Pub Date : 2024-02-14DOI: 10.3390/inorganics12020058
Silpa Padmakumar Sheelakumari, M. V. Cappellari, M. B. Rivas Aiello, A. Hepp, C. Strassert
We herein report on the synthesis and structural characterization, as well as on the photophysical properties, of a series of isoleptic Pt(II) and Pd(II) complexes featuring tridentate N^N^N chelators as luminophores while bearing diverse ancillary co-ligands. Six new palladium complexes were synthesized using 2,6-bis(3-(tert-butyl/trifluoromethyl)-1H-1,2,4-triazol-5-yl)pyridine (tbu or CF3, respectively) in combination with four distinct ancillary ligands, namely: 4-amylpyridine (AmPy), 2,6-dimethylphenyl isonitrile (CNR), triphenylphosphane (PPh3), and 1,3,5-triaza-7-phosphaadamantane (PTA). Thus, two novel Pt(II) complexes incorporating the co-ligands CNR and PTA were explored. The remaining platinum-based complexes, namely CF3-Pt-AmPy, tbu-Pt-AmPy, CF3-Pt-PPh3, and tbu-Pt-PPh3, were re-synthesized according to our previous work for a systematic comparison with their Pd(II) homologues. Thus, photophysical studies were performed in different solvents and conditions. The Pt(II) complexes demonstrated comparable or superior photophysical characteristics in toluene when compared with their solutions in liquid dichloromethane at room temperature. In contrast, the Pd(II) complexes exhibited no significant photoluminescence in dichloromethane, but a surprisingly clear emission was observed for tbu-Pd-AmPy, tbu-Pd-CNR, and tbu-Pd-PPh3 in liquid toluene at room temperature. The significant differences regarding excited state lifetimes and photoluminescence quantum yields underscore the impact of solvent selection on photophysical characteristics, emphasizing the need to consider metal-ligand interactions, as well as the surrounding microenvironment, for a comprehensive interpretation of their photophysical properties. In addition, it is clear that AmPy and CNR render better luminescence efficiencies, whereas PTA is only suitable in toluene.
{"title":"Synthesis and Photophysical Evaluation of Isoleptic Pt(II) and Pd(II) Complexes Utilizing N^N^N Ligands as Luminophoric Chelators with Different Ancillary Ligands","authors":"Silpa Padmakumar Sheelakumari, M. V. Cappellari, M. B. Rivas Aiello, A. Hepp, C. Strassert","doi":"10.3390/inorganics12020058","DOIUrl":"https://doi.org/10.3390/inorganics12020058","url":null,"abstract":"We herein report on the synthesis and structural characterization, as well as on the photophysical properties, of a series of isoleptic Pt(II) and Pd(II) complexes featuring tridentate N^N^N chelators as luminophores while bearing diverse ancillary co-ligands. Six new palladium complexes were synthesized using 2,6-bis(3-(tert-butyl/trifluoromethyl)-1H-1,2,4-triazol-5-yl)pyridine (tbu or CF3, respectively) in combination with four distinct ancillary ligands, namely: 4-amylpyridine (AmPy), 2,6-dimethylphenyl isonitrile (CNR), triphenylphosphane (PPh3), and 1,3,5-triaza-7-phosphaadamantane (PTA). Thus, two novel Pt(II) complexes incorporating the co-ligands CNR and PTA were explored. The remaining platinum-based complexes, namely CF3-Pt-AmPy, tbu-Pt-AmPy, CF3-Pt-PPh3, and tbu-Pt-PPh3, were re-synthesized according to our previous work for a systematic comparison with their Pd(II) homologues. Thus, photophysical studies were performed in different solvents and conditions. The Pt(II) complexes demonstrated comparable or superior photophysical characteristics in toluene when compared with their solutions in liquid dichloromethane at room temperature. In contrast, the Pd(II) complexes exhibited no significant photoluminescence in dichloromethane, but a surprisingly clear emission was observed for tbu-Pd-AmPy, tbu-Pd-CNR, and tbu-Pd-PPh3 in liquid toluene at room temperature. The significant differences regarding excited state lifetimes and photoluminescence quantum yields underscore the impact of solvent selection on photophysical characteristics, emphasizing the need to consider metal-ligand interactions, as well as the surrounding microenvironment, for a comprehensive interpretation of their photophysical properties. In addition, it is clear that AmPy and CNR render better luminescence efficiencies, whereas PTA is only suitable in toluene.","PeriodicalId":507601,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139778547","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-02-11DOI: 10.3390/inorganics12020057
Yuan-Gee Lee, Hui-Hsuan Chiao, Yu-Ching Weng, C. Lay
Unlike the flat Cu sheet, we employed Cu foam to explore the specific porous effect on the expanding specific area. We found that the foam structure is superior to the sheet feature in the specific location from the morphology investigation. In the practical measurement of surface area, we found that the adsorbate could aptly agglomerate, resulting in a consequential block in the transport path. The specific location of the Cu foam was underestimated because the channels of the deep foam layer were blocked by the agglomerated adsorbate. To explore the protonation process of the electro-reduction, we adopted the carbonate electrolyte as the control group in contrast to the experimental group, the bicarbonate electrolyte. In the carbonate electrolyte, the primary intermediate was shown to be CO molecules, as verified using XPS spectra. In the bicarbonate electrolyte, the intermediate CO disappeared; instead, it was hydrogenated as a hydrocarbon intermediate, CHO*. The bicarbonate ion was also found to suppress electrocatalysis in the deep structure of the Cu foam because its high-molecular-weight intermediates accumulated in the diffusion paths. Furthermore, we found a promotion of the oxidation valence on the electrode from Cu2O to CuO, when the electrode structure transformed from sheet to foam. Cyclic voltammograms demonstrate a succession of electro-reduction consequences: at low reduction potential, hydrogen liberated by the decomposition of water; at elevated reduction potential, formic acid and CO produced; and at high reduction potential, CH4 and C2H4 were formed from −1.4 V to −1.8 V.
与平面铜片不同，我们采用了泡沫铜来探索特定多孔结构对特定区域膨胀的影响。通过形态学研究，我们发现泡沫结构在特定位置上优于片状结构。在表面积的实际测量中，我们发现吸附剂会适当地聚集，从而导致传输路径受阻。由于聚结的吸附剂堵塞了泡沫深层的通道，因此低估了铜泡沫的具体位置。为了探索电还原的质子化过程，我们采用碳酸盐电解质作为对照组，与实验组碳酸氢盐电解质形成对比。在碳酸盐电解质中，经 XPS 光谱验证，主要中间产物是 CO 分子。在碳酸氢盐电解质中，中间体 CO 消失了；取而代之的是氢化成碳氢化合物中间体 CHO*。我们还发现，碳酸氢根离子抑制了泡沫铜深层结构中的电催化，因为它的高分子量中间产物在扩散路径中积聚。此外，我们还发现，当电极结构从片状转变为泡沫状时，电极上的氧化价从 Cu2O 上升到了 CuO。循环伏安图显示了一系列电还原后果：在低还原电位下，水分解释放出氢；在高还原电位下，产生甲酸和 CO；在高还原电位下，从 -1.4 V 到 -1.8 V 之间形成 CH4 和 C2H4。
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Pub Date : 2024-02-11DOI: 10.3390/inorganics12020057
Yuan-Gee Lee, Hui-Hsuan Chiao, Yu-Ching Weng, C. Lay
Unlike the flat Cu sheet, we employed Cu foam to explore the specific porous effect on the expanding specific area. We found that the foam structure is superior to the sheet feature in the specific location from the morphology investigation. In the practical measurement of surface area, we found that the adsorbate could aptly agglomerate, resulting in a consequential block in the transport path. The specific location of the Cu foam was underestimated because the channels of the deep foam layer were blocked by the agglomerated adsorbate. To explore the protonation process of the electro-reduction, we adopted the carbonate electrolyte as the control group in contrast to the experimental group, the bicarbonate electrolyte. In the carbonate electrolyte, the primary intermediate was shown to be CO molecules, as verified using XPS spectra. In the bicarbonate electrolyte, the intermediate CO disappeared; instead, it was hydrogenated as a hydrocarbon intermediate, CHO*. The bicarbonate ion was also found to suppress electrocatalysis in the deep structure of the Cu foam because its high-molecular-weight intermediates accumulated in the diffusion paths. Furthermore, we found a promotion of the oxidation valence on the electrode from Cu2O to CuO, when the electrode structure transformed from sheet to foam. Cyclic voltammograms demonstrate a succession of electro-reduction consequences: at low reduction potential, hydrogen liberated by the decomposition of water; at elevated reduction potential, formic acid and CO produced; and at high reduction potential, CH4 and C2H4 were formed from −1.4 V to −1.8 V.
与平面铜片不同，我们采用了泡沫铜来探索特定多孔结构对特定区域膨胀的影响。通过形态学研究，我们发现泡沫结构在特定位置上优于片状结构。在表面积的实际测量中，我们发现吸附剂会适当地聚集，从而导致传输路径受阻。由于聚结的吸附剂堵塞了泡沫深层的通道，因此低估了铜泡沫的具体位置。为了探索电还原的质子化过程，我们采用碳酸盐电解质作为对照组，与实验组碳酸氢盐电解质形成对比。在碳酸盐电解质中，经 XPS 光谱验证，主要中间产物是 CO 分子。在碳酸氢盐电解质中，中间体 CO 消失了；取而代之的是氢化成碳氢化合物中间体 CHO*。我们还发现，碳酸氢根离子抑制了泡沫铜深层结构中的电催化，因为它的高分子量中间产物在扩散路径中积聚。此外，我们还发现，当电极结构从片状转变为泡沫状时，电极上的氧化价从 Cu2O 上升到了 CuO。循环伏安图显示了一系列电还原后果：在低还原电位下，水分解释放出氢；在高还原电位下，产生甲酸和 CO；在高还原电位下，从 -1.4 V 到 -1.8 V 之间形成 CH4 和 C2H4。
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Pub Date : 2024-02-09DOI: 10.3390/inorganics12020056
Zhi-Wei Tao, Han-Yi Zou, Hong-Hui Li, Bin Wang, Wen-Jie Chen
Density functional theory (DFT) and coupled cluster theory (CCSD(T)) calculations are performed to investigate the geometric and electronic structures and chemical bonding of a series of Cu-doped zinc oxide clusters: CunZn3O3 (n = 1–4). The structural evolution of CunZn3O3 (n = 1–4) clusters may reveal the aggregation behavior of Cu atoms on the Zn3O3 cluster. The planar seven-membered ring of the CuZn3O3 cluster plays an important role in the structural evolution; that is, the Cu atom, Cu dimer (Cu2) and Cu trimer (Cu3) anchor on the CuZn3O3 cluster. Additionally, it is found that CunZn3O3 clusters become more stable as the Cu content (n) increases. Bader charge analysis points out that with the doping of Cu atoms, the reducibility of Cu aggregation (Cun−1) on the CuZn3O3 cluster increases. Combined with the d-band centers and the surface electrostatic potential (ESP), the reactivity and the possible reaction sites of CunZn3O3 (n = 1–4) clusters are also illustrated.
通过密度泛函理论（DFT）和耦合团簇理论（CCSD(T)）计算，研究了一系列掺铜氧化锌团簇的几何结构、电子结构和化学键：CunZn3O3（n = 1-4）。CunZn3O3 (n = 1-4) 团簇的结构演变可能揭示了 Zn3O3 团簇上铜原子的聚集行为。CuZn3O3 团簇的平面七元环在结构演变中起着重要作用，即 Cu 原子、Cu 二聚体（Cu2）和 Cu 三聚体（Cu3）锚定在 CuZn3O3 团簇上。此外，研究还发现，随着铜含量（n）的增加，CunZn3O3 团簇变得更加稳定。巴德尔电荷分析指出，随着铜原子的掺入，CuZn3O3 团簇上铜聚集（Cun-1）的还原性增加。结合 d 带中心和表面静电势 (ESP)，还说明了 CunZn3O3（n = 1-4）团簇的反应性和可能的反应位点。
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Pub Date : 2024-02-09DOI: 10.3390/inorganics12020056
Zhi-Wei Tao, Han-Yi Zou, Hong-Hui Li, Bin Wang, Wen-Jie Chen
Density functional theory (DFT) and coupled cluster theory (CCSD(T)) calculations are performed to investigate the geometric and electronic structures and chemical bonding of a series of Cu-doped zinc oxide clusters: CunZn3O3 (n = 1–4). The structural evolution of CunZn3O3 (n = 1–4) clusters may reveal the aggregation behavior of Cu atoms on the Zn3O3 cluster. The planar seven-membered ring of the CuZn3O3 cluster plays an important role in the structural evolution; that is, the Cu atom, Cu dimer (Cu2) and Cu trimer (Cu3) anchor on the CuZn3O3 cluster. Additionally, it is found that CunZn3O3 clusters become more stable as the Cu content (n) increases. Bader charge analysis points out that with the doping of Cu atoms, the reducibility of Cu aggregation (Cun−1) on the CuZn3O3 cluster increases. Combined with the d-band centers and the surface electrostatic potential (ESP), the reactivity and the possible reaction sites of CunZn3O3 (n = 1–4) clusters are also illustrated.
通过密度泛函理论（DFT）和耦合团簇理论（CCSD(T)）计算，研究了一系列掺铜氧化锌团簇的几何结构、电子结构和化学键：CunZn3O3（n = 1-4）。CunZn3O3 (n = 1-4) 团簇的结构演变可能揭示了 Zn3O3 团簇上铜原子的聚集行为。CuZn3O3 团簇的平面七元环在结构演变中起着重要作用，即 Cu 原子、Cu 二聚体（Cu2）和 Cu 三聚体（Cu3）锚定在 CuZn3O3 团簇上。此外，研究还发现，随着铜含量（n）的增加，CunZn3O3 团簇变得更加稳定。巴德尔电荷分析指出，随着铜原子的掺入，CuZn3O3 团簇上铜聚集（Cun-1）的还原性增加。结合 d 带中心和表面静电势 (ESP)，还说明了 CunZn3O3（n = 1-4）团簇的反应性和可能的反应位点。
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The YxNi2−yMny system was investigated in the region 0.825 ≤ x ≤ 0.95, 0.1 ≤ y ≤ 0.3. The alloys were synthesized by induction melting and corresponding annealing. The substitution of Mn for Ni (y = 0.1) favors the formation of a C15 structure with disordered Y vacancies against the superstructure of Y0.95Ni2. For y = 0.2 and 0.3, Mn can substitute in both Y and Ni sites. Single-phase compounds with a C15 structure can be formed by adjusting both the Y and Mn contents. Their hydrogen absorption–desorption properties were measured by pressure–composition isotherm (PCI) measurements at 150 °C, and the hydrides were characterized at room temperature by X-ray diffraction and TG–DSC experiments. The PCIs show two plateaus corresponding to the formation of crystalline and amorphous hydrides. The heating of the amorphous hydrides leads to an endothermic desorption at first and then a recrystallization into Y(Ni, Mn)3 and YHx phases. At higher temperatures, the Y hydride desorbs, and a recombination into a Y(Ni, Mn)2 Laves phase compound is observed. For y = 0.1, vacancy formation in the Y site and partial Mn substitution in the Ni site enhance the structural stability and suppress the hydrogen-induced amorphization (HIA). However, for a larger Mn content (y ≥ 0.2), Mn substitutes also in the Y sites at the expense of Y vacancies. This yields worse structural stability upon hydrogenation than for y = 0.1, as the mean ratio r(Y, Mn)/r(Ni/Mn) becomes larger than for y = 0.1 r(Y, ☐)/r(Ni/Mn).
研究了 0.825 ≤ x ≤ 0.95, 0.1 ≤ y ≤ 0.3 区域内的 YxNi2-yMny 系统。合金是通过感应熔化和相应的退火工艺合成的。用锰代替镍（y = 0.1）有利于形成带有无序 Y 空位的 C15 结构，而不是 Y0.95Ni2 的上层结构。当 y = 0.2 和 0.3 时，锰可同时取代 Y 和 Ni 位点。通过调整 Y 和 Mn 的含量，可以形成具有 C15 结构的单相化合物。它们的氢吸收-解吸特性是在 150 °C 下通过压力-沉积等温线（PCI）测量得到的，氢化物在室温下的特性则是通过 X 射线衍射和 TG-DSC 实验得到的。PCI 显示出两个高原，分别对应于结晶水化物和无定形水化物的形成。加热无定形氢化物首先导致内热解吸，然后再结晶成 Y（Ni，Mn）3 和 YHx 相。在较高温度下，Y 氢化物解吸，并重新结合成 Y（Ni，Mn）2 Laves 相化合物。当 y = 0.1 时，Y 位点的空位形成和镍位点的部分锰置换增强了结构的稳定性，并抑制了氢致非晶化（HIA）。然而，当锰含量较高时（y≥ 0.2），锰也会取代 Y 位点，而牺牲 Y 空位。这导致氢化时的结构稳定性比 y = 0.1 时更差，因为平均比率 r（Y，Mn）/r（Ni/Mn）变得比 y = 0.1 时的 r（Y，☐）/r（Ni/Mn）更大。
{"title":"Structural Evolution and Hydrogen Sorption Properties of YxNi2−yMny (0.825 ≤ x ≤ 0.95, 0.1 ≤ y ≤ 0.3) Laves Phase Compounds","authors":"Hao Shen, Valérie Paul-Boncour, Ping Li, Lijun Jiang, Junxian Zhang","doi":"10.3390/inorganics12020055","DOIUrl":"https://doi.org/10.3390/inorganics12020055","url":null,"abstract":"The YxNi2−yMny system was investigated in the region 0.825 ≤ x ≤ 0.95, 0.1 ≤ y ≤ 0.3. The alloys were synthesized by induction melting and corresponding annealing. The substitution of Mn for Ni (y = 0.1) favors the formation of a C15 structure with disordered Y vacancies against the superstructure of Y0.95Ni2. For y = 0.2 and 0.3, Mn can substitute in both Y and Ni sites. Single-phase compounds with a C15 structure can be formed by adjusting both the Y and Mn contents. Their hydrogen absorption–desorption properties were measured by pressure–composition isotherm (PCI) measurements at 150 °C, and the hydrides were characterized at room temperature by X-ray diffraction and TG–DSC experiments. The PCIs show two plateaus corresponding to the formation of crystalline and amorphous hydrides. The heating of the amorphous hydrides leads to an endothermic desorption at first and then a recrystallization into Y(Ni, Mn)3 and YHx phases. At higher temperatures, the Y hydride desorbs, and a recombination into a Y(Ni, Mn)2 Laves phase compound is observed. For y = 0.1, vacancy formation in the Y site and partial Mn substitution in the Ni site enhance the structural stability and suppress the hydrogen-induced amorphization (HIA). However, for a larger Mn content (y ≥ 0.2), Mn substitutes also in the Y sites at the expense of Y vacancies. This yields worse structural stability upon hydrogenation than for y = 0.1, as the mean ratio r(Y, Mn)/r(Ni/Mn) becomes larger than for y = 0.1 r(Y, ☐)/r(Ni/Mn).","PeriodicalId":507601,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139855280","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The YxNi2−yMny system was investigated in the region 0.825 ≤ x ≤ 0.95, 0.1 ≤ y ≤ 0.3. The alloys were synthesized by induction melting and corresponding annealing. The substitution of Mn for Ni (y = 0.1) favors the formation of a C15 structure with disordered Y vacancies against the superstructure of Y0.95Ni2. For y = 0.2 and 0.3, Mn can substitute in both Y and Ni sites. Single-phase compounds with a C15 structure can be formed by adjusting both the Y and Mn contents. Their hydrogen absorption–desorption properties were measured by pressure–composition isotherm (PCI) measurements at 150 °C, and the hydrides were characterized at room temperature by X-ray diffraction and TG–DSC experiments. The PCIs show two plateaus corresponding to the formation of crystalline and amorphous hydrides. The heating of the amorphous hydrides leads to an endothermic desorption at first and then a recrystallization into Y(Ni, Mn)3 and YHx phases. At higher temperatures, the Y hydride desorbs, and a recombination into a Y(Ni, Mn)2 Laves phase compound is observed. For y = 0.1, vacancy formation in the Y site and partial Mn substitution in the Ni site enhance the structural stability and suppress the hydrogen-induced amorphization (HIA). However, for a larger Mn content (y ≥ 0.2), Mn substitutes also in the Y sites at the expense of Y vacancies. This yields worse structural stability upon hydrogenation than for y = 0.1, as the mean ratio r(Y, Mn)/r(Ni/Mn) becomes larger than for y = 0.1 r(Y, ☐)/r(Ni/Mn).
研究了 0.825 ≤ x ≤ 0.95, 0.1 ≤ y ≤ 0.3 区域内的 YxNi2-yMny 系统。合金是通过感应熔化和相应的退火工艺合成的。用锰代替镍（y = 0.1）有利于形成带有无序 Y 空位的 C15 结构，而不是 Y0.95Ni2 的上层结构。当 y = 0.2 和 0.3 时，锰可同时取代 Y 和 Ni 位点。通过调整 Y 和 Mn 的含量，可以形成具有 C15 结构的单相化合物。它们的氢吸收-解吸特性是在 150 °C 下通过压力-沉积等温线（PCI）测量得到的，氢化物在室温下的特性则是通过 X 射线衍射和 TG-DSC 实验得到的。PCI 显示出两个高原，分别对应于结晶水化物和无定形水化物的形成。加热无定形氢化物首先导致内热解吸，然后再结晶成 Y（Ni，Mn）3 和 YHx 相。在较高温度下，Y 氢化物解吸，并重新结合成 Y（Ni，Mn）2 Laves 相化合物。当 y = 0.1 时，Y 位点的空位形成和镍位点的部分锰置换增强了结构的稳定性，并抑制了氢致非晶化（HIA）。然而，当锰含量较高时（y≥ 0.2），锰也会取代 Y 位点，而牺牲 Y 空位。这导致氢化时的结构稳定性比 y = 0.1 时更差，因为平均比率 r（Y，Mn）/r（Ni/Mn）变得比 y = 0.1 时的 r（Y，☐）/r（Ni/Mn）更大。
{"title":"Structural Evolution and Hydrogen Sorption Properties of YxNi2−yMny (0.825 ≤ x ≤ 0.95, 0.1 ≤ y ≤ 0.3) Laves Phase Compounds","authors":"Hao Shen, Valérie Paul-Boncour, Ping Li, Lijun Jiang, Junxian Zhang","doi":"10.3390/inorganics12020055","DOIUrl":"https://doi.org/10.3390/inorganics12020055","url":null,"abstract":"The YxNi2−yMny system was investigated in the region 0.825 ≤ x ≤ 0.95, 0.1 ≤ y ≤ 0.3. The alloys were synthesized by induction melting and corresponding annealing. The substitution of Mn for Ni (y = 0.1) favors the formation of a C15 structure with disordered Y vacancies against the superstructure of Y0.95Ni2. For y = 0.2 and 0.3, Mn can substitute in both Y and Ni sites. Single-phase compounds with a C15 structure can be formed by adjusting both the Y and Mn contents. Their hydrogen absorption–desorption properties were measured by pressure–composition isotherm (PCI) measurements at 150 °C, and the hydrides were characterized at room temperature by X-ray diffraction and TG–DSC experiments. The PCIs show two plateaus corresponding to the formation of crystalline and amorphous hydrides. The heating of the amorphous hydrides leads to an endothermic desorption at first and then a recrystallization into Y(Ni, Mn)3 and YHx phases. At higher temperatures, the Y hydride desorbs, and a recombination into a Y(Ni, Mn)2 Laves phase compound is observed. For y = 0.1, vacancy formation in the Y site and partial Mn substitution in the Ni site enhance the structural stability and suppress the hydrogen-induced amorphization (HIA). However, for a larger Mn content (y ≥ 0.2), Mn substitutes also in the Y sites at the expense of Y vacancies. This yields worse structural stability upon hydrogenation than for y = 0.1, as the mean ratio r(Y, Mn)/r(Ni/Mn) becomes larger than for y = 0.1 r(Y, ☐)/r(Ni/Mn).","PeriodicalId":507601,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139795448","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-02-06DOI: 10.3390/inorganics12020054
Sanja Burazer, Jasminka Popović
In recent decades, the field of materials research has put significant emphasis on developing innovative platforms that have the potential to address the increasing global energy demand. Batteries have demonstrated their enormous effectiveness in the context of energy storage and consumption. However, safety issues associated with liquid electrolytes combined with a low abundance of lithium in the Earth’s crust gave rise to the development of solid-state electrolytes and cations other than lithium. The commercial production of solid-state batteries demands the scaling up of solid-state electrolyte syntheses as well as the mixing of electrode composites containing solid electrolytes. This review is motivated by the recent literature, and it gives a thorough overview of solid-state electrolytes and highlights the significance of the employed milling and dispersing procedures for the resulting ionic transport properties.
{"title":"Mechanochemical Synthesis of Solid-State Electrolytes","authors":"Sanja Burazer, Jasminka Popović","doi":"10.3390/inorganics12020054","DOIUrl":"https://doi.org/10.3390/inorganics12020054","url":null,"abstract":"In recent decades, the field of materials research has put significant emphasis on developing innovative platforms that have the potential to address the increasing global energy demand. Batteries have demonstrated their enormous effectiveness in the context of energy storage and consumption. However, safety issues associated with liquid electrolytes combined with a low abundance of lithium in the Earth’s crust gave rise to the development of solid-state electrolytes and cations other than lithium. The commercial production of solid-state batteries demands the scaling up of solid-state electrolyte syntheses as well as the mixing of electrode composites containing solid electrolytes. This review is motivated by the recent literature, and it gives a thorough overview of solid-state electrolytes and highlights the significance of the employed milling and dispersing procedures for the resulting ionic transport properties.","PeriodicalId":507601,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139860861","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-02-06DOI: 10.3390/inorganics12020054
Sanja Burazer, Jasminka Popović
In recent decades, the field of materials research has put significant emphasis on developing innovative platforms that have the potential to address the increasing global energy demand. Batteries have demonstrated their enormous effectiveness in the context of energy storage and consumption. However, safety issues associated with liquid electrolytes combined with a low abundance of lithium in the Earth’s crust gave rise to the development of solid-state electrolytes and cations other than lithium. The commercial production of solid-state batteries demands the scaling up of solid-state electrolyte syntheses as well as the mixing of electrode composites containing solid electrolytes. This review is motivated by the recent literature, and it gives a thorough overview of solid-state electrolytes and highlights the significance of the employed milling and dispersing procedures for the resulting ionic transport properties.
{"title":"Mechanochemical Synthesis of Solid-State Electrolytes","authors":"Sanja Burazer, Jasminka Popović","doi":"10.3390/inorganics12020054","DOIUrl":"https://doi.org/10.3390/inorganics12020054","url":null,"abstract":"In recent decades, the field of materials research has put significant emphasis on developing innovative platforms that have the potential to address the increasing global energy demand. Batteries have demonstrated their enormous effectiveness in the context of energy storage and consumption. However, safety issues associated with liquid electrolytes combined with a low abundance of lithium in the Earth’s crust gave rise to the development of solid-state electrolytes and cations other than lithium. The commercial production of solid-state batteries demands the scaling up of solid-state electrolyte syntheses as well as the mixing of electrode composites containing solid electrolytes. This review is motivated by the recent literature, and it gives a thorough overview of solid-state electrolytes and highlights the significance of the employed milling and dispersing procedures for the resulting ionic transport properties.","PeriodicalId":507601,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139801393","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-02-04DOI: 10.3390/inorganics12020053
Arshad Khan, Soheir E. Mohamed, T. I. Al-Naggar, Hasan B. Albargi, JariS. Algethami, Ayman M. Abdalla
Zinc oxide (ZnO) nanoparticles were synthesized hydrothermally using zinc acetate dihydrate and sodium thiosulfate pentahydrate precursors. The synthesized powders were sintered in air at 600 °C for different durations with a Cl-doping concentration of 25 mg/g. The optimal sintering time was found to be 5 h, resulting in the successful formation of the ZnO phase with small particle sizes of around 90 nm, nominal atomic fractions of Zn and O (~50%, ~50%), and increased luminescence intensity. The ideal concentration of Cl was discovered to be 25 mg/g of ZnO, which resulted in the highest luminescence intensity. The ZnO luminescence characteristics were observed in emission bands peaking at approximately 503 nm attributed to the transition from oxygen vacancies. A considerable improvement in the emission intensity was observed with increased Cl doping concentration, up to eight orders of magnitude, compared to pristine ZnO nanoparticles. However, the luminescence intensity decreased in samples with higher concentrations of Cl doping due to concentration quenching. These preliminary outcomes suggest that Cl-doped ZnO nanoparticles could be used for radiation detector development for radon monitoring and other related applications.
{"title":"Effect of Sintering Time and Cl Doping Concentrations on Structural, Optical, and Luminescence Properties of ZnO Nanoparticles","authors":"Arshad Khan, Soheir E. Mohamed, T. I. Al-Naggar, Hasan B. Albargi, JariS. Algethami, Ayman M. Abdalla","doi":"10.3390/inorganics12020053","DOIUrl":"https://doi.org/10.3390/inorganics12020053","url":null,"abstract":"Zinc oxide (ZnO) nanoparticles were synthesized hydrothermally using zinc acetate dihydrate and sodium thiosulfate pentahydrate precursors. The synthesized powders were sintered in air at 600 °C for different durations with a Cl-doping concentration of 25 mg/g. The optimal sintering time was found to be 5 h, resulting in the successful formation of the ZnO phase with small particle sizes of around 90 nm, nominal atomic fractions of Zn and O (~50%, ~50%), and increased luminescence intensity. The ideal concentration of Cl was discovered to be 25 mg/g of ZnO, which resulted in the highest luminescence intensity. The ZnO luminescence characteristics were observed in emission bands peaking at approximately 503 nm attributed to the transition from oxygen vacancies. A considerable improvement in the emission intensity was observed with increased Cl doping concentration, up to eight orders of magnitude, compared to pristine ZnO nanoparticles. However, the luminescence intensity decreased in samples with higher concentrations of Cl doping due to concentration quenching. These preliminary outcomes suggest that Cl-doped ZnO nanoparticles could be used for radiation detector development for radon monitoring and other related applications.","PeriodicalId":507601,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139807569","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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