Pub Date : 2024-07-03DOI: 10.1134/s0036023623603057
A. Yu. Pavlikov, S. V. Saikova, A. S. Samoilo, D. V. Karpov, S. A. Novikova
Abstract
Copper(II) oxide nanoparticles are promising materials for use in catalysis, biomedicine, and photovoltaics. They can also be used to prepare nanocomposites and hybrid nanoparticles. This paper presents a new one-pot method for preparing CuO nanoparticles without long-term washing and heat treatment. The proposed anion-exchange precipitation is a facile and fast process, and is easily reproducible under standard laboratory conditions. Anion-exchange precipitation of copper from copper chloride or copper sulfate solutions in the presence of the polysaccharide dextran-40 produces well-crystallized hydroxychloride Cu2Cl(OH)3 and hydroxysulfate Cu4(SO4)(OH)6, respectively; from copper nitrate solutions, a poorly crystallized Cu(OH)2 phase is formed. In the absence of polysaccharides, the product is copper oxide nanoparticles regardless of the anion in the precursor salt. The thus-prepared materials were used to prepare hydrosols. The hydrosols had high aggregation and sedimentation stability over a wide pH range (from 5 to 11) as shown by dynamic and electrophoretic light scattering. They were stable for more than three months at a concentration of 2 g/L (the average hydrodynamic diameter of the particles was 245 nm; the average ζ-potential was –31.1 mV). The optical and electronic properties of the prepared hydrosols imply that they could be of interest for use in photocatalysis and in optoelectronic devices.
{"title":"Synthesis of Copper(II) Oxide Nanoparticles by Anion-Exchange Resin-Assisted Precipitation and Production of Their Stable Hydrosols","authors":"A. Yu. Pavlikov, S. V. Saikova, A. S. Samoilo, D. V. Karpov, S. A. Novikova","doi":"10.1134/s0036023623603057","DOIUrl":"https://doi.org/10.1134/s0036023623603057","url":null,"abstract":"<h3 data-test=\"abstract-sub-heading\">Abstract</h3><p>Copper(II) oxide nanoparticles are promising materials for use in catalysis, biomedicine, and photovoltaics. They can also be used to prepare nanocomposites and hybrid nanoparticles. This paper presents a new one-pot method for preparing CuO nanoparticles without long-term washing and heat treatment. The proposed anion-exchange precipitation is a facile and fast process, and is easily reproducible under standard laboratory conditions. Anion-exchange precipitation of copper from copper chloride or copper sulfate solutions in the presence of the polysaccharide dextran-40 produces well-crystallized hydroxychloride Cu<sub>2</sub>Cl(OH)<sub>3</sub> and hydroxysulfate Cu<sub>4</sub>(SO<sub>4</sub>)(OH)<sub>6,</sub> respectively; from copper nitrate solutions, a poorly crystallized Cu(OH)<sub>2</sub> phase is formed. In the absence of polysaccharides, the product is copper oxide nanoparticles regardless of the anion in the precursor salt. The thus-prepared materials were used to prepare hydrosols. The hydrosols had high aggregation and sedimentation stability over a wide pH range (from 5 to 11) as shown by dynamic and electrophoretic light scattering. They were stable for more than three months at a concentration of 2 g/L (the average hydrodynamic diameter of the particles was 245 nm; the average ζ-potential was –31.1 mV). The optical and electronic properties of the prepared hydrosols imply that they could be of interest for use in photocatalysis and in optoelectronic devices.</p>","PeriodicalId":762,"journal":{"name":"Russian Journal of Inorganic Chemistry","volume":"96 1","pages":""},"PeriodicalIF":2.1,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141551816","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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: 10.1134/s0036023623603008
D. N. Grishchenko, A. B. Podgorbunsky, M. A. Medkov
Abstract
Using the method of pyrolysis of solutions in a melt, the phase formation of sodium and zirconium silicophosphates Na1+xZr2SixP3–xO12 has been studied depending on the concentrations of sodium and phosphorus in the precursors. The influence of the content of these components and calcination conditions on the change in the ionic conductivity of NASICON has been studied. X-ray powder diffraction analysis, scanning electron microscopy, full-profile Rietveld analysis, and electrochemical impedance spectroscopy have been used. The specific values of grain conductivity (σb) and grain boundaries (σgb) of the samples were calculated. It has been found that the cause for the change in ionic conductivity is a change in the composition of NASICON with increasing concentrations of sodium and phosphorus in the precursor. The main condition for high conductivity of the material is the formation of a crystalline phase corresponding to the composition Na3Zr2Si2PO12, as well as a minimal amount of impurities and glass phase. The conductivity of the NASICON sample (x = 2) under certain processing conditions is ~ 1 × 10–3 S/cm.
{"title":"Effect of Superstoichiometric Amounts of Sodium and Phosphorus on the Phase Composition and Ionic Conductivity of Zirconium and Sodium Silicophosphates (NASICON)","authors":"D. N. Grishchenko, A. B. Podgorbunsky, M. A. Medkov","doi":"10.1134/s0036023623603008","DOIUrl":"https://doi.org/10.1134/s0036023623603008","url":null,"abstract":"<h3 data-test=\"abstract-sub-heading\">Abstract</h3><p>Using the method of pyrolysis of solutions in a melt, the phase formation of sodium and zirconium silicophosphates Na<sub>1+<i>x</i></sub>Zr<sub>2</sub>Si<sub><i>x</i></sub>P<sub>3–<i>x</i></sub>O<sub>12</sub> has been studied depending on the concentrations of sodium and phosphorus in the precursors. The influence of the content of these components and calcination conditions on the change in the ionic conductivity of NASICON has been studied. X-ray powder diffraction analysis, scanning electron microscopy, full-profile Rietveld analysis, and electrochemical impedance spectroscopy have been used. The specific values of grain conductivity (σ<sub>b</sub>) and grain boundaries (σ<sub>gb</sub>) of the samples were calculated. It has been found that the cause for the change in ionic conductivity is a change in the composition of NASICON with increasing concentrations of sodium and phosphorus in the precursor. The main condition for high conductivity of the material is the formation of a crystalline phase corresponding to the composition Na<sub>3</sub>Zr<sub>2</sub>Si<sub>2</sub>PO<sub>12</sub>, as well as a minimal amount of impurities and glass phase. The conductivity of the NASICON sample (<i>x</i> = 2) under certain processing conditions is ~ 1 × 10<sup>–3</sup> S/cm.</p>","PeriodicalId":762,"journal":{"name":"Russian Journal of Inorganic Chemistry","volume":"44 1","pages":""},"PeriodicalIF":2.1,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141551818","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-05-02DOI: 10.1134/s0036023624600588
Meng-Ke Bai, Jin-Ke Ma, Jing Chen, You-Juan Zhang, Qing-Lun Wang
Abstract
Using two flexible and functional nitronyl nitroxide radicals as ligands, three novel complexes [Zn(hfac)2(NIToPh3Py)]2 (1), [Zn(hfac)2(NITmPh3Py)]2 (2), and {[Zn(hfac)2]3[(NITmPh3Py)]2}n (3) (where NIToPh3Py is 2-[2-methoxyphenyl(3-pyridinyl)]-4,4,5,5 -tetramethyl-imidazoline1-oxyl-3-oxide; NITmPh3Py is 2-[3-methoxyphenyl(3-pyridinyl)]-4,4,5,5-tetramethyl-imidazoline1-oxyl-3-oxide; hfac is hexafluoroacetylacetonate) have been obtained by the reactions of Zn(hfac)2⋅2H2O with NIToPh3Py/NITmPh3Py in n-heptane upon adjusting the experimental conditions. Their crystal structures and magnetic properties have been studied. X-ray crystal diffraction studies have revealed that complexes 1 and 2 display binuclear cyclic structure, while 3 presents a ring-chain polymer consisting of cyclic [Zn-Radical]2 dimers connected by Zn(hfac)2 units. The magnetic behaviors of the complexes 1–3 have been investigated and discussed in connection with their crystal structures.
{"title":"Three Novel Cyclic Zn(II)–Nitronyl Nitroxide Radical Complexes: Synthesis, Crystal Structures, and Properties","authors":"Meng-Ke Bai, Jin-Ke Ma, Jing Chen, You-Juan Zhang, Qing-Lun Wang","doi":"10.1134/s0036023624600588","DOIUrl":"https://doi.org/10.1134/s0036023624600588","url":null,"abstract":"<h3 data-test=\"abstract-sub-heading\">Abstract</h3><p>Using two flexible and functional nitronyl nitroxide radicals as ligands, three novel complexes [Zn(hfac)<sub>2</sub>(NIT<i>o</i>Ph3Py)]<sub>2</sub> (<b>1</b>), [Zn(hfac)<sub>2</sub>(NIT<i>m</i>Ph3Py)]<sub>2</sub> (<b>2</b>), and {[Zn(hfac)<sub>2</sub>]<sub>3</sub>[(NIT<i>m</i>Ph<sub>3</sub>Py)]<sub>2</sub>}<sub><i>n</i></sub> (<b>3</b>) (where NIT<i>o</i>Ph3Py is 2-[2-methoxyphenyl(3-pyridinyl)]-4,4,5,5 -tetramethyl-imidazoline1-oxyl-3-oxide; NIT<i>m</i>Ph3Py is 2-[3-methoxyphenyl(3-pyridinyl)]-4,4,5,5-tetramethyl-imidazoline1-oxyl-3-oxide; hfac is hexafluoroacetylacetonate) have been obtained by the reactions of Zn(hfac)<sub>2</sub>⋅2H<sub>2</sub>O with NIT<i>o</i>Ph3Py/NIT<i>m</i>Ph3Py in <i>n</i>-heptane upon adjusting the experimental conditions. Their crystal structures and magnetic properties have been studied. X-ray crystal diffraction studies have revealed that complexes <b>1</b> and <b>2</b> display binuclear cyclic structure, while <b>3</b> presents a ring-chain polymer consisting of cyclic [Zn-Radical]<sub>2</sub> dimers connected by Zn(hfac)<sub>2</sub> units. The magnetic behaviors of the complexes <b>1</b>–<b>3</b> have been investigated and discussed in connection with their crystal structures.</p>","PeriodicalId":762,"journal":{"name":"Russian Journal of Inorganic Chemistry","volume":"28 1","pages":""},"PeriodicalIF":2.1,"publicationDate":"2024-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140886389","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Rapid industrialization and ever-growing human activities have caused more and more serious water pollution in the last few decades, posing great threats towards both human health and ecological environment. Organic dyes, as one of the major water pollutants, are usually toxic, chemically stable, and hard to degrade. Photocatalytic technology, with its unique advantages, has become a focus of scientific research and is widely used in the treatment of organic pollutants in wastewater. In this paper, electrospinning technology was used to prepare visible light catalyst TPPZn/Ag3PO4 nanofiber and the morphology was studied by SEM. The TPPZn/Ag3PO4 nanofiber was used as both adsorbent and photocatalyst for removal methylene blue (MB) and rhodamine B (RhB). After 165 min of xenon lamp irradiation, the total removal rate of MB reached 99.05%, and after 300 min of irradiation, the total removal rate of RhB reached 94.85%. In addition, the reusability research shows that the TPPZn/Ag3PO4 material has stable performance and can be reused.
{"title":"Preparation of TPPZn/Ag3PO4 Electrospun Fiber Material and Removal of Organic Dyes","authors":"Xin Xu, Shuo Zhao, Ying Zhang, Xiao-yan Bai, Xin-ru Hui, Er-jun Sun","doi":"10.1134/s003602362460031x","DOIUrl":"https://doi.org/10.1134/s003602362460031x","url":null,"abstract":"<h3 data-test=\"abstract-sub-heading\">Abstract</h3><p>Rapid industrialization and ever-growing human activities have caused more and more serious water pollution in the last few decades, posing great threats towards both human health and ecological environment. Organic dyes, as one of the major water pollutants, are usually toxic, chemically stable, and hard to degrade. Photocatalytic technology, with its unique advantages, has become a focus of scientific research and is widely used in the treatment of organic pollutants in wastewater. In this paper, electrospinning technology was used to prepare visible light catalyst TPPZn/Ag<sub>3</sub>PO<sub>4</sub> nanofiber and the morphology was studied by SEM. The TPPZn/Ag<sub>3</sub>PO<sub>4</sub> nanofiber was used as both adsorbent and photocatalyst for removal methylene blue (MB) and rhodamine B (RhB). After 165 min of xenon lamp irradiation, the total removal rate of MB reached 99.05%, and after 300 min of irradiation, the total removal rate of RhB reached 94.85%. In addition, the reusability research shows that the TPPZn/Ag<sub>3</sub>PO<sub>4</sub> material has stable performance and can be reused.</p>","PeriodicalId":762,"journal":{"name":"Russian Journal of Inorganic Chemistry","volume":"62 1","pages":""},"PeriodicalIF":2.1,"publicationDate":"2024-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140886454","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-04-18DOI: 10.1134/s0036023623603501
Divakar Singh, Surbhi Agarwal, D. K. Dwivedi, Pooja Lohia, Rajnish Raj, Pravin Kumar Singh
Abstract
The present work describes the glass stability parameters of quaternary GeTe2 – x(SeSb)x (x = 0, 0.2, 0.4, 0.6) chalcogenide glasses. The thin-film samples of thickness ~500 nm was deposited by thermal evaporation technique. DSC analysis of GeTe2–x(SeSb)x chalcogenide glasses for studying different glass stability criteria at various heating rate (β = 5, 10, 15 and 20°C/min) were carried out. Many optical parameters of GeTe2 studied by UV-vis and glass stability parameters like HLL, HMM, HCS, etc. were determined. These criteria can be attained by the interrelationship between the characteristic temperatures. According to the onset and peak crystallization temperature, two groups of these criteria were investigated. The value of absorption coefficient is larger than 104 cm, therefore it is useful for optical data storage. The optical band gap energy is observed at 2.834 eV and material has direct allowed transition. The refractive index is observed to be increased with increase in wavelength. All investigated parameters revealed that studied composition is suitable for optical data storage applications.
{"title":"Optical and Glass Stability Parameters of Ge–Te–Se–Sb Chalcogenide Glasses for Optical Data Storage","authors":"Divakar Singh, Surbhi Agarwal, D. K. Dwivedi, Pooja Lohia, Rajnish Raj, Pravin Kumar Singh","doi":"10.1134/s0036023623603501","DOIUrl":"https://doi.org/10.1134/s0036023623603501","url":null,"abstract":"<h3 data-test=\"abstract-sub-heading\">Abstract</h3><p>The present work describes the glass stability parameters of quaternary GeTe<sub>2 – <i>x</i></sub>(SeSb)<sub><i>x</i></sub> (<i>x</i> = 0, 0.2, 0.4, 0.6) chalcogenide glasses. The thin-film samples of thickness ~500 nm was deposited by thermal evaporation technique. DSC analysis of GeTe<sub>2–<i>x</i></sub>(SeSb)<sub><i>x</i></sub> chalcogenide glasses for studying different glass stability criteria at various heating rate (β = 5, 10, 15 and 20°C/min) were carried out. Many optical parameters of GeTe<sub>2</sub> studied by UV-vis and glass stability parameters like H<sub>LL</sub>, H<sub>MM</sub>, H<sub>CS</sub>, etc. were determined. These criteria can be attained by the interrelationship between the characteristic temperatures. According to the onset and peak crystallization temperature, two groups of these criteria were investigated. The value of absorption coefficient is larger than 104 cm, therefore it is useful for optical data storage. The optical band gap energy is observed at 2.834 eV and material has direct allowed transition. The refractive index is observed to be increased with increase in wavelength. All investigated parameters revealed that studied composition is suitable for optical data storage applications.</p>","PeriodicalId":762,"journal":{"name":"Russian Journal of Inorganic Chemistry","volume":"3 1","pages":""},"PeriodicalIF":2.1,"publicationDate":"2024-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140624889","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A Tb3+-activated orthorhombic BaSrLa4O8 nanocrystal system with good green luminescence was prepared using the energy-saving combustion method. Its crystal structure is orthorhombic, it belongs to the Pnma (162) space group, and its particle shape and diameter range from 42 nm to 66 nm. Morphological aspects were examined by scanning and transmission electron microscopies. When exposed to ultra-violet radiation, the nanocrystal emits vibrant green light with a wavenumber of 18 348 cm–1 due to the change of electronic state 5D0 → 7F2. The effect of energy transfer is also demonstrated. The maximum emission intensity was observed at 5.0 mol % Tb3+ concentration when excited at 281 nm. This phenomenon can be attributed to the concentration-quenched d–d interaction leading to decreased luminescence intensity. According to the chromaticity diagram, the composite color falls in the green region and the relative color temperature of the optimized sample BaSrLa3.8Tb0.2O8 is measured at 5688 K. These nanocrystals are especially best for producing white light for advanced optoelectronic applications.
{"title":"Study of Charge Transfer Green Luminescence in Tb3+ Activated BaSrLa4O8 Nanophosphor for Advanced Indoor Lighting Applications","authors":"Manav Kaushik, Ritu Kataria, Pallavi Bhardwaj, Mukesh Kumar","doi":"10.1134/s0036023624600242","DOIUrl":"https://doi.org/10.1134/s0036023624600242","url":null,"abstract":"<h3 data-test=\"abstract-sub-heading\">Abstract</h3><p>A Tb<sup>3+</sup>-activated orthorhombic BaSrLa<sub>4</sub>O<sub>8</sub> nanocrystal system with good green luminescence was prepared using the energy-saving combustion method. Its crystal structure is orthorhombic, it belongs to the <i>Pnma</i> (162) space group, and its particle shape and diameter range from 42 nm to 66 nm. Morphological aspects were examined by scanning and transmission electron microscopies. When exposed to ultra-violet radiation, the nanocrystal emits vibrant green light with a wavenumber of 18 348 cm<sup>–1</sup> due to the change of electronic state <sup>5</sup>D<sub>0</sub> → <sup>7</sup>F<sub>2</sub>. The effect of energy transfer is also demonstrated. The maximum emission intensity was observed at 5.0 mol % Tb<sup>3+</sup> concentration when excited at 281 nm. This phenomenon can be attributed to the concentration-quenched <i>d</i>–<i>d</i> interaction leading to decreased luminescence intensity. According to the chromaticity diagram, the composite color falls in the green region and the relative color temperature of the optimized sample BaSrLa<sub>3.8</sub>Tb<sub>0.2</sub>O<sub>8</sub> is measured at 5688 K. These nanocrystals are especially best for producing white light for advanced optoelectronic applications.</p>","PeriodicalId":762,"journal":{"name":"Russian Journal of Inorganic Chemistry","volume":"100 1","pages":""},"PeriodicalIF":2.1,"publicationDate":"2024-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140625127","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Solid-liquid phase equilibrium of the quaternary system KCl–KH2PO4–CO(NH2)2–H2O and its subsystems KH2PO4–CO(NH2)2–H2O and KCl–KH2PO4–H2O at 323.15 and 333.15 K were investigated through the isothermal solution equilibrium method in this study. The equilibrium solid phases were determined by Schreinemaker’s wet residue method and X-ray powder diffraction method. The isothermal dissolution phase diagrams of the ternary systems and isothermal dry salt phase diagrams and water diagrams of the quaternary system were plotted based on the measured solubility data. The results indicates that there is one invariant point, two univariant curves, three crystallization regions and one undersaturated solution region in the isothermal dissolution phase diagrams of ternary subsystems KH2PO4–CO(NH2)2–H2O and KCl–KH2PO4–H2O. The isothermal dry salt phase diagrams of quaternary system KCl–KH2PO4–CO(NH2)2–H2O contain an invariant point, three univariant curves, three crystallization regions. The solubilities of the three systems were correlated and calculated by the extended Pitzer model based on the electrolyte solution theory. The maximum values of relative average deviation (RAD) and root mean square deviation (RMSD) of calculated values and experimental values of the ternary system KCl–KH2PO4–H2O at two temperatures are 1.75%, 0.34, respectively; that of the ternary system KH2PO4–CO(NH2)2–H2O are 0.71%, 0.19, respectively; that of the quaternary system KCl–KH2PO4–CO(NH2)2–H2O are 2.06%, 0.52, respectively; which indicates the model can be used for the correlation calculation of these systems due to good consistency in this study.
{"title":"Determination and Correlation of Phase Equilibria of Quaternary System KCl–KH2PO4–CO(NH2)2–H2O and Its Ternary Subsystems at 323.15 and 333.15 K","authors":"Lin-Rui Zhong, Tian-Xiang Li, Lian-Jun Shi, Yan-Feng Sui, Shi-Han Wang, Ze-Yu Meng, Feng Yi, Song-Lin Liu, Jing Zhu","doi":"10.1134/s0036023624600230","DOIUrl":"https://doi.org/10.1134/s0036023624600230","url":null,"abstract":"<h3 data-test=\"abstract-sub-heading\">Abstract</h3><p>Solid-liquid phase equilibrium of the quaternary system KCl–KH<sub>2</sub>PO<sub>4</sub>–CO(NH<sub>2</sub>)<sub>2</sub>–H<sub>2</sub>O and its subsystems KH<sub>2</sub>PO<sub>4</sub>–CO(NH<sub>2</sub>)<sub>2</sub>–H<sub>2</sub>O and KCl–KH<sub>2</sub>PO<sub>4</sub>–H<sub>2</sub>O at 323.15 and 333.15 K were investigated through the isothermal solution equilibrium method in this study. The equilibrium solid phases were determined by Schreinemaker’s wet residue method and X-ray powder diffraction method. The isothermal dissolution phase diagrams of the ternary systems and isothermal dry salt phase diagrams and water diagrams of the quaternary system were plotted based on the measured solubility data. The results indicates that there is one invariant point, two univariant curves, three crystallization regions and one undersaturated solution region in the isothermal dissolution phase diagrams of ternary subsystems KH<sub>2</sub>PO<sub>4</sub>–CO(NH<sub>2</sub>)<sub>2</sub>–H<sub>2</sub>O and KCl–KH<sub>2</sub>PO<sub>4</sub>–H<sub>2</sub>O. The isothermal dry salt phase diagrams of quaternary system KCl–KH<sub>2</sub>PO<sub>4</sub>–CO(NH<sub>2</sub>)<sub>2</sub>–H<sub>2</sub>O contain an invariant point, three univariant curves, three crystallization regions. The solubilities of the three systems were correlated and calculated by the extended Pitzer model based on the electrolyte solution theory. The maximum values of relative average deviation (RAD) and root mean square deviation (RMSD) of calculated values and experimental values of the ternary system KCl–KH<sub>2</sub>PO<sub>4</sub>–H<sub>2</sub>O at two temperatures are 1.75%, 0.34, respectively; that of the ternary system KH<sub>2</sub>PO<sub>4</sub>–CO(NH<sub>2</sub>)<sub>2</sub>–H<sub>2</sub>O are 0.71%, 0.19, respectively; that of the quaternary system KCl–KH<sub>2</sub>PO<sub>4</sub>–CO(NH<sub>2</sub>)<sub>2</sub>–H<sub>2</sub>O are 2.06%, 0.52, respectively; which indicates the model can be used for the correlation calculation of these systems due to good consistency in this study.</p>","PeriodicalId":762,"journal":{"name":"Russian Journal of Inorganic Chemistry","volume":"101 1","pages":""},"PeriodicalIF":2.1,"publicationDate":"2024-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140631005","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-04-18DOI: 10.1134/s0036023624600564
Jinjian Li, Xin Zhou, Aidang Lu, Dongchan Li
Abstract
Solid-liquid phase equilibria and phase diagram of the quaternary system (NH4Cl–MgCl2–SrCl2–H2O) is very important for the separation of ammonium, magnesium and strontium salts from the salt lake brines. In this paper, the solid-liquid phase equilibria of the quaternary system (NH4Cl–MgCl2–SrCl2–H2O) at 293.15 and 318.15 K were determined with the method of isothermal dissolution equilibrium. Based on the experimental results, the phase diagrams of the system were plotted. In the phase diagrams of the system there are two invariant points, five univariant curves, and four salt crystal regions. The MgCl2·6H2O crystallization region occupies the smallest area, demonstrating that magnesium chloride has a strong desalting effect on the other salts. Comparison of isothermal sections of the quaternary system phase diagram at 293.15 and 318.15 K, it was observed that the crystallization zone of NH4Cl·MgCl2·6H2O and SrCl2·6H2O expands with the increasing of temperature, but the crystallization zone of NH4Cl shrinks, while the area of crystallization zone of MgCl2·6H2O was almost constant. It can be concluded that the temperature has a remarkable impact on phase behavior of this quaternary system.
{"title":"Solid-liquid Phase Equilibria of the Quaternary System (NH4Cl–MgCl2–SrCl2–H2O) at 293.15 and 318.15 K","authors":"Jinjian Li, Xin Zhou, Aidang Lu, Dongchan Li","doi":"10.1134/s0036023624600564","DOIUrl":"https://doi.org/10.1134/s0036023624600564","url":null,"abstract":"<h3 data-test=\"abstract-sub-heading\">Abstract</h3><p>Solid-liquid phase equilibria and phase diagram of the quaternary system (NH<sub>4</sub>Cl–MgCl<sub>2</sub>–SrCl<sub>2</sub>–H<sub>2</sub>O) is very important for the separation of ammonium, magnesium and strontium salts from the salt lake brines. In this paper, the solid-liquid phase equilibria of the quaternary system (NH<sub>4</sub>Cl–MgCl<sub>2</sub>–SrCl<sub>2</sub>–H<sub>2</sub>O) at 293.15 and 318.15 K were determined with the method of isothermal dissolution equilibrium. Based on the experimental results, the phase diagrams of the system were plotted. In the phase diagrams of the system there are two invariant points, five univariant curves, and four salt crystal regions. The MgCl<sub>2</sub>·6H<sub>2</sub>O crystallization region occupies the smallest area, demonstrating that magnesium chloride has a strong desalting effect on the other salts. Comparison of isothermal sections of the quaternary system phase diagram at 293.15 and 318.15 K, it was observed that the crystallization zone of NH<sub>4</sub>Cl·MgCl<sub>2</sub>·6H<sub>2</sub>O and SrCl<sub>2</sub>·6H<sub>2</sub>O expands with the increasing of temperature, but the crystallization zone of NH<sub>4</sub>Cl shrinks, while the area of crystallization zone of MgCl<sub>2</sub>·6H<sub>2</sub>O was almost constant. It can be concluded that the temperature has a remarkable impact on phase behavior of this quaternary system.</p>","PeriodicalId":762,"journal":{"name":"Russian Journal of Inorganic Chemistry","volume":"90 1","pages":""},"PeriodicalIF":2.1,"publicationDate":"2024-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140625117","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The NaF–KF–AlF3 is a promising low-temperature electrolyte for industrial application. Herein, we used a molecular dynamics and first-principles calculations to simulate NaF–KF–AlF3 molten salts with molar ratios(n(NaF + KF)/AlF3) of 1.3–1.6 and 30 mol % NaF at 1123 K. The results of the study reveal the law of influence of molar ratio on the structural properties and transport properties of the NaF–KF–AlF3 system. The results show that the average coordination number of the NaF–KF–AlF3 system was about 4.8, and the ionic structure was mainly [AlF4]– and [AlF5]2–, with strong covalent interactions between Al-F ions. As the molar ratio increased five-coordinated [AlF5]2– gradually became the dominant population in the molten salts, and the proportion of bridging fluoride ions increased, promoting ionic polymerization in the molten salts and the formation of complex ionic groups. The order of ion diffusion ability in the molten salts followed the order of K+ > Na+ > F– > Al3+, when the molar ratio was 1.3 and 1.4, changing to Na+ > K+ > F– > Al3+, when the molar ratio was 1.5 and 1.6. The viscosities and ionic conductivities of the molten salts were in the range of 1.1–1.65 mPa s, and 0.85–1.15 S/cm, respectively.
{"title":"Study on the Structure and Transport Properties of Molten Salts of NaF–KF–AlF3 Electrolytes by First-Principles Molecular Dynamics Simulation","authors":"Qibo Liu, Laixin Zhang, Hengwei Yan, Zhanwei Liu, Xiumin Chen","doi":"10.1134/s0036023624600163","DOIUrl":"https://doi.org/10.1134/s0036023624600163","url":null,"abstract":"<h3 data-test=\"abstract-sub-heading\">Abstract</h3><p>The NaF–KF–AlF<sub>3</sub> is a promising low-temperature electrolyte for industrial application. Herein, we used a molecular dynamics and first-principles calculations to simulate NaF–KF–AlF<sub>3</sub> molten salts with molar ratios(<i>n</i>(NaF + KF)/AlF<sub>3</sub>) of 1.3–1.6 and 30 mol % NaF at 1123 K. The results of the study reveal the law of influence of molar ratio on the structural properties and transport properties of the NaF–KF–AlF<sub>3</sub> system. The results show that the average coordination number of the NaF–KF–AlF<sub>3</sub> system was about 4.8, and the ionic structure was mainly [AlF<sub>4</sub>]<sup>–</sup> and [AlF<sub>5</sub>]<sup>2–</sup>, with strong covalent interactions between Al-F ions. As the molar ratio increased five-coordinated [AlF<sub>5</sub>]<sup>2–</sup> gradually became the dominant population in the molten salts, and the proportion of bridging fluoride ions increased, promoting ionic polymerization in the molten salts and the formation of complex ionic groups. The order of ion diffusion ability in the molten salts followed the order of K<sup>+</sup> > Na<sup>+</sup> > F<sup>–</sup> > Al<sup>3+</sup>, when the molar ratio was 1.3 and 1.4, changing to Na<sup>+</sup> > K<sup>+</sup> > F<sup>–</sup> > Al<sup>3+</sup>, when the molar ratio was 1.5 and 1.6. The viscosities and ionic conductivities of the molten salts were in the range of 1.1–1.65 mPa s, and 0.85–1.15 S/cm, respectively.</p>","PeriodicalId":762,"journal":{"name":"Russian Journal of Inorganic Chemistry","volume":"65 1","pages":""},"PeriodicalIF":2.1,"publicationDate":"2024-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140601226","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-04-12DOI: 10.1134/s0036023624600138
A. E. Likhonina, G. M. Mamardashvili, N. Z. Mamardashvili
Abstract
A number of metal-linked porphyrin oligomers of different structures were synthesized and their luminescent sensitivity to temperature was studied. Density functional theory (DFT) was used to geometrically optimize the resulting compounds structure. Coordination Sn(IV)-dipyridylporphyrin tetramers formed through the interaction of pyridyl fragments of the macrocycle with Pd(II) and Pt(II) cations, as well as the octamer assembled by coordination of pyridyl groups with Pd(II) cations and bis-chelate binding of bidentate ligands in the axial positions of Sn(IV)-porphyrins with the Cu(II) cation, were shown to exhibit fluorescent thermal sensitivity in the temperature range of 328–383 K in the region of 600–650 nm. In this section, the dependence of the fluorescence quantum yield (fluorescence intensity) with a temperature increase is a monotonic pseudolinear trend. The flare-up ranges from 1.5 to 4.5 times, depending on the structure of porphyrin oligomers. At temperatures above 383 K, all studied porphyrin assemblies obtained on the basis of Pd(II) exhibit a decrease in fluorescence intensity. At the same time, their structure is preserved. The porphyrin tetramer obtained from Pt(II) undergoes a structural rearrangement, transforming into a presumably cyclometalated organoplatinum compound that exhibits effective luminescence at 493 nm. The results obtained could be used for the development of new temperature-assisted optoelectronic devices such as sensors, molecular reactors and catalysts.
{"title":"Synthesis and Design of Metalloporphyrin Oligomers with Temperature-Assisted Spectral-Luminescent Properties","authors":"A. E. Likhonina, G. M. Mamardashvili, N. Z. Mamardashvili","doi":"10.1134/s0036023624600138","DOIUrl":"https://doi.org/10.1134/s0036023624600138","url":null,"abstract":"<h3 data-test=\"abstract-sub-heading\">Abstract</h3><p>A number of metal-linked porphyrin oligomers of different structures were synthesized and their luminescent sensitivity to temperature was studied. Density functional theory (DFT) was used to geometrically optimize the resulting compounds structure. Coordination Sn(IV)-dipyridylporphyrin tetramers formed through the interaction of pyridyl fragments of the macrocycle with Pd(II) and Pt(II) cations, as well as the octamer assembled by coordination of pyridyl groups with Pd(II) cations and bis-chelate binding of bidentate ligands in the axial positions of Sn(IV)-porphyrins with the Cu(II) cation, were shown to exhibit fluorescent thermal sensitivity in the temperature range of 328–383 K in the region of 600–650 nm. In this section, the dependence of the fluorescence quantum yield (fluorescence intensity) with a temperature increase is a monotonic pseudolinear trend. The flare-up ranges from 1.5 to 4.5 times, depending on the structure of porphyrin oligomers. At temperatures above 383 K, all studied porphyrin assemblies obtained on the basis of Pd(II) exhibit a decrease in fluorescence intensity. At the same time, their structure is preserved. The porphyrin tetramer obtained from Pt(II) undergoes a structural rearrangement, transforming into a presumably cyclometalated organoplatinum compound that exhibits effective luminescence at 493 nm. The results obtained could be used for the development of new temperature-assisted optoelectronic devices such as sensors, molecular reactors and catalysts.</p>","PeriodicalId":762,"journal":{"name":"Russian Journal of Inorganic Chemistry","volume":"65 1","pages":""},"PeriodicalIF":2.1,"publicationDate":"2024-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140601216","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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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