Chemistry Approach to Catalytic Synthesis of Ethyl Levulinate
by Martina Sušjenka, Fran Prašnikar, Martina Jakovljević Kovač, Maja Molnar, Luz Fernandes, Ana Vital Marques Nunes, Ana Rita Cruz Duarte and Małgorzata Ewa Zakrzewska
Catalysts 2024, 14(12), 842; https://doi.org/10.3390/catal14120842 - 21 Nov 2024
Viewed by 278
Abstract
Esterification of levulinic acid with ethanol was investigated using deep eutectic systems based on choline chloride and oxalic or p-toluenesulfonic acid as catalysts under conventional heating and alternative energy inputs, namely microwave, ultrasound, and mechanochemical treatment. The experiments were performed under varying operating [...] Read more.
Esterification of levulinic acid with ethanol was investigated using deep eutectic systems based on choline chloride and oxalic or p-toluenesulfonic acid as catalysts under conventional heating and alternative energy inputs, namely microwave, ultrasound, and mechanochemical treatment. The experiments were performed under varying operating conditions such as catalyst type and loading, alcohol to carboxylic acid molar ratio, temperature, or time. The obtained results demonstrate the overall better catalytic performance of the p-toluenesulfonic acid-based deep eutectic mixture in comparison with the oxalic acid-based analogue. The best results: levulinic acid conversion of 76% and 58%, for p-toluenesulfonic and oxalic acid containing deep eutectic systems, respectively, with 100% selectivity for both cases, were achieved for microwave-assisted synthesis with 5 wt.% of catalyst and excess alcohol to acid (molar ratio 5), at 413.15 K and for 10 min. The main advantage of all of the alternative activation methods studied (microwaves, ultrasounds, and ball mill processing) was the significant reduction in the reaction time. Full article
(This article belongs to the Special Issue Ionic Liquids and Eutectic Mixtures for Green Catalytic Processes)
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<p>The main routes of ester synthesis.</p>
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<p>Mass-based liquid–liquid phase diagrams for pseudo-ternary systems composed of (<b>a</b>) LA, EL, and DES (circles, ChCl:OxAc, or triangles, ChCl:pTSA), or (<b>b</b>) EtOH, EL, and DES (squares, ChCl:OxAc, or diamonds, ChCl:pTSA), at 313.15 K (filled symbols) and 333.15 K (empty symbols).</p>
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<p>Mass-based liquid–liquid phase diagrams for pseudo-ternary systems composed of (<b>a</b>) LA, EL, and DES (circles, ChCl:OxAc, or triangles, ChCl:pTSA), or (<b>b</b>) EtOH, EL, and DES (squares, ChCl:OxAc, or diamonds, ChCl:pTSA), at 313.15 K (filled symbols) and 333.15 K (empty symbols).</p>
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<p>Effect of the ChCl:OxAc loading on the esterification of LA to EL (circles with continuous line, LA conversion; triangles with dotted line, EL yield; and diamonds with dashed line, EL selectivity), at 343.15 K, 3 h, and alcohol:acid alcohol:acid molar ratio of 5.</p>
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<p>Influence of process temperature on the esterification of LA to (circles with continuous line, LA conversion; triangles with dotted line, EL yield; and diamonds with dashed lines EL selectivity) at 343.15 K, 3 h, and for 5 wt.% of ChCl:OxAc catalyst and alcohol:acid molar ratio of 5.</p>
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<p>Kinetic data for the esterification of LA to EL (circles with continuous line, LA conversion; triangles with dotted line, EL yield; and diamonds with dashed line, EL selectivity), at 343.15 K, and for 5 wt.% of ChCl:OxAc catalyst and alcohol:acid molar ratio of 5.</p>
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<p>Effect of the alcohol to acid ratio on the esterification of LA to EL (circles with continuous line, LA conversion; triangles with dotted line, EL yield; and diamonds with dashed line, EL selectivity) for 5 wt.% of ChCl:OxAc catalyst, 3 h, and at 343.15 K.</p>
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<p>Ultrasound-mediated esterification of LA to EL with an alcohol:acid molar ratio of 5 at 343.15 K and 5 wt.% of (<b>a</b>) ChCl:OxAc (empty symbols) or (<b>b</b>) ChCl:pTSA (filled symbols); (circles with continuous lines, LA conversion; triangles with dotted lines, and EL yield; diamonds with dashed lines, EL selectivity).</p>
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<p>Mechanosynthesis of EL from LA and EtOH with an alcohol:acid molar ratio of 5 at 343.15 K and 5 wt.% of (<b>a</b>) ChCl:OxAc (empty symbols) or (<b>b</b>) ChCl:pTSA (filled symbols); (circles with continuous lines, LA conversion; triangles with dotted lines, EL yield; and diamonds with dashed lines, EL selectivity).</p>
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<p>Microwave-mediated esterification of EL from LA and EtOH with an alcohol:acid molar ratio of 5 at 343.15 K and 5 wt.% of (<b>a</b>) ChCl:OxAc (empty symbols) or (<b>b</b>) ChCl:pTSA (filled symbols); (circles with continuous lines, LA conversion; triangles with dotted lines, EL yield; and diamonds with dashed lines, EL selectivity).</p>
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<p>Influence of the temperature on the microwave-assisted esterification of LA to EL with an alcohol:acid molar ratio of 5 during 10 min and 5 wt.% of (<b>a</b>) ChCl:OxAc (empty symbols) or (<b>b</b>) ChCl:pTSA (filled symbols); (circles with continuous lines, LA conversion; triangles with dotted lines, EL yield; and diamonds with dashed lines, EL selectivity).</p>
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<p>Tentative mechanism of esterification of levulinic acid with ethanol in the presence of ChCl:OxAc DES.</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 240
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
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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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14 pages, 23867 KiB  
Article
Solid-State Synthesis for High-Tetragonality, Small-Particle Barium Titanate
by Tianyu Hao, Jing Shen, Qiaochu Peng, Jie Liu, Wenbin Hu and Cheng Zhong
Materials 2024, 17(22), 5655; https://doi.org/10.3390/ma17225655 - 20 Nov 2024
Viewed by 250
Abstract
This study successfully synthesized high-tetragonality barium titanate (BaTiO3) particles with a small particle size by implementing ball milling in the solid-state synthesis of BaTiO3 and utilizing nanoscale raw materials. This study also addressed the issues of impurities and uneven particle [...] Read more.
This study successfully synthesized high-tetragonality barium titanate (BaTiO3) particles with a small particle size by implementing ball milling in the solid-state synthesis of BaTiO3 and utilizing nanoscale raw materials. This study also addressed the issues of impurities and uneven particle size distribution that could exist in the synthesized BaTiO3 particles. The crystal structure, morphology, and particle size of the synthesized BaTiO3 particles have been meticulously analyzed and discussed through the use of techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), and the laser particle size analyzer. BaTiO3 has been successfully synthesized, exhibiting a uniform particle size with an average diameter of 170 nm and a high tetragonality value of 1.01022. This new solid-state synthesis method provided insights to avoid the impact of “size effects” during the process of electronic device miniaturization. Full article
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<p>Flow chart for the preparation of BaTiO<sub>3</sub> samples.</p>
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<p>XRD pattern of BaTiO<sub>3</sub> sample BT-TS.</p>
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<p>Main XRD patterns of BaTiO<sub>3</sub> samples synthesized with and without ball milling: (<b>a</b>) BT0-0, (<b>b</b>) BT0-1, (<b>c</b>) BT1-0, and (<b>d</b>) BT1-1.</p>
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<p>SEM images of BaTiO<sub>3</sub> samples synthesized with and without ball milling: (<b>a</b>) BT0-0, (<b>b</b>) BT0-1, (<b>c</b>) BT1-0, and (<b>d</b>) BT1-1.</p>
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<p>XRD patterns of BaTiO<sub>3</sub> samples synthesized by BaCO<sub>3</sub> with different particle sizes: (<b>a</b>) BC-μm and (<b>b</b>) BC-nm.</p>
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<p>XRD patterns of BaTiO<sub>3</sub> samples synthesized using different sizes of TiO<sub>2</sub> precursors: (<b>a</b>) XRD patterns of BT5-10, BT25, and BT40; (<b>b</b>) XRD patterns of BT5-10, BT25, and BT40 after amplification.</p>
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<p>SEM images of BT5-10, BT25, and BT40: (<b>a</b>) SEM image of BT5-10; (<b>b</b>) SEM image of BT25; (<b>c</b>) SEM image of BT40.</p>
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<p>EDS images of BT5-10.</p>
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<p>XPS images of BT5-10: (<b>a</b>) full spectra XPS of BT5-10; (<b>b</b>) High resolution XPS spectra of C 2<span class="html-italic">p</span>.</p>
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11 pages, 6860 KiB  
Article
Effect of Powder Preparation Techniques on Microstructure, Mechanical Properties, and Wear Behaviors of Graphene-Reinforced Copper Matrix Composites
by Doan Dinh Phuong, Pham Van Trinh, Phan Ngoc Minh, Alexandr A. Shtertser and Vladimir Y. Ulianitsky
Crystals 2024, 14(11), 1000; https://doi.org/10.3390/cryst14111000 - 19 Nov 2024
Viewed by 294
Abstract
In this study, the effect of powder preparation techniques on microstructure, mechanical properties, and wear behaviors of graphene-reinforced copper matrix (Gr/Cu) composites was investigated. The composite powders were prepared by two different techniques including high-energy ball (HEB) milling and nanoscale dispersion (ND). The [...] Read more.
In this study, the effect of powder preparation techniques on microstructure, mechanical properties, and wear behaviors of graphene-reinforced copper matrix (Gr/Cu) composites was investigated. The composite powders were prepared by two different techniques including high-energy ball (HEB) milling and nanoscale dispersion (ND). The obtained results showed that the ND technique allows the preparation of the composite powder with a smaller and more uniform grain size compared to the HEB technique. By adding Gr, the mechanical properties and wear resistance of the composite were much improved compared to pure Cu. In addition, the composite using the powder prepared by the ND technique exhibits the best performance with the improvement in hardness (40%), tensile strength (66%) and wear resistance (38%) compared to pure Cu. This results from the uniform grain size of the Cu matrix and the good bonding between Cu matrix and Gr. The strengthening mechanisms were also analyzed to clarify the contribution of the powder preparation techniques on the load transfer strengthening mechanisms of the prepared composite. Full article
(This article belongs to the Special Issue Processing, Structure and Properties of Metal Matrix Composites)
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<p>Schematic view of the preparation process for Gr/Cu powder by using high energy ball milling (HEB-Approach 1) and nanoscale dispersion (ND, Approach 2).</p>
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<p>SEM images of (<b>a</b>) Cu powder and (<b>b</b>) graphene powders.</p>
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<p>Sintering process of Gr/Cu composite by hot isostatic pressing technique.</p>
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<p>SEM images and EDS spectra of Gr/Cu powder prepared by using different techniques (<b>a</b>) HEB and (<b>b</b>) ND.</p>
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<p>SEM images of Gr/Cu composite using powder prepared by using different techniques: (<b>a</b>) HEB and (<b>b</b>) ND.</p>
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<p>EBSD inverse pole figure (IPF) maps of (<b>a</b>) pure Cu (HEB), (<b>b</b>) Gr/Cu (HEB), (<b>c</b>) pure Cu (ND), and (<b>d</b>) Gr/Cu (ND).</p>
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<p>(<b>a</b>) XRD patterns and (<b>b</b>) crystallite size of pure Cu and Gr/Cu with powder prepared by HEB and ND techniques.</p>
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<p>(<b>a</b>) Microhardness and (<b>b</b>) tensile strength of pure Cu and Gr/Cu with powder prepared by HEB and ND techniques.</p>
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<p>Contribution of strengthening mechanisms to the yield strength of Gr/Cu composites with powder prepared by HEB technique.</p>
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<p>Contribution of strengthening mechanisms to the yield strength of Gr/Cu composites with powder prepared by ND technique.</p>
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<p>(<b>a</b>,<b>b</b>) Friction coefficient and (<b>c</b>) wear rate of pure Cu and Gr/Cu with powder prepared by HEB and ND techniques.</p>
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12 pages, 4508 KiB  
Article
Nanocrystalline/Amorphous Tuning of Al–Fe–Nb (Mn) Alloy Powders Produced via High-Energy Ball Milling
by Nguyen Thi Hoang Oanh, Dao Truong An and Nguyen Hoang Viet
Materials 2024, 17(22), 5627; https://doi.org/10.3390/ma17225627 - 18 Nov 2024
Viewed by 676
Abstract
The demand for advanced Al-based alloys with tailored structural and magnetic properties has intensified for applications requiring a high thermal stability and performance under challenging conditions. This study investigated the phase evolution, magnetic properties, thermal stability, and microstructural changes in the Al-based alloys [...] Read more.
The demand for advanced Al-based alloys with tailored structural and magnetic properties has intensified for applications requiring a high thermal stability and performance under challenging conditions. This study investigated the phase evolution, magnetic properties, thermal stability, and microstructural changes in the Al-based alloys Al82Fe16Nb2 and Al82Fe14Nb2Mn2, synthesized via mechanical alloying (MA), using stearic acid as a process control agent. The X-ray diffraction results indicated that Al82Fe16Nb2 achieved a β-phase solid solution with 13–14 nm crystallite sizes after 5 h of milling, reaching an amorphous state after 10 h. In contrast, Al82Fe14Nb2Mn2 formed a partially amorphous structure within 10 h, with enhanced stability with additional milling. Magnetic measurements indicated that both alloys possessed soft magnetic behavior under shorter milling times (1–5 h) and transitioned to hard magnetic behavior as amorphization progressed. This phenomenon was associated with a decrease in saturation magnetization (Ms) and an increase in coercivity (Hc) due to structural disorder and residual stresses. Thermal stability analyses on 10 h milled samples conducted via differential scanning calorimetry showed exothermic peaks between 300 and 800 °C, corresponding to phase transformations upon heating. Post-annealing analyses at 550 °C demonstrated the presence of phases including Al, β-phase solid solutions, Al₁3Fe₄, and residual amorphous regions. At 600 °C, the Al3Nb phase emerged as the β-phase, and the amorphous content decreased, while annealing at 700 °C fully decomposed the amorphous phases into stable crystalline forms. Microstructural analyses demonstrated a consistent reduction in and homogenization of particle sizes, with particles decreasing to 1–3 μm in diameter after 10 h. Altogether, these findings highlight MA’s effectiveness in tuning the microstructure and magnetic properties of Al–Fe–Nb (Mn) alloys, making these materials suitable for applications requiring a high thermal stability and tailored magnetic responses. Full article
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<p>Surface morphology of starting elemental powders of (<b>a</b>) Al, (<b>b</b>) Fe, (<b>c</b>) Nb, and (<b>d</b>) Mn.</p>
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<p>XRD patterns of starting mixture powders of (<b>a</b>) Al–Fe–Nb and (<b>b</b>) Al–Fe–Nb–Mn.</p>
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<p>XRD patterns of (<b>a</b>) Al<sub>82</sub>Fe<sub>16</sub>Nb<sub>2</sub> and (<b>b</b>) Al<sub>82</sub>Fe<sub>14</sub>Nb<sub>2</sub>Mn<sub>2</sub> powders milled for different milling times.</p>
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<p>SEM micrographs of the Al<sub>82</sub>Fe<sub>16</sub>Nb<sub>2</sub> powders milled for (<b>a</b>) 1 h, (<b>b</b>) 2 h, (<b>c</b>) 5 h, and (<b>d</b>) 10 h.</p>
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<p>SEM micrographs of the Al<sub>82</sub>Fe<sub>14</sub>Nb<sub>2</sub>Mn<sub>2</sub> powders milled for (<b>a</b>) 1 h, (<b>b</b>) 2 h, (<b>c</b>) 5 h, and (<b>d</b>) 10 h.</p>
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<p>Hysteresis curves of Al<sub>82</sub>Fe<sub>16</sub>Nb<sub>2</sub> powders milled for different milling times.</p>
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<p>Hysteresis curves of Al<sub>82</sub>Fe<sub>14</sub>Nb<sub>2</sub>Mn<sub>2</sub> powders milled for different milling times.</p>
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<p>DSC curves of the powder compositions (<b>a</b>) Al<sub>82</sub>Fe<sub>16</sub>Nb<sub>2</sub> and (<b>b</b>) Al<sub>82</sub>Fe<sub>14</sub>Nb<sub>2</sub>Mn<sub>2</sub>. Powders were milled for 10 h, and DSC was performed after heating from room temperature to 800 °C.</p>
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<p>XRD patterns for Al<sub>82</sub>Fe<sub>16</sub>Nb<sub>2</sub>: (<b>a</b>) a mixture of powders (Al, Fe, and Nb); powders milled for (<b>b</b>) 2 h and (<b>c</b>) 10 h, followed by heat treatment for 15 min at (<b>d</b>) 550 °C, (<b>e</b>) 600 °C, and (<b>f</b>) 700 °C.</p>
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<p>XRD patterns for Al<sub>82</sub>Fe<sub>14</sub>Nb<sub>2</sub>Mn<sub>2</sub>: (<b>a</b>) a mixture of powders (Al, Fe, Nb, and Mn); powders milled for (<b>b</b>) 2 h and (<b>c</b>) 10 h, followed by heat treatment for 15 min at (<b>d</b>) 550 °C, (<b>e</b>) 600 °C, and (<b>f</b>) 700 °C.</p>
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15 pages, 7304 KiB  
Article
Preparation and Characteristics of Ball-Milled Blueberry Peel Particles and Their Application in Ice Cream
by Li-Hua Pan, Jia-Hui Lin, Mei-Jia Li, Lei Cao, Xiao-Yu Liu, Yuan-Yuan Deng, Shui-Zhong Luo and Zhi Zheng
Foods 2024, 13(22), 3660; https://doi.org/10.3390/foods13223660 - 17 Nov 2024
Viewed by 382
Abstract
Ice cream is popular but contains high amounts of saturated fats and few health-promoting ingredients. In the presence of xanthan gum (0.25%), blueberry peel particles prepared through ball-milling treatment (BMPs) were used to prepare ice cream containing camellia oil as a fat replacer. [...] Read more.
Ice cream is popular but contains high amounts of saturated fats and few health-promoting ingredients. In the presence of xanthan gum (0.25%), blueberry peel particles prepared through ball-milling treatment (BMPs) were used to prepare ice cream containing camellia oil as a fat replacer. The BMPs possessed smaller particle sizes, larger contact angles, and higher contents of anthocyanin aglycone compared with commonly milled blueberry peel particles. BMPs with the largest contact angle (66.30°) were obtained by ball-milling the blueberry peel at 15 Hz for 6 h (BMP15Hz6h). The ice cream mixes were depicted as linear viscoelastic gel-like solids, and their apparent viscosity, G′ and G′, increased with the increase in the BMP15Hz6h concentration. Ice cream with strong antioxidant activity and good freeze–thaw stability was acceptable and desirable in the presence of 0.5% BMP15Hz6h. Full article
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<p>Effects of ball milling frequency and ball milling time on contact angle (<b>A</b>) and microstructure (<b>B</b>) of blueberry peel particles.</p>
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<p>Rheological properties of ice cream mixes with different levels of BMP<sub>15Hz1.5h</sub> added. (<b>A</b>), G’, storage modulus; (<b>B</b>), apparent viscosity.</p>
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<p>Antioxidant activities (<b>A</b>), storage physical stability (<b>B</b>), and sensory scores (<b>C</b>,<b>D</b>) of ice cream prepared with different levels of BMP<sub>15Hz1.5h</sub>. Means with different lowercase letters in the same row are significantly different (<span class="html-italic">p</span> &lt; 0.05).</p>
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<p>Visuals (<b>A</b>), optical microscopy images (<b>B</b>), and confocal micrographs (<b>C</b>) of ice cream prepared with different levels of BMP<sub>15Hz1.5h</sub>. (Red and green in (<b>C</b>) represent fat globules and protein granules, respectively.)</p>
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18 pages, 14402 KiB  
Article
Steel Chips as a Raw Material for MEX
by Catarina Duarte Batista and Maria Teresa Freire Vieira
Metals 2024, 14(11), 1293; https://doi.org/10.3390/met14111293 - 15 Nov 2024
Viewed by 371
Abstract
In recent years, metal chip powders obtained from solid-state processes have shown great potential as a sustainable raw material for powder technologies. The material and fragmentation process of the chips has a significant role in the final characteristics of the powder particles, such [...] Read more.
In recent years, metal chip powders obtained from solid-state processes have shown great potential as a sustainable raw material for powder technologies. The material and fragmentation process of the chips has a significant role in the final characteristics of the powder particles, such as size and particle size distribution, shape, surface, and structure, which are essential parameters to consider when converting chips to powder for applications. However, tool steel chips as a powder raw material have not yet been significantly studied. In this study, the steel chips were from machining AISI H13 steel and the milling process used a ball mill, and the challenge was to obtain powder particle sizes of around 20 µm with suitable properties from the application of envisaged material extrusion (MEX). A comparison study with the commercial raw material for MEX, such as powder metal filament extrusion, was performed. This study highlights the behaviors of chip powders during all steps of MEX, namely, feedstock and filament production, 3D object shaping, thermal de-binding, and sintering. A comparison of the mixture based on powder from chips and commercial powders for MEX was performed after evaluating the mixing torque of the powder and the system of binders and additives suitable for the rheological characteristics required for an extrusion mixture, and optimizing the binder removal and the sintering conditions. The 3D objects resulting from chip powders had a refined microstructure, showing an increase of 15% in the microhardness when compared with the those resulting from commercial powders. Full article
(This article belongs to the Special Issue Advances in Recycling and Reuse of Metals)
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<p>Publications on chip milling: (<b>a</b>) evolution in the last years by the type of metallic material [<a href="#B2-metals-14-01293" class="html-bibr">2</a>,<a href="#B3-metals-14-01293" class="html-bibr">3</a>,<a href="#B4-metals-14-01293" class="html-bibr">4</a>,<a href="#B5-metals-14-01293" class="html-bibr">5</a>,<a href="#B6-metals-14-01293" class="html-bibr">6</a>,<a href="#B7-metals-14-01293" class="html-bibr">7</a>,<a href="#B8-metals-14-01293" class="html-bibr">8</a>,<a href="#B9-metals-14-01293" class="html-bibr">9</a>,<a href="#B10-metals-14-01293" class="html-bibr">10</a>,<a href="#B11-metals-14-01293" class="html-bibr">11</a>,<a href="#B12-metals-14-01293" class="html-bibr">12</a>,<a href="#B13-metals-14-01293" class="html-bibr">13</a>,<a href="#B14-metals-14-01293" class="html-bibr">14</a>,<a href="#B15-metals-14-01293" class="html-bibr">15</a>,<a href="#B16-metals-14-01293" class="html-bibr">16</a>,<a href="#B17-metals-14-01293" class="html-bibr">17</a>,<a href="#B18-metals-14-01293" class="html-bibr">18</a>,<a href="#B19-metals-14-01293" class="html-bibr">19</a>,<a href="#B20-metals-14-01293" class="html-bibr">20</a>,<a href="#B21-metals-14-01293" class="html-bibr">21</a>,<a href="#B22-metals-14-01293" class="html-bibr">22</a>,<a href="#B23-metals-14-01293" class="html-bibr">23</a>,<a href="#B24-metals-14-01293" class="html-bibr">24</a>,<a href="#B25-metals-14-01293" class="html-bibr">25</a>,<a href="#B26-metals-14-01293" class="html-bibr">26</a>,<a href="#B27-metals-14-01293" class="html-bibr">27</a>,<a href="#B28-metals-14-01293" class="html-bibr">28</a>,<a href="#B29-metals-14-01293" class="html-bibr">29</a>,<a href="#B30-metals-14-01293" class="html-bibr">30</a>,<a href="#B31-metals-14-01293" class="html-bibr">31</a>,<a href="#B32-metals-14-01293" class="html-bibr">32</a>,<a href="#B33-metals-14-01293" class="html-bibr">33</a>,<a href="#B34-metals-14-01293" class="html-bibr">34</a>,<a href="#B35-metals-14-01293" class="html-bibr">35</a>,<a href="#B36-metals-14-01293" class="html-bibr">36</a>,<a href="#B37-metals-14-01293" class="html-bibr">37</a>,<a href="#B38-metals-14-01293" class="html-bibr">38</a>] and (<b>b</b>) by the milling process versus material [<a href="#B2-metals-14-01293" class="html-bibr">2</a>,<a href="#B3-metals-14-01293" class="html-bibr">3</a>,<a href="#B4-metals-14-01293" class="html-bibr">4</a>,<a href="#B5-metals-14-01293" class="html-bibr">5</a>,<a href="#B6-metals-14-01293" class="html-bibr">6</a>,<a href="#B7-metals-14-01293" class="html-bibr">7</a>,<a href="#B8-metals-14-01293" class="html-bibr">8</a>,<a href="#B9-metals-14-01293" class="html-bibr">9</a>,<a href="#B10-metals-14-01293" class="html-bibr">10</a>,<a href="#B11-metals-14-01293" class="html-bibr">11</a>,<a href="#B12-metals-14-01293" class="html-bibr">12</a>,<a href="#B13-metals-14-01293" class="html-bibr">13</a>,<a href="#B14-metals-14-01293" class="html-bibr">14</a>,<a href="#B15-metals-14-01293" class="html-bibr">15</a>,<a href="#B16-metals-14-01293" class="html-bibr">16</a>,<a href="#B17-metals-14-01293" class="html-bibr">17</a>,<a href="#B18-metals-14-01293" class="html-bibr">18</a>,<a href="#B19-metals-14-01293" class="html-bibr">19</a>,<a href="#B20-metals-14-01293" class="html-bibr">20</a>,<a href="#B21-metals-14-01293" class="html-bibr">21</a>,<a href="#B22-metals-14-01293" class="html-bibr">22</a>,<a href="#B23-metals-14-01293" class="html-bibr">23</a>,<a href="#B24-metals-14-01293" class="html-bibr">24</a>,<a href="#B25-metals-14-01293" class="html-bibr">25</a>,<a href="#B26-metals-14-01293" class="html-bibr">26</a>,<a href="#B27-metals-14-01293" class="html-bibr">27</a>,<a href="#B28-metals-14-01293" class="html-bibr">28</a>,<a href="#B29-metals-14-01293" class="html-bibr">29</a>,<a href="#B30-metals-14-01293" class="html-bibr">30</a>,<a href="#B31-metals-14-01293" class="html-bibr">31</a>,<a href="#B32-metals-14-01293" class="html-bibr">32</a>,<a href="#B35-metals-14-01293" class="html-bibr">35</a>,<a href="#B37-metals-14-01293" class="html-bibr">37</a>].</p>
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<p>AISI H13 steel chips.</p>
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<p>Micrographs (SEM) of AISI H13 steel chips: (<b>a</b>) morphology, (<b>b</b>) front surface, and (<b>c</b>) back surface.</p>
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<p>Micrographs (SEM) of Sandvick Osprey’s atomized AISI H13 steel powder at different magnifications: (<b>a</b>) 5000×, (<b>b</b>) 10,000×, and (<b>c</b>) 37,500×.</p>
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<p>Chip EBSD.</p>
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<p>EBSD of chip with identification of LAGBs (5–15°; green) and HAGBs (15–180°; blue).</p>
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<p>Chip diffractogram.</p>
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<p>Size distribution at different milling conditions (A and B).</p>
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<p>Micrography (SEM) of chip powders particles at different magnifications: (<b>a</b>) 500×, (<b>b</b>) 5000×, and (<b>c</b>) 10,000×.</p>
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<p>Particle size distribution of powder particles from chips with d<sub>max</sub> &lt; 30 µm.</p>
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<p>EBSD of powders from milling chips.</p>
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<p>EBSD of the chip with identification of LAGBs (5–15°; green) and HAGBs (15–180°; blue).</p>
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<p>Chip powder diffractogram.</p>
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<p>Variation of mixing torque of the different H13 steel powders and chip powder contents.</p>
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<p>Thermogravimetric analysis of selected mixtures in He atmosphere.</p>
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<p>Filaments produced with feedstock from (<b>a</b>) chip powder (55% vol.) and (<b>b</b>) commercial powder (55% vol.).</p>
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<p>Micrographs (SEM) of the filament chip powder (55% vol.): (<b>a</b>) global, (<b>b</b>) edge, and (<b>c</b>) center.</p>
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<p>Micrographs (SEM) of the filament commercial powder (55% vol.): (<b>a</b>) global, (<b>b</b>) edge, and (<b>c</b>) center.</p>
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<p>Microtomography of the filament (55% vol.) from (<b>a</b>) chip powder and (<b>b</b>) commercial powder.</p>
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<p>Maximum flexural strength of the filaments. Right: chip powder (55% vol.) and left: commercial powder (55% vol.).</p>
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<p>Cylinders produced through MEX from (<b>a</b>) chip powder and (<b>b</b>) commercial powder.</p>
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<p>Micro-CT of a 3D-shaped green object from feedstock: (<b>a</b>) chip powder and (<b>b</b>) commercial powder.</p>
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<p>Thermal cycle of de-binding and sintering.</p>
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<p>Micro-CT of the 3D object after sintering from feedstock with (<b>a</b>) chip powder and (<b>b</b>) commercial powder.</p>
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<p>Micrographs (OM) after etching by Nital reagent of 3D objects sintered from (<b>a</b>) chip powder and (<b>b</b>) commercial powder.</p>
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20 pages, 13368 KiB  
Article
Effect of Surface-Textured AlSiTiN Coating Parameters on the Performance of Ball-End Milling Cutter in Titanium Alloy Milling
by Shucai Yang, Dongqi Yu and Dawei Wang
Coatings 2024, 14(11), 1458; https://doi.org/10.3390/coatings14111458 - 15 Nov 2024
Viewed by 456
Abstract
In the high-speed milling of titanium alloys, the combined application of surface texture and coatings can significantly enhance the performance of cemented carbide tools. Investigating the synergistic effect of surface texture and AlSiTiN coating on tool performance is crucial for advancing the development [...] Read more.
In the high-speed milling of titanium alloys, the combined application of surface texture and coatings can significantly enhance the performance of cemented carbide tools. Investigating the synergistic effect of surface texture and AlSiTiN coating on tool performance is crucial for advancing the development of their integrated preparation process. Therefore, in this study, a cemented carbide ball-end milling cutter is taken as the research object, and a surface-textured AlSiTiN coating is applied to the rake face. The effects of texture and coating parameters on the milling performance of titanium alloys are analyzed, and a regression model is developed to optimize the relevant parameters. The results indicate that the surface texture effectively reduces the actual contact area between the tool and the chip, serves as a storage space for chips, and enhances the wear resistance of the AlSiTiN coating. The coating thickness significantly affects milling force, milling temperature, and surface wear. An increase in coating thickness improves the hardness and integrity of the coating surface, and it also strengthens the adhesion of the texture to the coating. Additionally, precise control of the laser power plays a key role in reducing the milling temperature, while both the number of scans and the scanning speed significantly influence surface wear. Furthermore, maintaining an appropriate distance from the edge is crucial for enhancing the surface roughness of the workpiece. The optimized parameters for surface texture and coating preparation are as follows: coating thickness (h) = 3.0 µm, laser power (p) = 40 W, scanning speed (v) = 1590 µm/min, number of scans (n) = 6, texture diameter (d) = 42 µm, texture spacing (l) = 143 µm, and distance from the edge (l1) = 104 µm. The optimized milling performance of the milling cutter shows a significant improvement. Full article
(This article belongs to the Special Issue Cutting Performance of Coated Tools)
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<p>Coating deposition and surface texture preparation of ball-end milling cutter.</p>
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<p>Test equipment and data measuring device.</p>
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<p>Significant findings and the influence trends of each parameter on the milling force.</p>
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<p>Mechanism diagram of the influence of coating and texture preparation parameters on milling force.</p>
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<p>Significant findings and the influence trends of each parameter on the milling temperature.</p>
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<p>Mechanism diagram of the influence of coating and texture preparation parameters on milling temperature.</p>
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<p>Part of ball-end milling cutter wear morphology of the rake face tool–chip contact area.</p>
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<p>Significant findings and the influence trends of each parameter on the surface wear of ball-end milling cutter.</p>
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<p>Mechanism diagram of the influence of coating and texture preparation parameters on the surface wear of ball-end milling cutter.</p>
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<p>Significant findings and the influence trends of each parameter on the surface roughness of workpieces.</p>
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<p>Different evaluation index regression model residual Quantile–Quantile plot.</p>
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<p>Flow chart of artificial bee colony algorithm optimization parameters and comparison of milling performance results before and after optimization of coating and texture parameters.</p>
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12 pages, 4933 KiB  
Article
Mineral Liberation and Concentration Characteristics of Apatite Comminuted by High-Pressure GRU
by Yongbo Fan, Genghao Zhang, Shihai Li, Li Zhang, Jianqiang Guo and Chun Feng
Minerals 2024, 14(11), 1148; https://doi.org/10.3390/min14111148 - 13 Nov 2024
Viewed by 327
Abstract
Mineral liberation and concentration have always been the core issues in ore processing. The goal of multi-stage crushing and ball milling is liberation because mineral liberation is the foundation of beneficiation. High energy consumption and environmental pollution have always been unavoidable topics. We [...] Read more.
Mineral liberation and concentration have always been the core issues in ore processing. The goal of multi-stage crushing and ball milling is liberation because mineral liberation is the foundation of beneficiation. High energy consumption and environmental pollution have always been unavoidable topics. We put forward the method of high-pressure gas rapid unloading (GRU). Particle size followed MR-R distribution. The scanning electron microscopy data showed that the liberation of apatite particles smaller than 4 mm was sufficient by high-pressure GRU methods, and high-grade apatite concentrated in the particle size range of 0.5 to 4 mm. The average grade of the preferred particle size interval was 3%–5% higher than the original ore. Liberation degrees of apatite less than 4 mm are above 88%, which was beneficial for mineral processing. Compared to the traditional crushing method, the GRU method had a higher liberation and concentration in the particle size range of 0.5 to 4 mm. The total energy consumption was about 1.76 kW·h/t, less than that of the traditional crushing method. Full article
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<p>Apatite ore production of China, 2010–2022.</p>
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<p>Schematic diagram of experimental apparatus.</p>
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<p>BGRIMM Process Mineralogy Analyzer (BPMA).</p>
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<p>Fitting curve of different phosphate ores. (<b>a</b>) Chuan phosphate, (<b>b</b>) high magnesium phosphate, (<b>c</b>) Yinjiaping phosphate, (<b>d</b>) Sujiapo phosphate.</p>
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<p>(<b>a</b>) SEM observation images of 2–4 mm apatite particles associated with multiple minerals; (<b>b</b>) SEM observation images of 1–2 mm apatite particles associated with multiple minerals; (<b>c</b>) SEM observation images of 0.5–1 mm apatite particles associated with multiple minerals; (<b>d</b>) SEM observation images of 0.15–0.5 mm apatite particles associated with multiple minerals; (<b>e</b>) SEM observation images of 0.074–0.15 mm apatite particles associated with multiple minerals; (<b>f</b>) SEM observation images of &lt;0.074 mm apatite particles associated with multiple minerals.</p>
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<p>High-grade apatite concentrated in the specific particle size interval. (<b>a</b>) Apatite associated with dolomite, (<b>b</b>) apatite associated with dolomite after the first experiment, (<b>c</b>) apatite associated with dolomite after the second experiment, (<b>d</b>) P<sub>2</sub>O<sub>5</sub> grade of Yinjiaping, (<b>e</b>) apatite associated with shale, (<b>f</b>) P<sub>2</sub>O<sub>5</sub> grade of Sujiapo.</p>
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<p>Quality proportion and liberation degree of different particle size intervals of apatite. (<b>a</b>) Quality proportion. (<b>b</b>) Liberation degree.</p>
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<p>Comparative experiment between GRU method and conventional crushing method.</p>
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<p>Energy consumption of traditional method.</p>
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12 pages, 6109 KiB  
Article
Facile Construction of Supported Polyoxometalate Ionic Liquids for Deep Oxidative Desulfurization of Fuel
by Shuang Tong, Tianqi Huang, Mengyue Chen, Zidan Zhu, Chao Wang, Hongping Li and Ming Zhang
Catalysts 2024, 14(11), 796; https://doi.org/10.3390/catal14110796 - 7 Nov 2024
Viewed by 461
Abstract
A series of commercial silica-supported polyoxometalate ionic liquids ([Cnmim]3PMo12O40) with different substitutes in the imidazole ring were prepared via a facile ball milling method and employed as catalysts in the oxidative desulfurization of organosulfur compounds. [...] Read more.
A series of commercial silica-supported polyoxometalate ionic liquids ([Cnmim]3PMo12O40) with different substitutes in the imidazole ring were prepared via a facile ball milling method and employed as catalysts in the oxidative desulfurization of organosulfur compounds. The experimental results demonstrated that the active polyoxometalate center was successfully immobilized with a highly uniform dispersion on the silica. Without any organic solvent as the extractant, sulfur removal with the sample C16PMo/SiO2-BM reached 99.5% in 30 min under the optimal condition, which was ascribed to the high specific surface area and lipophilicity. In addition, the active site was verified by a free radical trapping experiment and an ESR spin capture experiment. In addition, the oxidative product was confirmed by GC-MS analysis. Full article
(This article belongs to the Special Issue Ionic Liquids and Eutectic Mixtures for Green Catalytic Processes)
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<p>Wide-angle XRD pattern of various samples.</p>
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<p>FT-IR spectra of different catalysts: (<b>a</b>) 4000–400 cm<sup>−1</sup> and (<b>b</b>)1500–400 cm<sup>−1</sup>.</p>
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<p>Raman spectra of different catalysts.</p>
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<p>Mo 3d spectra of C<sub>16</sub>PMo and C<sub>16</sub>PMo/SiO<sub>2</sub>-BM.</p>
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<p>SEM images of (<b>a</b>) C<sub>16</sub>PMo/SiO<sub>2</sub> and (<b>b</b>) C<sub>16</sub>PMo/SiO<sub>2</sub>-BM.</p>
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<p>N<sub>2</sub> adsorption–desorption isotherms of various samples.</p>
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<p>The contact angle on the surface of C<sub>4</sub>PMo/SiO<sub>2</sub>-BM, C<sub>8</sub>PMo/SiO<sub>2</sub>-BM, C<sub>12</sub>PMo/SiO<sub>2</sub>-BM, and C<sub>16</sub>PMo/SiO<sub>2</sub>-BM for a water droplet (<b>a</b>–<b>d</b>) and a dodecane (<b>e</b>–<b>h</b>) droplet.</p>
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<p>UV-vis DRS spectra of different catalysts.</p>
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<p>(<b>a</b>) Desulfurization efficiency with different catalysts. Experimental conditions: m (catalyst) = 20 mg, T = 60 °C, O/S = 3. (<b>b</b>) Pseudo first-order kinetic curves of different desulfurization systems. (<b>c</b>) Desulfurization efficiency with different sulfur-containing substances. Experimental conditions: m (catalyst) = 20 mg, T = 60 °C, O/S = 3. (<b>d</b>) Desulfurization efficiency with varied reaction temperatures. Experimental conditions: m (catalyst) = 20 mg, O/S = 3. (<b>e</b>) Desulfurization efficiency with varied O/S molar ratios. Experimental conditions: m (catalyst) = 20 mg, T = 60 °C. (<b>f</b>) Desulfurization efficiency with different catalyst dosages. Experimental conditions: T = 60 °C, O/S = 3.</p>
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<p>(<b>a</b>) Recycling performance test of C<sub>16</sub>PMo/SiO<sub>2</sub>-BM. Experimental conditions: m (catalyst) = 20 mg, T = 60 °C, and O/S = 3. (<b>b</b>) FT-IR spectra of fresh catalyst and recycled catalyst.</p>
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<p>Free radical capture experiments of catalyst C<sub>16</sub>PMo/SiO<sub>2</sub>-BM in ODS process. Experimental conditions: m (catalyst) = 20 mg, T = 60 °C, and O/S = 3.</p>
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<p>ESR spectra of DMPO-•OH generated in oxidation reaction of DBT with C<sub>16</sub>PMo/SiO<sub>2</sub>-BM.</p>
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<p>GC-MS analysis of the oil phase (<b>A</b>) and the catalyst phase (<b>B</b>) during the reaction. The experimental conditions: m(catalyst) = 20 mg, T = 60 °C, and O/S = 3.</p>
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16 pages, 4809 KiB  
Article
The Effect of CeO2 on the Catalytic Activity and SO2 Resistance of the V2O5-MoO3/TiO2 Catalyst Prepared Using the Ball Milling Method for the NH3-SCR of NO
by Xuehong Zi, Jingtong Ye, Yao Cheng, Shuangye Li, Xiangru Li, Xingtong Li, Wenge Qiu and Liyun Song
Catalysts 2024, 14(11), 794; https://doi.org/10.3390/catal14110794 - 7 Nov 2024
Viewed by 483
Abstract
V2O5-WO3(MoO3)/TiO2 catalysts are widely used in industrial denitrification (deNOx) processes based on the selective catalytic reduction (SCR) technique. To lower their cost and shorten the production cycle, V2O5-MoO [...] Read more.
V2O5-WO3(MoO3)/TiO2 catalysts are widely used in industrial denitrification (deNOx) processes based on the selective catalytic reduction (SCR) technique. To lower their cost and shorten the production cycle, V2O5-MoO3/TiO2 catalysts with and without CeO2 modification were prepared using the ball milling method. This study demonstrates that the CeO2-modified catalyst has high NO conversion and a broader temperature window due to the decreased amount of easily reducible vanadium species and the enhanced property of oxygen species activation in CeO2. Meanwhile, the SO2 resistance of the catalyst is restrained due to the strong adsorption and oxidation of SO2 over CeO2 in the catalyst. Full article
(This article belongs to the Section Catalytic Materials)
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<p>NO conversion over the 3V6MoxCeTiO<sub>2</sub> catalysts. Reaction conditions: [NO] = [NH<sub>3</sub>] = 1000 ppm, [O<sub>2</sub>] = 6 vol%; N<sub>2</sub> (balance); total flow rate = 500 mL/min; GHSV = 30,000 h<sup>−1</sup>.</p>
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<p>NO conversion rate of the selected catalysts (3V6MoTiO<sub>2</sub>, 3V6Mo5CeTiO<sub>2</sub>, 3V6Mo20CeTiO<sub>2</sub>) in the presence/absence of SO<sub>2</sub> and H<sub>2</sub>O at 200 °C.</p>
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<p>(<b>a</b>) XRD patterns and (<b>b</b>) SEM images of the 3V6MoTiO<sub>2</sub> and 3V6Mo20CeTiO<sub>2</sub> catalysts.</p>
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<p>N<sub>2</sub> adsorption–desorption isotherms of 3V6MoTiO<sub>2</sub> (<b>A</b>), 3V6Mo5CeTiO<sub>2</sub> (<b>B</b>), and 3V6Mo20CeTiO<sub>2</sub> (<b>C</b>) catalysts at liquid N<sub>2</sub> temperature.</p>
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<p>FT-IR spectra of TiO<sub>2</sub>, 3V6MoTiO<sub>2,</sub> and 3V6Mo20CeTiO<sub>2</sub>.</p>
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<p>Raman spectra of TiO<sub>2</sub>, 3V6MoTiO<sub>2</sub>, and 3V6Mo20CeTiO<sub>2</sub>.</p>
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<p>H<sub>2</sub>-TPR profiles of the 3V6MoxCeTiO<sub>2</sub> catalysts.</p>
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<p>NH<sub>3</sub>-TPD profiles of 3V6MoTiO<sub>2</sub> and 3V6Mo20CeTiO<sub>2</sub> catalysts.</p>
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<p>XPS of the 3V6MoTiO<sub>2</sub> and 3V6Mo20CeTiO<sub>2</sub> catalysts.</p>
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<p>In situ DRIFTs of 3V6MoTiO<sub>2</sub> and 3V6Mo20CeTiO<sub>2</sub> catalysts in presence of (<b>a</b>) NH<sub>3</sub> and (<b>b</b>) NO in O<sub>2</sub> environment.</p>
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<p>Transient reaction of NO with pre-adsorbed NH<sub>3</sub> over the (<b>a</b>) 3V6MoTiO<sub>2</sub> and (<b>b</b>) 3V6Mo20CeTiO<sub>2</sub> catalysts at 150 °C.</p>
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<p>Transient reaction of NH<sub>3</sub> with pre-adsorbed NO + O<sub>2</sub> on the (<b>a</b>) 3V6MoTiO<sub>2</sub> and (<b>b</b>) 3V6Mo20CeTiO<sub>2</sub> catalysts at 150 °C.</p>
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<p>In situ DRIFT spectra of the 3V6MoTiO<sub>2</sub> and 3V6Mo20CeTiO<sub>2</sub> catalyst treated in SO<sub>2</sub> at room temperature (<b>a</b>) and then purged with O<sub>2</sub> at 200 °C (<b>b</b>).</p>
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18 pages, 6906 KiB  
Article
Sustainable Scalable Mechanochemical Synthesis of CdS/Bi2S3 Nanocomposites for Efficient Hydrogen Evolution
by Zhandos Shalabayev, Abylay Abilkhan, Natalya Khan, Saparbek Tugelbay, Anar Seisembekova, Batukhan Tatykayev and Matej Balaz
Nanomaterials 2024, 14(22), 1785; https://doi.org/10.3390/nano14221785 - 6 Nov 2024
Viewed by 616
Abstract
In the present study, a green, scalable, and environmentally friendly approach was developed for the fabrication of Bi2S3-decorated CdS nanoparticles with an efficient hydrogen generation ability from the water. As a sulfur source, thiourea was used. The process was [...] Read more.
In the present study, a green, scalable, and environmentally friendly approach was developed for the fabrication of Bi2S3-decorated CdS nanoparticles with an efficient hydrogen generation ability from the water. As a sulfur source, thiourea was used. The process was completed in two stages: mechanical activation and thermal annealing. The presence of spherical CdS nanoparticles and Bi2S3 nanorods in the CdS/Bi2S3 nanocomposite was confirmed and proved by XRD, Raman spectroscopy, SEM-EDS, and TEM. The synthesized CdS/Bi2S3 nanocomposites were evaluated for their photocatalytic hydrogen evolution capabilities. The CdS/Bi2S3 photocatalyst exhibited 25% higher photocatalytic activity compared to CdS, reaching a hydrogen evolution rate of 996.68 μmol h−1g−1 (AQE 0.87%) after 3.5 h under solar-light irradiation. Full article
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<p>Illustration scheme of CdS/Bi<sub>2</sub>S<sub>3</sub> nanocomposite’s preparation.</p>
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<p>XRD patterns of the CdS, Bi<sub>2</sub>S<sub>3</sub>, and CdS/Bi<sub>2</sub>S<sub>3</sub> samples.</p>
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<p>Raman spectra (<b>a</b>) and FTIR spectra (<b>b</b>) of the bare CdS, Bi<sub>2</sub>S<sub>3</sub>, and CdS/Bi<sub>2</sub>S<sub>3</sub> nanocomposite.</p>
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<p>UV-Vis spectra (<b>a</b>) and Tauc plot graph (<b>b</b>) of as-synthesized CdS, Bi<sub>2</sub>S<sub>3</sub>, and CdS/Bi<sub>2</sub>S<sub>3</sub> samples.</p>
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<p>XPS spectra of the CdS (<b>a</b>,<b>b</b>) and Bi<sub>2</sub>S<sub>3</sub> (<b>c</b>) samples. (<b>d</b>) XPS valence-band spectra, the maximum value of the tangent intersection and the minimum value of the tangent intersection of CdS and Bi<sub>2</sub>S<sub>3</sub> samples.</p>
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<p>SEM images of the CdS (<b>a</b>,<b>b</b>), Bi<sub>2</sub>S<sub>3</sub> (<b>c</b>,<b>d</b>), and CdS/Bi<sub>2</sub>S<sub>3</sub> (<b>e</b>,<b>f</b>) samples.</p>
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<p>TEM images of the CdS (<b>a</b>), Bi<sub>2</sub>S<sub>3</sub> (<b>b</b>), CdS/Bi<sub>2</sub>S<sub>3</sub> (<b>c</b>,<b>d</b>), and HR-TEM images of CdS/Bi<sub>2</sub>S<sub>3</sub> (<b>e</b>,<b>f</b>) samples.</p>
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<p>HER (<b>a</b>) and AQE values (<b>b</b>) at 30-minute intervals of the CdS, Bi<sub>2</sub>S<sub>3</sub>, and CdS/Bi<sub>2</sub>S<sub>3</sub> samples.</p>
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<p>Study of photocatalytic activity of nanocomposite (<b>a</b>) using different sacrificial agents and (<b>b</b>) cyclic experiments to study the stability of the photocatalyst.</p>
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<p>Energy band-structure diagram of CdS/Bi<sub>2</sub>S<sub>3</sub> and S-scheme pathway for the photocatalytic mechanism of photocatalytic H<sub>2</sub> evolution.</p>
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