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39 pages, 7466 KiB  
Article
Evaluation of Adsorption Ability of Lewatit® VP OC 1065 and Diaion™ CR20 Ion Exchangers for Heavy Metals with Particular Consideration of Palladium(II) and Copper(II)
by Anna Wołowicz and Zbigniew Hubicki
Molecules 2024, 29(18), 4386; https://doi.org/10.3390/molecules29184386 (registering DOI) - 15 Sep 2024
Abstract
The adsorption capacities of ion exchangers with the primary amine (Lewatit® VP OC 1065) and polyamine (Diaion™ CR20) functional groups relative to Pd(II) and Cu(II) ions were tested in a batch system, taking into account the influence of the acid concentration (HCl: [...] Read more.
The adsorption capacities of ion exchangers with the primary amine (Lewatit® VP OC 1065) and polyamine (Diaion™ CR20) functional groups relative to Pd(II) and Cu(II) ions were tested in a batch system, taking into account the influence of the acid concentration (HCl: 0.1–6 mol/L; HCl-HNO3: 0.9–0.1 mol/L HCl—0.1–0.9 mol/L HNO3), phase contact time (1–240 min), initial concentration (10–1000 mg/L), agitation speed (120–180 rpm), bead size (0.385–1.2 mm), and temperature (293–333 K), as well as in a column system where the variable operating parameters were HCl and HNO3 concentrations. There were used the pseudo-first order, pseudo-second order, and intraparticle diffusion models to describe the kinetic studies and the Langmuir and Freundlich isotherm models to describe the equilibrium data to obtain better knowledge about the adsorption mechanism. The physicochemical properties of the ion exchangers were characterized by the nitrogen adsorption/desorption analyses, CHNS analysis, Fourier transform infrared spectroscopy, the sieve analysis, and points of zero charge measurements. As it was found, Lewatit® VP OC 1065 exhibited a better ability to remove Pd(II) than Diaion™ CR20, and the adsorption ability series for heavy metals was as follows: Pd(II) >> Zn(II) ≈ Ni(II) >> Cu(II). The optimal experimental conditions for Pd(II) sorption were 0.1 mol/L HCl, agitation speed 180 rpm, temperature 293 K, and bead size fraction 0.43 mm ≤ f3 < 0.6 mm for Diaion™ CR20 and 0.315–1.25 mm for Lewatit® VP OC 1065. The maximum adsorption capacities were 289.68 mg/g for Lewatit® VP OC 1065 and 208.20 mg/g for Diaion™ CR20. The greatest adsorption ability of Lewatit® VP OC 1065 for Pd(II) was also demonstrated in the column studies. The working ion exchange in the 0.1 mol/L HCl system was 0.1050 g/mL, much higher compared to Diaion™ CR20 (0.0545 g/mL). The best desorption yields of %D1 = 23.77% for Diaion™ CR20 and 33.57% for Lewatit® VP OC 1065 were obtained using the 2 mol/L NH3·H2O solution. Full article
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<p>Palladium and copper application, impact on the body, dietary sources and prices, supply, demand, and uses.</p>
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<p>Palladium and copper application, impact on the body, dietary sources and prices, supply, demand, and uses.</p>
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<p>(<b>a</b>) Percentage content of elements and (<b>b</b>) comparison of <span class="html-italic">pH<sub>PZC</sub></span> values in/for Lewatit<sup>®</sup> VP OC 1065 and Diaion™ CR20 ion exchange resins.</p>
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<p>Low-temperature adsorption/desorption nitrogen isotherm of (<b>a</b>) Diaion™ CR20 and (<b>b</b>) Lewatit<sup>®</sup> VP OC 1065 ion exchangers.</p>
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<p>ATR/FT-IR spectra of (<b>a</b>) Diaion™ CR20 and (<b>b</b>) Lewatit<sup>®</sup> VP OC 1065 before and after loading with Pd(II) and Cu(II) ions.</p>
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<p>Comparison of M(II) sorption efficiency expressed in <span class="html-italic">q<sub>t</sub></span> values for Diaion™ CR20 (<b>a</b>,<b>c</b>,<b>e</b>,<b>g</b>) and Lewatit<sup>®</sup> VP OC 1065 (<b>b</b>,<b>d</b>,<b>f</b>,<b>h</b>).</p>
Full article ">Figure 5 Cont.
<p>Comparison of M(II) sorption efficiency expressed in <span class="html-italic">q<sub>t</sub></span> values for Diaion™ CR20 (<b>a</b>,<b>c</b>,<b>e</b>,<b>g</b>) and Lewatit<sup>®</sup> VP OC 1065 (<b>b</b>,<b>d</b>,<b>f</b>,<b>h</b>).</p>
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<p>Effects of contact time and agitation speed on the Pd(II) adsorption on Diaion™ CR20 (<b>a</b>) and Lewatit<sup>®</sup> VP OC 1065 (<b>b</b>).</p>
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<p>Effects of contact time and the initial Pd(II) concentration on Pd(II) adsorption on Diaion™ CR20 (<b>a</b>) and Lewatit<sup>®</sup> VP OC 1065 (<b>b</b>).</p>
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<p>Effects of contact time and bead size of ion exchangers (f5 &lt; 0.385 mm; 0.385 mm ≤ f4 &lt; 0.43 mm; 0.43 mm ≤ f3 &lt; 0.6 mm; 0.6 mm ≤ f2 &lt; 0.75 mm; 0.75 mm ≤ f1 &lt; 1.2 mm) on Pd(II) adsorption on Diaion™ CR20 (<b>a</b>,<b>c</b>) and Lewatit<sup>®</sup> VP OC 1065 (<b>b</b>,<b>d</b>).</p>
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<p>Effects of contact time and temperature on the Pd(II) adsorption on Diaion™ CR20 (<b>a</b>) and Lewatit<sup>®</sup> VP OC 1065 (<b>b</b>).</p>
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<p>Effects of contact time and initial concentration (<b>a</b>), agitation speed (<b>b</b>), bead size of ion exchanger (f5 &lt; 0.385 mm; 0.385 mm ≤ f4 &lt; 0.43 mm; 0.43 mm ≤ f3 &lt; 0.6 mm; 0.6 mm ≤ f2 &lt; 0.75 mm; 0.75 mm ≤ f1 &lt; 1.2 mm), (<b>c</b>) and temperature (<b>d</b>) on Cu(II) adsorption on Diaion™ CR20 from 6 mol/L HCl—10 (<b>a</b>) or 50 mg Cu(II)/L (<b>a</b>–<b>d</b>).</p>
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<p>PFO (<b>a</b>,<b>b</b>), PSO (<b>c</b>,<b>d</b>), and IPD (<b>e</b>,<b>f</b>) plots and fitting of the experimental data of Pd(II) ion adsorption on Diaion™ CR20 (<b>g</b>) and Lewatit<sup>®</sup> VP OC 1065 (<b>h</b>).</p>
Full article ">Figure 11 Cont.
<p>PFO (<b>a</b>,<b>b</b>), PSO (<b>c</b>,<b>d</b>), and IPD (<b>e</b>,<b>f</b>) plots and fitting of the experimental data of Pd(II) ion adsorption on Diaion™ CR20 (<b>g</b>) and Lewatit<sup>®</sup> VP OC 1065 (<b>h</b>).</p>
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<p>Experimental points and fitting of the Langmuir and Freundlich isotherms for Pd(II) (<b>a</b>,<b>c</b>) and Cu(II) (<b>b</b>,<b>d</b>) ion adsorption on the Diaion™ CR20 (<b>a</b>,<b>b</b>) and Lewatit<sup>®</sup> VP OC 1065 (<b>c</b>,<b>d</b>).</p>
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<p>Comparison of the breakthrough curves of Pd(II) ion adsorption on Lewatit<sup>®</sup> VP OC 1065 (<b>a</b>,<b>c</b>) and Diaion™ CR20 (<b>b</b>,<b>d</b>) from the chloride 0.1–6 mol/L HCl—100 mg Pd(II)/L (<b>a</b>,<b>b</b>) and the chloride-nitrate(V) solutions 0.1–0.9 mol/L HCl—0.9–0.1 mol/L HNO<sub>3</sub>—100 mg Pd(II)/L (<b>c</b>,<b>d</b>).</p>
Full article ">Figure 13 Cont.
<p>Comparison of the breakthrough curves of Pd(II) ion adsorption on Lewatit<sup>®</sup> VP OC 1065 (<b>a</b>,<b>c</b>) and Diaion™ CR20 (<b>b</b>,<b>d</b>) from the chloride 0.1–6 mol/L HCl—100 mg Pd(II)/L (<b>a</b>,<b>b</b>) and the chloride-nitrate(V) solutions 0.1–0.9 mol/L HCl—0.9–0.1 mol/L HNO<sub>3</sub>—100 mg Pd(II)/L (<b>c</b>,<b>d</b>).</p>
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<p>Comparison of the adsorption (%<span class="html-italic">S</span>) and desorption (%<span class="html-italic">D</span>) efficiency of Pd(II) ions on/from (<b>a</b>) Diaion™ CR20, (<b>b</b>) Lewatit<sup>®</sup> VP OC 1065 ion exchangers in three adsorption–desorption cycles using ammonium hydroxide solutions.</p>
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<p>Effects of simultaneous presence of Pd(II) and Cu(II) ions in the solutions on their sorption yield on the Diaion™ CR20 and Lewatit<sup>®</sup> VP OC 1065 ion exchangers from the S (single) and B (bi-component) solutions.</p>
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<p>Diaion™ CR20 (<b>a</b>,<b>c</b>) and Lewatit<sup>®</sup> VP OC 1065 (<b>b</b>,<b>d</b>) ion exchange resins beads before the adsorption (<b>a</b>,<b>b</b>) (magnification 5×) and after the Cu(II) and Pd(II) adsorption (<b>c</b>,<b>d</b>) (magnification 2.5×).</p>
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34 pages, 8537 KiB  
Review
Biodegradable Natural Hydrogels for Tissue Engineering, Controlled Release, and Soil Remediation
by Ane Garcia-Garcia, Sara Muñana-González, Senentxu Lanceros-Mendez, Leire Ruiz-Rubio, Leyre Perez Alvarez and José Luis Vilas-Vilela
Polymers 2024, 16(18), 2599; https://doi.org/10.3390/polym16182599 (registering DOI) - 14 Sep 2024
Viewed by 271
Abstract
This article provides insights into hydrogels of the most promising biodegradable natural polymers and their mechanisms of degradation, highlighting the different possibilities of controlling hydrogel degradation rates. Since biodegradable hydrogels can be designed as scaffolding materials to mimic the physical and biochemical properties [...] Read more.
This article provides insights into hydrogels of the most promising biodegradable natural polymers and their mechanisms of degradation, highlighting the different possibilities of controlling hydrogel degradation rates. Since biodegradable hydrogels can be designed as scaffolding materials to mimic the physical and biochemical properties of natural tissues, these hydrogels have found widespread application in the field of tissue engineering and controlled release. In the same manner, their potential as water reservoirs, macro- and microelement carriers, or matrixes for the selective adsorption of pollutants make them excellent candidates for sustainable soil amendment solutions. Accordingly, this article summarizes the recent advances in natural biodegradable hydrogels in the fields of tissue engineering, controlled release, and soil remediation, emphasizing the new opportunities that degradability and its tunability offer for the design and applicability of hydrogels. Full article
(This article belongs to the Section Biobased and Biodegradable Polymers)
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<p>Degradation pathways of hydrogels based on possible bond cleavage points.</p>
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<p>Photolytic cleavage mechanism of NB-based linkers.</p>
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<p>Set of reactions during disulfide–thiol interchange via SN<sub>2</sub> substitution.</p>
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<p>Natural biodegradable polymers for hydrogel synthesis.</p>
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<p>Schematic illustration of the degradation products of starch according to the corresponding degradation mechanisms.</p>
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<p>Schematic illustration of the degradation products of cellulose according to the corresponding degradation mechanisms.</p>
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<p>Schematic illustration of the degradation products of chitin and chitosan according to the corresponding degradation mechanisms.</p>
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<p>Schematic illustration of the degradation products of alginate according to the corresponding degradation mechanisms.</p>
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<p>Schematic illustration of the degradation products of gelatin according to the corresponding degradation mechanisms.</p>
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<p>(<b>a</b>) Two-dimensional and (<b>b</b>) 3D live/dead fluorescence images of 3D-printed cells in MeGC-30, MeGC-50, MeGC-70, and MeGC-90 for 7 days of culture. Scale bars in (<b>a</b>) represent 200 μm. (<b>c</b>) Optical density and cell proliferation rate of printed MG-63 cells for 1, 3, 5, and 7 days (* <span class="html-italic">p</span> &lt; 0.05). Reprinted permission from [<a href="#B108-polymers-16-02599" class="html-bibr">108</a>], Copyright (2022) Elsevier.</p>
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<p>In vivo assessment of hydrogels for wound healing. Representative images of wounds treated with nothing (control), SA/BG hydrogel (SA/BG), physically encapsulated DFO-SA/BG hydrogel (F-DFO-SA/BG), and chemically grafted DFO-SA/BG hydrogel (G-DFO-SA/BG). Copyright © 2021. Zhang et al. [<a href="#B113-polymers-16-02599" class="html-bibr">113</a>].</p>
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<p>Proliferation study of ATDC-5 cells on ADA-GEL. Calcein AM/Hoechst stained ATDC-5 cells cultured on ADA-GEL crosslinked with 2.5%, 5%, and 10% (<span class="html-italic">w</span>/<span class="html-italic">v</span>) mTG for 1, 7, and 14 days (<span class="html-italic">n</span> = 3); scale bars = 100 μm. Adapted with permission from [<a href="#B122-polymers-16-02599" class="html-bibr">122</a>]. Copyright 2020, American Chemical Society.</p>
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<p>Controlled drug release mechanisms.</p>
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<p>Schematic representation of the double crosslinked chitosan-based hydrogel for enhanced rheological properties and controlled release of sodium diclofenac. Citric acid acts as the ionic crosslinker and the trehalose derivative as the covalent crosslinker. Copyright © The Royal Society of Chemistry 2020, reproduced with permission from Iglesias et al. [<a href="#B136-polymers-16-02599" class="html-bibr">136</a>].</p>
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<p>Applications of polymeric nanocarriers in the agricultural sector. Copyright © The Royal Society of Chemistry 2020, reproduced with permission from Shakiba et al. [<a href="#B158-polymers-16-02599" class="html-bibr">158</a>].</p>
Full article ">
15 pages, 10921 KiB  
Article
First-Principles Investigation on Ru-Doped Janus WSSe Monolayer for Adsorption of Dissolved Gases in Transformer Oil: A Novel Sensing Candidate Exploration
by Liang Cao, Ruilong Ma, Mingxin Ran and Hao Cui
Sensors 2024, 24(18), 5967; https://doi.org/10.3390/s24185967 (registering DOI) - 14 Sep 2024
Viewed by 173
Abstract
Using first-principles theory, this work purposes Ru-doped Janus WSSe (Ru-WSSe) monolayer as a potential gas sensor for detection of three typical gas species (CO, C2H2, and C2H4), in order to evaluate the operation status of [...] Read more.
Using first-principles theory, this work purposes Ru-doped Janus WSSe (Ru-WSSe) monolayer as a potential gas sensor for detection of three typical gas species (CO, C2H2, and C2H4), in order to evaluate the operation status of the oil-immersed transformers. The Ru-doping behavior on the WSSe surface is analyzed, giving rise to the preferred doping site by the replacement of a Se atom with the formation energy of 0.01 eV. The gas adsorption of three gas species onto the Ru-WSSe monolayer is conducted, and chemisorption is identified for all three gas systems with the adsorption energy following the order: CO (−2.22 eV) > C2H2 (−2.01 eV) > C2H4 (−1.70 eV). Also, the modulated electronic properties and the frontier molecular orbital are investigated to uncover the sensing mechanism of Ru-WSSe monolayer upon three typical gases. Results reveal that the sensing responses of the Ru-WSSe monolayer, based on the variation of energy gap, to CO, C2H2, and C2H4 molecules are calculated to be 1.67 × 106, 2.10 × 105, and 9.61 × 103, respectively. Finally, the impact of the existence of O2 molecule for gas adsorption and sensing is also analyzed to uncover the potential of Ru-WSSe monolayer for practical application in the air atmosphere. The obtained high electrical responses manifest strong potential as a resistive sensor for detection of three gases. The findings hold practical implications for the development of novel gas sensing materials based on Janus WSSe monolayer. We anticipate that our results will inspire further research in this domain, particularly for applications in electrical engineering where the reliable detection of fault gases is paramount for maintaining the integrity and safety of power systems. Full article
(This article belongs to the Section Chemical Sensors)
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<p>Configurations of pristine Janus WSSe monolayer (<b>a1</b>,<b>a2</b>), and Ru-doping from the Se-surface (<b>b1</b>,<b>b2</b>) and from the S-surface (<b>c1</b>,<b>c2</b>) of the WSSe monolayer.</p>
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<p>(<b>a</b>) CDD of Ru-WSSe monolayer, (<b>b</b>) BS of Ru-WSSe monolayer, and (<b>c</b>) orbital DOS of Ru and W atoms. In CDD, the cyan and violet areas are electron accumulation and depletion, respectively, with the isosurface of 0.02 e/Å<sup>3</sup>. In BS, the black value is the bandgap of Ru-WSSe monolayer.</p>
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<p>CO molecule (<b>a</b>), related gas adsorption configurations (<b>b</b>,<b>c</b>) and related CDD (<b>d</b>). In CDD, the settings are the same as <a href="#sensors-24-05967-f002" class="html-fig">Figure 2</a>.</p>
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<p>C<sub>2</sub>H<sub>2</sub> molecule (<b>a</b>), related gas adsorption configurations (<b>b</b>,<b>c</b>) and related CDD (<b>d</b>). In CDD, the settings are the same as <a href="#sensors-24-05967-f002" class="html-fig">Figure 2</a>.</p>
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<p>C<sub>2</sub>H<sub>4</sub> molecule (<b>a</b>), related gas adsorption configurations (<b>b</b>,<b>c</b>) and related CDD (<b>d</b>). In CDD, the set are the same as <a href="#sensors-24-05967-f002" class="html-fig">Figure 2</a>.</p>
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<p>Electronic properties of gas adsorbed Ru-WSSe systems. (<b>a1</b>–<b>a3</b>) CO system, (<b>b1</b>–<b>b3</b>) C<sub>2</sub>H<sub>2</sub> system and (<b>c1</b>–<b>c3</b>) C<sub>2</sub>H<sub>4</sub> system. The settings here are the same as <a href="#sensors-24-05967-f002" class="html-fig">Figure 2</a>.</p>
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<p>Distributions and energy levels of the HOMO and LUMO for both the isolated and gas adsorbed Ru-WSSe monolayers.</p>
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<p>Adsorption of O<sub>2</sub>, co-adsorption of O<sub>2</sub> and typical gases on Ru-WSSe monolayer and related BS. In BS, the black values are bandgap. (<b>a1</b>,<b>a2</b>) O<sub>2</sub> system, (<b>b1</b>,<b>b2</b>) O<sub>2</sub>@CO system, (<b>c1</b>,<b>c2</b>) O<sub>2</sub>@C<sub>2</sub>H<sub>2</sub> system and (<b>d1</b>,<b>d2</b>) O<sub>2</sub>@C<sub>2</sub>H<sub>4</sub> system.</p>
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14 pages, 2618 KiB  
Review
A Critical Review of the Crucial Role of the Yellow River’s Sediment in the Interfacial Migration and Fate of Pollutants and Prospects for the Application of Environmental Sediment Restoration
by Xiaojuan Sun, Zhenzhen Yu, Qiting Zuo, Quantao Cui, Ziyu Song, Lin Gong, Shoushu Liu and Wei Zhang
Toxics 2024, 12(9), 669; https://doi.org/10.3390/toxics12090669 (registering DOI) - 14 Sep 2024
Viewed by 161
Abstract
Considering the increasing sediment content and increasing sediment flux of the Yellow River over the years, it is of significance to investigate the potential interfacial force mechanism between pollutants and Yellow River sediment. This article has reviewed the current research on the Yellow [...] Read more.
Considering the increasing sediment content and increasing sediment flux of the Yellow River over the years, it is of significance to investigate the potential interfacial force mechanism between pollutants and Yellow River sediment. This article has reviewed the current research on the Yellow River sediments’ mineral structures while investigating the potential interaction force between sediment and pollutants in the water environment. This article has conducted a comprehensive analysis of the influence of sediment on the migration of pollutants in the water environment. What is more, the authors have provided an outlook on the future applications of sediment in ecological environmental systems. Yellow River sediment mainly included minerals and some clay phases, while its irregular surface provided sites for the interface adsorption of pollutants. The interface force between the sediment and pollutants is mainly attributed to promoting bacterial growth on the surface of sediments, physisorption, and chemisorption forces. The sediments carry and transport pollutants during the long-distance water flow migration process. The sediment should be effectively utilized and better integrated into ecological or environmental restoration systems. This article provides a reference for studying the behavior of Yellow River sediment and the direction of future efficient utilization. Full article
(This article belongs to the Section Toxicity Reduction and Environmental Remediation)
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<p>(<b>a</b>) The main geological conditions along the Yellow River and the dominant mineral composition in the collected sediment samples; (<b>b</b>) SEM image of the collected suspended sediments downstream of the Yellow River [<a href="#B14-toxics-12-00669" class="html-bibr">14</a>,<a href="#B22-toxics-12-00669" class="html-bibr">22</a>]; and (<b>c</b>) XRD patterns of the collected suspended sediments downstream of the Yellow River [<a href="#B14-toxics-12-00669" class="html-bibr">14</a>,<a href="#B22-toxics-12-00669" class="html-bibr">22</a>].</p>
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<p>The potential interface interactions between the sediment and pollutants: (<b>A</b>) sediment acting in the nitrification/denitrification process. (<b>B</b>) contributions of different components of sediment to the adsorption of TC. Herein, (a) presenting adsorption capacity of different components of SS to TC; (b) K<sub>d</sub> values and (c) presenting the contributions of different mineral fractions to the overall adsorption coefficients; adsorption energies (d) SiO<sub>2</sub>, (e) Al<sub>2</sub>O<sub>3</sub>, and (f) Fe<sub>2</sub>O<sub>3</sub> for TC adsorption. (<b>C</b>) sediment interfacial reaction with heavy metal ions; (<b>D</b>) potential interfacial reaction between sediment (collected from the Lanzhou section) and CTC.</p>
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<p>The potential influence of SS on transport pathways and dispersion of pollutants: (<b>a</b>) SS with oil pollutants; (<b>b</b>) SS with trace metals; (<b>c</b>) SS with P; (<b>d</b>) SS with heavy metals.</p>
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<p>Potential application of sediment in the environmental restoration process: (<b>a</b>) sediment application in eco-concrete materials; (<b>b</b>) a mechanism diagram of sediment acting in the environmental remediation process.</p>
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12 pages, 4198 KiB  
Article
Decorating TiO2 Nanoparticle Thin Film with SnSx (x < 1): Preparation, Characterization, and Photocatalytic Activity
by Fang Xu, Nicola Scaramuzza and Carlo Versace
Coatings 2024, 14(9), 1185; https://doi.org/10.3390/coatings14091185 - 12 Sep 2024
Viewed by 267
Abstract
We report a study on the SnSx (x < 1) decoration of porous TiO2 nanoparticle thin films using the ionic layer adsorption and reaction (ILAR) method. UV-vis absorption measurements revealed a direct bandgap of 1.40–2.10 eV for SnSx (with [...] Read more.
We report a study on the SnSx (x < 1) decoration of porous TiO2 nanoparticle thin films using the ionic layer adsorption and reaction (ILAR) method. UV-vis absorption measurements revealed a direct bandgap of 1.40–2.10 eV for SnSx (with x = 0.85) and 3.15 eV for TiO2. Degradation of rhodamine B molecules in aqueous solutions shows that coating with a Sn-to-Ti molar ratio of 2% improves the efficiency of the photocatalytic performance of titanium dioxide, but excessive coverage decreases it. We interpret the observed behavior as due to a delicate balance of many competing factors. The formation of intimate interfaces guaranteed by the ILAR growth technique and a nearly optimal alignment of conduction band edges facilitate electron transfer, reducing electron–hole recombination rates. However, the valence hole transfer from TiO2 to SnS reduces the oxidative potential, which is crucial in the degradation mechanism. Full article
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<p>SEM images of a pure TiO<sub>2</sub> thin film (<b>A</b>,<b>C</b>) and an SnS<span class="html-italic"><sub>x</sub></span> (Sn100S600)-coated TiO<sub>2</sub> film (<b>B</b>,<b>D</b>). The beam energy was 5 keV for (<b>A</b>,<b>B</b>) and 10 keV for (<b>C</b>,<b>D</b>), while the magnification was 500 k for all images.</p>
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<p>Cross-sectional SEM image showing a TiO<sub>2</sub> thin film about 11 μm thick.</p>
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<p>EDX spectra for a pure TiO<sub>2</sub> thin film (<b>A</b>) and two SnS<span class="html-italic"><sub>x</sub></span>-coated TiO<sub>2</sub> thin films (<b>B</b>,<b>C</b>). Also indicated are the molar ratios between various elements.</p>
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<p>XRD pattern for a pure TiO<sub>2</sub> nanoparticle (P25) thin film deposited on an FTO-grazed glass substrate (a); decorated with SnS<span class="html-italic"><sub>x</sub></span> Sn020S120 (b); Sn100S600 (c); and Sn100S600 (5 cycles) (d).</p>
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<p>XPS spectra of Ti 2p, O 1s, Sn 3d, and S 2p levels for films of pure TiO<sub>2</sub> (Sn000S000) and SnS<span class="html-italic"><sub>x</sub></span>-coated (Sn100S600) TiO<sub>2</sub> films.</p>
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<p>Upper panel: UV-vis optical absorption spectra of pure TiO<sub>2</sub> thin film and decorated TiO<sub>2</sub> films with SnS<span class="html-italic"><sub>x</sub></span> NPs of different amounts; Lower panel: bandgap energy determination made using the Tauc plots.</p>
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<p>Upper panel: Time evolution of the RhB absorption spectra for the sample Sn005S030. Middle panel: Relative RhB concentration change C(t)/C<sub>0</sub> as a function of Xe lamp irradiation time t for various SnS<span class="html-italic"><sub>x</sub></span>@TiO<sub>2</sub> films. The lines are the linear fittings. Lower panel: The zero-order degradation rate constant vs. Sn-to-Ti molar ratio.</p>
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<p>Energy level potential diagram of SnS, TiO<sub>2</sub>, RhB, and relevant redox reactions.</p>
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20 pages, 5062 KiB  
Article
Preparation of NH2-MIL-101(Fe) Metal Organic Framework and Its Performance in Adsorbing and Removing Tetracycline
by Yiting Luo and Rongkui Su
Int. J. Mol. Sci. 2024, 25(18), 9855; https://doi.org/10.3390/ijms25189855 - 12 Sep 2024
Viewed by 196
Abstract
Tetracycline’s accumulation in the environment poses threats to human health and the ecological balance, necessitating efficient and rapid removal methods. Novel porous metal–organic framework (MOF) materials have garnered significant attention in academia due to their distinctive characteristics. This paper focuses on studying the [...] Read more.
Tetracycline’s accumulation in the environment poses threats to human health and the ecological balance, necessitating efficient and rapid removal methods. Novel porous metal–organic framework (MOF) materials have garnered significant attention in academia due to their distinctive characteristics. This paper focuses on studying the adsorption and removal performance of amino-modified MIL-101(Fe) materials towards tetracycline, along with their adsorption mechanisms. The main research objectives and conclusions are as follows: (1) NH2-MIL-101(Fe) MOF materials were successfully synthesized via the solvothermal method, confirmed through various characterization techniques including XRD, FT-IR, SEM, EDS, XPS, BET, and TGA. (2) NH2-MIL-101(Fe) exhibited a 40% enhancement in tetracycline adsorption performance compared to MIL-101(Fe), primarily through chemical adsorption following pseudo-second-order kinetics. The adsorption process conformed well to Freundlich isotherm models, indicating multilayer and heterogeneous adsorption characteristics. Thermodynamic analysis revealed the adsorption process as a spontaneous endothermic reaction. (3) An increased adsorbent dosage and temperature correspondingly improved NH2-MIL-101(Fe)’s adsorption efficiency, with optimal performance observed under neutral pH conditions. These findings provide new strategies for the effective removal of tetracycline from the environment, thus holding significant implications for environmental protection. Full article
(This article belongs to the Special Issue Molecular Research on Nanosorbent Materials)
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<p>XRD spectrum of MIL-101(Fe) and NH<sub>2</sub>-MIL-101(Fe).</p>
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<p>FT-IR spectrum of NH<sub>2</sub>-MIL-101(Fe) and MIL-101(Fe).</p>
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<p>SEM and EDS images of NH<sub>2</sub>-MIL-101(Fe).</p>
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<p>XPS spectrum of NH<sub>2</sub>-MIL-101(Fe).</p>
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<p>N<sub>2</sub> adsorption–desorption isotherm (<b>a</b>) and pore size analysis (<b>b</b>) of NH<sub>2</sub>-MIL-101(Fe).</p>
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<p>Thermogravimetric analysis of NH<sub>2</sub>-MIL-101(Fe).</p>
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<p>Comparison of adsorption performance between MIL-101(Fe) and NH<sub>2</sub>-MIL-101(Fe).</p>
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<p>Adsorption isotherms.</p>
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<p>Langmuir Model adsorption isotherm fitting.</p>
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<p>Freundlich Model adsorption isotherm fitting.</p>
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<p>Relationship between ln<span class="html-italic">K</span><sub>F</sub> and 1/T.</p>
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<p>Adsorption efficiency of different NH<sub>2</sub>-MIL-101(Fe) dosages.</p>
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<p>pH effect on NH<sub>2</sub>-MIL-101(Fe) adsorption capacity.</p>
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27 pages, 15488 KiB  
Review
Gels for Water Remediation: Current Research and Perspectives
by Gabriela Buema, Adina-Elena Segneanu, Dumitru-Daniel Herea and Ioan Grozescu
Gels 2024, 10(9), 585; https://doi.org/10.3390/gels10090585 - 12 Sep 2024
Viewed by 351
Abstract
The development of cost-effective and high-performance technologies for wastewater treatment is essential for achieving a sustainable economy. Among the various methods available for water remediation, adsorption is widely recognized as an effective and straightforward approach for removing a range of pollutants. Gel materials, [...] Read more.
The development of cost-effective and high-performance technologies for wastewater treatment is essential for achieving a sustainable economy. Among the various methods available for water remediation, adsorption is widely recognized as an effective and straightforward approach for removing a range of pollutants. Gel materials, particularly hydrogels and aerogels, have attracted significant research interest due to their unique properties. Hydrogels, for instance, are noted for their ability to be regenerated and reused, ease of separation and handling, and suitability for large-scale applications. Additionally, their low cost, high water absorption capacity, and contribution to environmental protection are important advantages. Aerogels, on the other hand, are distinguished by their low thermal conductivity, transparency, flexibility, high porosity, mechanical strength, light weight, large surface area, and ultralow dielectric constant. This review provides a comprehensive analysis of the current literature, highlighting gaps in knowledge regarding the classification, preparation, characterization, and key properties of these materials. The potential application of hydrogels and aerogels in water remediation, particularly in removing contaminants such as dyes, heavy metals, and various organic and inorganic pollutants, is also discussed. Full article
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<p>Reusability studies of the hydrogels on the adsorption of methylene blue (<b>left</b>); effect of the initial methylene blue concentration on the adsorption of Ag/TPP/rGH (<b>right</b>). Source [<a href="#B35-gels-10-00585" class="html-bibr">35</a>] with permission from the Elsevier and Copyright Clearance Center.</p>
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<p>(<b>a</b>) Adsorption capacity of the CMCS-PA composite hydrogels for methyl orange and congo red dyes in different ratios; (<b>b</b>) Adsorption capacity for methyl orange and congo red dyes of the CMCS-PA (3:1 ratio) at different solution pH values. Source [<a href="#B39-gels-10-00585" class="html-bibr">39</a>], with permission from Elsevier and the Copyright Clearance Center.</p>
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<p>(<b>a</b>,<b>b</b>) SEM images of GO; (<b>c</b>,<b>d</b>) SEM images of freeze-dried agar-GO; (<b>e</b>,<b>f</b>) SEM images of powdered pure agar; (<b>g</b>) Photograph of the produced hydrogel. Source [<a href="#B41-gels-10-00585" class="html-bibr">41</a>], with permission from Elsevier and the Copyright Clearance Center.</p>
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<p>Changes in the absorption spectrum: (<b>a</b>) brilliant green (BG); (<b>b</b>) crystal violet (CV); (<b>c</b>) bismark brown (BB); (<b>d</b>) rose bengal (RB); (<b>e</b>) eosin blue (EB); (<b>f</b>) fuchsin acid (FA); (<b>g</b>) malachite green (MG); (<b>h</b>) the mixture of malachite green (MG) and fuchsin acid (FA). Source [<a href="#B43-gels-10-00585" class="html-bibr">43</a>] with permission from the Elsevier and Copyright Clearance Center.</p>
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<p>Schematic diagram of the study. Source [<a href="#B60-gels-10-00585" class="html-bibr">60</a>], with permission from Elsevier and the Copyright Clearance Center.</p>
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<p>Effect of co-existing cations on the adsorption of (<b>a</b>) Pb(II) and (<b>b</b>) Cu(II). Source [<a href="#B64-gels-10-00585" class="html-bibr">64</a>], with permission from Elsevier and the Copyright Clearance Center.</p>
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<p>Schematic diagram of the synthesis of hydrogel. Source [<a href="#B68-gels-10-00585" class="html-bibr">68</a>], with permission from Elsevier and the Copyright Clearance Center.</p>
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<p>(<b>a</b>) UV–vis absorption spectra of Rhodamine B, solution adsorbed by graphene oxide/locust bean gum (GO/LBG) aerogels with GO/LBG mass ratios of 1:4 (GO/LBG-1), 1:8 (GO/LBG-2), 1:16 (GO/LBG-3) for 24 h, (<b>b</b>) the maximum adsorption quantity on Rhodamine B of GO/LBG-1, GO/LBG-2, and GO/LBG-3 aerogels, (<b>c</b>) UV–vis absorption spectra of Indigo carmine solution adsorbed by GO/LBG-1, GO/LBG-2, and GO/LBG-3 aerogels for 24 h, and (<b>d</b>) the maximum adsorption quantity on Indigo carmine of GO/LBG-1, GO/LBG-2, and GO/LBG-3 aerogels. Source [<a href="#B88-gels-10-00585" class="html-bibr">88</a>] with permission from the Elsevier and Copyright Clearance Center.</p>
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<p>SEM images of CMC/O (<b>a</b>), CMC/CNF–C (<b>b</b>), CMC/CNFs (<b>c</b>), and CMC/CNWs (<b>d</b>). Source [<a href="#B81-gels-10-00585" class="html-bibr">81</a>], with permission from Elsevier and the Copyright Clearance Center.</p>
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<p>(<b>a</b>) Adsorption quantity of variable organic dyes, methylene blue (MB), malachite green (MG), rhodamine 6G (Rh6G), Rose bengal (RB), and methyl orange (MO) by CGA as a function of time. (<b>b</b>) Dye adsorption efficiency of CGA at equilibrium, along with the demonstration of the molecular structure of each dye. Source [<a href="#B89-gels-10-00585" class="html-bibr">89</a>] with permission from the Elsevier and Copyright Clearance Center.</p>
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<p>Schematic diagram of the synthesis of MOF-801 (<b>a</b>) and TMPA@MOF-801 aerogel (<b>b</b>). Source [<a href="#B91-gels-10-00585" class="html-bibr">91</a>], with permission from Elsevier and the Copyright Clearance Center.</p>
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16 pages, 5784 KiB  
Article
Diatom-Based Artificial Anode—Uniform Coating of Intrinsic Carbon to Enhance Lithium Storage
by Junlong Luo, Jun Cai, De Gong, Aoping Guo, Jaw-Kai Wang and Jiangtao Zhang
Materials 2024, 17(18), 4473; https://doi.org/10.3390/ma17184473 - 12 Sep 2024
Viewed by 274
Abstract
Pursuing improved electrode materials is essential for addressing the challenges associated with large-scale Li-ion battery applications. Specifically, silicon oxide (SiOx) has emerged as a promising alternative to graphite anodes, despite issues related to volume expansion and rapid capacity degradation. In this [...] Read more.
Pursuing improved electrode materials is essential for addressing the challenges associated with large-scale Li-ion battery applications. Specifically, silicon oxide (SiOx) has emerged as a promising alternative to graphite anodes, despite issues related to volume expansion and rapid capacity degradation. In this study, we synthesized carbon-coated SiOx using diatom biomass derived from artificially cultured diatoms. However, the inherent carbon content from diatoms poses a significant challenge for the electrochemical performance of diatom-based anodes in large-scale applications. Subsequently, we conducted further research and demonstrated excellent performance with a carbon content of 33 wt.% as anodes. Additionally, real-time characterization of the carbonization process was achieved using thermogravimetry coupled with infrared spectroscopy and gas chromatography mass spectrometry (TG-FTIR-GCMS), revealing the emission of CO and C3O2 during carbonization. Furthermore, electrochemical tests of the processed diatom and carbon (PD@C) anode exhibited outstanding rate capability (~500 mAh g−1 at 2 A g−1), high initial Coulomb efficiency (76.95%), and a DLi+ diffusion rate of 1.03 × 10−12 cm2 s−1. Moreover, structural characterization techniques such as HRTEM-SAED were employed, along with DFT calculations, to demonstrate that the lithium storage process involves not only reversible transport in Li2Si2O5 and Li22Si5, but also physical adsorption between the PD and C layers. Exploring the integration of diatom frustules with the intrinsic carbon content in the fabrication of battery anodes may contribute to a deeper understanding of the mechanisms behind their successful application. Full article
(This article belongs to the Special Issue Artificial Biomimetic Materials)
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<p>Schematic illustration of characterization of diatom biomass and their applications as lithium anodes.</p>
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<p>(<b>a</b>) Manufacturing process of carbon layer, and (<b>b</b>) capacity of different carbon content after different cycles. (<b>c</b>) SEM comparison figures of purified diatoms and processed purified diatoms with carbon content of 33 wt.%. * Optimum electrochemical performance.</p>
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<p>TG−FTIR−GCMS results of the process in the carbonization: (<b>a</b>) TG−DSC curves, (<b>b</b>) 3D TG−FTIR spectra, and (<b>c</b>) chromatogram of GC−MS to identify the emitting compounds; refer to <a href="#app1-materials-17-04473" class="html-app">Figure S4</a> for further MS information.</p>
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<p>Test results of sample before and after carbonization: (<b>a</b>) XRD, (<b>b</b>) Raman, (<b>c</b>) FTIR, and (<b>d</b>) BET.</p>
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<p>Test results of sample after carbonization: (<b>a</b>–<b>d</b>) XPS, (<b>e</b>) SEM-EDS.</p>
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<p>Electrochemical performance of the PD@C anode: (<b>a</b>) CV curves, (<b>b</b>) selected galvanostatic charge/discharge profiles, (<b>c</b>) rate ratio, (<b>d</b>) cycling performance, (<b>e</b>,<b>f</b>) EIS and the curves of Z’ and ω<sup>−1/2</sup>, and (<b>g</b>) schematic illustration of the bonds formed between the <math display="inline"><semantics> <mrow> <msub> <mi mathvariant="italic">SiO</mi> <mi>x</mi> </msub> </mrow> </semantics></math> shell and the lithiation product in sufficient electrical contact.</p>
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<p>(<b>a</b>) Macropores, mesopores, and micropores of the PD@C via TEM, (<b>b</b>) SEI layer formed after the first cycle, TEM-SAED pattern of the anode (<b>c</b>) after 200 cycles and (<b>d</b>) before cycling, and (<b>e</b>,<b>f</b>) TEM images of the anode after 200 cycles.</p>
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<p>(<b>a</b>) Side view and top view of three sites of Li<sup>+</sup> adsorption, (<b>b</b>) density of states of C, SiO<sub>2</sub>, and SiO<sub>2</sub>@C, (<b>c</b>) adsorption energies of different positions, and (<b>d</b>) differential charge results of the SiO<sub>2</sub>@C.</p>
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<p>(<b>a</b>) CV curves of PD @ C electrode materials at different sweeping rates, (<b>b</b>) fitting diagram of sweep speed and current, (<b>c</b>) proportion of pseudocapacitance at a sweep rate of 0.4 mV s<sup>−1</sup>, (<b>d</b>) contributions of volume control and diffusion control at different scan rates.</p>
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11 pages, 4147 KiB  
Article
Introducing Molecular Sieve into Activated Carbon to Achieve High-Effective Adsorption for Ethylene Oxide
by Feng Liu, Lingyan Qin, Pingwei Ye, Bo Yang, Qiong Wu, Li Li, Yuwei Dai, Chuan Zhou and Sumin Li
Nanomaterials 2024, 14(18), 1482; https://doi.org/10.3390/nano14181482 - 12 Sep 2024
Viewed by 340
Abstract
Presently, ethylene oxide (EtO) is posing a significant threat to both human health and the environment due to occasional or deliberate emissions. However, few works so far have focused on this issue. It is urgent to explore novel and effective technology to protect [...] Read more.
Presently, ethylene oxide (EtO) is posing a significant threat to both human health and the environment due to occasional or deliberate emissions. However, few works so far have focused on this issue. It is urgent to explore novel and effective technology to protect against the threat of EtO. Herein, a series of AC/ZSM-5 composites were prepared to improve the adsorption performance for EtO, evaluated by dynamic breakthrough experiments. Particularly, the AC/ZSM-20% composite demonstrated a more excellent adsorption capacity of 81.9 mg/g at 25 °C and 50% RH than that of pristine AC and ZSM-5 with 32.5 and 52.3 mg/g, respectively. Moreover, the adsorption capacity of the AC/ZSM-20% composite remained constant even after five adsorption-desorption cycles. The adsorption mechanism of EtO on the composite is further revealed by density functional theory (DFT) calculations. Full article
(This article belongs to the Section Nanocomposite Materials)
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<p>Schematic diagram of the synthesis of the AC/ZSM-5 composite.</p>
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<p>SEM images of (<b>a</b>) AC-R; (<b>e</b>) ZSM-R; (<b>b</b>,<b>f</b>) AC/ZSM-10% at different magnifications; (<b>c</b>,<b>g</b>) AC/ZSM-20% at different magnifications; and (<b>d</b>,<b>h</b>) AC/ZSM-30% at different magnifications.</p>
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<p>(<b>a</b>) XRD patterns, (<b>b</b>) TGA curves, (<b>c</b>) FT-IR spectra, (<b>d</b>) N<sub>2</sub> adsorption-desorption isotherms, (<b>e</b>) DFT pore size distributions, and (<b>f</b>) BJH pore size distributions of samples.</p>
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<p>Comparison of dynamic adsorption performance of EtO at 25 °C and 50% RH (<b>a</b>) breakthrough curves and (<b>b</b>) histograms of calculated EtO adsorption capacity.</p>
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<p>Comparison of saturated adsorption capacity of EtO adsorbed by different adsorbents; data are processed according to <a href="#app1-nanomaterials-14-01482" class="html-app">Tables S1 and S2</a>.</p>
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<p>Comparison of dynamic adsorption performance of AC/ZSM-20% for EtO at different humidity levels (<b>a</b>) breakthrough curves, (<b>b</b>) EtO adsorption capacity, (<b>c</b>) calculated adsorption capacity for five cycles at 0% RH and (<b>d</b>) water vapor adsorption-desorption isotherm at 25 °C.</p>
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<p>Mathematical adsorption simulation curves for (<b>a</b>) AC/ZSM-5 composites and (<b>b</b>) AC/ZSM-20% under different humidity conditions.</p>
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<p>Comparison of DFT-calculated adsorption performance of AC, ZSM-5, and AC/ZSM-20% for EtO. (<b>a</b>) AC adsorption configuration, (<b>b</b>) ZSM-5 adsorption configuration, (<b>c</b>) AC/ZSM-20% adsorption configuration, and (<b>d</b>) comparison of adsorbent configuration and adsorption capacity.</p>
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38 pages, 1278 KiB  
Review
Innovative Adsorbents for Pollutant Removal: Exploring the Latest Research and Applications
by Muhammad Saeed Akhtar, Sajid Ali and Wajid Zaman
Molecules 2024, 29(18), 4317; https://doi.org/10.3390/molecules29184317 - 11 Sep 2024
Viewed by 281
Abstract
The growing presence of diverse pollutants, including heavy metals, organic compounds, pharmaceuticals, and emerging contaminants, poses significant environmental and health risks. Traditional methods for pollutant removal often face limitations in efficiency, selectivity, and sustainability. This review provides a comprehensive analysis of recent advancements [...] Read more.
The growing presence of diverse pollutants, including heavy metals, organic compounds, pharmaceuticals, and emerging contaminants, poses significant environmental and health risks. Traditional methods for pollutant removal often face limitations in efficiency, selectivity, and sustainability. This review provides a comprehensive analysis of recent advancements in innovative adsorbents designed to address these challenges. It explores a wide array of non-conventional adsorbent materials, such as nanocellulose, metal–organic frameworks (MOFs), graphene-based composites, and biochar, emphasizing their sources, structural characteristics, and unique adsorption mechanisms. The review discusses adsorption processes, including the basic principles, kinetics, isotherms, and the factors influencing adsorption efficiency. It highlights the superior performance of these materials in removing specific pollutants across various environmental settings. The practical applications of these adsorbents are further explored through case studies in industrial settings, pilot studies, and field trials, showcasing their real-world effectiveness. Additionally, the review critically examines the economic considerations, technical challenges, and environmental impacts associated with these adsorbents, offering a balanced perspective on their viability and sustainability. The conclusion emphasizes future research directions, focusing on the development of scalable production methods, enhanced material stability, and sustainable regeneration techniques. This comprehensive assessment underscores the transformative potential of innovative adsorbents in pollutant remediation and their critical role in advancing environmental protection. Full article
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<p>Mechanism of adsorption process.</p>
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<p>Overview of innovative adsorbent types.</p>
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17 pages, 13949 KiB  
Article
One-Pot Synthesis of Biochar from Industrial Alkali Lignin with Superior Pb(II) Immobilization Capability
by Jiale Li, Taoze Liu and Zhanghong Wang
Molecules 2024, 29(18), 4310; https://doi.org/10.3390/molecules29184310 - 11 Sep 2024
Viewed by 273
Abstract
This study synthesized biochar through a one-pot pyrolysis process using IALG as the raw material. The physicochemical properties of the resulting biochar (IALG-BC) were characterized and compared with those of biochar derived from acid-treated lignin with the ash component removed (A-IALG-BC). This study [...] Read more.
This study synthesized biochar through a one-pot pyrolysis process using IALG as the raw material. The physicochemical properties of the resulting biochar (IALG-BC) were characterized and compared with those of biochar derived from acid-treated lignin with the ash component removed (A-IALG-BC). This study further investigated the adsorption performances and mechanisms of these two lignin-based biochars for Pb(II). The results revealed that the high ash content in IALG, primarily composed of Na, acts as an effective catalyst during pyrolysis, reducing the activation energy and promoting the development of the pore structure in the resulting biochar (IALG-BC). Moreover, after pyrolysis, Na-related minerals transformed into particulate matter sized between 80 and 150 nm, which served as active adsorption sites for the efficient immobilization of Pb(II). Adsorption results demonstrated that IALG-BC exhibited a significantly superior adsorption performance for Pb(II) compared to that of A-IALG-BC. The theoretical maximum adsorption capacity of IALG-BC for Pb(II), derived from the Langmuir model, was determined to be 809.09 mg/g, approximately 40 times that of A-IALG-BC. Additionally, the adsorption equilibrium for Pb(II) with IALG-BC was reached within approximately 0.5 h, whereas A-IALG-BC required more than 2 h. These findings demonstrate that the presence of inorganic mineral components in IALG plays a crucial role in its resource utilization. Full article
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<p>Thermal pyrolysis behavior of IALG and A-IALG.</p>
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<p>N<sub>2</sub> adsorption/desorption isotherm curves of IALG-BC and A-IALG-BC.</p>
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<p>Surface functional groups of IALG-BC and A-IALG-BC.</p>
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<p>SEM images of biochars: (<b>a</b>) 5000× IALG-BC; (<b>b</b>) 150,000× IALG-BC; (<b>c</b>) 5000× A-IALG-BC.</p>
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<p>XRD patterns of IALG-BC and A-IALG-BC.</p>
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<p>Effect of Pb(II) initial concentration of the adsorption capabilities of IALG-BC and A-IALG-BC.</p>
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<p>Effect of contact time on the adsorption capabilities of IALG-BC and A-IALG-BC.</p>
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<p>Effect of ambient temperature on the adsorption capabilities of IALG-BC and A-IALG-BC.</p>
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<p>Forms of Pb(II) at different solution pH values (<b>a</b>) and effect of solution pH on the adsorption capabilities of IALG-BC and A-IALG-BC (<b>b</b>).</p>
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<p>Adsorption isotherm fitting for the adsorption of Pb(II) on IALG-BC and A-IALG-BC.</p>
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<p>Adsorption kinetic fitting for the adsorption of Pb(II) on IALG-BC and A-IALG-BC (<b>a</b>), SEM image of 5000× IALG-BC after Pb(II) adsorption (<b>b</b>) and SEM image of 150,000× IALG-BC after Pb(II) adsorption (<b>c</b>).</p>
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12 pages, 1611 KiB  
Article
Application of High-Resolution Infrared Thermography to Study the Effects of Technologically Processed Antibodies on the Near-Surface Layer of Aqueous Solutions
by Elena Don, Evgenii Zubkov, Ekaterina Moroshkina, Irina Molodtsova, Anastasia Petrova and Sergey Tarasov
Molecules 2024, 29(18), 4309; https://doi.org/10.3390/molecules29184309 - 11 Sep 2024
Viewed by 235
Abstract
A new class of biologics is obtained using the technologically processed of antibodies (TPA), which are used as the initial substance, and their dilution at each stage is accompanied by a controlled external vibrational (mechanical) treatment. This article focuses on the development and [...] Read more.
A new class of biologics is obtained using the technologically processed of antibodies (TPA), which are used as the initial substance, and their dilution at each stage is accompanied by a controlled external vibrational (mechanical) treatment. This article focuses on the development and validation of a novel technique that can be applied for assessing the identity of TPA-based drugs. It has previously been found that after such treatment, the resulting solution either acquired new properties that were not present in the initial substance or a quantitative change in properties compared to the initial substance was observed. The use of mechanical treatment during the manufacture of the TPA-based drugs can cause the formation of new bonds between the solvent and antibody molecules. These changes manifest themselves in altered adsorption at the surface of the test solutions, which results in the formation of a near-surface film. One of the indicators of such events is the change in the surface temperature of the solution, which can be analyzed using high-resolution thermography. Unlike other methods, the high-resolution thermography allows the near-surface layer of a heterogeneous aqueous solution to be clearly visualized and quantified. A number of experiments were performed: seven replicates of sample preparations were tested; the influence of factors “day” or “operator” was investigated during 12 days of testing by two operators. The method also allowed us to distinguish between technologically processed antibodies and samples containing technologically processed buffer. The thermographic analysis has proven to be a simple, specific, and reproducible technique that can be used to analyze the identity of TPA-based drugs, regardless of the dosage form tested. Full article
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<p>The mean surface area free of film for samples of one batch of the test sample and placebo. (*—<span class="html-italic">p</span> &lt; 0.1 vs. placebo, all q &gt; 17.8, qcrit = 3.98, Tukey test).</p>
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<p>An example of a scatter plot with straight line approximation and its confidence interval.</p>
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<p>Confidence intervals which show the difference in the mean surface areas free of film for the compared groups of samples.</p>
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<p>Mean surface area free of film (in relative units) for samples of TPAs to various molecules, and control (*—<span class="html-italic">p</span> &lt; 0.1 vs. placebo sample, q1 = 36.5, q2 = −25.5, qcrit = 2.95, Tukey test).</p>
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<p>A representative image of a Petri dish with a surface film formed during cooling. The film is the dark part of the image. The lighter part of the image shows the area free of film.</p>
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18 pages, 7995 KiB  
Article
Oily Wastewater Treatment by Using Fe3O4/Bentonite in Fixed-Bed Adsorption Column
by Mohammed A. Sarran, Adnan A. AbdulRazak, Mohammed F. Abid, Alaa Dhari Jawad Al-Bayati, Khalid T. Rashid, Mohammed Ahmed Shehab, Haidar Hasan Mohammed, Saad Alsarayefi, Mahmood Alhafadhi and Mohammed Alktranee
ChemEngineering 2024, 8(5), 92; https://doi.org/10.3390/chemengineering8050092 - 10 Sep 2024
Viewed by 324
Abstract
Oily wastewater is a major environmental issue resulting from different industrial and manufacturing activities. Contaminated water with oil represents a significant environmental hazard that can harm numerous life forms. Several methodologies have been tested for the removal of oily wastewater from aqueous solutions, [...] Read more.
Oily wastewater is a major environmental issue resulting from different industrial and manufacturing activities. Contaminated water with oil represents a significant environmental hazard that can harm numerous life forms. Several methodologies have been tested for the removal of oily wastewater from aqueous solutions, and adsorption in a flow-through reactor is an effective mechanism to reduce these effluents. This study focuses on evaluating the ability of Fe3O4/Bent material to adsorb gasoline emulsion from a solution using a fixed-bed column, and it involves analyzing the resulting breakthrough curves. The FT-IR, SEM, EDX, and XRD techniques were used to characterize Fe3O4/Bent. Various ranges of variables were examined, including bed height (2–4 cm), flow rate (3–3.8 mL/min), and initial concentration (200–1000 mg/L), to determine their impacts on the mass transfer zone (MTZ) length and the adsorption capacity (qe). It was shown that a higher bed height and a lower flow rate contributed to a longer time of breakthrough and exhaustion. At the same time, it was noted that under high initial gasoline concentrations, the fixed-bed system rapidly reached breakthrough and exhaustion. Models like the Yoon–Nelson and Thomas kinetic column models were employed to predict the breakthrough curves. Thomas and Yoon–Nelson’s breakthrough models provided a good fit for the breakthrough curves with a correlation coefficient of R2 > 0.95. Furthermore, with a fixed-bed system, the Thomas and Yoon–Nelson models best describe the breakthrough curves for gasoline removal. Full article
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<p>Emulsion stock solution.</p>
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<p>Chemical oxygen demand device.</p>
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<p>pH point of zero charge of Fe<sub>3</sub>O<sub>4</sub>/Bent.</p>
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<p>Fixed-bed adsorption.</p>
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<p>SEM micrographs: (<b>a</b>) raw bentonite, (<b>b</b>) Fe<sub>3</sub>O<sub>4</sub>/Bent.</p>
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<p>FTIR for raw bentonite, modified Fe<sub>3</sub>O<sub>4</sub>/Bent, and Fe<sub>3</sub>O<sub>4</sub>/Bent after adsorption gasoline.</p>
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<p>XRD analysis of raw bentonite and Fe<sub>3</sub>O<sub>4</sub>/Bent.</p>
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<p>The impact of bed height on the breakthrough capability of a fixed-bed containing Fe<sub>3</sub>O<sub>4</sub>/Bent for the elimination of gasoline.</p>
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<p>Effect of flow rate on breakthrough capacity of fixed-bed Fe<sub>3</sub>O<sub>4</sub>/Bent for removal of gasoline.</p>
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<p>Effect of initial concentration on breakthrough capacity of fixed-bed Fe<sub>3</sub>O<sub>4</sub>/Bent for gasoline removal.</p>
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<p>Thomas and Yoon–Nelson modeling results based on experimental and theoretical breakthrough curves of gasoline adsorption on Fe<sub>3</sub>O<sub>4</sub>/Bent at various (<b>a</b>) flow rates, (<b>b</b>) bed heights, and (<b>c</b>) initial concentrations.</p>
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<p>Thomas and Yoon–Nelson modeling results based on experimental and theoretical breakthrough curves of gasoline adsorption on Fe<sub>3</sub>O<sub>4</sub>/Bent at various (<b>a</b>) flow rates, (<b>b</b>) bed heights, and (<b>c</b>) initial concentrations.</p>
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22 pages, 7061 KiB  
Article
Preparation of Polymeric Aluminum Chloride-Loaded Porous Carbon and Evaluation of Its Pb2+ Immobilization Mechanisms in Soil
by Huanquan Cheng, Longgui Peng, Bin Zheng, Rong Wang, Jiushuang Huang and Jianye Yang
Agronomy 2024, 14(9), 2072; https://doi.org/10.3390/agronomy14092072 - 10 Sep 2024
Viewed by 316
Abstract
In recent years, the remediation of heavy metal-contaminated soils has attracted great attention worldwide. Previous research on the removal of toxic heavy metals from wastewater effluents through adsorption by typical solid wastes (e.g., fly ash and coal gangue) has mainly focused on the [...] Read more.
In recent years, the remediation of heavy metal-contaminated soils has attracted great attention worldwide. Previous research on the removal of toxic heavy metals from wastewater effluents through adsorption by typical solid wastes (e.g., fly ash and coal gangue) has mainly focused on the control of wastewater pollutants. In this study, a coal gangue (CG) by-product from Hancheng City was used as a raw material to prepare polymeric aluminum chloride-loaded coal gangue-based porous carbon (PAC-CGPC) by hydrothermal synthesis. This material was subsequently employed to assess its performance in mitigating Pb2+ in soils. In addition, the effects of the pore structure of the prepared material on the adsorption rates, adsorption mechanisms, and plant root uptakes of soil Pb2+ were investigated in this study. The raw CG and prepared PAC-CGPC materials exhibited specific surface areas of 1.8997 and 152.7892 m2/g, respectively. The results of adsorption kinetics and isotherms indicate that the adsorption of Pb2+ based on PAC-CGPC mainly follows a pseudo-second-order kinetic model, suggesting that chemisorption may be the dominant process. In addition, the adsorption isotherm results showed that the Freundlich model explained better the adsorption process of Pb2+, suggests that the adsorption sites of lead ions on APC-CGPC are not uniformly distributed and tend to be enriched in APC, and also shows the ion exchange between aluminum and lead ions. The thermodynamic model fitting results demonstrated the occurrence of spontaneous and exothermic PAC-CGPC-based adsorption of Pb2+, involving ion exchange and surface complexation. The effects of the PAC-CGPC addition on soybean plants were further explored through pot experiments. The results revealed substantial decreases in the Pb2+ contents in the soybean organs (roots, stems, and leaves) following the addition of the PAC-CGPC material at a dose of 3% compared with the control and raw CG groups. Furthermore, the addition of the PAC-CGPC material at a dose of 3% effectively reduced the bioavailable Pb2+ content in the soil by 82.11 and enhanced soybean growth by 15.3%. These findings demonstrated the inhibition effect of the PAC-CGPC material on the translocation of Pb2+ in the soybean seedlings. The modified CG adsorbent has highly pore structure and good hydrophilicity, making it prone to migration in unsaturated soils and, consequently, enhancing Pb2+ immobilization. This research provides theoretical support for the development of CG-based materials capable of immobilizing soil pollutants. Full article
(This article belongs to the Section Agricultural Biosystem and Biological Engineering)
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<p>Flowchart of the preparation of PAC-CGPC.</p>
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<p>XRD spectra of CG, CGPC, and PAC-CGPC (<b>a</b>); infrared spectra of CG, CGPC, and PAC-CGPC (<b>b</b>).</p>
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<p>SEM images of CG (<b>a</b>–<b>c</b>), CGPC (<b>d</b>–<b>f</b>), and PAC-CGPC (<b>g</b>–<b>i</b>).</p>
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<p>N<sub>2</sub> adsorption–desorption curves and BJH pore size distribution curves of CG (<b>a</b>), CGPC (<b>b</b>), and PAC-CGPC (<b>c</b>).</p>
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<p>XPS spectra of CG (<b>a</b>), CGPC (<b>b</b>), and PAC-CGPC (<b>c</b>).</p>
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<p>EDS images of CG (<b>a</b>), CGPC (<b>b</b>), and PAC-CGPC (<b>c</b>).</p>
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<p>Soybean growth process (<b>a</b>) control group and CG 1.5; (<b>b</b>) control group and CG 3; (<b>c</b>) control group and PAC-CGPC 1.5; (<b>d</b>) control group and PAC-CGPC 3.</p>
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<p>Effects of CG and PAC-CGPC on dry (<b>a</b>), fresh (<b>b</b>), and height (<b>c</b>) weight of aboveground and underground parts of plants.</p>
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<p>Changes of Pb<sup>2+</sup> content in root, stalk, and leaf of soybean.</p>
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<p>Effects of different treatments on soil pH value (<b>a</b>), electrical conductivity (<b>b</b>) after soybean planting.</p>
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<p>Effects of different treatments on soil organic matter content (<b>a</b>), hydrolyzability N (<b>b</b>), available P (<b>c</b>), available K (<b>d</b>), available Pb<sup>2+</sup> content (<b>e</b>), and Pb<sup>2+</sup> morphological distribution (<b>f</b>) after soybean planting. (S1 = water soluble fraction, S2 = carbonate-bound fraction, S3 = Fe–Mn oxides fraction, S4 = organic-bound fraction, S5 = residual fraction).</p>
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<p>Langmuir (<b>a</b>) and Freundlich (<b>b</b>); quasi-first-order and quasi-second-order kinetic curves (<b>c</b>,<b>d</b>), the left and right y-axes correspond to PFO and PSO models, respectively. Thermodynamic curves (<b>e</b>,<b>f</b>) adsorption isothermal curves of Pb<sup>2+</sup> adsorption by CG and PAC-CGPC.</p>
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<p>Initial solution concentration (<b>a</b>) and adsorption time (<b>b</b>) versus solution free Al<sup>3+</sup>. In (<b>a</b>), the adsorption time is still 2 h and the adsorbent dosage is 0.2 g. In (<b>b</b>), the initial concentration of lead is 100 mg/L and the adsorbent dosage is 0.2 g).</p>
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<p>Mechanism of Pb<sup>2+</sup> removal by APC-CGPC in soil.</p>
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20 pages, 10304 KiB  
Article
Chemical and Physical Characterization of Three Oxidic Lithological Materials for Water Treatment
by José G. Prato, Fernando Millán, Marin Senila, Erika Andrea Levei, Claudiu Tănăselia, Luisa Carolina González, Anita Cecilia Ríos, Luis Sagñay Yasaca and Guillermo Eduardo Dávalos
Sustainability 2024, 16(18), 7902; https://doi.org/10.3390/su16187902 - 10 Sep 2024
Viewed by 416
Abstract
Water treatment necessitates the sustainable use of natural resources. This paper focuses on the characterization of three oxidic lithological materials (OLMs) with the aim of utilizing them to prepare calcined adsorbent substrates for ionic adsorption. The three materials have pH levels of [...] Read more.
Water treatment necessitates the sustainable use of natural resources. This paper focuses on the characterization of three oxidic lithological materials (OLMs) with the aim of utilizing them to prepare calcined adsorbent substrates for ionic adsorption. The three materials have pH levels of 7.66, 4.63, and 6.57, respectively, and organic matter contents less than 0.5%. All of the materials are sandy loam or loamy sand. Their electric conductivities (0.18, 0.07, and 0.23 dS/m) show low levels of salinity and solubility. Their CEC (13.40, 13.77, and 6.76 cmol(+)kg) values are low, similar to those of amphoteric oxides and kaolin clays. Their aluminum contents range from 7% up to 12%, their iron contents range from 3% up to 7%, their titanium contents range from 0.3% to 0.63%, and their manganese contents range from 0.007% up to 0.033%. The amphoteric oxides of these metals are responsible for their ionic adsorption reactions due to their variable charge surfaces. Their zirconium concentrations range from 100 to 600 mg/g, giving these materials the refractory properties necessary for the preparation of calcined adsorbent substrates. Our XRD analysis shows they share a common mineralogical composition, with quartz as the principal component, as well as albite, which leads to their thermal properties and mechanical resistance against abrasion. The TDA and IR spectra show the presence of kaolinite, which is lost during thermal treatments. The results show that the OLMs might have potential as raw materials to prepare calcined adsorbent substrates for further applications and as granular media in the sustainable treatment of both natural water and wastewater. Full article
(This article belongs to the Section Environmental Sustainability and Applications)
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<p>Point of zero charge for the raw materials.</p>
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<p>(<b>a</b>) BET surface area and external surface area for the three granulometric fractions of the three OLMs L, G, and V, in three granulometric fractions: GF (1200–425 µm), MF (425–250 µm), and FF (&lt;250 µm). (<b>b</b>) Linear correlation between external SA and BET SA.</p>
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<p>Pore volume, micropore volume, and micropore area in the three lithological materials L, G, and V in the three granulometric fractions: GF (1200–425 µm), MF (425–250 µm), and FF (&lt;250 µm).</p>
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<p>Effect of calcination pores on the external surface area and pore volume in the three lithological materials L, G, and V in three granulometric fractions: GF (1200–425 µm), MF (425–250 µm), and FF (&lt;250 µm).</p>
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<p>XR diffractograms of the L material in three granulometric fractions: GF (1200–425 µm), MF (425–250 µm), and FF (&lt;250 µm).</p>
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<p>XR diffractograms from the G material in three granulometric fractions: GF (1200–425 µm), MF (425–250 µm), and FF (&lt;250 µm).</p>
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<p>XR diffractograms from V material in three granulometric fractions: GF (1200–425 µm), MF (425–250 µm), and FF (&lt;250 µm).</p>
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<p>DTA from the L material in three granulometric fractions: GF (1200–425 µm), MF (425–250 µm), and FF (&lt;250 µm).</p>
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<p>DTA from the G material in three granulometric fractions: GF (1200–425 µm), MF (425–250 µm), and FF (&lt;250 µm).</p>
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<p>DTA from the V material in three granulometric fractions: GF (1200–425 µm), MF (425–250 µm), and FF (&lt;250 µm).</p>
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<p>Fe, Al, Ti, and Mn contents in the three lithological materials L, G, and V in the three granulometric fractions: GF (1200–425 µm), MF (425–250 µm), and FF (&lt;250 µm).</p>
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<p>Other metallic contents greater than 1000 mg/g in the three lithological materials L, G, and V in the three granulometric fractions: GF (1200–425 µm), MF (425–250 µm), and FF (&lt;250 µm).</p>
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<p>Metallic contents between 10 and 100 mg/g in the three lithological materials L, G, and V in three granulometric fractions: GF (1200–425 µm), MF (425–250 µm), and FF (&lt;250 µm).</p>
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<p>Metallic contents between 1 and 10 mg/g in the three lithological materials L, G, and V in three granulometric fractions: GF (1200–425 µm), MF (425–250 µm), and FF (&lt;250 µm).</p>
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<p>Metallic contents below 1 mg/g in the three lithological materials L, G, and V in three granulometric fractions: GF (1200–425 µm), MF (425–250 µm), and FF (&lt;250 µm).</p>
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<p>IR spectra from raw and calcined material from L, G, and V OLMs.</p>
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