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Sustain. Chem., Volume 6, Issue 1 (March 2025) – 7 articles

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24 pages, 3564 KiB  
Review
High-Temperature Stability of LiFePO4/Carbon Lithium-Ion Batteries: Challenges and Strategies
by Guangyao Jin, Wanwei Zhao, Jianing Zhang, Wenyu Liang, Mingyang Chen and Rui Xu
Sustain. Chem. 2025, 6(1), 7; https://doi.org/10.3390/suschem6010007 - 27 Feb 2025
Viewed by 132
Abstract
Lithium-ion batteries that use lithium iron phosphate (LiFePO4) as the cathode material and carbon (graphite or MCMB) as the anode have gained significant attention due to their cost-effectiveness, low environmental impact, and strong safety profile. These advantages make them suitable for [...] Read more.
Lithium-ion batteries that use lithium iron phosphate (LiFePO4) as the cathode material and carbon (graphite or MCMB) as the anode have gained significant attention due to their cost-effectiveness, low environmental impact, and strong safety profile. These advantages make them suitable for a wide range of applications including electric vehicles, stationary energy storage, and backup power systems. However, their adoption is hindered by a critical challenge: capacity degradation at elevated temperatures. This review systematically summarizes the corresponding modification strategies including surface modification of the anode and cathode as well as modification of the electrolyte, separator, binder, and collector. We further discuss the control of the charge state, early warning prevention, control of thermal runaway, and the rational application of ML and DFT to enhance the LFP/C high temperature cycling stability. Finally, in light of the current research challenges, promising research directions are presented, aiming at enhancing their performance and stability in such harsh thermal environments. Full article
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<p>Crystal structures of LiFePO<sub>4</sub> and FePO<sub>4</sub>. During charging, LiFePO<sub>4</sub> changes to FePO<sub>4</sub> by delithiation. In the discharge process, a reversible transformation from FePO<sub>4</sub> to LiFePO<sub>4</sub> occurs by lithiation. The image was taken with permission [<a href="#B8-suschem-06-00007" class="html-bibr">8</a>].</p>
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<p>The structure of graphite. The image was taken with permission [<a href="#B19-suschem-06-00007" class="html-bibr">19</a>].</p>
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<p>The structures of MCMBs. The image was taken with permission [<a href="#B22-suschem-06-00007" class="html-bibr">22</a>].</p>
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<p>Schematic diagram of SEI degradation pattern on the graphite anode side of the LFP cell. The image was taken with permission [<a href="#B33-suschem-06-00007" class="html-bibr">33</a>].</p>
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<p>Schematic of LFP cathode iron dissolution. The image was taken with permission [<a href="#B42-suschem-06-00007" class="html-bibr">42</a>].</p>
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<p>Cycle performance of LiFePO<sub>4</sub>/MCMB cells with different metal coatings including Au, Cu, Fe, Co, Ni, and Ti on the MCMB electrode surface (<b>a</b>). All cells were cycled at 1 C charge/discharge rate at 55 °C in the voltage window of 2.5–4.0 V. The image was taken with permission [<a href="#B51-suschem-06-00007" class="html-bibr">51</a>]. Relationship between reversible capacity retention and cycle number for SMG/LiFePO<sub>4</sub> 18650 batteries containing different binders cycled at 55 °C (<b>b</b>). The image was taken with permission [<a href="#B54-suschem-06-00007" class="html-bibr">54</a>]. SEM micrographs of cycled graphitic anode containing PVDF binder after 1 cycle (<b>c</b>); SBR/CMC binder after 1 cycle (<b>d</b>). The image was taken with permission [<a href="#B54-suschem-06-00007" class="html-bibr">54</a>].</p>
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<p>LTO-LFP/C synthesis flowchart (<b>a</b>). The image was taken with permission [<a href="#B57-suschem-06-00007" class="html-bibr">57</a>]. The cycling and CE performance for SS-LFP/C, SP-LFP/C and 3 and 5 wt.% LTO coated SP-LFP/C composites at 1C/3C rate at 25 and 55 °C (<b>b</b>). The image was taken with permission [<a href="#B57-suschem-06-00007" class="html-bibr">57</a>]. Cycle performances of ① LiFePO<sub>4</sub>; ② LiFePO<sub>3.98</sub>S<sub>0.03</sub> at 50 °C and ③ LiFePO<sub>4</sub>; and ④ LiFePO<sub>3.98</sub>S<sub>0.03</sub> at 60 °C (<b>c</b>). The image was taken with permission [<a href="#B59-suschem-06-00007" class="html-bibr">59</a>].</p>
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<p>Comparison of the cycle life of LiFePO<sub>4</sub>/graphite full cells at 55 °C (<b>a</b>); SEM micrographs of the anodes in the cells without VC (<b>b</b>) and with VC (<b>c</b>) after 100 cycles at 55 °C. The image was taken with permission [<a href="#B68-suschem-06-00007" class="html-bibr">68</a>].</p>
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<p>EIS at different SOC values when charging, with 10 min rest time at 25 °C (<b>a</b>). The image was taken with permission [<a href="#B90-suschem-06-00007" class="html-bibr">90</a>]. Trend in the relative capacity of the cycle degradation tests at 50% DOD and C-rates of 1.0, 2.0, 4.0, and 8.0 C at 40 °C (<b>b</b>). The images were taken with permission [<a href="#B92-suschem-06-00007" class="html-bibr">92</a>].</p>
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<p>Chain reactions of LFP batteries during TR (<b>a</b>). The images were taken with permission [<a href="#B94-suschem-06-00007" class="html-bibr">94</a>]. The sequence and advantages of warning signal response (<b>b</b>).The images were taken with permission [<a href="#B94-suschem-06-00007" class="html-bibr">94</a>].</p>
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18 pages, 15043 KiB  
Article
Use of Domestic Polymeric Waste for Surfactant Removal from Wastewater
by Thaiara Ramires dos Reis, Donizeti Leonardo Mancini Tolari, Ana Claudia Pedrozo da Silva, Elton Guntendorfer Bonafé, Rafael Block Samulewski and André Luiz Tessaro
Sustain. Chem. 2025, 6(1), 6; https://doi.org/10.3390/suschem6010006 - 14 Feb 2025
Viewed by 521
Abstract
This study addresses the environmental challenge of surfactant removal from wastewater, focusing on the increased surfactant use during the COVID-19 pandemic. Polymeric waste, specifically polyurethane (PU) and polyamide (PA), was repurposed for surfactant adsorption to mitigate these environmental impacts. Methods included preparing surfactant [...] Read more.
This study addresses the environmental challenge of surfactant removal from wastewater, focusing on the increased surfactant use during the COVID-19 pandemic. Polymeric waste, specifically polyurethane (PU) and polyamide (PA), was repurposed for surfactant adsorption to mitigate these environmental impacts. Methods included preparing surfactant solutions of sodium linear alkylbenzene sulfonate (LAS) and dodecyl pyridinium chloride (DPC) and the mechanical processing of polymeric residues. PU and PA were characterized by FTIR-ATR and by the pH at the point of zero charge, which yielded pH = 8.0 for both polymers. The adsorption efficiency was optimized using a central composite face-centered design, varying pH, temperature, and time. The results indicated that PU and PA effectively adsorbed anionic and cationic surfactants, with specific conditions enhancing performance. From the optimized experimental conditions, four assays were carried out to evaluate the adsorption isotherms and kinetics. Among the fitted models, the SIPS model was the most representative, indicating a heterogeneous surface. Regarding LAS, the maximum adsorption capacity values were ~90 and 15 mg g−1, respectively, for PU and PA. Considering the DPC surfactant, lower values were obtained (~36 mg g−1 for PU and 16 mg g−1 for PA). The results are satisfactory because the adsorbents used in this study were second-generation waste and were used without treatment or complex modifications. The study concluded that using polymeric waste for surfactant removal offers a sustainable solution, transforming waste management while addressing environmental contamination. This approach provides a method for reducing surfactant levels in wastewater and adds value to otherwise discarded materials, promoting a circular economy and sustainable waste reuse. Full article
(This article belongs to the Special Issue Recycling and Upcycling of Plastic Wastes)
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<p>Polymeric wastes of (<b>A</b>) PU and (<b>B</b>) PA used in the adsorption experiments. The samples were mechanically processed before use.</p>
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<p>(<b>A</b>) Ultraviolet absorption spectra of aqueous solutions of the surfactants LAS and DPC (50 ppm). Calibration curves of the surfactants (<b>B</b>) LAS and (<b>C</b>) DPC in water at room temperature.</p>
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<p>(<b>A</b>) Adsorbent characterization at pH at the point of zero charge (pH<sub>PZC</sub>) and FTIR-ATR spectra of polymeric residues: (<b>B</b>) PA and (<b>C</b>) PU.</p>
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<p>Response surface of the LAS adsorption by PU material evaluating pH × Temperature (<b>A</b>) and pH × Time (<b>B</b>).</p>
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<p>Response surface of LAS adsorption by PA material evaluating pH × Temperature (<b>A</b>) and pH × Time (<b>B</b>).</p>
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<p>Response surface of the DPC adsorption by PU material evaluating pH × Temperature (<b>A</b>) and pH × Time (<b>B</b>).</p>
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<p>Response surface of the DPC adsorption by PA material evaluating pH × Temperature (<b>A</b>) and pH × Time (<b>B</b>).</p>
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<p>Adsorption isotherms after 24 h for (<b>A</b>) assay 1; (<b>B</b>) assay 2; (<b>C</b>) assay 3; and (<b>D</b>) assay 4. The red curves represent the fits by the SIPS model.</p>
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<p>Adsorption kinetics of (<b>A</b>) LAS (assay 1) and (<b>B</b>) DPC (assay 2).</p>
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35 pages, 2643 KiB  
Article
Surfactant-Enhanced Guava Seed Biosorbent for Lead and Cadmium Removal: Kinetics, Thermodynamics, and Reusability Insights
by Gabriela Elizabeth Tapia-Quiroz, Selene Anaid Valencia-Leal, Adriana Vázquez-Guerrero, Ruth Alfaro-Cuevas-Villanueva, Ramiro Escudero-García and Raúl Cortés-Martínez
Sustain. Chem. 2025, 6(1), 5; https://doi.org/10.3390/suschem6010005 - 17 Jan 2025
Viewed by 820
Abstract
Heavy metal pollution in water resources, particularly cadmium and lead, poses a significant environmental and public health challenge, requiring the development of sustainable, efficient, and cost-effective water treatment methods. Therefore, this study investigates the biosorption capabilities of natural (SN) and surfactant-modified (SM) guava [...] Read more.
Heavy metal pollution in water resources, particularly cadmium and lead, poses a significant environmental and public health challenge, requiring the development of sustainable, efficient, and cost-effective water treatment methods. Therefore, this study investigates the biosorption capabilities of natural (SN) and surfactant-modified (SM) guava seed biosorbents to remove Cd and Pb from aqueous solutions. Guava seeds, an agricultural waste material, were treated with hexadecyltrimethylammonium bromide (HDTMA-Br) to enhance their adsorption efficiency. The biosorbents were characterized by FTIR, SEM-EDS, and zeta potential analysis to explain the surface modifications and their influence on the adsorption mechanisms. Batch experiments were performed to evaluate the effects of pH, contact time, temperature, biosorbent dosage, and concentration on Cd and Pb removal efficiencies. Adsorption isotherm and kinetic data were analyzed using mathematical models to obtain the basic parameters of the systems under study. The results showed that SM exhibited superior adsorption capacities of 328 mg/g for Cd and 594 mg/g for Pb at 25 °C, significantly outperforming SN. The study analyzed the thermodynamic parameters of adsorption systems, revealing endothermic and exothermic properties for SN and SM. Functional groups like hydroxyl and carbonyl were crucial for metal ion binding. HDTMA-Br introduced active sites and enhanced surface charge interactions. Regeneration tests showed reusability, maintaining over 85% efficiency after four cycles. Guava seeds could be cost-effective and sustainable biosorbents for heavy metal removal. Full article
17 pages, 2089 KiB  
Article
BiVO4-Based Systems Magnetron Sputtered with Silver Nanoparticles for the Artificial Photosynthesis Reaction
by Eva Naughton, Emerson C. Kohlrausch, Jesum Alves Fernandes and James A. Sullivan
Sustain. Chem. 2025, 6(1), 4; https://doi.org/10.3390/suschem6010004 - 17 Jan 2025
Viewed by 766
Abstract
The incorporation of Ag nanoparticles onto BiVO4 (a known H2O oxidising photocatalyst) through magnetron sputtering to form a composite was studied. ICP-OES results showed that the loading of Ag on BiVO4 was below 1% in all cases. UV-Vis DRS [...] Read more.
The incorporation of Ag nanoparticles onto BiVO4 (a known H2O oxidising photocatalyst) through magnetron sputtering to form a composite was studied. ICP-OES results showed that the loading of Ag on BiVO4 was below 1% in all cases. UV-Vis DRS and CO2-TPD analyses demonstrated that upon incorporation of Ag onto BiVO4, an increase in the extent of visible light absorption and CO2 adsorption was seen. TEM imaging showed the presence of Ag particles on the surface of larger BiVO4 particles, while XRD analysis provided evidence for some doping of Ag into BiVO4 lattices. The effect of the composite formation on the activity of the materials in the artificial photosynthesis reaction was significant. BiVO4 alone produces negligible amounts of gaseous products. However, the Ag-sputtered composites produce both CO and CH4, with a higher loading of Ag leading to higher levels of product formation. This reactivity is ascribed to the generation of a heterojunction in the composite material. It is suggested that the generation of holes in BiVO4 following photon absorption is used to provide protons (from H2O oxidation), and the decay of an SPR response on the Ag NPs provides hot electrons, which together with the protons reduce CO2 to produce CH4, CO, and adsorbed hydrocarbonaceous species. Full article
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Graphical abstract

Graphical abstract
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<p>Valence (VB) and conduction (CB) band-edge positions of some semiconductors relative to the energy levels of the redox couples involved in the reduction of CO<sub>2</sub> and oxidation of H<sub>2</sub>O vs. NHE at pH = 7. Values for CB<sub>m</sub> and VB<sub>m</sub> obtained from Tamirat et al. [<a href="#B16-suschem-06-00004" class="html-bibr">16</a>].</p>
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<p>UV-Vis DRS spectra of the silver-sputtered BiVO<sub>4</sub> materials (<b>top left</b>) and their Tauc plots.</p>
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<p>XRD profiles of the sputtered BiVO<sub>4</sub> materials, and their reference profiles (<b>left</b>), and peak shifts between the profiles of unmodified BiVO<sub>4</sub> and the Ag-sputtered samples (<b>right</b>).</p>
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<p>TEM micrographs of (<b>a</b>) BiVO<sub>4</sub>, (<b>b</b>) Ag/BiVO<sub>4</sub> 100, and (<b>c</b>) Ag/BiVO<sub>4</sub> 250, where the red circles highlight Ag NPs present on BiVO<sub>4</sub> surfaces. Particle size distribution histograms can be found in the <a href="#app1-suschem-06-00004" class="html-app">Supplementary Material</a> (<a href="#app1-suschem-06-00004" class="html-app">Figure S1</a>).</p>
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<p>CO<sub>2</sub>-TPD profiles from all three materials.</p>
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<p>Gaseous reactant and product evolution vs. time over the BiVO<sub>4</sub> and Ag/BiVO<sub>4</sub> catalysts, (<b>a</b>) CH<sub>4</sub>, (<b>b</b>) CO, (<b>c</b>) CO<sub>2</sub>, and (<b>d</b>) O<sub>2</sub>.</p>
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<p>Proposed mechanism of a photocatalytic redox reaction over Ag/BiVO<sub>4</sub>, where “A” is an electron acceptor, “D” is an electron donor, and “VB” and “CB” are valence and conduction bands, respectively.</p>
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<p>Pre- and post-reaction IR spectra of the two Ag-sputtered BiVO<sub>4</sub> samples.</p>
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13 pages, 2255 KiB  
Article
Correlation Between Conductivity and Oxygen Evolution Reaction Activity in Perovskite Oxides CaMnO3-δ, Ca0.5Sr0.5MnO3-δ and SrMnO3-δ
by Amara Martinson, Mandy Guinn, Peter Mortensen and Ram Krishna Hona
Sustain. Chem. 2025, 6(1), 3; https://doi.org/10.3390/suschem6010003 - 13 Jan 2025
Viewed by 1020
Abstract
The perovskite oxides CaMnO3-δ, Ca0.5Sr0.5MnO3-δ, and SrMnO3-δ were synthesized in air using a solid-state method, and their structural, electrical, and electrocatalytic properties were studied in relation to their oxygen evolution reaction (OER) performance. Iodometric [...] Read more.
The perovskite oxides CaMnO3-δ, Ca0.5Sr0.5MnO3-δ, and SrMnO3-δ were synthesized in air using a solid-state method, and their structural, electrical, and electrocatalytic properties were studied in relation to their oxygen evolution reaction (OER) performance. Iodometric titration showed δ values of 0.05, 0.05, and 0.0, respectively, indicating that Mn is predominantly in the 4+ oxidation state across all materials, consistent with prior reports. Detailed characterization was performed using X-ray diffraction (XRD), scanning electron microscopy (SEM), iodometric titration, and variable-temperature conductivity measurements. Four-point probe DC measurements revealed that CaMnO3-δ (δ = 0.05) has a semiconductive behavior over a temperature range from 25 °C to 300 °C, with its highest conductivity attributed to polaron activity. Cyclic voltammetry (CV) in 0.1 M KOH was employed to assess OER catalytic performance, which correlated with room-temperature conductivity. CaMnO3-δ exhibited superior catalytic activity, followed by Ca0.5Sr0.5MnO3-δ and SrMnO3-δ, demonstrating that increased conductivity enhances OER performance. The conductivity trend, CaMnO3-δ > Ca0.5Sr0.5MnO3-δ > SrMnO3-δ, aligns with OER activity, underscoring a direct link between electronic transport properties and catalytic efficiency within this series. Full article
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<p>CaMnO<sub>3-δ</sub> (<b>a</b>) crystallographic structure with unit cell, (<b>b</b>) Reitveld refinement profile for the PXRD.</p>
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<p>Ca<sub>0.5</sub>Sr<sub>0.5</sub>MnO<sub>3-δ</sub> (<b>a</b>) crystallographic structure with unit cell, (<b>b</b>) Reitveld refinement profile for the PXRD.</p>
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<p>SrMnO<sub>3-δ</sub> (<b>a</b>) crystallographic structure with unit cell, (<b>b</b>) Reitveld refinement profile for the PXRD.</p>
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<p>Scanning electron microscopy images of CaMnO<sub>3-δ</sub> (<b>a</b>), Ca<sub>0.5</sub>Sr<sub>0.5</sub>MnO<sub>3-δ</sub> (<b>b</b>), and SrMnO<sub>3-δ</sub> (<b>c</b>) from left to right.</p>
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<p>Temperature-dependent total electrical conductivity of CaMnO<sub>3-δ</sub> (red stars), Ca<sub>0.5</sub>Sr<sub>0.5</sub>MnO<sub>3-δ</sub> (green spheres), and SrMnO<sub>3-δ</sub> (blue triangles).</p>
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<p>(<b>a</b>) Polarization curves of OER with the mass activities in inset and (<b>b</b>) Tafel slope for CaMnO<sub>3</sub> (red), Ca<sub>0.5</sub>Sr<sub>0.5</sub>MnO<sub>3-δ</sub> (green) and SrMnO<sub>3</sub> (blue).</p>
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20 pages, 2265 KiB  
Review
Chemistry and Health: A Multidimensional Approach
by Alcione S. de Carvalho, Iva S. de Jesus, Patrícia G. Ferreira, Acácio S. de Souza, Rafael P. R. F. de Oliveira, Debora O. Futuro and Vitor Francisco Ferreira
Sustain. Chem. 2025, 6(1), 2; https://doi.org/10.3390/suschem6010002 - 9 Jan 2025
Viewed by 693
Abstract
This review explores both the positive and negative impacts of chemistry on society, focusing on the intersection between pharmaceutical, natural, and synthetic chemicals. On the one hand, drugs developed through medicinal chemistry have saved lives, improved people’s quality of life, and increased longevity. [...] Read more.
This review explores both the positive and negative impacts of chemistry on society, focusing on the intersection between pharmaceutical, natural, and synthetic chemicals. On the one hand, drugs developed through medicinal chemistry have saved lives, improved people’s quality of life, and increased longevity. However, they also pose risks, including fatalities and environmental damage. Pharmaceutical chemistry has revolutionized medical practice by enabling the treatment and cure of fatal or debilitating diseases, significantly contributing to the rise in global life expectancy through the research and development of new bioactive substances. This article also highlights the harmful effects of toxic synthetic substances, which negatively impact human health and the environment, affecting plants, animals, air, water, soil, and food. Full article
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<p>Examples of chemical substances that have had an impact on human health.</p>
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<p>Quinine-derived (1) origin of the antimalarial compounds mefloquine (8), chloroquine (7) and amodiaquine (9).</p>
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<p>The synthesis of acetylsalicylic acid, Aspirin<sup>®</sup>, a synthetic prodrug derived from white willow (<span class="html-italic">Salix alba</span>).</p>
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<p>Use of acetylsalicylic acid (Aspirin<sup>®</sup>) (2) and salicylic acid (9) in the research and development (R&amp;D) of new bioactive molecules, such as 10 and 12, employing the molecular hybridization principle.</p>
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<p>Morphine (3) application in the research and development (R&amp;D) of new classes of bioactive molecules, such as 4-phenylpiperidine (13), utilizing the molecular hybridization principle.</p>
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<p>The application of penicillin (6) in the research and development (R&amp;D) of new classes of antibacterial molecules involves mapping its pharmacophoric entities.</p>
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<p>Substances that lead to negative human health and environmental effects.</p>
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<p>By-products present in commercial DDT (14).</p>
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<p>Fosdrin (22) and fipronil (23), two examples of highly toxic pesticides that lack selectivity.</p>
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<p>Chemical structure of the racemic drug thalidomide (16), (±)2-(2,6-dioxo-3-piperidinyl)-1<span class="html-italic">H</span>-isoindole-1,3-(2<span class="html-italic">H</span>)-dione; or (±)-phthalimidoglutarimide.</p>
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<p>The chemical reaction caused by mixing tetraethyl lead (17) to gasoline to obtain higher octane ratings.</p>
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16 pages, 3520 KiB  
Article
Low Temperature Synthesis of 3d Metal (Fe, Co, Ni, Cu)-Doped TiO2 Photocatalyst via Liquid Phase Deposition Technique
by Mitsuhiro Honda, Yusaku Yoshii, Nobuchika Okayama and Yo Ichikawa
Sustain. Chem. 2025, 6(1), 1; https://doi.org/10.3390/suschem6010001 - 24 Dec 2024
Viewed by 747
Abstract
The titanium dioxide (TiO2) photocatalyst is an important semiconducting material that exhibits environmental purification functions when exposed to light. Elemental doping of TiO2 is considered an important strategy to improve its photocatalytic activity. Herein, we have achieved the low-temperature, atmospheric-pressure [...] Read more.
The titanium dioxide (TiO2) photocatalyst is an important semiconducting material that exhibits environmental purification functions when exposed to light. Elemental doping of TiO2 is considered an important strategy to improve its photocatalytic activity. Herein, we have achieved the low-temperature, atmospheric-pressure synthesis of anatase TiO2 particles with doping of 3d metals (Fe, Co, Ni and Cu) based on the liquid phase deposition technique. All products prepared by adding 3d metals were found to consist of TiO2 crystals in the anatase phase with a fine protruding structure of about 40 nm on the surface, as was the case without the addition of metal ions. Iron and copper were observed to be incorporated at higher concentrations than cobalt and nickel, with an elemental addition of up to 4 at% and 1 at%, respectively, when 10 mM iron and copper nitrate were applied. Such doping efficiency could be explained by the difference in ionic radius and chemical stability. A narrowing of the optical band gap with doping elements was also observed, and it was found that optical sensitivity could be imparted down to the visible-light region of 2.4 eV (Fe: 4 at% addition). Furthermore, the 3d metal-doped TiO2 demonstrated in this study was shown to exhibit photocatalytic methane degradation activity. The amount of methane degradation per unit area of the microparticles was twice as great when iron and copper were added, compared to the undoped counterpart. It has been demonstrated that the strategy of doping TiO2 with 3d metal ions by low-temperature synthesis methods is effective in enhancing carrier dynamics and introducing surface active sites, thus increasing methane degradation activity. Full article
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<p>Schematic illustration of the setup for testing photocatalysis to degrade methane. (Inset: picture of the setup).</p>
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<p>SEM images of the products prepared with doping Fe (<b>a</b>–<b>c</b>), Co (<b>d</b>–<b>f</b>), Ni (<b>g</b>–<b>i</b>), and Cu (<b>j</b>–<b>l</b>). The scale bar corresponds to 200 nm.</p>
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<p>Raman spectra of the products prepared with doping of Fe (orange), Co (red), Ni (blue), and Cu (green). Undoped TiO<sub>2</sub> (LPD, commercial) is displayed in black color. E<sub>g</sub>, B<sub>1g</sub> and A<sub>1g</sub> indicate vibrational modes, which are derived from anatase TiO<sub>2</sub>.</p>
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<p>Molar concentration dependence on FWHM values of E<sub>g</sub> mode. Orange, blue, red and green colors indicate Fe, Ni, Co and Cu doping, respectively.</p>
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<p>Molar concentration dependence on peak wavenumber of E<sub>g</sub> mode. Orange, blue, red and green colors indicate Fe, Ni, Co and Cu doping, respectively.</p>
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<p>Atomic concentration of dopant elements in the product depends on the molar concentration. Orange, blue, red and green colors indicate Fe, Ni, Co and Cu doping, respectively.</p>
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<p>Correlation between bandgaps and molar concentrations. Orange, blue, red and green colors indicate Fe, Ni, Co and Cu doping, respectively.</p>
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<p>Reduction rate of methane with TiO<sub>2</sub> doping Fe, Co, Ni and Cu. The initial concentration of methane gas was (3600 ± 100) ppm. Photocatalytic reaction was initiated by illuminating 24 mg of photocatalyst powder entirely with black light (wavelength: 360 nm, power: (1.60 ± 0.05) mW/cm<sup>2</sup>).</p>
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<p>Rate of methane reduction per unit area. Photocatalytic reaction was initiated by illuminating the photocatalyst powder (24 mg) entirely with black light (wavelength: 360 nm, power: (1.60 ± 0.05) mW/cm<sup>2</sup>), while the methane reduction rate per unit area was calculated by dividing the reduction rate by the surface area.</p>
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<p>Narrow scans for O1s (<b>a</b>) and Ti2p (<b>b</b>) peaks for undoped and doped TiO<sub>2</sub>. The concentration of solutes applied corresponds to 0.1 mM. Dotted spectra are Voigt functions obtained through the deconvolution of spectra.</p>
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<p>Narrow scans for doped elements: (<b>a</b>) Fe2p, (<b>b</b>) Co2p, (<b>c</b>) Ni2p, and (<b>d</b>) Cu2p. Colors are prescribed to spectra of the samples in the same manner as those in <a href="#suschem-06-00001-f003" class="html-fig">Figure 3</a>, <a href="#suschem-06-00001-f004" class="html-fig">Figure 4</a>, <a href="#suschem-06-00001-f005" class="html-fig">Figure 5</a>, <a href="#suschem-06-00001-f006" class="html-fig">Figure 6</a> and <a href="#suschem-06-00001-f007" class="html-fig">Figure 7</a>. The applied concentration corresponds to 0.1 mM.</p>
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