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20 pages, 9188 KiB  
Article
3D-Printed Reactor for Coupling Photoelectrochemical (Sea)Water Splitting with Solid-State H2 Storage
by Paweł Wyżga, Joanna Macyk, Yuan-Chih Lin, Emil Høj Jensen, Matylda N. Guzik, Krzysztof Bieńkowski, Renata Solarska and Wojciech Macyk
Catalysts 2024, 14(12), 941; https://doi.org/10.3390/catal14120941 - 20 Dec 2024
Viewed by 682
Abstract
The modular photoelectrochemical (PEC) reactor accommodating eight photoelectrodes with a total active area of up to 46 cm2 has been designed and manufactured using the fused deposition modeling method. The device was equipped with an electrolyte flow system, a relay module for [...] Read more.
The modular photoelectrochemical (PEC) reactor accommodating eight photoelectrodes with a total active area of up to 46 cm2 has been designed and manufactured using the fused deposition modeling method. The device was equipped with an electrolyte flow system, a relay module for the photoelectrode connection, and a feedback-loop module for switching between counter electrodes. The performance and durability of the system were tested within three case study experiments. The water splitting process was successfully combined with an in situ hydrogen storage in the form of metal hydride phases (confirmed by powder X-ray diffraction) using Fe2O3- or WO3-based photoanodes and LaNi5-based cathodes. The PEC water oxidation at the anodes was realized either in a strongly alkaline electrolyte (pH > 13.5) or in acidified synthetic seawater (pH < 2) for Fe2O3 and WO3 electrodes, respectively. In the latter case, the photoresponse of the anodes decreased the cell charging voltage by 1.7 V at the current density of 60 mA∙g−1. When the seawater was used as an anolyte, the oxygen evolution reaction was accompanied by the chlorine evolution reaction. The manufactured PEC-metal hydride reactor revealed mechanical and chemical stability during a prolonged operation over 300 h and in the broad range of pH values. Full article
(This article belongs to the Special Issue Environmental Catalysis in Advanced Oxidation Processes, 2nd Edition)
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Graphical abstract
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<p>Linear sweep voltammetry (LSV, scan rate: 10 mV·s<sup>−1</sup>) experiments with Fe<sub>2</sub>O<sub>3</sub> photoanodes, conducted in 1M NaOH under the illumination of a solar simulator: (<b>a</b>) Power density of simulated solar light for each photoelectrode. Electrodes are highlighted with bold lines and labels. The power density was measured at three points per electrode, and, then, the average value was taken for further analysis. (<b>b</b>) The photocurrent for individual Fe2O3 electrodes and all together connected in parallel (bold line). Measurements were collected under constant and modulated illumination. Reference electrode (RE): Hg/HgO; Counter electrode (CE): Ni-helix. (<b>c</b>) Photocurrent density normalized by light power density. (<b>d</b>) Applied bias photon-to-current efficiency (ABPE) derived from data in (<b>b</b>).</p>
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<p>Photo-assisted charging/discharging (C/D) experiments of (<b>a</b>,<b>c</b>) LaNi<sub>4.7</sub>Al<sub>0.3</sub> and (<b>b</b>,<b>d</b>) LaNi<sub>4.3</sub>Co<sub>0.4</sub>Al<sub>0.3</sub> cathodes. The absolute values of charging/discharging currents and potential changes upon illumination are given in red.</p>
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<p>Specific discharge capacities for LaNi<sub>5</sub>-based cathodes derived from C/D measurements. The discharge current densities are given in red.</p>
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<p>Experimental (dot), calculated (red line), and differential (black line) profiles from Rietveld refinement of electrochemically charged LaNi<sub>4.7</sub>Al<sub>0.3</sub> (<b>a</b>) and LaNi<sub>4.3</sub>Co<sub>0.4</sub>Al<sub>0.3</sub> (<b>b</b>) samples. Bragg peaks indicated with * appeared after C/D experiment (see <a href="#app1-catalysts-14-00941" class="html-app">Figure S5</a>) in both samples but could not be indexed with any well-known secondary phase.</p>
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<p>LSV (scan rate: 20 mV·s<sup>−1</sup>) experiments with WO<sub>3</sub> photoanodes, conducted in acidified synthetic seawater (pH = 1.55) under the illumination of the solar simulator: (<b>a</b>) Light power density per electrode (average of three points). The average power density equals 52.4 mW∙cm<sup>−2</sup>. (<b>b</b>) The photocurrent for individual electrodes and all-together connected electrically in parallel (bold line). (<b>c</b>) Photocurrent density normalized by light power density. (<b>d</b>) ABPE efficiency derived from (<b>b</b>). The noisy signal for W1 and W5 samples (top row of electrodes) is probably connected to poor contact with the current collector. The color code is the same in subfigures (<b>b</b>–<b>d</b>). RE: Ag/AgCl (sat. KCl), CE: Pt-coil.</p>
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<p>LSV (scan rate: 20 mV·s<sup>−1</sup>) experiments with WO<sub>3</sub> photoanodes, conducted in acidified 0.5M Na<sub>2</sub>SO<sub>4</sub> (pH = 1.55) under the illumination of the solar simulator: (<b>a</b>) Photocurrent density normalized by light power density. (<b>b</b>) Applied bias photon-to-current efficiency derived from the photocurrent. The noisy signal for W1 and W5 samples (top row of electrodes) is probably connected with poor contact with the current collector. RE: Ag/AgCl (sat. KCl), CE: Pt-coil.</p>
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<p>(<b>a</b>) The two-electrode chronoamperometric (CA) measurement in acidified synthetic seawater (pH = 1.55) under approx. 0.5 Sun illumination at the potential of 1.23 V vs. CE. WE: 8 WO<sub>3</sub> photoanodes connected electrically in parallel, CE: stainless steel foil. (<b>b</b>) The potential of WE vs. RE (Ag/AgCl electrode). It was measured independently from the CA setup using auxiliary potentiostat.</p>
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<p>(<b>a</b>) Photo-assisted C/D experiments of the LaNi<sub>4.3</sub>Co<sub>0.4</sub>Al<sub>0.3</sub> cathode. Data of potential vs. RHE during 4–7. cycles are missing because the RE was temporarily above the electrolyte. (<b>b</b>) The first twelve hours of the experiment. The absolute values of charging/discharging currents and potential changes upon illumination are given in red.</p>
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<p>Short photo-assisted C/D experiments with different charging rates. The specific current densities of 20, 50, 60, and 200 mA·g<sup>−1</sup> correspond to absolute current values of 2.02, 5.05, 6.06, and 20.18 mA, respectively. Modulated light was applied to photoanodes during experiments.</p>
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<p>A schematic assembly of the PEC-MH reactor: (1) an anodic compartment, (2) a cathodic compartment, (3) lids with ports for electrodes, (4) fixing plates with windows, (5) silicone gaskets, (6) an electric contact (the other seven are not shown), (7) a photoanode, (8) a reference electrode (optional), (9) cathode, (10) an ion-exchange membrane/diaphragm, and (11) the PMMA/glass plate. For clarity, some elements of the assembly are not shown, e.g., the cathode holder, additional counter electrode, hydraulic fittings, electrolyte tubing, screws, and nuts.</p>
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13 pages, 6235 KiB  
Article
Revisiting Mechanism of NaOH Dechlorination Treatments for Bronze Conservation in Quantitative Study
by Xin Yang, Wei Wu and Kunlong Chen
Materials 2024, 17(24), 6126; https://doi.org/10.3390/ma17246126 - 14 Dec 2024
Viewed by 460
Abstract
Dechlorination is a crucial strategy for archeological bronze stabilization to resist corrosion induced by cuprous chloride (CuCl). Conventional samples, either archeological or simulated ones, have deficiencies in revealing dechlorination mechanisms for their complex rust layers and difficulties in quantifying chlorine content. In this [...] Read more.
Dechlorination is a crucial strategy for archeological bronze stabilization to resist corrosion induced by cuprous chloride (CuCl). Conventional samples, either archeological or simulated ones, have deficiencies in revealing dechlorination mechanisms for their complex rust layers and difficulties in quantifying chlorine content. In this work, samples with fixed chlorine amounts were prepared by compressing method to solve overcomplicated and unquantifiable problems. Then, patina profiles and desalinization solutions were analyzed to revisit the dechlorination mechanism across varying solution concentrations and current densities after dechlorination treatments. Results indicate that the sodium hydroxide (NaOH) desalinization method is achieved by converting CuCl to trihydroxychloride (Cu2(OH)3Cl). However, this transformation leads to an expansion of the CuCl layer, nearly doubling the CuCl layer thickness at the current density of 25 μA/cm2. Dechlorination solution measurements provide information on quantifying chlorine removal and dechlorination progress. Theoretically, the endpoint (c0) for the NaOH dechlorination method is supposed to be a chloride ion concentration of 358.2 ppm. As the NaOH solution concentrations vary from 10−6 to 10−2, CuCl dechlorination progress (Et=24h) calculations are at about 3% to 6% at 24 h. Applying the current significantly improves the effectiveness of dechlorination at 2.5 μA/cm2. However, the chloride ion concentration in the solution starts to decrease after reaching a current density of 12.5 μA/cm2, even dropping to 12.07 ppm at 25 μA/cm2. According to a theoretical analysis, chlorine evolution during electrolytic processes would be responsible for this phenomenon. Full article
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<p>Procedures for preparing simulated samples of bronze with patina.</p>
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<p>The final CuCl powder product after immersion in the NaOH solution for 24 h.</p>
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<p>XRD patterns of the final CuCl powder product after immersion in the NaOH solution for 24 h; (<b>a<sub>1</sub></b>) high-O<sub>2</sub>-concentration groups, (<b>a<sub>2</sub></b>) characteristic peak of Cu<sub>2</sub>O in high-O<sub>2</sub>-concentration groups, (<b>b<sub>1</sub></b>) low-O<sub>2</sub>-concentration groups, (<b>b<sub>2</sub></b>) characteristic peak of Cu<sub>2</sub>O in low-O<sub>2</sub>-concentration groups.</p>
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<p>Quantitative results of the final product after immersing CuCl powder in a NaOH solution for 24 h according to XRD spectra; (<b>a</b>,<b>b</b>): high-O<sub>2</sub>-concentration groups, low-O<sub>2</sub>-concentration groups.</p>
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<p>XRD patterns of black particles in pH = 12 groups.</p>
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<p>Structural and elemental map distribution of simulated sample; (<b>a</b>) cross-section of layer, (<b>b</b>) CuCl layer.</p>
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<p>The cross-sectional composition and structure of rust layers treated with a NaOH solution at different concentrations; (<b>a</b>–<b>c</b>): pH = 8, pH = 10, pH = 12.</p>
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<p>SEM-EDS analysis of cross-section of sample after constant-current NaOH dechlorination treatment; (<b>a</b>–<b>d</b>): 0 μA/cm<sup>2</sup>, 2.5 μA/cm<sup>2</sup>, 12.5 μA/cm<sup>2</sup>, 25 μA/cm<sup>2</sup>.</p>
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<p>Chloride ion concentration in dechlorination solution after immersion in NaOH solution with different concentration.</p>
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<p>Chloride ion concentration in dechlorination solution after immersion in NaOH solution with different current densities.</p>
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20 pages, 3264 KiB  
Review
In Situ and Ex Situ Bioremediation of Different Persistent Soil Pollutants as Agroecology Tool
by A. Perez-Vazquez, P. Barciela and M. A. Prieto
Processes 2024, 12(10), 2223; https://doi.org/10.3390/pr12102223 - 12 Oct 2024
Cited by 1 | Viewed by 2484
Abstract
Contamination or pollution of our environment has become a real global concern, especially in parallel with the increasing evolution of urbanization and industrialization, which in turn have released a plethora of different pollutants that end up being deposited in soils. It is crucial [...] Read more.
Contamination or pollution of our environment has become a real global concern, especially in parallel with the increasing evolution of urbanization and industrialization, which in turn have released a plethora of different pollutants that end up being deposited in soils. It is crucial to investigate solutions that can minimize the extent of damage, and that are cost-effective, feasible and environmentally friendly, to treat a wide variety of contaminants in soils, as well as to detoxify various compounds. Bioremediation is a safe technique that has demonstrated satisfactory results and is easy to apply and maintain. This technique explores the degradation pathways of various biological agents (microorganisms, plants, algae, etc.) to neutralize contaminants. It is based on biodegradation through a complete mineralization of organic pollutants into inorganic innocuous compounds, such as carbon dioxide and water. This review aims to determine the feasibility of bioremediation as a cleanup technology for soils contaminated with pesticides, agrochemicals, chlorinated compounds, heavy metals, organic halogens, greenhouse gases, petroleum hydrocarbons, and many others, either in situ or ex situ. Different bioremediation approaches are described and compared, showing their advantages and drawbacks from a critical point of view. Moreover, both the economic and technical barriers of bioremediation are addressed, along with the outlook for the role of microorganisms in the process, the aim to identify future directions, and the application feasibility of this process. Full article
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<p>Summary of the following: (<b>A</b>) bioremediation processes classification; (<b>B</b>) advantages and disadvantages of bioremediations processes; and (<b>C</b>) generic limitations of bioremediation processes. Created with BioRender.com.</p>
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<p>Schematic representation of two bioremediation processes: (<b>A</b>) phytoremediation process; (<b>B</b>) bioreactor process. Created with BioRender.com.</p>
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<p>Overview of the general principles of bioaugmentation and biostimulation techniques. Created with BioRender.com.</p>
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<p>Indigenous bacteria versus engineered microorganisms for the elimination of pollutants present in soil. Created with BioRender.com.</p>
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16 pages, 3640 KiB  
Article
Cobalt Molybdenum Telluride as an Efficient Trifunctional Electrocatalyst for Seawater Splitting
by Rajarshi Kar, Amideddin Nouralishahi, Harish Singh and Manashi Nath
Catalysts 2024, 14(10), 684; https://doi.org/10.3390/catal14100684 - 2 Oct 2024
Viewed by 941
Abstract
A mixed-metal ternary chalcogenide, cobalt molybdenum telluride (CMT), has been identified as an efficient tri-functional electrocatalyst for seawater splitting, leading to enhanced oxygen evolution reaction (OER), hydrogen evolution reaction (HER), and oxygen reduction reaction (ORR). The CMT was synthesized by a single step [...] Read more.
A mixed-metal ternary chalcogenide, cobalt molybdenum telluride (CMT), has been identified as an efficient tri-functional electrocatalyst for seawater splitting, leading to enhanced oxygen evolution reaction (OER), hydrogen evolution reaction (HER), and oxygen reduction reaction (ORR). The CMT was synthesized by a single step hydrothermal technique. Detailed electrochemical studies of the CMT-modified electrodes showed that CMT has a promising performance for OER in the simulated seawater solutions, exhibiting a small overpotential of 385 mV at 20 mA cm−2, and superior catalyst durability for prolonged period of continuous oxygen evolution. Interestingly, while gas chromatography analysis confirmed the evolution of oxygen in an anodic chamber, it showed that there was no chlorine evolution from these electrodes in alkaline seawater, highlighting the novelty of this catalyst. CMT also displayed remarkable ORR activity in simulated seawater as indicated by its four-electron reduction pathway forming water as the dominant product. One of the primary challenges of seawater splitting is chlorine evolution from the oxidation of dissolved chloride salts. The CMT catalyst successfully and significantly lowers the water oxidation potential, thereby separating the chloride and water oxidation potentials by a larger margin. These results suggest that CMT can function as a highly active tri-functional electrocatalyst with significant stability, making it suitable for clean energy generation and environmental applications using seawater. Full article
(This article belongs to the Special Issue Electrocatalytic Water Oxidation, 2nd Edition)
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<p>(<b>a</b>) PXRD patterns of CMT; (<b>b</b>) SEM images of CMT.</p>
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<p>The deconvoluted XPS spectra of CMT electrocatalyst: (<b>a</b>) Mo 3d, (<b>b</b>) Te 3d, (<b>c</b>) Co 2p peaks.</p>
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<p>(<b>a</b>) LSV plots of the as-prepared CMT at different salt concentration (measured with a scan rate of 10 mV s <sup>−1</sup>). (<b>b</b>) The Tafel plots of CMT at different salt concentration. (<b>c</b>) Comparative LSV results at 1 M KOH + 0.3 M NaCl. (<b>d</b>) Chronoamperometry test of CMT at a 600 mV of applied potential.</p>
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<p>Post activity characterization data of CMT. (<b>a</b>) SEM images after chronoamperometry; (<b>b</b>) PXRD pattern before and after chronoamperometry; (<b>c</b>) XPS spectra of Mo; (<b>d</b>) XPS spectra of Te; (<b>e</b>) XPS spectra of Co.</p>
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<p>Chromatogram of gas products of OER on CMT electrocatalyst after chronoamperometry experiment at 600 mV for 17 h, as well as pure chlorine, oxygen, and nitrogen gases.</p>
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<p>Electrochemical impedance spectra of CoMoTe electrocatalyst in 1 M KOH and 1 M KOH + 0.3 M NaCl electrolytes. The EIS data have been recorded at 400 mV (vs Ag|AgCl) in the frequency range of 0.1 Hz to 100 kHz.</p>
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<p>(<b>a</b>) LSV plots of HER reaction CMT at different NaCl concentrations at scan rate of 10 mV s<sup>−1</sup>. (<b>b</b>) Chronoamperometry plots illustrating long-term stability of CMT electrode under −500 mV of applied potential. (<b>c</b>) LSV curve of the full water electrolysis on CMT.</p>
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<p>LSV plots of the as-prepared CMT electrocatalyst at RRDE electrodes with different rotation speed at potential scan rate of 10 mV s<sup>−1</sup> and (<b>a</b>) 1 M KOH, (<b>b</b>) 1 M KOH + 0.1 M NaCl, and (<b>c</b>) 1 M KOH + 0.3 M NaCl. (<b>d</b>) Reduction current densities in 0.1 V at different electrolytes.</p>
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<p>K–L plots of CMT electrode in O<sub>2</sub>-saturated (<b>a</b>) 1 M KOH, (<b>b</b>) 1 M KOH + 0.3 M NaCl solution, and (<b>c</b>) 1 M KOH + 0.1 M NaCl, collected using RDE set-up.</p>
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19 pages, 10547 KiB  
Article
Bimetallic Ni–Mn Electrocatalysts for Stable Oxygen Evolution Reaction in Simulated/Alkaline Seawater and Overall Performance in the Splitting of Alkaline Seawater
by Sukomol Barua, Aldona Balčiūnaitė, Daina Upskuvienė, Jūrate Vaičiūnienė, Loreta Tamašauskaitė-Tamašiūnaitė and Eugenijus Norkus
Coatings 2024, 14(8), 1074; https://doi.org/10.3390/coatings14081074 - 22 Aug 2024
Viewed by 1616
Abstract
The perfect strategy for the generation of green and renewable hydrogen (H2) fuels is the direct electrocatalytic splitting of plentiful seawater rather than scarce freshwater. One of the half-reactions taking place during the electrocatalytic splitting of seawater is oxygen evolution (OER). [...] Read more.
The perfect strategy for the generation of green and renewable hydrogen (H2) fuels is the direct electrocatalytic splitting of plentiful seawater rather than scarce freshwater. One of the half-reactions taking place during the electrocatalytic splitting of seawater is oxygen evolution (OER). However, the OER is affected by slow four-electron transfer kinetics as well as competitive chlorine evolution reactions (CERs) in seawater. To overcome the kinematic and competitive barriers of seawater splitting and achieve an excellent overall performance of seawater splitting, we herein report a facile, low-cost, one-step fabrication procedure of 3D structured nickel–manganese (NiMn) coatings using a dynamic hydrogen bubble template (DHBT) technique. The electrocatalytic activities of the thus synthesized catalytic materials for OER in simulated seawater (0.5 M NaCl + 1 M KOH, denoted as SSW) and alkaline natural seawater (natural seawater + 1 M KOH, denoted as ASW) were investigated using linear sweep voltammetry (LSV) at varying temperatures from 25 to 75 °C. Scanning electron microscopy (SEM) and inductively coupled plasma–optical emission spectroscopy (ICP–OES) were used to examine the surface morphology and composition of the prepared catalysts. It was found that the prepared NiMn/Ti-1 catalyst in a plating bath containing a molar ratio of 1:1 Ni2+:Mn2+ and having the lowest Mn loading of 13.43 µg cm−2 exhibited quite reasonable activity for OER in Cl ion rich SSW and ASW. To achieve the benchmark current density of 10 mA cm−2 in SSW and ASW, the NiMn/Ti-1 electrocatalyst requires overpotentials of 386 and 388 mV, respectively. In addition, this optimal bimetallic electrocatalyst also demonstrated superior long-run stability at 1.81 V (vs. RHE) and 10 mA cm−2 for 24 h in both working electrolytes. Impressively, the two-electrode electrolyzer—NiMn/Ti-5(−)||NiMn/Ti-1(+)—needs only 1.619 V to deliver 10 mA cm−2 current density for overall alkaline seawater electrolysis, which is even 0.075 V lower than the noble metal-based electrolyzer (Pt(−)||NiMn/Ti-1(+)). Full article
(This article belongs to the Special Issue New Advance in Nanoparticles, Fiber, and Coatings)
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<p>Illustration of the fabrication approach of NiMn/Ti catalysts (<b>a</b>) and the SEM mapping images of NiMn/Ti-1 (<b>b</b>), NiMn/Ti-2 (<b>c</b>), and NiMn/Ti-3 (<b>d</b>) catalysts.</p>
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<p>XRD patterns of NiMn/Ti-1. The symbols show the positions of the XRD peaks of Ti (COD. No. 9016190), Ni (COD No. 2102269), MnO (COD No. 1010898), and Mn<sub>2</sub>NiO<sub>4</sub> (COD No. 1530384).</p>
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<p>The OER polarization curves recorded on NiMn/Ti catalysts in SSW at 10 mV s<sup>−1</sup> and a temperature range from 25 to 75 °C (<b>a</b>), LSVs obtained at 25 °C (<b>b</b>), the corresponding Tafel plots (<b>c</b>), and the overpotential values needed to achieve 10, 20, and 50 mA cm<sup>−2</sup> current densities (<b>d</b>).</p>
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<p>The OER LSVs recorded on NiMn/Ti catalysts in ASW at 10 mV s<sup>−1</sup> and a temperature range of 25 to 75 °C (<b>a</b>), LSVs recorded at 25 °C (<b>b</b>), the corresponding Tafel plots (<b>c</b>), and the overpotential values needed to reach 10, 20, and 50 mA cm<sup>−2</sup> current densities (<b>d</b>).</p>
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<p>(<b>a</b>) CVs of NiMnTi-1 collected in N<sub>2</sub>-deaerated 1 M KOH solution at varied scan rates. (<b>b</b>) Dependence of charging current on scan rate.</p>
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<p>The chronopotentiometric (<b>a</b>) and chronoamperometric (<b>b</b>) curves of NiMn/Ti-1 in simulated seawater and alkaline natural seawater at a static current density of 10 mA cm<sup>−2</sup> and a constant potential of 1.81 V for 24 h, respectively.</p>
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<p>A schematic representation of the overall alkaline seawater splitting (<b>a</b>), a digital photograph of the assembled two-electrode NiMn/Ti-5<sub>(−)</sub>||NiMn/Ti-1<sub>(+)</sub> cell (left) and the bubbles on the electrodes (right) (<b>b</b>). LSVs for the overall alkaline seawater splitting at 25 °C (<b>c</b>). A comparison of activity of the assembled electrolyzer with that of recently reported catalysts (<b>d</b>) and a long-time durability test of the assembled NiMn/Ti-5<sub>(−)</sub>||NiMn/Ti-1<sub>(+)</sub> electrolyzer (<b>e</b>) for the overall alkaline natural seawater splitting.</p>
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16 pages, 43800 KiB  
Article
Study on the Binding Behavior of Chloride Ion and Ettringite in Nano-Metakaolin Cement by Seawater Mixing and Curing Temperatures
by Zhisheng Fang, Shiyi Zhang, Wenjie Qi, Yingfang Fan, Surendra P. Shah and Junjie Zheng
Materials 2024, 17(16), 3943; https://doi.org/10.3390/ma17163943 - 8 Aug 2024
Viewed by 1274
Abstract
Mixing cement with seawater will cause the hydration process of cement to be different from that of ordinary cement, which will significantly affect cement’s mechanical properties and durability. This article investigates the effects of chloride ion concentration, curing temperature, and nano-metakaolin content on [...] Read more.
Mixing cement with seawater will cause the hydration process of cement to be different from that of ordinary cement, which will significantly affect cement’s mechanical properties and durability. This article investigates the effects of chloride ion concentration, curing temperature, and nano-metakaolin content on the evolution process of Friedel’s salts and ettringite (AFt) crystals in cement pastes. The study was conducted using X-ray diffraction (XRD), thermal analysis (TG), scanning electron microscopy (SEM), and mercury-intrusion porosimetry (MIP). The results show that chlorine salt can increase the production of Friedel’s salt and ettringite, and the delayed AFt production increases by up to 27.95% after the addition of chlorine salt, which has an adverse effect on cement-based materials. Increasing the curing temperature and increasing the nano-metakaolin dosage increased the generation of Friedel’s salt and decreased the delayed AFt generation, which resulted in a decrease in the length and diameter of the AFt crystals. After 28 days of high-temperature curing and the addition of nano-metakaolin, Friedel’s salt production increased by 13.40% and 14.34%, respectively, and ettringite production decreased by 9.68% and 7.93%, respectively. Increasing the curing temperature and adding nano-metakaolin can reduce the adverse effect of delayed ettringite increases due to chloride ion binding. Full article
(This article belongs to the Special Issue Application and Modification of Clay Minerals)
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<p>Microstructure of cement and NMK. (<b>a</b>) Cement, (<b>b</b>) NMK.</p>
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<p>Schematic diagram of specimen production and experimental procedures.</p>
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<p>XRD patterns of samples with different chloride content for standard curing.</p>
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<p>TG curves of specimens with different chloride content for standard curing. (<b>a</b>) 3 days, (<b>b</b>) 28 days.</p>
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<p>Friedel’s salt production with different chlorine content for standard curing.</p>
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<p>Micromorphologies of Friedel’s salt and AFt with different chlorine content at 28 days. (<b>a</b>) NC3C0, (<b>b</b>) NC3C1, (<b>c</b>) NC3C2.</p>
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<p>XRD patterns of samples (NC3C1) with different curing temperatures.</p>
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<p>TG curves of specimen (NC3C1) with different curing temperatures. (<b>a</b>) 3 days, (<b>b</b>) 28 days.</p>
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<p>Friedel’s salt production of specimen (NC3C1) with different curing temperatures.</p>
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<p>Micromorphologies of Friedel’s salt and AFt with different curing temperature of specimen (NC3C1) at 28 days. (<b>a</b>) 5 °C, (<b>b</b>) 20 °C, (<b>c</b>) 50 °C.</p>
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<p>XRD patterns of samples with different nano-metakaolin content for standard curing.</p>
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<p>TG curves of specimens with different nano-metakaolin content for standard curing. (<b>a</b>) 3 days, (<b>b</b>) 28 days.</p>
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<p>Friedel’s salt production with different nano-metakaolin content for standard curing.</p>
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<p>Micromorphologies of Friedel’s salt and AFt with different nano-metakaolin content at 28 days. (<b>a</b>) NC0C1, (<b>b</b>) NC3C1, (<b>c</b>) NC5C1.</p>
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16 pages, 3293 KiB  
Article
Improved Operation of Chloralkaline Reversible Cells with Mixed Metal Oxide Electrodes Made Using Microwaves
by Jamylle Y. C. Ribeiro, Gessica O. S. Santos, Aline R. Dória, Iñaki Requena, Marcos R. V. Lanza, Giancarlo R. Salazar-Banda, Katlin I. B. Eguiluz, Justo Lobato and Manuel A. Rodrigo
Nanomaterials 2024, 14(8), 693; https://doi.org/10.3390/nano14080693 - 17 Apr 2024
Viewed by 1497
Abstract
This study focuses on the synthesis of mixed metal oxide anodes (MMOs) with the composition Ti/RuO2Sb2O4Ptx (where x = 0, 5, 10 mol) using hybrid microwave irradiation heating. The synthesized electrodes were characterized using scanning electron [...] Read more.
This study focuses on the synthesis of mixed metal oxide anodes (MMOs) with the composition Ti/RuO2Sb2O4Ptx (where x = 0, 5, 10 mol) using hybrid microwave irradiation heating. The synthesized electrodes were characterized using scanning electron microscopy, X-ray energy-dispersive analysis, X-ray diffraction, cyclic voltammetry, and electrochemical impedance spectroscopy. These electrodes were then evaluated in both bulk electrolytic and fuel cell tests within a reversible chloralkaline electrochemical cell. The configurations using the electrodes Ti/(RuO2)0.7-(Sb2O4)0.3 and Ti/(RuO2)66.5-(Sb2O4)28.5-Pt5 presented lower onset potential for oxygen and chlorine evolution reactions and reduced resistance to charge transfer compared to the Ti/(RuO2)63-(Sb2O4)27-Pt10 variant. These electrodes demonstrated notable performance in reversible electrochemical cells, achieving Coulombic efficiencies of up to 60% when operating in the electrolytic mode at current densities of 150 mA cm−2. They also reached maximum power densities of 1.2 mW cm−2 in the fuel cell. In both scenarios, the presence of platinum in the MMO coating positively influenced the process. Furthermore, a significant challenge encountered was crossover through the membranes, primarily associated with gaseous Cl2. This study advances our understanding of reversible electrochemical cells and presents possibilities for further exploration and refinement. It demonstrated that the synergy of innovative electrode synthesis strategies and electrochemical engineering can lead to promising and sustainable technologies for energy conversion. Full article
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<p>Schematic representation of the electrode preparation procedure using microwave hybrid heating and ionic liquid methods. (<b>a</b>) pretreatment of titanium plates, (<b>b</b>) preparation of the precursor solution, and (<b>c</b>) subsequent calcination processes.</p>
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<p>Micrographs obtained by MEV of two electrodes prepared using microwave hybrid heating: (<b>A</b>) Ti/(RuO<sub>2</sub>)<sub>70</sub>-(Sb<sub>2</sub>O<sub>4</sub>)<sub>30</sub>, (<b>B</b>) Ti/(RuO<sub>2</sub>)<sub>66.5</sub>-(Sb<sub>2</sub>O<sub>4</sub>)<sub>28.5</sub>-Pt<sub>5</sub>, and (<b>C</b>) Ti/(RuO<sub>2</sub>)<sub>63</sub>-(Sb<sub>2</sub>O<sub>4</sub>)<sub>27</sub>-Pt<sub>10</sub>.</p>
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<p>(<b>a</b>) Cyclic voltammograms and (<b>b</b>) Nyquist plots acquired using Ti/(RuO<sub>2</sub>)<sub>70</sub>-(Sb<sub>2</sub>O<sub>4</sub>)<sub>30</sub>, Ti/(RuO<sub>2</sub>)<sub>66.5</sub>-(Sb<sub>2</sub>O<sub>4</sub>)<sub>28.5</sub>-Pt<sub>5</sub>, and Ti/(RuO<sub>2</sub>)<sub>63</sub>-(Sb<sub>2</sub>O<sub>4</sub>)<sub>27</sub>-Pt<sub>10</sub> electrodes. Electrolyte: H<sub>2</sub>SO<sub>4</sub> 0.5 mol L<sup>−1</sup>. Scan rate: 50 mV s<sup>−1</sup>.</p>
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<p>Temporal evolution of the oxidized chlorine species produced (● and ▲) and supplied power (○ and Δ) during the electrolysis of 2.0 mol L<sup>−1</sup> sodium chloride aqueous solutions at (●) 50 mA cm<sup>−2</sup> and (▲) 150 mA cm<sup>−2</sup>.</p>
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<p>Time evolution of OCS in the anodic (● and ▲) and cathodic (○ and Δ) compartments during the electrolysis of 2.0 mol L<sup>−1</sup> sodium chloride aqueous solutions at ● 50 mA cm<sup>−2</sup>, ▲150 mA cm<sup>−2</sup>. Inset: OCS values obtained from different tests performed with the same apparatus after 80 min of electrolysis.</p>
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<p>(<b>a</b>) Temporal evolution of gaseous OCS within the cathodic compartment during electrolysis of 2.0 mol L<sup>−1</sup> sodium chloride aqueous solutions at current densities of (●) 50 mA cm<sup>−2</sup> and (▲) 150 mA cm<sup>−2</sup>. Empty symbols represent the ratio of gaseous OCS, whereas full symbols denote the absolute amount of gaseous OCS. (<b>b</b>) time-course of the pH variations in the anolyte and catholyte during the electrolysis of 2.0 mol L<sup>−1</sup> sodium chloride aqueous solutions at (●) 50 mA cm<sup>−2</sup> and (▲) 150 mA cm<sup>−2</sup>.</p>
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<p>Production of hydrogen during electrolysis of 2.0 mol L<sup>−1</sup> NaCl at (●, ○) 50 mA cm<sup>−2</sup> and (▲, Δ) 150 mA cm<sup>−2</sup>. The dashed and continuous lines correspond to the theoretical expected values considering 100% faradaic efficiency at 50 and 150 mA cm<sup>−2</sup>, respectively. The empty symbols represent experimental points calculated from pH via the proton and hydroxyl ion balance, while the solid symbols denote experimental points derived from the cumulative gas content in the cathodic gasometer.</p>
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<p>Operation of the reversible chloralkaline electrochemical cell as a fuel cell. (<b>a</b>) Current intensity (●) and energy produced (▲); (<b>b</b>) cathodic pH (▲), anodic pH (●), and OCS consumption (□).</p>
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<p>Influence of the platinum content in the electrocatalyst on the Coulombic efficiency (<b>a</b>) and energy efficiency (<b>b</b>). Operation current density: (●) 50 mA cm<sup>−2</sup> and (▲)150 mA cm<sup>−2</sup>.</p>
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<p>Polarization (<b>a</b>) and power curves (<b>b</b>) of fuel cells equipped with electrodes with different platinum ratios as cathodes: (●) Ti/(RuO<sub>2</sub>)<sub>70</sub>-(Sb<sub>2</sub>O<sub>4</sub>)<sub>30</sub>, (▲) Ti/(RuO<sub>2</sub>)<sub>66.5</sub>-(Sb<sub>2</sub>O<sub>4</sub>)<sub>28.5</sub>-Pt<sub>5</sub>, (■) Ti/(RuO<sub>2</sub>)<sub>63</sub>-(Sb<sub>2</sub>O<sub>4</sub>)<sub>27</sub>-Pt<sub>10</sub>.</p>
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10 pages, 2002 KiB  
Review
The Impact of the Hunga Tonga–Hunga Ha’apai Volcanic Eruption on the Stratospheric Environment
by Qian Sun, Taojun Lu, Dan Li and Jingyuan Xu
Atmosphere 2024, 15(4), 483; https://doi.org/10.3390/atmos15040483 - 13 Apr 2024
Cited by 1 | Viewed by 1870
Abstract
In this study, an overview of two years of research findings concerning the 2022 Hunga Tonga–Hunga Ha’apai (HTHH) volcanic eruption in the stratospheric environment is provided, focusing on water vapor, aerosols, and ozone. Additionally, the potential impacts of these changes on aviation equipment [...] Read more.
In this study, an overview of two years of research findings concerning the 2022 Hunga Tonga–Hunga Ha’apai (HTHH) volcanic eruption in the stratospheric environment is provided, focusing on water vapor, aerosols, and ozone. Additionally, the potential impacts of these changes on aviation equipment materials are discussed. The HTHH volcanic eruption released a large amount of particles (e.g., ash and ice) and gases (e.g., H2O, SO2, and HCl), significantly affecting the redistribution of stratospheric water vapor and aerosols. Stratospheric water vapor increased by approximately 140–150 Tg (8–10%), with a concentration peak observed in the height range of 22.2–27 km (38–17 hPa). Satellite measurements indicate that the HTHH volcano injected approximately 0.2–0.5 Tg of sulfur dioxide into the stratosphere, which was partially converted into sulfate aerosols. In-situ observations revealed that the volcanic aerosols exhibit hygroscopic characteristics, with particle sizes ranging from 0.22–0.42 μm under background conditions to 0.42–1.27 μm. The moist stratospheric conditions increased the aerosol surface area, inducing heterogeneous chlorine chemical reactions on the aerosol surface, resulting in stratospheric ozone depletion in the HTHH plume within one week. In addition, atmospheric disturbances and ionospheric disruptions triggered by volcanic eruptions may adversely affect aircraft and communication systems. Further research is required to understand the evolution of volcanic aerosols and the impact of volcanic activity on aviation equipment materials. Full article
(This article belongs to the Section Meteorology)
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<p>(<b>left</b>) MLS/Aura time series of mean (30° S–5° N) stratospheric water vapor anomalies (ppmv) from 100 to 1 hPa after the HTHH eruption (15 January 2022), from January–April 2022. The anomalies are calculated by subtracting the water vapor averaged 0–10 days prior to the eruption of the HTHH from the daily water vapor data. (<b>middle</b>) Zonal mean water vapor anomalies (ppmv) as a function of latitude and time at 38–17 hPa levels. The locations of the HTHH volcano and Lijiang are marked with a black plus symbol and a triangle, respectively. (<b>right</b>) Vertical profiles of water vapor at Lijiang on 9 April 2022, derived from in-situ observations (blue), and MLS remote sensing observations (black). The gray line shows the mean April water vapor with standard deviations derived from MLS during 2005–2020 (adapted from Xu et al., [<a href="#B19-atmosphere-15-00483" class="html-bibr">19</a>]).</p>
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<p>(<b>a</b>) Vertical profiles of the backscatter ratio (blue for 455 nm, red for 940 nm) data derived from the COBALD sonde and the effective radius (green) from the POPS measurements obtained in Lijiang on 9 April 2022. (<b>b</b>) Vertical profiles of the aerosol number density for bins of eight sizes from the POPS measurements obtained on 9 April 2022. (<b>c</b>) Profiles of water vapor on different days in Lijiang. (<b>d</b>) The European Centre for Medium-range Weather Forecasts (ECMWF) Reanalysis version 5 (ERA5) streamline data obtained at 30 hPa on 9 April 2022. The yellow dots mark the CALIPSO footprints when volcanic plumes (with altitudes of 22–25 km) were detected by an expedited level 2 vertical feature mask (VFM) algorithm on 7, 8, and 9 April. The asterisk marks the Lijiang site (from Figure 2 of Bian et al. [<a href="#B18-atmosphere-15-00483" class="html-bibr">18</a>]).</p>
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<p>Panels (top, bottom) show zonal and latitude band averages as a function of time for the CALIOP 532 nm scattering ratio (color) and MLS water vapor (contours, ppmv) for the 15–5° S and 25–15° S latitude bands, respectively (adapted from Legras et al. [<a href="#B23-atmosphere-15-00483" class="html-bibr">23</a>]).</p>
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<p>After the HTHH eruption, a balloon campaign took place at Reunion Island. Plume dynamics showcase the volcanic injection of H<sub>2</sub>O vapor, sulfur dioxide (SO<sub>2</sub>), and HCl, promoting rapid chlorine activation in hydrated volcanic aerosols and O3 depletion in the stratosphere. The 22 January 2022 O<sub>3</sub> profile (black line) contrasts with Reunion’s climatology (red line), displaying a notable decline (from the first figure of Evan et al. [<a href="#B34-atmosphere-15-00483" class="html-bibr">34</a>]).</p>
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19 pages, 10995 KiB  
Article
Iron–Titanium Oxide–Apatite–Sulfide–Sulfate Microinclusions in Gabbro and Adakite from the Russian Far East Indicate Possible Magmatic Links to Iron Oxide–Apatite and Iron Oxide–Copper–Gold Deposits
by Pavel Kepezhinskas, Nikolai Berdnikov, Valeria Krutikova and Nadezhda Kozhemyako
Minerals 2024, 14(2), 188; https://doi.org/10.3390/min14020188 - 11 Feb 2024
Cited by 1 | Viewed by 1506
Abstract
Mesozoic gabbro from the Stanovoy convergent margin and adakitic dacite lava from the Pliocene–Quaternary Bakening volcano in Kamchatka contain iron–titanium oxide–apatite–sulfide–sulfate (ITOASS) microinclusions along with abundant isolated iron–titanium minerals, sulfides and halides of base and precious metals. Iron–titanium minerals include magnetite, ilmenite and [...] Read more.
Mesozoic gabbro from the Stanovoy convergent margin and adakitic dacite lava from the Pliocene–Quaternary Bakening volcano in Kamchatka contain iron–titanium oxide–apatite–sulfide–sulfate (ITOASS) microinclusions along with abundant isolated iron–titanium minerals, sulfides and halides of base and precious metals. Iron–titanium minerals include magnetite, ilmenite and rutile; sulfides include chalcopyrite, pyrite and pyrrhotite; sulfates are represented by barite; and halides are predominantly composed of copper and silver chlorides. Apatite in both gabbro and adakitic dacite frequently contains elevated chlorine concentrations (up to 1.7 wt.%). Mineral thermobarometry suggests that the ITOASS microinclusions and associated Fe-Ti minerals and sulfides crystallized from subduction-related metal-rich melts in mid-crustal magmatic conduits at depths of 10 to 20 km below the surface under almost neutral redox conditions (from the unit below to the unit above the QFM buffer). The ITOASS microinclusions in gabbro and adakite from the Russian Far East provide possible magmatic links to iron oxide–apatite (IOA) and iron oxide–copper–gold (IOCG) deposits and offer valuable insights into the early magmatic (pre-metasomatic) evolution of the IOA and ICOG mineralized systems in paleo-subduction- and collision-related geodynamic environments. Full article
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<p>Location of Ildeus mafic–ultramafic arc root complex in the Stanovoy Suture Zone and Bakening volcano in the Kamchatka arc. Map of the main geologic structures and elements of Eastern Siberia and the Russian Far East is modified after [<a href="#B62-minerals-14-00188" class="html-bibr">62</a>]. Locations of IOA and IOCG deposits and showings in the Russian Far East are also shown for comparative purposes.</p>
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<p>Petrographic features of marginal gabbro from the Ildeus mafic–ultramafic intrusion (<b>a</b>,<b>b</b>) and adakitic dacite from the Bakening complex (<b>c</b>,<b>d</b>). (<b>a</b>) Hypidiomorphic–granular texture of marginal gabbro (parallel nicols). (<b>b</b>) Contact between marginal gabbro and adakite veinlet (parallel nicols). (<b>c</b>) Plagioclase-dominated porphyritic texture of the Bakening adakitic dacite (crossed nicols). (<b>d</b>) Amphibole-dominated porphyritic texture with trachytic groundmass of the Bakening adakitic dacite (parallel nicols). Opx—orthopyroxene, Cpx—clinopyroxene, Amp—amphibole, Mag—magnetite, Ap—apatite. Scale line 20 µm.</p>
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<p>Chemical composition of amphibole (<b>a</b>) and plagioclase (<b>b</b>) phenocrysts in adakitic dacite from the Bakening volcano (Kamchatka). Fields of amphibole phenocryst compositions in the Shiveluch (Central Kamchatka Depression) and Valovayam (Northern Kamchatka) adakites are based on data from [<a href="#B65-minerals-14-00188" class="html-bibr">65</a>,<a href="#B82-minerals-14-00188" class="html-bibr">82</a>,<a href="#B83-minerals-14-00188" class="html-bibr">83</a>].</p>
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<p>BSE images of quasi-spherical segregations of microinclusions in marginal gabbro from the Ildeus arc root complex. (<b>a</b>) Partially deformed and compacted segregation of magnetite, apatite, chalcopyrite, pyrite and barite microinclusions. (<b>b</b>) Spherical-type mineral segregation composed of rutile, apatite, orthopyroxene, pyrite and barite. Opx—orthopyroxene, Amp—amphibole, Qz—quartz, Mag—magnetite, Ilm—ilmenite, Rt—rutile, Ap—apatite, Ccp—chalcopyrite, Py—pyrite, Brt—barite. Original SEM-EDS spectra used for identification of the indexed mineral phases in these BSE images are summarized in <a href="#app1-minerals-14-00188" class="html-app">Figure S1</a> (<a href="#app1-minerals-14-00188" class="html-app">Supplementary Materials</a>).</p>
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<p>BSE images of microinclusions in marginal gabbro ILN-009 from the Ildeus arc root complex. (<b>a</b>) Ilmenite–rutile microinclusion in amphibole. (<b>b</b>) Rutile–chalcopyrite–pyrrhotite–pyrite–barite microinclusions in amphibole. (<b>c</b>) Magnetite–chalcopyrite–barite microinclusion in quartz–plagioclase–amphibole matrix. (<b>d</b>) Euhedral Ni-bearing pyrite microinclusion in amphibole. (<b>e</b>) Microinclusion of Cu-Ag-Cl halide in amphibole. (<b>f</b>) Microinclusion of cupriferous silver in quartz. Mineral abbreviations: Amp—amphibole, Qz—quartz, Ilm—ilmenite, Rt—rutile, Mag—magnetite, Ccp—chalcopyrite, Py—pyrite, Po—pyrrhotite, Brt—barite.</p>
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<p>BSE images of iron oxide–apatite inclusions in adakite lava from the Bakening volcano (Kanchatka). (<b>a</b>) Ilmenite grain with microinclusions of chlorapatite in association with magnetite in silica-rich glass. (<b>b</b>) Magnetite grain with apatite microinclusions in silica-rich glass. Ilm—ilmenite, Mag—magnetite, Cl-Ap—chlorine-bearing (0.7 wt.% of chlorine based on the SEM-EDS analysis) apatite.</p>
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<p>BSE images of magnetite microinclusions in adakitic dacite from the Bakening volcano. (<b>a</b>–<b>c</b>) Magnetite inclusions in amphibole (<b>a</b>), biotite (<b>b</b>) and K-Na feldspar (<b>c</b>). (<b>d</b>) Magnetite inclusion in amphibole and glassy groundmass. (<b>e</b>) Magnetite inclusion in Fe-K-rich glass. (<b>f</b>) Framboidal-type magnetite aggregate at the contact between amphibole and quartz. Amp—amphibole, Bt—biotite, K-Na Fsp—K-Na feldspar, Qz—quartz, Mag—magnetite.</p>
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<p>BSE images of sulfide, sulfate and halide microinclusions in adakitic dacite from the Bakening volcano. (<b>a</b>) Euhedral pyrite inclusion in the quartz–plagioclase groundmass. (<b>b</b>) Subhedral pyrite inclusion in silica-rich groundmass glass. (<b>c</b>) Anhedral acanthite (Ag<sub>2</sub>S) inclusion in quartz. (<b>d</b>) Barite inclusion in quartz microphenocryst. (<b>e</b>) Anhedral inclusion of spongy silver chloride in amphibole phenocryst. (<b>f</b>) Anhedral aggregate of spongy silver chloride in plagioclase phenocryst. Amp—amphibole, Pl—plagioclase, Qz—quartz, Py—pyrite, Aca—acanthite, Brt—barite.</p>
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14 pages, 5351 KiB  
Article
Boosted Electrocatalytic Degradation of Levofloxacin by Chloride Ions: Performances Evaluation and Mechanism Insight with Different Anodes
by Keda Yang, Peiwei Han, Yinan Liu, Hongxia Lv, Xiaofei Chen, Yihan Lei, Lian Yu, Lei Ma and Pingzhou Duan
Molecules 2024, 29(3), 662; https://doi.org/10.3390/molecules29030662 - 31 Jan 2024
Cited by 5 | Viewed by 1412
Abstract
As chloride (Cl) is a commonly found anion in natural water, it has a significant impact on electrocatalytic oxidation processes; yet, the mechanism of radical transformation on different types of anodes remains unexplored. Therefore, this study aims to investigate the influence [...] Read more.
As chloride (Cl) is a commonly found anion in natural water, it has a significant impact on electrocatalytic oxidation processes; yet, the mechanism of radical transformation on different types of anodes remains unexplored. Therefore, this study aims to investigate the influence of chlorine-containing environments on the electrocatalytic degradation performance of levofloxacin using BDD, Ti4O7, and Ru-Ti electrodes. The comparative analysis of the electrode performance demonstrated that the presence of Cl improved the removal and mineralization efficiency of levofloxacin on all the electrodes. The enhancement was the most pronounced on the Ti4O7 electrode and the least significant on the Ru-Ti electrode. The evaluation experiments and EPR characterization revealed that the increased generation of hydroxyl radicals and active chlorine played a major role in the degradation process, particularly on the Ti4O7 anode. The electrochemical performance tests indicated that the concentration of Cl affected the oxygen evolution potentials of the electrode and consequently influenced the formation of hydroxyl radicals. This study elucidates the mechanism of Cl participation in the electrocatalytic degradation of chlorine-containing organic wastewater. Therefore, the highly chlorine-resistant electrocatalytic anode materials hold great potential for the promotion of the practical application of the electrocatalytic treatment of antibiotic wastewater. Full article
(This article belongs to the Section Electrochemistry)
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<p>XRD patterns of (<b>a</b>) Ti<sub>n</sub>O<sub>2n−1</sub>, (<b>b</b>) Ru-Ti; SEM images of (<b>c</b>) Ti<sub>n</sub>O<sub>2n−1</sub>, (<b>d</b>) Ru-Ti.</p>
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<p>Degradation of levofloxacin by BDD electrode, titanium suboxide electrode, and Ru-Ti electrode in response to (<b>a</b>) LVX conversion rate and (<b>b</b>) TOC removal efficiency.</p>
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<p>Effect of the amount of chloride ions on the conversion and TOC removal rate of levofloxacin degradation by titanium oxide electrode (<b>a</b>,<b>b</b>) and Ru-Ti electrode (<b>c</b>,<b>d</b>).</p>
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<p>Effect of the amount of chloride ions on the EPR signal of hydroxyl radicals in the degradation of levofloxacin by titanium oxide electrode: (<b>a</b>) 0‰; (<b>b</b>) 4‰; (<b>c</b>) 8‰; (<b>d</b>) 12‰.</p>
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<p>Effect of the amount of chloride ions on the EPR signal of chlorine radicals in the degradation of levofloxacin by titanium oxide electrode: (<b>a</b>) 0‰; (<b>b</b>) 4‰; (<b>c</b>) 8‰; (<b>d</b>) 12‰.</p>
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<p>Electrochemical characterization–LSV curves of (<b>a</b>) the titanium suboxide electrodes and (<b>b</b>) Ru-Ti electrodes.</p>
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<p>Mechanism of the electrochemical degradation of levofloxacin in wastewater.</p>
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13 pages, 6108 KiB  
Article
Nonthermal Plasma Synthesis of Metallic Ti Nanocrystals
by Qiaomiao Tu, David L. Poerschke and Uwe R. Kortshagen
Nanomaterials 2024, 14(3), 264; https://doi.org/10.3390/nano14030264 - 26 Jan 2024
Cited by 1 | Viewed by 1366
Abstract
Nanoscale metallic titanium (Ti) offers unique energetic and biocompatible characteristics for the aerospace and biomedical industries. A rapid and sustainable method to form purified Ti nanocrystals is still in demand due to their high oxygen affinity. Herein, we report the production of highly [...] Read more.
Nanoscale metallic titanium (Ti) offers unique energetic and biocompatible characteristics for the aerospace and biomedical industries. A rapid and sustainable method to form purified Ti nanocrystals is still in demand due to their high oxygen affinity. Herein, we report the production of highly purified Ti nanoparticles with a nonequilibrium face center cubic (FCC) structure from titanium tetrachloride (TiCl4) via a capacitively coupled plasma (CCP) route. Furthermore, we demonstrate a secondary H2 treatment plasma as an effective strategy to improve the air stability of a thin layer of nanoparticles by further removal of chlorine from the particle surface. Hexagonal and cubic-shaped Ti nanocrystals of high purity were maintained in the air after the secondary H2 plasma treatment. The FCC phase potentially originates from small-sized grains in the initial stage of nucleation inside the plasma environment, which is revealed by a size evolution study with variations of plasma power input. Full article
(This article belongs to the Section Synthesis, Interfaces and Nanostructures)
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<p>Characterization of as-synthesized metallic Ti nanoparticles prior to hydrogen plasma post-treatment. (<b>a</b>) XPS high-resolution spectrum of Ti 2p, inset shows the ratio of different valence states according to integrated intensities. (<b>b</b>) XRD pattern of the as-synthesized nanoparticles. (<b>c</b>) CTEM images of as-synthesized nanoparticles; inset shows zoomed-in view of lattice fringes of 0.24 nm corresponding to FCC (111) crystal plane. (<b>d</b>) Size distribution statistics determined by TEM of 300 particles with geometric mean and standard deviation of the lognormal fit.</p>
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<p>(<b>a</b>) CTEM images of Ti nanoparticles after the secondary H<sub>2</sub> plasma treatment (<b>b</b>) SAED pattern from the collection of Ti nanoparticles (<b>c</b>) HRTEM of cubic shaped nanoparticle (<b>d</b>) HRTEM of hexagonal shaped nanoparticle.</p>
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<p>HAADF-STEM-EDS mapping images of cubic-shaped nanoparticles treated with a secondary H<sub>2</sub> plasma (<b>a</b>) HAADF and EDS mapping images (<b>b</b>) schematic of the model of core-shell spherical nanoparticle (<b>c</b>) measured and fitted line scan profiles across the particle, with calculated NRMSE in inset table (<b>d</b>) schematic of the fitted core-shell nanoparticle.</p>
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<p>HAADF-STEM-EDS mapping images of hexagonal-shaped nanoparticles treated with a secondary H<sub>2</sub> plasma (<b>a</b>) HAADF and EDS mapping images (<b>b</b>) schematic of the model of core-shell spherical nanoparticle (<b>c</b>) measured and fitted line scanning profile across the particle, with calculated NRMSE in inset table (<b>d</b>) schematic of the fitted core-shell nanoparticle.</p>
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<p>CTEM images of as-synthesized nanoparticles with plasma power of (<b>a</b>) 50 W (<b>b</b>) 80 W (<b>c</b>) 100 W (<b>d</b>) 150 W and (<b>e</b>) size distribution statistics from 300 particles with geometric mean and standard deviation of the lognormal fit.</p>
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26 pages, 8240 KiB  
Review
The Recent Progresses of Electrodes and Electrolysers for Seawater Electrolysis
by Fan Zhang, Junjie Zhou, Xiaofeng Chen, Shengxiao Zhao, Yayun Zhao, Yulong Tang, Ziqi Tian, Qihao Yang, Evelina Slavcheva, Yichao Lin and Qiuju Zhang
Nanomaterials 2024, 14(3), 239; https://doi.org/10.3390/nano14030239 - 23 Jan 2024
Cited by 4 | Viewed by 4404
Abstract
The utilization of renewable energy for hydrogen production presents a promising pathway towards achieving carbon neutrality in energy consumption. Water electrolysis, utilizing pure water, has proven to be a robust technology for clean hydrogen production. Recently, seawater electrolysis has emerged as an attractive [...] Read more.
The utilization of renewable energy for hydrogen production presents a promising pathway towards achieving carbon neutrality in energy consumption. Water electrolysis, utilizing pure water, has proven to be a robust technology for clean hydrogen production. Recently, seawater electrolysis has emerged as an attractive alternative due to the limitations of deep-sea regions imposed by the transmission capacity of long-distance undersea cables. However, seawater electrolysis faces several challenges, including the slow kinetics of the oxygen evolution reaction (OER), the competing chlorine evolution reaction (CER) processes, electrode degradation caused by chloride ions, and the formation of precipitates on the cathode. The electrode and catalyst materials are corroded by the Cl under long-term operations. Numerous efforts have been made to address these issues arising from impurities in the seawater. This review focuses on recent progress in developing high-performance electrodes and electrolyser designs for efficient seawater electrolysis. Its aim is to provide a systematic and insightful introduction and discussion on seawater electrolysers and electrodes with the hope of promoting the utilization of offshore renewable energy sources through seawater electrolysis. Full article
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<p>Mechanism of HER in acidic (<b>a</b>) and alkaline (<b>b</b>) solutions [<a href="#B32-nanomaterials-14-00239" class="html-bibr">32</a>]. Copyright 2020, American Chemical Society. (<b>c</b>) Volcano plot for the HER for various pure metals and metal overlayers. (<b>d</b>) Computational high−throughput screening for |G<sub>H</sub>| on 256 pure metals and surface alloys [<a href="#B33-nanomaterials-14-00239" class="html-bibr">33</a>]. Copyright 2006, Nature.</p>
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<p>Mechanism of OER consists of (<b>a</b>) adsorbate evolution mechanism (AEM), (<b>b</b>) lattice oxygen mechanism (LOM) [<a href="#B34-nanomaterials-14-00239" class="html-bibr">34</a>]. Copyright 2023, American Chemical Society. (<b>c</b>) Pourbaix diagram for artificial seawater model. (<b>d</b>) Maximum allowed overpotential of OER to ensure 100% selective in seawater splitting [<a href="#B35-nanomaterials-14-00239" class="html-bibr">35</a>]. Copyright 2016, Wiley.</p>
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<p>(<b>a</b>) Diagram of Pt−Ni@NiMoN electrocatalyst for seawater HER [<a href="#B37-nanomaterials-14-00239" class="html-bibr">37</a>]. Copyright 2023, Royal Society of Chemistry. (<b>b</b>) Diagram of Ru−Cu nano-heterostructures for efficient HER [<a href="#B15-nanomaterials-14-00239" class="html-bibr">15</a>]. Copyright 2023, American Chemical Society. (<b>c</b>) Proposed structure of the Ni−SN@C catalyst [<a href="#B49-nanomaterials-14-00239" class="html-bibr">49</a>]. Copyright 2021, Wiley. (<b>d</b>) Scheme of hetero-structured CeO<sub>2</sub>/α−MoC/β−Mo<sub>2</sub>C electrocatalyst [<a href="#B44-nanomaterials-14-00239" class="html-bibr">44</a>]. Copyright 2022, Elsevier. (<b>e</b>) Scheme of Lewis acid to facilitate HER and prevent precipitate formation [<a href="#B62-nanomaterials-14-00239" class="html-bibr">62</a>]. Copyright 2023, Nature. (<b>f</b>) Scheme of Ni(OH)<sub>2</sub> membrane grown in situ to repel Cl<sup>−</sup> [<a href="#B63-nanomaterials-14-00239" class="html-bibr">63</a>]. Copyright 2023, Royal Society of Chemistry.</p>
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<p>Waterfallplot of normalized and background-subtracted (003) peak obtained during in situ WAXS in 0.1 M KOH and potential steps for (<b>a</b>) NiFe LDH and (<b>b</b>) CoFe LDH [<a href="#B71-nanomaterials-14-00239" class="html-bibr">71</a>]. Copyright 2022, Tsinghua University Press. (<b>c</b>) in situ Raman spectra collected for BZ-NiFe-LDH/CC at different potential [<a href="#B72-nanomaterials-14-00239" class="html-bibr">72</a>]. Copyright 2020, Nature.</p>
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<p>(<b>a</b>–<b>c</b>) The MnO<sub>x</sub> on top of the IrO<sub>x</sub> layer, blocking ClOR by preventing Cl<sup>−</sup> from reaching the IrO<sub>x</sub> underneath [<a href="#B77-nanomaterials-14-00239" class="html-bibr">77</a>]. Copyright 2018, American Chemical Society. Scheme of Cl<sup>−</sup> crossing through the NiFe−LDH with the PO<sub>4</sub><sup>3−</sup> anion (<b>d</b>) and without any anions intercalation (<b>e</b>) [<a href="#B79-nanomaterials-14-00239" class="html-bibr">79</a>], Copyright 2023, Wiley. (<b>f</b>) Catalysts optimization (<b>left</b>) and electrolyte optimization (<b>right</b>) to protect the metal substrate from Cl<sup>−</sup> corrosion by adsorbing SO<sub>4</sub><sup>2−</sup> layer [<a href="#B81-nanomaterials-14-00239" class="html-bibr">81</a>]. Copyright 2021, Wiley. (<b>g</b>) Lewis acid on the anode facilitates OER and inhibits chlorine chemistry [<a href="#B62-nanomaterials-14-00239" class="html-bibr">62</a>]. Copyright 2023, Nature. (<b>h</b>) The Schematic illustration of in situ AgCl effectively repel free Cl<sup>−</sup> through strong common-ion repulsive effect [<a href="#B16-nanomaterials-14-00239" class="html-bibr">16</a>]. Copyright 2023, Wiley. (<b>i</b>) The schematic illustration for structure evolution and OER mechanism transfer in alkaline pure water and alkaline seawater [<a href="#B82-nanomaterials-14-00239" class="html-bibr">82</a>]. Copyright 2023, Wiley. (<b>j</b>) The schematic diagram of the two pitting initiation mechanisms [<a href="#B83-nanomaterials-14-00239" class="html-bibr">83</a>]. Copyright 2023, Nature.</p>
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<p>Configuration for seawater electrolysis: (<b>a</b>) alkaline water electrolysis (AWE) electrolyser; (<b>b</b>) anion exchange membrane water electrolysis (AEMWE) electrolyser; (<b>c</b>) proton exchange membrane water electrolysis (PEMWE) electrolyser; (<b>d</b>) solid oxide electrolysis cell (SEOC) [<a href="#B85-nanomaterials-14-00239" class="html-bibr">85</a>]. Copyright 2023, Nature.</p>
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<p>(<b>a</b>) Overall water/seawater splitting performance of Ni<sub>2</sub>P-Fe<sub>2</sub>P/NF and the Pt/C||IrO<sub>2</sub> pair in 1 M KOH and 1 M KOH seawater. (<b>b</b>) Comparison of the voltages at a current density of 100 mA cm<sup>−2</sup> for seawater splitting between Ni<sub>2</sub>P-Fe<sub>2</sub>P/NF and other electrocatalysts [<a href="#B87-nanomaterials-14-00239" class="html-bibr">87</a>]. Copyright 2020, Wiley. (<b>c</b>) LSV curves of the NiFe@DG||Pt/C and RuO<sub>2</sub>||Pt/C electrolysers. (<b>d</b>) Comparison of voltages at 10 and 100 mA cm<sup>−2</sup> for the NiFe@DG||Pt/C pair with recently reported catalysts. (<b>e</b>) Durability measurement of the AWE electrolyser at 10 mA cm<sup>−2</sup>. (<b>f</b>) Photograph of seawater electrolysis driven by a commercial Si solar cell [<a href="#B88-nanomaterials-14-00239" class="html-bibr">88</a>]. Copyright 2023, American Chemical Society.</p>
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<p>(<b>a</b>) Schematic of a forward-osmosis water-splitting cell [<a href="#B28-nanomaterials-14-00239" class="html-bibr">28</a>]. Copyright 2022, American Chemical Society. (<b>b</b>) Schematic diagram of a typical seawater electrolysis system. (<b>c</b>) The liquid–gas–liquid phase transition-based migration mechanism of the water purification and migration process and the driving force [<a href="#B27-nanomaterials-14-00239" class="html-bibr">27</a>]. Copyright 2022, American Chemical Society.</p>
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<p>(<b>a</b>) Scheme for the asymmetric electrolyser with Na<sup>+</sup> exchange membrane. (<b>b</b>) The pourbaix diagram of water [<a href="#B19-nanomaterials-14-00239" class="html-bibr">19</a>]. Copyright 2023, Nature. (<b>c</b>) Water electrolyser using a vapor feed at the anode and saltwater at the cathode and (<b>d</b>) water electrolyser using saltwater at the anode and the cathode [<a href="#B20-nanomaterials-14-00239" class="html-bibr">20</a>]. Copyright 2021, Royal Society of Chemistry.</p>
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<p>(<b>a</b>) AEMWE electrolyser configured with asymmetric feeds [<a href="#B97-nanomaterials-14-00239" class="html-bibr">97</a>]. Copyright 2020, Royal Society of Chemistry. (<b>b</b>) schematic of AEMWE configuration on alkaline seawater electrolysis [<a href="#B98-nanomaterials-14-00239" class="html-bibr">98</a>]. Copyright 2023, American Chemical Society. Schematic representing (<b>c</b>) the cell configuration (<b>d</b>) the cell electrode assembly [<a href="#B22-nanomaterials-14-00239" class="html-bibr">22</a>]. Copyright 2023, Elsevier. (<b>e</b>) schematic illustration of hydrogen production by AEMWE electrolyser in practical alkaline seawater [<a href="#B21-nanomaterials-14-00239" class="html-bibr">21</a>]. Copyright 2021, Royal Society of Chemistry.</p>
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<p>(<b>a</b>) Scheme of water transport in BPM electrolysers [<a href="#B99-nanomaterials-14-00239" class="html-bibr">99</a>]. Copyright 2020, American Chemical Society. (<b>b</b>) Scheme of the hydroxide precipitation alleviated by the BPM designs [<a href="#B100-nanomaterials-14-00239" class="html-bibr">100</a>]. Copyright 2022, Wiley. Cross−sectional schematic of a zero−gap (<b>c</b>) BPMWE and (<b>d</b>) PEMWE [<a href="#B101-nanomaterials-14-00239" class="html-bibr">101</a>]. Copyright 2023, Cell. (<b>e</b>) BPM and AEMWE electrolyser reference polarization curves [<a href="#B99-nanomaterials-14-00239" class="html-bibr">99</a>]. Copyright 2020, American Chemical Society. (<b>f</b>) Structure and performance of a BPMWE MEA with the different thickness AEM impregnation layer at the anode [<a href="#B102-nanomaterials-14-00239" class="html-bibr">102</a>]. Copyright 2020, American Chemical Society.</p>
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<p>(<b>a</b>) Schematic of flat-tube solid oxide electrolysis cell; (<b>b</b>) Cross-sectional structure of the electrolysis cell; (<b>c</b>) schematic of the electrolysis test system [<a href="#B25-nanomaterials-14-00239" class="html-bibr">25</a>]. Copyright 2023, Elsevier. (<b>d</b>) Long-term electrolysis voltages of cells with different temperatures and seawater steam content [<a href="#B24-nanomaterials-14-00239" class="html-bibr">24</a>]. Copyright 2023, Royal Society of Chemistry. (<b>e</b>) Durability test for the contaminated cell at 0.8 A cm<sup>−2</sup> and 800 °C [<a href="#B103-nanomaterials-14-00239" class="html-bibr">103</a>]. Copyright 2017, Elsevier.</p>
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26 pages, 33727 KiB  
Article
Metal Scrap to Hydrogen: Manufacture of Hydroreactive Solid Shapes via Combination of Ball Milling, Cold Pressing, and Spark Plasma Sintering
by Olesya A. Buryakovskaya, Mikhail S. Vlaskin and Aleksey V. Butyrin
Nanomaterials 2023, 13(24), 3118; https://doi.org/10.3390/nano13243118 - 11 Dec 2023
Viewed by 1450
Abstract
Two sorts of tablets were manufactured from ball-milled powder (aluminum scrap and copper) by cold pressing and spark plasma sintering. Their microstructure, phase, and elemental compositions were investigated via scanning electron microscopy, X-ray diffraction analysis, and energy-dispersive X-ray spectroscopy. New phases, Al2 [...] Read more.
Two sorts of tablets were manufactured from ball-milled powder (aluminum scrap and copper) by cold pressing and spark plasma sintering. Their microstructure, phase, and elemental compositions were investigated via scanning electron microscopy, X-ray diffraction analysis, and energy-dispersive X-ray spectroscopy. New phases, Al2Cu and MgCuAl2, were detected in the samples. Their microstructure was formed by welded scrap particles, the intermetallides, and Cu-rich regions located majorly along ‘interparticle boundaries’ and, to a lesser extent, within small, micro- and nanosized ‘intraparticle spots’. The tablets were sealed with adhesive, so only the top surface was exposed to the environment, and tested in a chlorine aqueous solution for hydrogen generation performance. For both sample sorts, hydrogen yields of nearly 100% were achieved. The sintered tablets reacted faster than the cold-pressed ones: at 60, 70, and 80 °C, their entire ‘conversion into hydrogen’ took ~80, 40, and 30 min. vs. ~220, 100, and 70 min. The experimental kinetic curves were fitted with a contracting geometry equation, and those for the sintered samples were approximated with higher precision. The key effect of the additive was to enhance hydrogen evolution through the galvanic corrosion of Al in the regions adjacent to the intermetallic inclusions and Cu-rich spots. Full article
(This article belongs to the Special Issue Nanostructured Materials for Energy Applications)
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<p>Compacted pellets and experimental set: 1—reactor; 2—thermocouple; 3—magnetic mixer and stirring bar; 4—thermostat; 5—Drexel flask; 6—glass vessel; 7—resistance temperature detector; 8—flask; 9—scales; 10—multichannel thermometer; 11—computer; 12—barometer [<a href="#B13-nanomaterials-13-03118" class="html-bibr">13</a>].</p>
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<p>XRD patterns for different samples: (<b>a</b>) composite powder; (<b>b</b>) samples sintered at different temperatures; (<b>c</b>) sintered tablet for experiments; (<b>d</b>) cold-pressed tablet for experiments.</p>
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<p>SEM images (SE on the left and BSE on the right) for different samples: (<b>a</b>) aluminum scrap; (<b>b</b>) composite powder; (<b>c</b>) sintered tablet; (<b>d</b>) cold-pressed tablet.</p>
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<p>SEM images (SE on the left and BSE on the right) for different samples: (<b>a</b>) aluminum scrap; (<b>b</b>) composite powder; (<b>c</b>) sintered tablet; (<b>d</b>) cold-pressed tablet.</p>
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<p>SEM images (SE on the left and BSE on the right) for different samples: (<b>a</b>) aluminum scrap; (<b>b</b>) composite powder; (<b>c</b>) sintered tablet; (<b>d</b>) cold-pressed tablet.</p>
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<p>SEM microphotographs (BSE mode) with the marked points scanned using EDX for the starting materials and compacted samples: (<b>a</b>) aluminum alloy scrap; (<b>b</b>) composite powder; (<b>c</b>) cold-pressed pellet; (<b>d</b>) sintered pellet.</p>
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<p>Hydrogen evolution kinetic curves fitted with linear functions and Arrhenius plots: (<b>a</b>) cold-pressed tablets; (<b>b</b>) sintered tablets.</p>
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<p>Comparison of the hydrogen evolution kinetic curves for the cold-pressed tablets and relative powder from a previous work [<a href="#B75-nanomaterials-13-03118" class="html-bibr">75</a>].</p>
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<p>Illustrations during the reaction process and after it: (<b>a</b>) reacting cold-pressed tablet; (<b>b</b>) solid residuals (copper flocks).</p>
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<p>EDX analysis results (spectra) at the selected points for the starting materials and compacted samples: (<b>a</b>) aluminum alloy scrap; (<b>b</b>) composite powder; (<b>c</b>) cold pressed pellet; (<b>d</b>) sintered pellet.</p>
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<p>EDX analysis results (spectra) at the selected points for the starting materials and compacted samples: (<b>a</b>) aluminum alloy scrap; (<b>b</b>) composite powder; (<b>c</b>) cold pressed pellet; (<b>d</b>) sintered pellet.</p>
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<p>EDX analysis results (spectra) at the selected points for the starting materials and compacted samples: (<b>a</b>) aluminum alloy scrap; (<b>b</b>) composite powder; (<b>c</b>) cold pressed pellet; (<b>d</b>) sintered pellet.</p>
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<p>EDX analysis results (spectra) at the selected points for the starting materials and compacted samples: (<b>a</b>) aluminum alloy scrap; (<b>b</b>) composite powder; (<b>c</b>) cold pressed pellet; (<b>d</b>) sintered pellet.</p>
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<p>EDX analysis results (spectra) at the selected points for the starting materials and compacted samples: (<b>a</b>) aluminum alloy scrap; (<b>b</b>) composite powder; (<b>c</b>) cold pressed pellet; (<b>d</b>) sintered pellet.</p>
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21 pages, 6380 KiB  
Review
A Review of Silver Wire Bonding Techniques
by Bin An, Hongliang Zhou, Jun Cao, Pingmei Ming, John Persic, Jingguang Yao and Andong Chang
Micromachines 2023, 14(11), 2129; https://doi.org/10.3390/mi14112129 - 20 Nov 2023
Viewed by 2369
Abstract
The replacement of gold bonding wire with silver bonding wire can significantly reduce the cost of wire bonding. This paper provides a comprehensive overview of silver wire bonding technology. Firstly, it introduces various types of silver-based bonding wire currently being studied by researchers, [...] Read more.
The replacement of gold bonding wire with silver bonding wire can significantly reduce the cost of wire bonding. This paper provides a comprehensive overview of silver wire bonding technology. Firstly, it introduces various types of silver-based bonding wire currently being studied by researchers, including pure silver wire, alloy silver wire, and coated silver wire, and describes their respective characteristics and development statuses. Secondly, the development of silver-based bonding wire in manufacturing and bonding processes is analyzed, including common silver wire manufacturing processes and their impact on silver wire performance, as well as the impact of bonding parameters on silver wire bonding quality and reliability. Subsequently, the reliability of silver wire bonding is discussed, with a focus on analyzing the effects of corrosion, electromigration, and intermetallic compounds on bonding reliability, including the causes and forms of chlorination and sulfurization, the mechanism and path of electromigration, the formation and evolution of intermetallic compounds, and evaluating their impact on bonding strength and reliability. Finally, the development status of silver wire bonding technology is summarized and future research directions for silver wire are proposed. Full article
(This article belongs to the Special Issue MEMS Packaging Technologies and 3D Integration, 2nd Edition)
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<p>Solder joint deformation in high-temperature environments [<a href="#B13-micromachines-14-02129" class="html-bibr">13</a>].</p>
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<p>Ag bonding wire corrosion [<a href="#B13-micromachines-14-02129" class="html-bibr">13</a>].</p>
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<p>Ag ion migration rate of Ag bonding wires as a function of Pd and Au contents [<a href="#B22-micromachines-14-02129" class="html-bibr">22</a>].</p>
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<p>Morphology of the intermetallic compounds at the interfaces of the as-bonded Ag–Pd stud bumps on Al pads. (<b>a</b>) Standard Ag-2Pd stud bump bonded onto aluminum metallized Si chip, and magnified interfacial images of (<b>b</b>) Ag-2Pd, (<b>c</b>) Ag-10Pd and (<b>d</b>) Ag-12Pd [<a href="#B24-micromachines-14-02129" class="html-bibr">24</a>].</p>
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<p>FIB cross-sectional (<b>A</b>) SEM micrographs and (<b>B</b>) EDS analysis results after reliability test; (<b>a</b>) Ag wire, (<b>b</b>) Au-coated Ag wire (ACA) and (<b>c</b>) Au wire [<a href="#B35-micromachines-14-02129" class="html-bibr">35</a>].</p>
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<p>Microstructure of as-manufactured Ag-4Pd ribbon. (<b>a</b>) SEM image; (<b>b</b>) inverse pole figure map; (<b>c</b>) band contrast with grain boundary map [<a href="#B50-micromachines-14-02129" class="html-bibr">50</a>].</p>
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<p>BSE images of Ag-4Pd ribbons after heat treatment at (<b>a</b>) 623 K, (<b>b</b>) 773 K, (<b>c</b>) 923 K, and (<b>d</b>) 1073 K for 100 h [<a href="#B50-micromachines-14-02129" class="html-bibr">50</a>].</p>
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<p>(<b>a</b>) Hardness and (<b>b</b>) stress–strain curve of pure copper, Cu–10Ag alloy and Cu–15Ag alloy after cold rolling; The red circle in (<b>a</b>) marks the hardness of the three materials at a rolling strain of 3.9 [<a href="#B51-micromachines-14-02129" class="html-bibr">51</a>].</p>
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<p>(<b>a</b>) Air sulfidation of untreated silver alloy bonding wire; (<b>b</b>) Surface particles of silver sulfide bonding wire; (<b>c</b>) Distribution of surface composition of sulfurized silver bonding wire; (<b>d</b>) Passivated silver alloy bonding wire; (<b>e</b>) Surface structure of passivated silver alloy bonding wire [<a href="#B56-micromachines-14-02129" class="html-bibr">56</a>].</p>
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<p>Typical ball bond morphology after ball shear test [<a href="#B62-micromachines-14-02129" class="html-bibr">62</a>].</p>
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<p>Cross-section of silver alloy wire after aging for 4 h [<a href="#B75-micromachines-14-02129" class="html-bibr">75</a>].</p>
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<p>Distribution of atomic flux divergence by (<b>a</b>) current, (<b>b</b>) temperature gradient and (<b>c</b>) total atomic flux divergence (AFD) with current density of 0.8 MA/cm<sup>2</sup> [<a href="#B76-micromachines-14-02129" class="html-bibr">76</a>].</p>
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<p>The different behavior of silver wire with current supply for 1 h at different densities [<a href="#B76-micromachines-14-02129" class="html-bibr">76</a>].</p>
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<p>Cross-sectional TEM images of bonding interfaces: (<b>a</b>) pure Ag/CEL-A-2; (<b>b</b>) pure Ag/CEL-A-3 [<a href="#B77-micromachines-14-02129" class="html-bibr">77</a>].</p>
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<p>(<b>a</b>) The cross-sectional SEM image of the interfacial region prepared from as-bonded sample using FIB. (<b>b</b>) The EDS elemental mapping images of the corresponding area as shown in (<b>a</b>) [<a href="#B25-micromachines-14-02129" class="html-bibr">25</a>].</p>
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<p>(<b>a</b>) The cross-sectional SEM image of the interfacial region prepared from as-bonded sample using FIB. (<b>b</b>) The EDS elemental mapping images of the corresponding area as shown in (<b>a</b>) [<a href="#B25-micromachines-14-02129" class="html-bibr">25</a>].</p>
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21 pages, 8185 KiB  
Article
Mechanical Performance and Strengthening Mechanism of Polymer Concretes Reinforced with Carbon Nanofiber and Epoxy Resin
by Zhenfang Li, Aizhu Liu, Dong Gao, Chuanji Wu, Xin Liu and Haoran Zhai
Coatings 2023, 13(11), 1964; https://doi.org/10.3390/coatings13111964 - 17 Nov 2023
Viewed by 1571
Abstract
To address the issues of the brittleness, low tensile strength, insufficient bond strength, and reduced service life associated with ordinary cement concrete being used as a repair material, a water-based epoxy (WBE) and carbon-nanofiber-reinforced concrete composite repair material was designed, and the mechanical [...] Read more.
To address the issues of the brittleness, low tensile strength, insufficient bond strength, and reduced service life associated with ordinary cement concrete being used as a repair material, a water-based epoxy (WBE) and carbon-nanofiber-reinforced concrete composite repair material was designed, and the mechanical properties, bonding performance, and durability of the concrete modified using WBE and carbon fiber under various WBE contents were investigated and evaluated. In this paper, a self-emulsifying water-based epoxy curing agent with reactive, rigid, flexible, and water-soluble chains was obtained via chemical grafting, involving the incorporation of polyethylene glycol chain segments into epoxy resin molecules. The results demonstrated that a WBE has a contributing effect on improving the weak interfacial bond between the carbon fiber and concrete; moreover, the composite admixture of carbon fiber and WBE improves the mechanical properties and durability of concrete, in which the composite admixture of 1% carbon fiber and 10% WBE has the best performance. The flexural strength and chlorine ion permeability resistance of concrete were slightly reduced after more than 10% admixture, but bond strength, tensile strength, compressive strength, dry shrinkage resistance, and frost resistance were promoted. The addition of WBE significantly retards the cement hydration process while greatly improving the compactness and impermeability of the concrete. Furthermore, the combined effects of WBE and carbon fiber effectively prevented the generation and expansion of cracks. The interaction mechanism and microstructure evolution between the WBE, carbon fiber, and cement hydration were described by clarifying the mineral composition, organic–inorganic interactions, the evolution of the hydration products, and composite morphology at different scales. Carbon fiber and WBE exhibited synergistic effects on the tensile strength, ductility, and crack resistance of concrete. In the formed three-dimensional network structural system of concrete, the WBE formed an organic coating layer on the fiber surface and provided fiber protection as well as interfacial bonding reinforcement for the embedded cement particles. Full article
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<p>The photo and SEM image of carbon fiber. The photo (<b>a</b>) and SEM (<b>b</b>) image of carbon fiber.</p>
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<p>Experimental instruments and samples: (<b>a</b>) Pressure testing machine, (<b>b</b>) concrete rapid freeze–thaw tester, (<b>c</b>) various specimens, (<b>d</b>) concrete mixer.</p>
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<p>Various specimens for different measurements. (<b>a</b>) Bond strength test samples, (<b>b</b>) freeze-thaw samples, (<b>c</b>) chloride ion diffusion specimen, and (<b>d</b>) axial compressive strength test samples.</p>
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<p>XRD patterns of various WBE-modified concrete types.</p>
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<p>SEM images of WBE-modified concrete with varied WBE contents: (<b>a</b>,<b>b</b>) C, (<b>c</b>,<b>d</b>) W5CF, (<b>e</b>,<b>f</b>) W10CF, (<b>g</b>,<b>h</b>) W20CF.</p>
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<p>The chemical reaction of WBE with cement hydration products, and the formation of three-dimensional network structure.</p>
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<p>Compressive strength of WBE-modified concrete with various WBE contents.</p>
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<p>The 28-day compressive strength stress–strain curves of modified concrete with different WBE contents. (<b>a</b>) 0, (<b>b</b>) 5%, (<b>c</b>) 10%, (<b>d</b>) 20%.</p>
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<p>The 28-day compressive Poisson’s ratio curves of modified concrete with various WBE contents. (<b>a</b>,<b>b</b>) 0, (<b>c</b>,<b>d</b>) 5% (<b>e</b>,<b>f</b>) 10%, (<b>g</b>,<b>h</b>) 20%.</p>
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<p>Poisson’s ratio and elasticity modulus of WBE-modified concrete.</p>
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<p>Flexural strength of WBE-modified concrete with various curing ages.</p>
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<p>Effect of bending–compressive ratios of WBE-modified concrete with various curing times.</p>
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<p>(<b>a</b>) Concrete axial tensile strength test, (<b>b</b>) 28-day tensile stress–strain curve of WBE-modified concrete.</p>
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<p>(<b>a</b>) The interface bond strength test loading equipment, (<b>b</b>) The interface bond strength of various WBE-modified concrete samples with curing age of 28 days.</p>
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<p>(<b>a</b>) Chloride ion flux test instrument, (<b>b</b>) chloride ion diffusion coefficient results of WBE-modified concrete of various curing ages.</p>
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<p>Photos of WBE-modified concrete specimen after 25, 100, 300 freeze–thaw cycles, (<b>a</b>–<b>c</b>) CF, (<b>d</b>–<b>f</b>) W5CF, (<b>g</b>–<b>i</b>) W10CF.</p>
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<p>Relative dynamic elastic modulus of WBE-modified concrete after the freeze–thaw cycles, The number of cycles are 0, 25, 50, 100, 200, 300, respectively.</p>
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<p>(<b>a</b>) Vertical dry shrinkage instrument, (<b>b</b>) samples, (<b>c</b>) the drying shrinkage of WBE-modified concrete of various curing ages.</p>
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