Pub Date : 2024-07-17DOI: 10.3390/inorganics12070193
Jordan Burkhardt, Hayden Prescott, Wan-Lu Li
Boron, the neighbor element to carbon in the periodic table, is characterized by unique electron deficiency that fosters multicenter delocalized bonding, contributing to its diverse chemistry. Unlike carbon cages (fullerenes), which preserve their structural integrity under endohedral or exohedral doping, larger boron cages (borospherenes) exhibit diverse structural configurations. These configurations can differ from those of pure boron cages and are stabilized by various metals through unique metal–boron bonding, resulting in a variety of metalloborospherenes. Due to boron’s electron deficiency, metalloborospherenes exhibit fascinating chemical bonding patterns that vary with cluster size and the type of metal dopants. This review paper highlights recent advancements in metalloborospherene research, drawing comparisons with metallofullerenes, and focuses on the use of transition metals, lanthanides, and actinides as dopants across various cage dimensions.
{"title":"Metalloborospherene Analogs to Metallofullerene","authors":"Jordan Burkhardt, Hayden Prescott, Wan-Lu Li","doi":"10.3390/inorganics12070193","DOIUrl":"https://doi.org/10.3390/inorganics12070193","url":null,"abstract":"Boron, the neighbor element to carbon in the periodic table, is characterized by unique electron deficiency that fosters multicenter delocalized bonding, contributing to its diverse chemistry. Unlike carbon cages (fullerenes), which preserve their structural integrity under endohedral or exohedral doping, larger boron cages (borospherenes) exhibit diverse structural configurations. These configurations can differ from those of pure boron cages and are stabilized by various metals through unique metal–boron bonding, resulting in a variety of metalloborospherenes. Due to boron’s electron deficiency, metalloborospherenes exhibit fascinating chemical bonding patterns that vary with cluster size and the type of metal dopants. This review paper highlights recent advancements in metalloborospherene research, drawing comparisons with metallofullerenes, and focuses on the use of transition metals, lanthanides, and actinides as dopants across various cage dimensions.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":3.1,"publicationDate":"2024-07-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141829913","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-12DOI: 10.3390/inorganics12070190
Sandra Jimenez-Falcao, J. M. Méndez-Arriaga
Leishmaniasis is a complex disease present in a variety of manifestations listed by the World Health Organization (WHO) as one of the neglected diseases with a worse prognosis if not treated. Medicinal inorganic chemistry has provided a variety of drugs based on metal–organic complexes synthesized with different metal centers and organic ligands to fight against a great number of parasite maladies and specifically Leishmaniasis. Taking advantage of the natural properties that many metals present for biotechnological purposes, nanotechnology has offered, in recent years, a new approach consisting on the application of metal nanoparticles to treat a great number of parasitic diseases, as a drug vehicle or as a treatment themselves. The aim of this review is to gather the most widely used metal complexes and metallic nanoparticles and the most recent strategies proposed as antileishmanial agents.
{"title":"Recent Advances in Metal Complexes Based on Biomimetic and Biocompatible Organic Ligands against Leishmaniasis Infections: State of the Art and Alternatives","authors":"Sandra Jimenez-Falcao, J. M. Méndez-Arriaga","doi":"10.3390/inorganics12070190","DOIUrl":"https://doi.org/10.3390/inorganics12070190","url":null,"abstract":"Leishmaniasis is a complex disease present in a variety of manifestations listed by the World Health Organization (WHO) as one of the neglected diseases with a worse prognosis if not treated. Medicinal inorganic chemistry has provided a variety of drugs based on metal–organic complexes synthesized with different metal centers and organic ligands to fight against a great number of parasite maladies and specifically Leishmaniasis. Taking advantage of the natural properties that many metals present for biotechnological purposes, nanotechnology has offered, in recent years, a new approach consisting on the application of metal nanoparticles to treat a great number of parasitic diseases, as a drug vehicle or as a treatment themselves. The aim of this review is to gather the most widely used metal complexes and metallic nanoparticles and the most recent strategies proposed as antileishmanial agents.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":3.1,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141654401","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-12DOI: 10.3390/inorganics12070191
A. Al-Wasidi, S. Alreshaidan
This paper studies the synthesis, characterization, and application of ZnFe2O4 nanoparticles for the removal of rhodamine b dye from aqueous media. Utilizing the combustion procedure, ZnFe2O4 nanoparticles were synthesized using two different fuels: glutamine (SG) and L-arginine (SA). In addition, the synthesized ZnFe2O4 nanoparticles were characterized through various techniques, including Fourier transform infrared (FTIR), X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM), energy-dispersive X-ray (EDX), high resolution transmission electron microscope (HR-TEM), and Brunauer-Emmett-Teller (BET) surface area analysis. XRD analysis verified the creation of a ZnFe2O4 cubic spinel structure without any contaminants, revealing average crystallite sizes of 43.72 and 29.38 nm for the SG and SA samples, respectively. The FTIR spectra exhibited peaks indicative of metal-oxygen bond stretching, verifying the presence of a spinel formation. Elemental analysis via EDX confirmed the stoichiometric composition typical of zinc ferrite. In addition, FE-SEM imaging displayed that the SG and SA samples are composed of particles with irregular and spherical shapes, measuring average diameters of 135.11 and 59.89 nm, respectively. Furthermore, the BET surface area of the SG and SA samples is 60 and 85 m2/g, respectively. The maximum adsorption capacity of the SA sample (409.84 mg/g) towards rhodamine b dye was higher than that of the SG sample (279.33 mg/g), which was ascribed to its larger surface area and porosity. Kinetic and equilibrium studies revealed that the adsorption process of rhodamine b dye onto the SG and SA samples followed the Langmuir isotherm and pseudo-second-order model. Thermodynamic analysis indicated that the adsorption process was spontaneous, exothermic, and physical. The study concludes that ZnFe2O4 nanoparticles synthesized using L-arginine (SA) exhibit enhanced rhodamine b dye removal efficiency due to their smaller size, increased surface area, and higher porosity compared to those synthesized with glutamine (SG). The optimum conditions for the adsorption process of rhodamine b dye were found to be at pH 10, a contact time of 70 min, and a temperature of 298 K. These findings underscore the potential of L-arginine-synthesized ZnFe2O4 nanoparticles for effective and sustainable environmental cleanup applications.
本文研究了用于去除水介质中罗丹明 b 染料的 ZnFe2O4 纳米粒子的合成、表征和应用。采用燃烧法，利用谷氨酰胺（SG）和精氨酸（SA）两种不同的燃料合成了 ZnFe2O4 纳米粒子。此外，还通过多种技术对合成的 ZnFe2O4 纳米粒子进行了表征，包括傅立叶变换红外（FTIR）、X 射线衍射（XRD）、场发射扫描电子显微镜（FE-SEM）、能量色散 X 射线（EDX）、高分辨率透射电子显微镜（HR-TEM）和布鲁诺-埃美特-泰勒（BET）表面积分析。XRD 分析证实了 ZnFe2O4 立方尖晶石结构的形成，没有任何杂质，SG 和 SA 样品的平均结晶尺寸分别为 43.72 和 29.38 nm。傅立叶变换红外光谱显示出金属氧键伸展的峰值，验证了尖晶石的形成。通过 EDX 进行的元素分析证实了锌铁氧体的典型化学成分。此外，FE-SEM 成像显示，SG 和 SA 样品由不规则和球形颗粒组成，平均直径分别为 135.11 纳米和 59.89 纳米。此外，SG 和 SA 样品的 BET 表面积分别为 60 和 85 m2/g。SA 样品对罗丹明 b 染料的最大吸附容量（409.84 毫克/克）高于 SG 样品（279.33 毫克/克），这归因于其较大的比表面积和孔隙率。动力学和平衡研究表明，罗丹明 b 染料在 SG 样品和 SA 样品上的吸附过程遵循 Langmuir 等温线和伪秒阶模型。热力学分析表明，吸附过程是自发的、放热的和物理的。研究得出结论：与使用谷氨酰胺（SG）合成的 ZnFe2O4 纳米粒子相比，使用 L-精氨酸（SA）合成的 ZnFe2O4 纳米粒子尺寸更小、比表面积更大、孔隙率更高，因此罗丹明 b 染料去除效率更高。吸附罗丹明 b 染料的最佳条件是 pH 值为 10，接触时间为 70 分钟，温度为 298 K。
{"title":"Enhanced Removal of Rhodamine b Dye from Aqueous Media via Adsorption on Facilely Synthesized Zinc Ferrite Nanoparticles","authors":"A. Al-Wasidi, S. Alreshaidan","doi":"10.3390/inorganics12070191","DOIUrl":"https://doi.org/10.3390/inorganics12070191","url":null,"abstract":"This paper studies the synthesis, characterization, and application of ZnFe2O4 nanoparticles for the removal of rhodamine b dye from aqueous media. Utilizing the combustion procedure, ZnFe2O4 nanoparticles were synthesized using two different fuels: glutamine (SG) and L-arginine (SA). In addition, the synthesized ZnFe2O4 nanoparticles were characterized through various techniques, including Fourier transform infrared (FTIR), X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM), energy-dispersive X-ray (EDX), high resolution transmission electron microscope (HR-TEM), and Brunauer-Emmett-Teller (BET) surface area analysis. XRD analysis verified the creation of a ZnFe2O4 cubic spinel structure without any contaminants, revealing average crystallite sizes of 43.72 and 29.38 nm for the SG and SA samples, respectively. The FTIR spectra exhibited peaks indicative of metal-oxygen bond stretching, verifying the presence of a spinel formation. Elemental analysis via EDX confirmed the stoichiometric composition typical of zinc ferrite. In addition, FE-SEM imaging displayed that the SG and SA samples are composed of particles with irregular and spherical shapes, measuring average diameters of 135.11 and 59.89 nm, respectively. Furthermore, the BET surface area of the SG and SA samples is 60 and 85 m2/g, respectively. The maximum adsorption capacity of the SA sample (409.84 mg/g) towards rhodamine b dye was higher than that of the SG sample (279.33 mg/g), which was ascribed to its larger surface area and porosity. Kinetic and equilibrium studies revealed that the adsorption process of rhodamine b dye onto the SG and SA samples followed the Langmuir isotherm and pseudo-second-order model. Thermodynamic analysis indicated that the adsorption process was spontaneous, exothermic, and physical. The study concludes that ZnFe2O4 nanoparticles synthesized using L-arginine (SA) exhibit enhanced rhodamine b dye removal efficiency due to their smaller size, increased surface area, and higher porosity compared to those synthesized with glutamine (SG). The optimum conditions for the adsorption process of rhodamine b dye were found to be at pH 10, a contact time of 70 min, and a temperature of 298 K. These findings underscore the potential of L-arginine-synthesized ZnFe2O4 nanoparticles for effective and sustainable environmental cleanup applications.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":3.1,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141652680","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-12DOI: 10.3390/inorganics12070192
Leander Weinelt, Simon Steinberg
Over the decades, intensive explorations have been conducted to understand the nature of d10−d10 interactions. The recent establishment of a bonding indicator named the crystal orbital bond index stimulated our impetus to probe the capabilities of that approach for the examples of Ag–Ag interactions in different tellurides. In the framework of our quantum chemical explorations, we inspected the electronic structures of two tellurides which were previously reported to comprise d10−d10 interactions, while the third candidate material, i.e., RbCe2Ag3Te5, has been obtained from reactions of rubidium chloride, cerium, silver and tellurium for the very first time. The outcome of our explorations clearly shows that the nature of Ag–Ag interactions is well mirrored by the corresponding COBI.
{"title":"Exploring the Nature of Ag–Ag Interactions in Different Tellurides by Means of the Crystal Orbital Bond Index (COBI)","authors":"Leander Weinelt, Simon Steinberg","doi":"10.3390/inorganics12070192","DOIUrl":"https://doi.org/10.3390/inorganics12070192","url":null,"abstract":"Over the decades, intensive explorations have been conducted to understand the nature of d10−d10 interactions. The recent establishment of a bonding indicator named the crystal orbital bond index stimulated our impetus to probe the capabilities of that approach for the examples of Ag–Ag interactions in different tellurides. In the framework of our quantum chemical explorations, we inspected the electronic structures of two tellurides which were previously reported to comprise d10−d10 interactions, while the third candidate material, i.e., RbCe2Ag3Te5, has been obtained from reactions of rubidium chloride, cerium, silver and tellurium for the very first time. The outcome of our explorations clearly shows that the nature of Ag–Ag interactions is well mirrored by the corresponding COBI.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":3.1,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141654860","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-11DOI: 10.3390/inorganics12070189
Maged S. Al-Fakeh, Muneera Alrasheedi, Ard Mohammed, Ahmed Ibrahim, Sadeq M. Al-Hazmy, Ibrahim A. Alhagri, Sabri Messaoudi
Pd(II) with the Schiff base ligand 2-Hydroxy-3-Methoxy Benzaldehyde-Thiosemicarbazone (HMBATSC) (L2) and 2-aminobenzothiazole (2-ABZ) (L1) was synthesized. The Schiff base ligand and the Palladium(II) complex were characterized by C.H.N.S, FT-IR, conductance studies, magnetic susceptibility, XRD, and TGA. From the elemental analysis and spectral data, the complex was proposed to have the formula [Pd(HMBATSC)(2-ABZ)H2O]. The interaction between the Pd(II) complex and DNA was examined through various methods, including UV–Vis spectroscopy, fluorescence techniques, and DNA viscosity titrations. The findings provided strong evidence that the interaction between the Pd(II) complex and DNA occurs through the intercalation mode. The analysis yielded the following values: a Stern–Volmer quenching constant (ksv) of 1.67 × 104 M−1, a quenching rate constant (kq) of 8.35 × 1011 M−1 s−1, a binding constant (kb) of 5.20 × 105 M−1, and a number of binding the sites (n) of 1.392. DFT studies suggest that the azole derivative may act as an electron donor through pyridine nitrogen, while the Schiff base ligand may act as an electron donor via oxygen and sulfur atoms. TDDFT calculations indicate that the intramolecular charge transfer from the Schiff base to Pd(II) is responsible for the complex’s fluorescence quenching. The powder X-ray diffraction data revealed that the complex is arranged in a monoclinic system. The resulting Pd(II) complex was investigated for its antimicrobial activity and demonstrated antibacterial efficiency. Interestingly, it showed potent activity against E. coli and E. niger that was found to be more powerful than that recorded for Neomycin.
{"title":"Synthesis, Characterization, DNA, Fluorescence, Molecular Docking, and Antimicrobial Evaluation of Novel Pd(II) Complex Containing O, S Donor Schiff Base Ligand and Azole Derivative","authors":"Maged S. Al-Fakeh, Muneera Alrasheedi, Ard Mohammed, Ahmed Ibrahim, Sadeq M. Al-Hazmy, Ibrahim A. Alhagri, Sabri Messaoudi","doi":"10.3390/inorganics12070189","DOIUrl":"https://doi.org/10.3390/inorganics12070189","url":null,"abstract":"Pd(II) with the Schiff base ligand 2-Hydroxy-3-Methoxy Benzaldehyde-Thiosemicarbazone (HMBATSC) (L2) and 2-aminobenzothiazole (2-ABZ) (L1) was synthesized. The Schiff base ligand and the Palladium(II) complex were characterized by C.H.N.S, FT-IR, conductance studies, magnetic susceptibility, XRD, and TGA. From the elemental analysis and spectral data, the complex was proposed to have the formula [Pd(HMBATSC)(2-ABZ)H2O]. The interaction between the Pd(II) complex and DNA was examined through various methods, including UV–Vis spectroscopy, fluorescence techniques, and DNA viscosity titrations. The findings provided strong evidence that the interaction between the Pd(II) complex and DNA occurs through the intercalation mode. The analysis yielded the following values: a Stern–Volmer quenching constant (ksv) of 1.67 × 104 M−1, a quenching rate constant (kq) of 8.35 × 1011 M−1 s−1, a binding constant (kb) of 5.20 × 105 M−1, and a number of binding the sites (n) of 1.392. DFT studies suggest that the azole derivative may act as an electron donor through pyridine nitrogen, while the Schiff base ligand may act as an electron donor via oxygen and sulfur atoms. TDDFT calculations indicate that the intramolecular charge transfer from the Schiff base to Pd(II) is responsible for the complex’s fluorescence quenching. The powder X-ray diffraction data revealed that the complex is arranged in a monoclinic system. The resulting Pd(II) complex was investigated for its antimicrobial activity and demonstrated antibacterial efficiency. Interestingly, it showed potent activity against E. coli and E. niger that was found to be more powerful than that recorded for Neomycin.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":3.1,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141656746","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-08DOI: 10.3390/inorganics12070188
Syrine Sassi, Amal Bouich, A. Hajjaji, L. Khezami, B. Bessais, B. M. Soucase
Cu-doped TiO2 films were synthesized directly on FTO glass with a spin coating method. With a variation in copper amount, samples were prepared with 0%, 1%, 2%, 4% and 8% of dopant concentrations. Morphological and structural characterization of undoped and Cu-doped TiO2 samples were investigated and the obtained results showed the small, spherical shapes of the nanoparticles forming a thin film on top of FTO glass and their preferred orientation of TiO2 anatase (101), which is the same for each sample. However, this peak exhibited a slight shift for the 2% sample, related to the inflation of the microstrain compared to the other samples. For the optical properties, the 4% sample displayed the highest transmittance whereas the 2% sample exhibited the lowest band gap energy of 2.96 eV. Moreover, the PL intensity seems to be at its highest for the 2% sample due to the present peaking defects in the structure, whereas the 8% sample shows a whole new signal that is related to copper oxide. These properties make this material a potential candidate to perform as an electron transport layer (ETL) in solar cells and enhance their power conversion efficiency.
{"title":"Cu-Doped TiO2 Thin Films by Spin Coating: Investigation of Structural and Optical Properties","authors":"Syrine Sassi, Amal Bouich, A. Hajjaji, L. Khezami, B. Bessais, B. M. Soucase","doi":"10.3390/inorganics12070188","DOIUrl":"https://doi.org/10.3390/inorganics12070188","url":null,"abstract":"Cu-doped TiO2 films were synthesized directly on FTO glass with a spin coating method. With a variation in copper amount, samples were prepared with 0%, 1%, 2%, 4% and 8% of dopant concentrations. Morphological and structural characterization of undoped and Cu-doped TiO2 samples were investigated and the obtained results showed the small, spherical shapes of the nanoparticles forming a thin film on top of FTO glass and their preferred orientation of TiO2 anatase (101), which is the same for each sample. However, this peak exhibited a slight shift for the 2% sample, related to the inflation of the microstrain compared to the other samples. For the optical properties, the 4% sample displayed the highest transmittance whereas the 2% sample exhibited the lowest band gap energy of 2.96 eV. Moreover, the PL intensity seems to be at its highest for the 2% sample due to the present peaking defects in the structure, whereas the 8% sample shows a whole new signal that is related to copper oxide. These properties make this material a potential candidate to perform as an electron transport layer (ETL) in solar cells and enhance their power conversion efficiency.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":3.1,"publicationDate":"2024-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141667164","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-05DOI: 10.3390/inorganics12070187
Sascha A. Schäfer, Rose Jordan, Katharina M. Klupsch, Felix Carl-Heinz Herwede, Axel Klein
When synthesizing the versatile precursors (NMe4)[Ni(CF3)3(MeCN)] we recently encountered the problem that marked amounts of C2F5 were incorporated instead of CF3 under the chosen reaction conditions forming mixed-ligand nickelates [Ni(CF3)x(C2F5)y(MeCN)]− (x + y = 3). We studied the three products with y = 0, 1, or 2, using 19F nuclear magnetic resonance (NMR) spectroscopy and single-crystal X-ray diffraction. We were able to trace the reaction mechanism and solve the problem by modifying the experimental conditions.
在合成多用途前体 (NMe4)[Ni(CF3)3(MeCN)] 时，我们最近遇到了一个问题：在所选反应条件下，大量的 C2F5 取代 CF3 加入，形成了混合配体镍酸盐 [Ni(CF3)x(C2F5)y(MeCN)]- (x + y = 3)。我们利用 19F 核磁共振 (NMR) 光谱和单晶 X 射线衍射研究了 y = 0、1 或 2 的三种产物。通过修改实验条件，我们追溯到了反应机理并解决了问题。
{"title":"Synthesis of Tris(trifluoromethyl)nickelates(II)—Coping with “The C2F5 Problem”","authors":"Sascha A. Schäfer, Rose Jordan, Katharina M. Klupsch, Felix Carl-Heinz Herwede, Axel Klein","doi":"10.3390/inorganics12070187","DOIUrl":"https://doi.org/10.3390/inorganics12070187","url":null,"abstract":"When synthesizing the versatile precursors (NMe4)[Ni(CF3)3(MeCN)] we recently encountered the problem that marked amounts of C2F5 were incorporated instead of CF3 under the chosen reaction conditions forming mixed-ligand nickelates [Ni(CF3)x(C2F5)y(MeCN)]− (x + y = 3). We studied the three products with y = 0, 1, or 2, using 19F nuclear magnetic resonance (NMR) spectroscopy and single-crystal X-ray diffraction. We were able to trace the reaction mechanism and solve the problem by modifying the experimental conditions.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":3.1,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141675764","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-03DOI: 10.3390/inorganics12070186
J. Pereira, Reinaldo Souza, Ana S. Moita
The current study focuses on reviewing the actual progress of the use of ionic liquids and derivatives in several electrochemical application. Ionic liquids can be prepared at room temperature conditions and by including a solution that can be a salt in water, or a base or acid, and are composed of organic cations and many charge-delocalized organic or inorganic anions. The electrochemical properties, including the ionic and electronic conductivities of these innovative fluids and hybrids, are addressed in depth, together with their key influencing parameters including type, fraction, functionalization of the nanoparticles, and operating temperature, as well as the incorporation of surfactants or additives. Also, the present review assesses the recent applications of ionic liquids and corresponding hybrids with the addition of nanoparticles in diverse electrochemical equipment and processes, together with a critical evaluation of the related feasibility concerns in different applications. Those ranging from the metal-ion batteries, in which ionic liquids possess a prominent role as electrolytes and reference electrodes passing through the dye of sensitized solar cells and fuel cells, to finishing processes like the ones related with low-grade heat harvesting and supercapacitors. Moreover, the overview of the scientific articles on the theme resulted in the comparatively brief examination of the benefits closely linked with the use of ionic fluids and corresponding hybrids, such as improved ionic conductivity, thermal and electrochemical stabilities, and tunability, in comparison with the traditional solvents, electrolytes, and electrodes. Finally, this work analyzes the fundamental limitations of such novel fluids such as their corrosivity potential, elevated dynamic viscosity, and leakage risk, and highlights the essential prospects for the research and exploration of ionic liquids and derivatives in various electrochemical devices and procedures.
{"title":"A Review of Ionic Liquids and Their Composites with Nanoparticles for Electrochemical Applications","authors":"J. Pereira, Reinaldo Souza, Ana S. Moita","doi":"10.3390/inorganics12070186","DOIUrl":"https://doi.org/10.3390/inorganics12070186","url":null,"abstract":"The current study focuses on reviewing the actual progress of the use of ionic liquids and derivatives in several electrochemical application. Ionic liquids can be prepared at room temperature conditions and by including a solution that can be a salt in water, or a base or acid, and are composed of organic cations and many charge-delocalized organic or inorganic anions. The electrochemical properties, including the ionic and electronic conductivities of these innovative fluids and hybrids, are addressed in depth, together with their key influencing parameters including type, fraction, functionalization of the nanoparticles, and operating temperature, as well as the incorporation of surfactants or additives. Also, the present review assesses the recent applications of ionic liquids and corresponding hybrids with the addition of nanoparticles in diverse electrochemical equipment and processes, together with a critical evaluation of the related feasibility concerns in different applications. Those ranging from the metal-ion batteries, in which ionic liquids possess a prominent role as electrolytes and reference electrodes passing through the dye of sensitized solar cells and fuel cells, to finishing processes like the ones related with low-grade heat harvesting and supercapacitors. Moreover, the overview of the scientific articles on the theme resulted in the comparatively brief examination of the benefits closely linked with the use of ionic fluids and corresponding hybrids, such as improved ionic conductivity, thermal and electrochemical stabilities, and tunability, in comparison with the traditional solvents, electrolytes, and electrodes. Finally, this work analyzes the fundamental limitations of such novel fluids such as their corrosivity potential, elevated dynamic viscosity, and leakage risk, and highlights the essential prospects for the research and exploration of ionic liquids and derivatives in various electrochemical devices and procedures.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":3.1,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141682858","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-02DOI: 10.3390/inorganics12070185
Néstor Calabia Gascón, B. Wouters, Herman Terryn, Annick Hubin
Electrolytic capacitors store larger amounts of energy thanks to their thin dielectric layers and enlarged surface area. However, the benefits of using a liquid electrolyte are at the expense of the possibility of leakage, evaporation, or rupture of the device over time. As a solution, solid electrolytes, such as conductive polymers, substitute the liquid ones decreasing the internal resistance and enlarging the lifetime of these devices. PEDOT:PSS is a widely used conductive polymer in the formation of solid electrolytic capacitors. However, using the enlarged surface of the porous electrodes efficiently requires industrial processes, the efficacy of which has not been explored. In this work, porous aluminium electrodes with dielectric layers of different thicknesses were coated with PEDOT:PSS at different levels of doping in order to study the efficiency of the production of solid electrolytic capacitors in industry. The combination of odd random phase electrochemical impedance spectroscopy (ORP-EIS) with surface characterization techniques (SEM-EDX, GDOES) formed a methodology that allowed the study of both the electrical properties and the level of impregnation for these model systems. All samples consisting of a porous aluminium electrode with an amount of PEDOT:PSS deposited on top resulted in an inefficient degree of penetration between the two electrodes. However, the electrochemical analysis proved that the use of dopants produces systems with the highest capacitive properties. Consequently, the evolution towards better solid electrolytic capacitors does not rely solely on the proper coverage of the porous electrodes, but on the proper electrical properties of the PEDOT:PSS within the pores.
{"title":"Effect of Impregnation of PEDOT:PSS in Etched Aluminium Electrodes on the Performance of Solid State Electrolytic Capacitors","authors":"Néstor Calabia Gascón, B. Wouters, Herman Terryn, Annick Hubin","doi":"10.3390/inorganics12070185","DOIUrl":"https://doi.org/10.3390/inorganics12070185","url":null,"abstract":"Electrolytic capacitors store larger amounts of energy thanks to their thin dielectric layers and enlarged surface area. However, the benefits of using a liquid electrolyte are at the expense of the possibility of leakage, evaporation, or rupture of the device over time. As a solution, solid electrolytes, such as conductive polymers, substitute the liquid ones decreasing the internal resistance and enlarging the lifetime of these devices. PEDOT:PSS is a widely used conductive polymer in the formation of solid electrolytic capacitors. However, using the enlarged surface of the porous electrodes efficiently requires industrial processes, the efficacy of which has not been explored. In this work, porous aluminium electrodes with dielectric layers of different thicknesses were coated with PEDOT:PSS at different levels of doping in order to study the efficiency of the production of solid electrolytic capacitors in industry. The combination of odd random phase electrochemical impedance spectroscopy (ORP-EIS) with surface characterization techniques (SEM-EDX, GDOES) formed a methodology that allowed the study of both the electrical properties and the level of impregnation for these model systems. All samples consisting of a porous aluminium electrode with an amount of PEDOT:PSS deposited on top resulted in an inefficient degree of penetration between the two electrodes. However, the electrochemical analysis proved that the use of dopants produces systems with the highest capacitive properties. Consequently, the evolution towards better solid electrolytic capacitors does not rely solely on the proper coverage of the porous electrodes, but on the proper electrical properties of the PEDOT:PSS within the pores.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":3.1,"publicationDate":"2024-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141685316","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-14DOI: 10.3390/inorganics12060166
Marlo Schöneich, Lucas G. Balzat, Bettina V. Lotsch, Dirk Johrendt
Na1.36(Si0.86Ga0.14)2As2.98 and Li1.5Ga0.9Si3.1As4 were synthesized by heating mixtures of the elements at 950 °C. The crystal structures were determined by single crystal X-ray diffraction (Na1.36(Si0.86Ga0.14)2As2.98: I41/a, Z = 100, a = 19.8772(4) Å, c = 37.652(1) Å; Li1.5Ga0.9Si3.1As4: C2/c, Z = 8, a = 10.8838(6) Å, b = 10.8821(6) Å, c = 13.1591(7) Å). Na1.36(Si0.86Ga0.14)2As2.98 crystallizes similar to NaSi2P3 with interpenetrating networks of vertex-sharing T4 and T5 supertetrahedra. Gallium substitution at the silicon sites increases the charge of the cluster network, which is compensated for by a 36% higher sodium content. Since in contrast to NaSi2P3, all sodium sites are now fully occupied, there is no significant ion mobility, as indicated by 23Na-NMR. Consequently, the total sodium-ion conductivity of Na1.36(Si0.86Ga0.14)2As2.98 amounts to only 1.6(1) × 10−7 S cm−1 and is therefore three orders of magnitude lower than in NaSi2P3. Li1.5Ga0.9Si3.1As4 crystallizes in a new structure type with layers of edge-sharing (Si1−xGax)As4 tetrahedra alternating with layers that contain infinite Sin zigzag chains. Lithium ions reside in channels between the chains, and thus, the structure does not provide three dimensional pathways for ion conduction and the measured total Li-ion conductivity amounts to only 1.3(1) × 10−7 S cm−1.
{"title":"Sodium Filling in Superadamantoide Na1.36(Si0.86Ga0.14)2As2.98 and the Mixed Valent Arsenidosilicate-Silicide Li1.5Ga0.9Si3.1As4","authors":"Marlo Schöneich, Lucas G. Balzat, Bettina V. Lotsch, Dirk Johrendt","doi":"10.3390/inorganics12060166","DOIUrl":"https://doi.org/10.3390/inorganics12060166","url":null,"abstract":"Na1.36(Si0.86Ga0.14)2As2.98 and Li1.5Ga0.9Si3.1As4 were synthesized by heating mixtures of the elements at 950 °C. The crystal structures were determined by single crystal X-ray diffraction (Na1.36(Si0.86Ga0.14)2As2.98: I41/a, Z = 100, a = 19.8772(4) Å, c = 37.652(1) Å; Li1.5Ga0.9Si3.1As4: C2/c, Z = 8, a = 10.8838(6) Å, b = 10.8821(6) Å, c = 13.1591(7) Å). Na1.36(Si0.86Ga0.14)2As2.98 crystallizes similar to NaSi2P3 with interpenetrating networks of vertex-sharing T4 and T5 supertetrahedra. Gallium substitution at the silicon sites increases the charge of the cluster network, which is compensated for by a 36% higher sodium content. Since in contrast to NaSi2P3, all sodium sites are now fully occupied, there is no significant ion mobility, as indicated by 23Na-NMR. Consequently, the total sodium-ion conductivity of Na1.36(Si0.86Ga0.14)2As2.98 amounts to only 1.6(1) × 10−7 S cm−1 and is therefore three orders of magnitude lower than in NaSi2P3. Li1.5Ga0.9Si3.1As4 crystallizes in a new structure type with layers of edge-sharing (Si1−xGax)As4 tetrahedra alternating with layers that contain infinite Sin zigzag chains. Lithium ions reside in channels between the chains, and thus, the structure does not provide three dimensional pathways for ion conduction and the measured total Li-ion conductivity amounts to only 1.3(1) × 10−7 S cm−1.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2024-06-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141340080","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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