Pub Date : 2025-02-20DOI: 10.1016/j.jssc.2025.125269
Chang Liu , Xiaoxiao Gao , Pan Gao , Wenjing Tian , Zifan Wang , Yi Liu
The transition metal thiostannates, with their diverse structures and rich physical properties, have garnered substantial interest. In this research, two quaternary thiostannates CsCuSnS3 (1) and Cs2CdSnS4 (2) have been synthesized through a facile ionothermal reaction. Both compounds exhibit monoclinic crystal systems with the space group C2/c (no. 15) and possess a two-dimensional layered anionic skeleton. The sandwich-like anionic layer of CsCuSnS3 is constructed by [CuS4]n layer and [SnS4]n chains, while Cs2CdSnS4 is composed of vertex-sharing of T2 [Cd2Sn2S10] cluster. The equilibrium cation Cs+ is situated at the inner edge of the layer voids. Remarkably, compounds CsCuSnS3 (1) and Cs2CdSnS4 (2) display appropriate optical band gaps (1.38 eV and 2.50 eV) and good photocurrent response (1.5 μA/cm2 and 4.0 μA/cm2) under simulated solar irradiation. Theoretical studies uncover that the electron transfer is mainly contributed by Cu-3d, Cd-4d, Sn-5s, and S-3p states. Moreover, the dimensional reduction from three-dimensional (3D) framework Na2CdSnS4 to 2D layered Cs2CdSnS4 caused by Cs + cation is discussed.
{"title":"Ionothermal syntheses, structures, and photocurrent responses of two-dimensional layered thiostannates","authors":"Chang Liu , Xiaoxiao Gao , Pan Gao , Wenjing Tian , Zifan Wang , Yi Liu","doi":"10.1016/j.jssc.2025.125269","DOIUrl":"10.1016/j.jssc.2025.125269","url":null,"abstract":"<div><div>The transition metal thiostannates, with their diverse structures and rich physical properties, have garnered substantial interest. In this research, two quaternary thiostannates CsCuSnS<sub>3</sub> (<strong>1</strong>) and Cs<sub>2</sub>CdSnS<sub>4</sub> (<strong>2</strong>) have been synthesized through a facile ionothermal reaction. Both compounds exhibit monoclinic crystal systems with the space group <em>C</em>2/<em>c</em> (no. 15) and possess a two-dimensional layered anionic skeleton. The sandwich-like anionic layer of CsCuSnS<sub>3</sub> is constructed by [CuS<sub>4</sub>]<sub>n</sub> layer and [SnS<sub>4</sub>]<sub>n</sub> chains, while Cs<sub>2</sub>CdSnS<sub>4</sub> is composed of vertex-sharing of T2 [Cd<sub>2</sub>Sn<sub>2</sub>S<sub>10</sub>] cluster. The equilibrium cation Cs<sup>+</sup> is situated at the inner edge of the layer voids. Remarkably, compounds CsCuSnS<sub>3</sub> (<strong>1</strong>) and Cs<sub>2</sub>CdSnS<sub>4</sub> (<strong>2</strong>) display appropriate optical band gaps (1.38 eV and 2.50 eV) and good photocurrent response (1.5 μA/cm<sup>2</sup> and 4.0 μA/cm<sup>2</sup>) under simulated solar irradiation. Theoretical studies uncover that the electron transfer is mainly contributed by Cu-3d, Cd-4d, Sn-5s, and S-3p states. Moreover, the dimensional reduction from three-dimensional (3D) framework Na<sub>2</sub>CdSnS<sub>4</sub> to 2D layered Cs<sub>2</sub>CdSnS<sub>4</sub> caused by Cs <sup>+</sup> cation is discussed.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"346 ","pages":"Article 125269"},"PeriodicalIF":3.2,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143463386","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 : 2025-02-19DOI: 10.1016/j.jssc.2025.125282
Patrice Kenfack Tsobnang , Christelle Ivane Azambou , Roussin Lontio Fomekong , Tobie Junior Matemb Ma Ntep , Marcus N.A. Fetzer , Arnaud Kamdem Tamo , Christoph Janiak
Three heteroleptic one-dimensional (1D) (2-aminomethylpyridine-κ2N,N′)(μ-oxalato-κ2O,O'':κ2O',O‴) metal coordination polymers 1D-[Zn(ampy)(μ-ox)]·H2O (1), 1D-[Ni(ampy)(μ-ox)]·H2O (2) and 1D-[Cu(ampy)(μ-ox)H2O] (3) were synthesized and the product of their calcination was investigated. Compounds 1 and 2 are new and isomorphous. In their packing, the metal-oxalate units build zigzag chains along the a direction through the bisbidentate chelating and bridging coordination mode of oxalate. These chains build supramolecular layers in the ab plane through C–H···π interactions between the aminomethylpyridine ligands. The layers are connected with water molecules to form bilayers that run along the c-axis. The thermal decomposition process of the three materials in the air is complete at around 500 °C and yields ZnO, NiO, and CuO respectively while under N2, the decomposition mechanism is different and produces around 600 °C, ZnO, Ni, and Cu respectively. Further decomposition of this ZnO in this oxygen-free atmosphere is observed at 800 °C and the remaining material shows a smaller average apparent crystallite size and is more dispersed than the ZnO obtained in air where such mass loss is not observed. However, both ZnO show the same quantity of defects. This work shows the importance of the atomic absorption spectroscopy measurements of oxide materials that would have defects.
{"title":"Structural properties and thermal decomposition of three heteroleptic coordination polymers with oxalate, 2-aminomethylpyridine and metal = Zn2+, Ni2+ and Cu2+","authors":"Patrice Kenfack Tsobnang , Christelle Ivane Azambou , Roussin Lontio Fomekong , Tobie Junior Matemb Ma Ntep , Marcus N.A. Fetzer , Arnaud Kamdem Tamo , Christoph Janiak","doi":"10.1016/j.jssc.2025.125282","DOIUrl":"10.1016/j.jssc.2025.125282","url":null,"abstract":"<div><div>Three heteroleptic one-dimensional (1D) (2-aminomethylpyridine-κ<sup>2</sup>N,N′)(μ-oxalato-κ<sup>2</sup>O,O<em>''</em>:κ<sup>2</sup>O<em>'</em>,O‴) metal coordination polymers 1D-[Zn(ampy)(μ-ox)]·H<sub>2</sub>O (<strong>1</strong>), 1D-[Ni(ampy)(μ-ox)]·H<sub>2</sub>O (<strong>2</strong>) and 1D-[Cu(ampy)(μ-ox)H<sub>2</sub>O] (<strong>3</strong>) were synthesized and the product of their calcination was investigated. Compounds <strong>1</strong> and <strong>2</strong> are new and isomorphous. In their packing, the metal-oxalate units build zigzag chains along the <em>a</em> direction through the bisbidentate chelating and bridging coordination mode of oxalate. These chains build supramolecular layers in the <em>ab</em> plane through C–H···π interactions between the aminomethylpyridine ligands. The layers are connected with water molecules to form bilayers that run along the <em>c</em><em>-</em>axis. The thermal decomposition process of the three materials in the air is complete at around 500 °C and yields ZnO, NiO, and CuO respectively while under N<sub>2</sub>, the decomposition mechanism is different and produces around 600 °C, ZnO, Ni, and Cu respectively. Further decomposition of this ZnO in this oxygen-free atmosphere is observed at 800 °C and the remaining material shows a smaller average apparent crystallite size and is more dispersed than the ZnO obtained in air where such mass loss is not observed. However, both ZnO show the same quantity of defects. This work shows the importance of the atomic absorption spectroscopy measurements of oxide materials that would have defects.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"346 ","pages":"Article 125282"},"PeriodicalIF":3.2,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143474685","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 : 2025-02-18DOI: 10.1016/j.jssc.2025.125278
Jaegyeom Kim , Fouzia Khefif , Heeyoun Kim , Ji-Sun Lee , Seongsu Lee , Chung-Yul Yoo , Seung-Joo Kim
A protonated/deuterated compound, HTa2PO8/DTa2PO8, was synthesized via an ion-exchange reaction of LiTa2PO8 in aqueous HCl/DCl solution. The structure was analyzed to clarify the location of the proton (or deuterium) in the lattice, using synchrotron X-ray powder diffraction (SXPD) and neutron powder diffraction (NPD). The crystal structure of DTa2PO8 belongs to the monoclinic space group, C2/c, identical to that of parent LiTa2PO8. The deuterium atoms were found to partially occupy two distinct sites around oxygen atoms, located at the shared corners of two connected TaO6 octahedra. The two distinctive H+ sites were confirmed by the solid-state 1H nuclear magnetic resonance (NMR) spectrum of HTa2PO8. HTa2PO8 is thermally stable up to 400 °C, and as the temperature increases, it transforms into an intermediate compound, Ta2PO7.5, while maintaining its original framework structure. Above 1050 °C, it subsequently decomposes to Ta2O5 and TaPO5. Impedance spectroscopy measurements, performed in both dry and wet air, showed that HTa2PO8 exhibited an ion conductivity ranging from 10−5 to 10−8 S/cm in the temperature range of 200 °C∼400 °C, in which protons are the primary charge carriers.
{"title":"Crystal structure, thermal behavior, and proton conductivity of HTa2PO8 synthesized via ion-exchange from LiTa2PO8","authors":"Jaegyeom Kim , Fouzia Khefif , Heeyoun Kim , Ji-Sun Lee , Seongsu Lee , Chung-Yul Yoo , Seung-Joo Kim","doi":"10.1016/j.jssc.2025.125278","DOIUrl":"10.1016/j.jssc.2025.125278","url":null,"abstract":"<div><div>A protonated/deuterated compound, HTa<sub>2</sub>PO<sub>8</sub>/DTa<sub>2</sub>PO<sub>8</sub>, was synthesized via an ion-exchange reaction of LiTa<sub>2</sub>PO<sub>8</sub> in aqueous HCl/DCl solution. The structure was analyzed to clarify the location of the proton (or deuterium) in the lattice, using synchrotron X-ray powder diffraction (SXPD) and neutron powder diffraction (NPD). The crystal structure of DTa<sub>2</sub>PO<sub>8</sub> belongs to the monoclinic space group, <em>C</em>2/<em>c</em>, identical to that of parent LiTa<sub>2</sub>PO<sub>8</sub>. The deuterium atoms were found to partially occupy two distinct sites around oxygen atoms, located at the shared corners of two connected TaO<sub>6</sub> octahedra. The two distinctive H<sup>+</sup> sites were confirmed by the solid-state <sup>1</sup>H nuclear magnetic resonance (NMR) spectrum of HTa<sub>2</sub>PO<sub>8</sub>. HTa<sub>2</sub>PO<sub>8</sub> is thermally stable up to 400 °C, and as the temperature increases, it transforms into an intermediate compound, Ta<sub>2</sub>PO<sub>7.5</sub>, while maintaining its original framework structure. Above 1050 °C, it subsequently decomposes to Ta<sub>2</sub>O<sub>5</sub> and TaPO<sub>5</sub>. Impedance spectroscopy measurements, performed in both dry and wet air, showed that HTa<sub>2</sub>PO<sub>8</sub> exhibited an ion conductivity ranging from 10<sup>−5</sup> to 10<sup>−8</sup> S/cm in the temperature range of 200 °C∼400 °C, in which protons are the primary charge carriers.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"346 ","pages":"Article 125278"},"PeriodicalIF":3.2,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143474683","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 : 2025-02-17DOI: 10.1016/j.jssc.2025.125270
Geeta Patkare, Muhammed Shafeeq, Rohan Phatak, B.G. Vats, Meera Keskar
A pseudo ternary phase diagram of the SrO–ZrO2–P2O5 system was constructed at 1573 K and phase relations were established. A detailed investigation into the synthesis of reported ternary and quaternary compounds was carried out. These compounds as well as phase mixtures, used to draw the phase diagram, were prepared via solid state method at 1573 K. Powder X-ray diffraction (XRD) was employed to identify all phases present in the products. At 1573 K, no ternary compound could be established in ZrO2–P2O5 system whereas only one compound SrZrO3 was confirmed in SrO–ZrO2 system. In SrO–ZrO2–P2O5 system, SrZr4(PO4)6 [SZ4P6] and Sr7Zr(PO4)6 [S7ZP6] were synthesized in pure form whereas SrZr(PO4)2 [SZP2] could not be obtained in pure phase. A detailed structural study of cubic S7ZP6 was performed by refining its XRD data. Thermal expansion coefficients of SZ4P6 and S7ZP6 were calculated from 298 to 1273 K using high temperature X-ray diffraction data. SZ4P6 exhibited ultra low volume expansion while S7ZP6 showed positive expansion over the experimental range. Molar heat capacities of these compounds were measured from 308 to 863 K using Differential Scanning Calorimeter (DSC).
{"title":"Investigation of phase relations in SrO–ZrO2–P2O5 system at 1573 K; phase analysis and thermal study of phosphate compounds","authors":"Geeta Patkare, Muhammed Shafeeq, Rohan Phatak, B.G. Vats, Meera Keskar","doi":"10.1016/j.jssc.2025.125270","DOIUrl":"10.1016/j.jssc.2025.125270","url":null,"abstract":"<div><div>A pseudo ternary phase diagram of the SrO–ZrO<sub>2</sub>–P<sub>2</sub>O<sub>5</sub> system was constructed at 1573 K and phase relations were established. A detailed investigation into the synthesis of reported ternary and quaternary compounds was carried out. These compounds as well as phase mixtures, used to draw the phase diagram, were prepared via solid state method at 1573 K. Powder X-ray diffraction (XRD) was employed to identify all phases present in the products. At 1573 K, no ternary compound could be established in ZrO<sub>2</sub>–P<sub>2</sub>O<sub>5</sub> system whereas only one compound SrZrO<sub>3</sub> was confirmed in SrO–ZrO<sub>2</sub> system. In SrO–ZrO<sub>2</sub>–P<sub>2</sub>O<sub>5</sub> system, SrZr<sub>4</sub>(PO<sub>4</sub>)<sub>6</sub> [SZ4P6] and Sr<sub>7</sub>Zr(PO<sub>4</sub>)<sub>6</sub> [S7ZP6] were synthesized in pure form whereas SrZr(PO<sub>4</sub>)<sub>2</sub> [SZP2] could not be obtained in pure phase. A detailed structural study of cubic S7ZP6 was performed by refining its XRD data. Thermal expansion coefficients of SZ4P6 and S7ZP6 were calculated from 298 to 1273 K using high temperature X-ray diffraction data. SZ4P6 exhibited ultra low volume expansion while S7ZP6 showed positive expansion over the experimental range. Molar heat capacities of these compounds were measured from 308 to 863 K using Differential Scanning Calorimeter (DSC).</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"346 ","pages":"Article 125270"},"PeriodicalIF":3.2,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143453880","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 combined experimental and computational study was conducted on the non-centrosymmetric Cu(I) coordination polymers [Cu(thiourea)3]X (X = Cl (CTC), Br (CTB), I (CTI)) to investigate the relationships between their structural characteristics under varying external pressure and their mechanical, microstructural, thermophysical, optical and electronic properties. The crystal structure of the [Cu(thiourea)3]Cl complex was redetermined with higher precision, providing more refined structural details. All three compounds crystallize in a tetragonal system with similar polymeric connectivity but differ in halide ion size, significantly impacting their functional properties. Morphological and microstructural analyses, using various models, revealed insights into crystallite size, lattice strain, and crystal growth mechanisms. The elastic parameters were calculated using the PBE functional (Perdew-Burke-Ernzerhof) with the Generalized Gradient Approximation (GGA) to evaluate the ductility, anisotropy, machinability, and mechanical stability of the three coordination polymers. The electronic properties, including band structure and density of states, were analyzed under pressure. The results reveal moderate band gap values ranging from 1.71 to 1.98 eV, positioning these materials as promising candidates for optoelectronic devices. This study underscores the pivotal influence of halide anion radius and external pressure in tuning the functional properties of these polymers, providing valuable insights for the design and advancement of cutting-edge material applications.
{"title":"Exploring the effects of halide anions and pressure on the structural and functional properties of helical coordination polymers: Cu(SCN2H4)3X (X = Cl, Br, I)","authors":"Ayoub Eddhimi , Abdellatif Rafik , Mohamed Zouhairi , Ameni Brahmia , Riadh Marzouki , Hafid Zouihri","doi":"10.1016/j.jssc.2025.125271","DOIUrl":"10.1016/j.jssc.2025.125271","url":null,"abstract":"<div><div>A combined experimental and computational study was conducted on the non-centrosymmetric Cu(I) coordination polymers [Cu(thiourea)<sub>3</sub>]X (X = Cl (CTC), Br (CTB), I (CTI)) to investigate the relationships between their structural characteristics under varying external pressure and their mechanical, microstructural, thermophysical, optical and electronic properties. The crystal structure of the [Cu(thiourea)<sub>3</sub>]Cl complex was redetermined with higher precision, providing more refined structural details. All three compounds crystallize in a tetragonal system with similar polymeric connectivity but differ in halide ion size, significantly impacting their functional properties. Morphological and microstructural analyses, using various models, revealed insights into crystallite size, lattice strain, and crystal growth mechanisms. The elastic parameters were calculated using the PBE functional (Perdew-Burke-Ernzerhof) with the Generalized Gradient Approximation (GGA) to evaluate the ductility, anisotropy, machinability, and mechanical stability of the three coordination polymers. The electronic properties, including band structure and density of states, were analyzed under pressure. The results reveal moderate band gap values ranging from 1.71 to 1.98 eV, positioning these materials as promising candidates for optoelectronic devices. This study underscores the pivotal influence of halide anion radius and external pressure in tuning the functional properties of these polymers, providing valuable insights for the design and advancement of cutting-edge material applications.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"346 ","pages":"Article 125271"},"PeriodicalIF":3.2,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143444716","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 : 2025-02-15DOI: 10.1016/j.jssc.2025.125256
Minseop Lee , Ji-Ho Park , Dong-Jun Park , Seung-Min Paek
This study introduces a novel Ge/GeO2/Titanate composite to address the limitations of conventional Ge-based anode materials, including volume expansion, particle aggregation, and unstable SEI formation during repeated charge–discharge cycles. By combining two-dimensional (2D) layered titanate nanosheets with Ge/GeO2 nanoparticles, the composite achieves enhanced structural stability and outstanding electrochemical performance. The 2D titanate nanosheets effectively mitigate the volume expansion of Ge/GeO2 nanoparticles, prevent particle aggregation, and maintain the long-term structural stability of the electrode while enhancing lithium-ion and electron transport pathways. Moreover, the thin amorphous GeO2 layer on the Ge/GeO2 nanoparticles suppresses excessive reactions with the electrolyte, promotes uniform and stable SEI formation, reduces irreversible capacity loss, and further contributes to the electrode's long-term stability. The Ge/GeO2/Titanate composite exhibits exceptional performance, retaining a high capacity of 925.8 mAh/g (∼94 % of the theoretical capacity) after 350 cycles at 0.1 A/g. It also achieves capacity retention rates of 88.3 % and 73.4 % after 1200 charge–discharge cycles at high current densities of 2.0 A/g and 5.0 A/g, respectively.
{"title":"A Ge/GeO2/Titanate nanocomposite with high energy density and enhanced long-term stability for lithium-ion batteries","authors":"Minseop Lee , Ji-Ho Park , Dong-Jun Park , Seung-Min Paek","doi":"10.1016/j.jssc.2025.125256","DOIUrl":"10.1016/j.jssc.2025.125256","url":null,"abstract":"<div><div>This study introduces a novel Ge/GeO<sub>2</sub>/Titanate composite to address the limitations of conventional Ge-based anode materials, including volume expansion, particle aggregation, and unstable SEI formation during repeated charge–discharge cycles. By combining two-dimensional (2D) layered titanate nanosheets with Ge/GeO<sub>2</sub> nanoparticles, the composite achieves enhanced structural stability and outstanding electrochemical performance. The 2D titanate nanosheets effectively mitigate the volume expansion of Ge/GeO<sub>2</sub> nanoparticles, prevent particle aggregation, and maintain the long-term structural stability of the electrode while enhancing lithium-ion and electron transport pathways. Moreover, the thin amorphous GeO<sub>2</sub> layer on the Ge/GeO<sub>2</sub> nanoparticles suppresses excessive reactions with the electrolyte, promotes uniform and stable SEI formation, reduces irreversible capacity loss, and further contributes to the electrode's long-term stability. The Ge/GeO<sub>2</sub>/Titanate composite exhibits exceptional performance, retaining a high capacity of 925.8 mAh/g (∼94 % of the theoretical capacity) after 350 cycles at 0.1 A/g. It also achieves capacity retention rates of 88.3 % and 73.4 % after 1200 charge–discharge cycles at high current densities of 2.0 A/g and 5.0 A/g, respectively.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"346 ","pages":"Article 125256"},"PeriodicalIF":3.2,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427739","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 : 2025-02-15DOI: 10.1016/j.jssc.2025.125259
R. Rosentsveig , Y. Feldman , V. Kundrat , I. Pinkas , A. Zak , R. Tenne
Tungsten disulfide is an important compound with layered structure (2D-material). Chemically it is less stable than tungsten trioxide and hence undergoes oxidation upon exposure to the ambient atmosphere. Although nanoparticles of tungsten disulfide are metastable, hollow-closed nanostructures, i.e. fullerene-like WS2 (IF-WS2) and nanotubes thereof are kinetically stabilized because they present their basal (001) surface to the outer world. In this work, the oxidation of IF-WS2 and nanotubes stored under different conditions for 17–26 years have been studied. It was found that the degree of oxidation depends on the storage conditions. In fact, nanoparticles which were stored for long time and protected from the ambient atmosphere oxidized only marginally, while others kept under less favorable conditions suffered severe oxidation. Furthermore, the degradation of the IF nanoparticles is autocatalytic with clear acceleration over time. This work has also practical significance, since the shelf-life of IF-WS2 nanoparticles, which are used as solid-state lubricants commercially have not been studied before.
{"title":"Long-term aging of multiwall nanotubes and fullerene-like nanoparticles of WS2","authors":"R. Rosentsveig , Y. Feldman , V. Kundrat , I. Pinkas , A. Zak , R. Tenne","doi":"10.1016/j.jssc.2025.125259","DOIUrl":"10.1016/j.jssc.2025.125259","url":null,"abstract":"<div><div>Tungsten disulfide is an important compound with layered structure (2D-material). Chemically it is less stable than tungsten trioxide and hence undergoes oxidation upon exposure to the ambient atmosphere. Although nanoparticles of tungsten disulfide are metastable, hollow-closed nanostructures, i.e. fullerene-like WS<sub>2</sub> (IF-WS<sub>2</sub>) and nanotubes thereof are kinetically stabilized because they present their basal (<em>001</em>) surface to the outer world. In this work, the oxidation of IF-WS<sub>2</sub> and nanotubes stored under different conditions for 17–26 years have been studied. It was found that the degree of oxidation depends on the storage conditions. In fact, nanoparticles which were stored for long time and protected from the ambient atmosphere oxidized only marginally, while others kept under less favorable conditions suffered severe oxidation. Furthermore, the degradation of the IF nanoparticles is autocatalytic with clear acceleration over time. This work has also practical significance, since the shelf-life of IF-WS<sub>2</sub> nanoparticles, which are used as solid-state lubricants commercially have not been studied before.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"346 ","pages":"Article 125259"},"PeriodicalIF":3.2,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427738","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 : 2025-02-15DOI: 10.1016/j.jssc.2025.125253
Tio Putra Wendari , Muhammad Ali Akbar , Alfir Rizki , Zulhadjri , Yulia Eka Putri , Andon Insani , Nandang Mufti
In recent years, dielectric capacitors based on ferroelectric compounds have attracted great interest as energy storage materials. Solid solutions based on Na0.5Bi0.5TiO3 (NBT-based) exhibit relatively high polarization and are considered promising dielectric energy storage materials. We have prepared (Na0.5Bi0.5)1-xCaxTiO3 ceramics (x = 0, 0.125, and 0.25) by the molten salt method and investigated their structures, dielectric properties, and energy storage properties. The structural refinement using the Rietveld method reveals overall structural distortions in all samples, including A-site shifting, TiO6 octahedral distortion, and Ti–O–Ti tilting, which result in a non-centrosymmetric structure responsible for the observed ferroelectric properties. With the increase in Ca2+ content, the grain size and maximum dielectric constant gradually decrease. Furthermore, the peak of the maximum dielectric constant (Tm) shifts to lower temperatures, indicating the enhancement of polarization dynamics. As a result, optimum properties are identified in (Na0.5Bi0.5)0.75Ca0.25TiO3 (x = 0.25) with a recoverable energy density of 9.938 mJ/cm3 and an outstanding energy efficiency of 80.8 % at a low electric field of 25 kV/cm. A ferroelectric polarization measurement at 150–190 °C for samples with x = 0.25 showed an increase in the values of Pm, Wrec, and ƞ is stable at high temperatures. This indicates that the energy storage material has good thermal stability at high temperatures.
{"title":"Tuning the dielectric, ferroelectric, and energy storage properties of Ca-substituted Na0.5Bi0.5TiO3 perovskites synthesized via the molten salt method","authors":"Tio Putra Wendari , Muhammad Ali Akbar , Alfir Rizki , Zulhadjri , Yulia Eka Putri , Andon Insani , Nandang Mufti","doi":"10.1016/j.jssc.2025.125253","DOIUrl":"10.1016/j.jssc.2025.125253","url":null,"abstract":"<div><div>In recent years, dielectric capacitors based on ferroelectric compounds have attracted great interest as energy storage materials. Solid solutions based on Na<sub>0.5</sub>Bi<sub>0.5</sub>TiO<sub>3</sub> (NBT-based) exhibit relatively high polarization and are considered promising dielectric energy storage materials. We have prepared (Na<sub>0.5</sub>Bi<sub>0.5</sub>)<sub>1-<em>x</em></sub>Ca<sub><em>x</em></sub>TiO<sub>3</sub> ceramics (<em>x</em> = 0, 0.125, and 0.25) by the molten salt method and investigated their structures, dielectric properties, and energy storage properties. The structural refinement using the Rietveld method reveals overall structural distortions in all samples, including <em>A</em>-site shifting, TiO<sub>6</sub> octahedral distortion, and Ti–O–Ti tilting, which result in a non-centrosymmetric structure responsible for the observed ferroelectric properties. With the increase in Ca<sup>2+</sup> content, the grain size and maximum dielectric constant gradually decrease. Furthermore, the peak of the maximum dielectric constant (<em>T</em><sub><em>m</em></sub>) shifts to lower temperatures, indicating the enhancement of polarization dynamics. As a result, optimum properties are identified in (Na<sub>0.5</sub>Bi<sub>0.5</sub>)<sub>0.75</sub>Ca<sub>0.25</sub>TiO<sub>3</sub> (<em>x</em> = 0.25) with a recoverable energy density of 9.938 mJ/cm<sup>3</sup> and an outstanding energy efficiency of 80.8 % at a low electric field of 25 kV/cm. A ferroelectric polarization measurement at 150–190 °C for samples with <em>x</em> = 0.25 showed an increase in the values of <em>P</em><sub><em>m</em></sub>, <em>W</em><sub><em>rec</em></sub>, and <em>ƞ</em> is stable at high temperatures. This indicates that the energy storage material has good thermal stability at high temperatures.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"346 ","pages":"Article 125253"},"PeriodicalIF":3.2,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143437551","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 : 2025-02-14DOI: 10.1016/j.jssc.2025.125260
Chenglong Zou, Yan Zhou, Qun Wu, Fahui Nie, Sulin Xiang
Untreated rare earth wastewater contains large quantities of rare earth elements (REE), which can cause serious harm if they enter the human body or the environment. Therefore, the treatment of these wastewaters is of paramount importance. This study developed a novel type of bentonite composite material by grafting nanocellulose crystals onto the surface of magnetic bentonite for better adsorption properties of rare earth ions, especially La(III) ions. A suite of characterization techniques was employed, including SEM-EDS, XPS, FT-IR, XRD, and VSM. The results demonstrate that the nanocellulose crystals were successfully integrated with magnetic bentonite. And its BET specific surface area increased from 54.96 m2/g to 114.07 m2/g, which further enhanced its adsorption performance. Under optimal conditions (pH 6 and 303 K), where 0.9 g/L CMB was added to a 30 mg/L La(III) solution for the adsorption of rare earth ions for 360 min, the maximum adsorption removal rate was 97.52%. Furthermore, the experimental fitting curve conforms to the pseudo-second-order kinetic model and the Langmuir model. The results reveal that the adsorption process of La(III) ions by CMB is a chemisorption process that is influenced by both intraparticle diffusion and liquid film diffusion. The maximum adsorption capacity of CMB was 41.32 mg/g. Moreover, in the coexisting ion experiment, the lowest removal of La(III) ions by CMB was achieved at a Gd(III) ion concentration of 15 mg/L, which decreased to 82%. After seven sorption-desorption cycles, the removal rate of La(III) ions by CMB remained at 68.18%, indicating that it possessed excellent reusability.
{"title":"Synthesis of magnetic bentonite-based nanocellulose composites for the removal of La(Ⅲ) ions in aqueous solutions","authors":"Chenglong Zou, Yan Zhou, Qun Wu, Fahui Nie, Sulin Xiang","doi":"10.1016/j.jssc.2025.125260","DOIUrl":"10.1016/j.jssc.2025.125260","url":null,"abstract":"<div><div>Untreated rare earth wastewater contains large quantities of rare earth elements (REE), which can cause serious harm if they enter the human body or the environment. Therefore, the treatment of these wastewaters is of paramount importance. This study developed a novel type of bentonite composite material by grafting nanocellulose crystals onto the surface of magnetic bentonite for better adsorption properties of rare earth ions, especially La(III) ions. A suite of characterization techniques was employed, including SEM-EDS, XPS, FT-IR, XRD, and VSM. The results demonstrate that the nanocellulose crystals were successfully integrated with magnetic bentonite. And its BET specific surface area increased from 54.96 m<sup>2</sup>/g to 114.07 m<sup>2</sup>/g, which further enhanced its adsorption performance. Under optimal conditions (pH 6 and 303 K), where 0.9 g/L CMB was added to a 30 mg/L La(III) solution for the adsorption of rare earth ions for 360 min, the maximum adsorption removal rate was 97.52%. Furthermore, the experimental fitting curve conforms to the pseudo-second-order kinetic model and the Langmuir model. The results reveal that the adsorption process of La(III) ions by CMB is a chemisorption process that is influenced by both intraparticle diffusion and liquid film diffusion. The maximum adsorption capacity of CMB was 41.32 mg/g. Moreover, in the coexisting ion experiment, the lowest removal of La(III) ions by CMB was achieved at a Gd(III) ion concentration of 15 mg/L, which decreased to 82%. After seven sorption-desorption cycles, the removal rate of La(III) ions by CMB remained at 68.18%, indicating that it possessed excellent reusability.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"346 ","pages":"Article 125260"},"PeriodicalIF":3.2,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143444715","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 : 2025-02-13DOI: 10.1016/j.jssc.2025.125252
Han Yang , Fu-Chang Liang , Bo Tang, Hai-Xiong Chen, Si-Yun Fu, Song-Liang Cai, Wei-Guang Zhang, Jun Fan, Sheng-Run Zheng
The development of a chiral stationary phase (CSP) based on new matrices is still necessary because of the rapid growth of new chiral drugs and the limitations of the silica gel matrix. For the first time, MOF glass agZIF-62 was used as a matrix to fabricate a chiral stationary phase (CSP) by coating cellulose-tris(3,5-dimethylphenylcarbamate) (CDMPC). These MOF glass-based CSPs can separate various racemic compounds, including metalaxyl, epoxiconazole, TSO, cis-metconazole, and triticonazole with resolution values (Rs) ranging from 1.22 to 4.58 and separation factors (α) ranging from 1.8 to 6.79. In addition, the HPLC enantiomer separation performances of MOF glass-based and MOF crystal-based CSPs were compared.
{"title":"Preparation of a metal‒organic framework glass‒based chiral stationary phase for HPLC enantiomer separation","authors":"Han Yang , Fu-Chang Liang , Bo Tang, Hai-Xiong Chen, Si-Yun Fu, Song-Liang Cai, Wei-Guang Zhang, Jun Fan, Sheng-Run Zheng","doi":"10.1016/j.jssc.2025.125252","DOIUrl":"10.1016/j.jssc.2025.125252","url":null,"abstract":"<div><div>The development of a chiral stationary phase (CSP) based on new matrices is still necessary because of the rapid growth of new chiral drugs and the limitations of the silica gel matrix. For the first time, MOF glass agZIF-62 was used as a matrix to fabricate a chiral stationary phase (CSP) by coating cellulose-tris(3,5-dimethylphenylcarbamate) (CDMPC). These MOF glass-based CSPs can separate various racemic compounds, including metalaxyl, epoxiconazole, TSO, <em>cis</em>-metconazole, and triticonazole with resolution values (Rs) ranging from 1.22 to 4.58 and separation factors (α) ranging from 1.8 to 6.79. In addition, the HPLC enantiomer separation performances of MOF glass-based and MOF crystal-based CSPs were compared.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"346 ","pages":"Article 125252"},"PeriodicalIF":3.2,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143420928","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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