Pub Date : 2025-04-15DOI: 10.1016/j.jssc.2025.125379
Shingo Machida
The solid-state reaction of purified kaolinite (Si/Al = 1.03 molar ratio) and barium carbonate (BaCO3) to form hexacelsian, the metastable phase of BaAl2Si2O8, was conducted at various calcination conditions. As the calcination temperature increases, X-ray diffraction (XRD) patterns of calcined specimens for 48 h indicate the follows; 1) the exclusive formation of hexacelsian is achieved in the 1000–1100 °C range; 2) celsian, the stable phase of BaAl2Si2O8, becomes predominant in the 1100–1300 °C range; 3) celsian content decreases in the 1300–1500 °C range; and 4) celsian disappears, with only hexacelsian observed at 1600 °C. Scanning electron microscope images reveal that the particles size of hexacelsian in specimens calcined at 1600 °C is significantly larger than in those calcined at 1300 °C. Notably, hexacelsian remains predominant, but celsian reflections slightly appear in the XRD patterns of the specimen calcined at 1600 °C for 72 h. Therefore, the phase transformation of hexacelsin to celsian, which generally proceeds at around 1000 °C in many studies using Kaolin clays containing kaolinite or halloysite with by-products, is delayed when hexacelsian particles are relatively larger. Furthermore, the exclusive formation of hexacelsian is achieved at 1600 °C for 72 h when using another purified kaolinite (Si/Al = 1.01 in molar ratio) and finer BaCO3 particles as raw materials. Consequently, the findings in this study demonstrate a “pseudo-reversal phase transformation” at higher temperatures and shorter calcination times.
{"title":"Pseudo-reversal phase transformation of hexacelsian to celsian in a purified kaolinite system","authors":"Shingo Machida","doi":"10.1016/j.jssc.2025.125379","DOIUrl":"10.1016/j.jssc.2025.125379","url":null,"abstract":"<div><div>The solid-state reaction of purified kaolinite (Si/Al = 1.03 molar ratio) and barium carbonate (BaCO<sub>3</sub>) to form hexacelsian, the metastable phase of BaAl<sub>2</sub>Si<sub>2</sub>O<sub>8</sub>, was conducted at various calcination conditions. As the calcination temperature increases, X-ray diffraction (XRD) patterns of calcined specimens for 48 h indicate the follows; 1) the exclusive formation of hexacelsian is achieved in the 1000–1100 °C range; 2) celsian, the stable phase of BaAl<sub>2</sub>Si<sub>2</sub>O<sub>8</sub>, becomes predominant in the 1100–1300 °C range; 3) celsian content decreases in the 1300–1500 °C range; and 4) celsian disappears, with only hexacelsian observed at 1600 °C. Scanning electron microscope images reveal that the particles size of hexacelsian in specimens calcined at 1600 °C is significantly larger than in those calcined at 1300 °C. Notably, hexacelsian remains predominant, but celsian reflections slightly appear in the XRD patterns of the specimen calcined at 1600 °C for 72 h. Therefore, the phase transformation of hexacelsin to celsian, which generally proceeds at around 1000 °C in many studies using Kaolin clays containing kaolinite or halloysite with by-products, is delayed when hexacelsian particles are relatively larger. Furthermore, the exclusive formation of hexacelsian is achieved at 1600 °C for 72 h when using another purified kaolinite (Si/Al = 1.01 in molar ratio) and finer BaCO<sub>3</sub> particles as raw materials. Consequently, the findings in this study demonstrate a “pseudo-reversal phase transformation” at higher temperatures and shorter calcination times.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"348 ","pages":"Article 125379"},"PeriodicalIF":3.2,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143854965","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}
Perovskites are known for their exceptional photocatalytic properties, owing to their unique optoelectronic characteristics and structural versatility. However, the inherent instability and toxicity of conventional perovskites have restricted their practical application. The development of double perovskite materials has successfully addressed some of these issues. Nevertheless, problems such as significant charge recombination and slow surface catalytic reactions continue to hinder their practical application. In this study, we develop a novel and highly efficient composite, the Cs2AgBiI6/g-C3N4 (CABI/CN) heterojunction photocatalyst, synthesized through a simple anti-solvent recrystallization process. Under visible light (λ ≥ 420 nm, 300 W Xe lamp), the CABI/CN-20 composite achieved 97 % degradation of rhodamine B in 180 min, outperforming Cs2AgBiI6 by a factor of 1.3. In contrast, g-C3N4 showed minimal degradation under the same conditions. The enhanced photocatalytic performance of the CABI/CN-20 heterojunction is attributed not only to improved charge separation efficiency within the photocatalyst but also to the facilitation of photogenerated carrier transfer across the heterojunction interface due to the potential difference. Consequently, this leads to optimal redox capacity and significantly enhances the photocatalytic degradation performance. This study introduces novel methods for synthesizing Cs2AgBiI6/g-C3N4 heterojunctions and emphasizes their efficient separation of photogenerated carriers.
{"title":"Lead-free double halide perovskite Cs2AgBiI6/g-C3N4 heterojunction photocatalysts for effective visible-light photocatalytic activity","authors":"Zhiyang Xue, Peng Yan, Aikelaimu Aihemaiti, Ailijiang Tuerdi, Abdukader Abdukayum","doi":"10.1016/j.jssc.2025.125355","DOIUrl":"10.1016/j.jssc.2025.125355","url":null,"abstract":"<div><div>Perovskites are known for their exceptional photocatalytic properties, owing to their unique optoelectronic characteristics and structural versatility. However, the inherent instability and toxicity of conventional perovskites have restricted their practical application. The development of double perovskite materials has successfully addressed some of these issues. Nevertheless, problems such as significant charge recombination and slow surface catalytic reactions continue to hinder their practical application. In this study, we develop a novel and highly efficient composite, the Cs<sub>2</sub>AgBiI<sub>6</sub>/g-C<sub>3</sub>N<sub>4</sub> (CABI/CN) heterojunction photocatalyst, synthesized through a simple anti-solvent recrystallization process. Under visible light (λ ≥ 420 nm, 300 W Xe lamp), the CABI/CN-20 composite achieved 97 % degradation of rhodamine B in 180 min, outperforming Cs<sub>2</sub>AgBiI<sub>6</sub> by a factor of 1.3. In contrast, g-C<sub>3</sub>N<sub>4</sub> showed minimal degradation under the same conditions. The enhanced photocatalytic performance of the CABI/CN-20 heterojunction is attributed not only to improved charge separation efficiency within the photocatalyst but also to the facilitation of photogenerated carrier transfer across the heterojunction interface due to the potential difference. Consequently, this leads to optimal redox capacity and significantly enhances the photocatalytic degradation performance. This study introduces novel methods for synthesizing Cs<sub>2</sub>AgBiI<sub>6</sub>/g-C<sub>3</sub>N<sub>4</sub> heterojunctions and emphasizes their efficient separation of photogenerated carriers.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"348 ","pages":"Article 125355"},"PeriodicalIF":3.2,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143851683","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 : 2025-04-15DOI: 10.1016/j.jssc.2025.125381
Wen-Ze Li , Zhe Yuan , Sheng Qu , Jian Luan
With the rapid development of industry, the discharge of wastewater containing emulsified oils and water-soluble dyes has been increasing, posing a serious threat to the environment and human health. Therefore, the development of an easy-to-manufacture, energy-efficient and highly effective separating material has become a top priority. In this study, copper-based metal-organic frameworks (Cu-MOFs) were combined with carbon nanotubes (CNTs) by hydrothermal synthesis as well as superhydrophilic mixed matrix membranes (MMMs) were constructed using ultrasonication and vacuum-assisted self-assembly techniques. As a result, the prepared Cu-MOF@CNT membranes exhibited excellent separation efficiency (flux of 5376 L m−2 h−1, and separation efficiency of 97.7 %) in treating hexane emulsion, which was attributed to their excellent water permeability and oil rejection. In addition, due to the porous and negatively charged surface of the Cu-MOF@CNT membranes, their removal of cationic dyes (gentian violet (GV) and methylene blue (MB)) were efficient, which was achieved by a one-step filtration method, with a flux of 5900 L m−2 h−1, and separation efficiencies of 99.7 % and 98.6 %, respectively. The stability and efficiency of combining Cu-MOF with CNT were the key factors in the separation. This study not only presents a simple and easy-to-control method for the preparation of Cu-MOF@CNT membranes, but also provides an important reference for rational design and potential applications in sustainable chemistry.
{"title":"Robust superhydrophilic and underwater superoleophobic membrane based on copper-organic framework modified carbon nanotube for oil-water and dye separation","authors":"Wen-Ze Li , Zhe Yuan , Sheng Qu , Jian Luan","doi":"10.1016/j.jssc.2025.125381","DOIUrl":"10.1016/j.jssc.2025.125381","url":null,"abstract":"<div><div>With the rapid development of industry, the discharge of wastewater containing emulsified oils and water-soluble dyes has been increasing, posing a serious threat to the environment and human health. Therefore, the development of an easy-to-manufacture, energy-efficient and highly effective separating material has become a top priority. In this study, copper-based metal-organic frameworks (Cu-MOFs) were combined with carbon nanotubes (CNTs) by hydrothermal synthesis as well as superhydrophilic mixed matrix membranes (MMMs) were constructed using ultrasonication and vacuum-assisted self-assembly techniques. As a result, the prepared Cu-MOF@CNT membranes exhibited excellent separation efficiency (flux of 5376 L m<sup>−2</sup> h<sup>−1</sup>, and separation efficiency of 97.7 %) in treating hexane emulsion, which was attributed to their excellent water permeability and oil rejection. In addition, due to the porous and negatively charged surface of the Cu-MOF@CNT membranes, their removal of cationic dyes (gentian violet (GV) and methylene blue (MB)) were efficient, which was achieved by a one-step filtration method, with a flux of 5900 L m<sup>−2</sup> h<sup>−1</sup>, and separation efficiencies of 99.7 % and 98.6 %, respectively. The stability and efficiency of combining Cu-MOF with CNT were the key factors in the separation. This study not only presents a simple and easy-to-control method for the preparation of Cu-MOF@CNT membranes, but also provides an important reference for rational design and potential applications in sustainable chemistry.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"348 ","pages":"Article 125381"},"PeriodicalIF":3.2,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143838962","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}
Due to the diverse structural configurations and exceptional thermal stability, energetic complexes have been extensively utilized as catalysts for the thermal decomposition of ammonium perchlorate (AP). Nevertheless, enhancing the catalytic activity of these energetic complexes remains a significant challenge. In this study, three nitrogen-rich heterocyclic complexes, M(Hapza)2(H2O)4 (M = Co, Zn, and Cd), were successfully synthesized by the hydrothermal method using 3-aminopyrazole-4-carboxylic acid (H2apza) as an energetic ligand. Single-crystal X-ray diffraction analysis revealed that the three complexes are single-nucleated and isomorphic, forming thermally stable three-dimensional supramolecular structures through extensive hydrogen bonding networks. The incorporation of these complexes significantly advanced the high decomposition peak of AP by 26.9–51.4 °C and reduced the activation energy (Ea) by 41.19–52.99 kJ mol−1, demonstrating their remarkable catalytic effect on AP. The detonation properties of the complexes were evaluated using the Kamlet-Jacobs equation, revealing that these complexes possess higher detonation velocities (8.9–9.4 km s−1) and detonation pressures (36.1–42.4 GPa) compared to traditional energetic materials. Further investigation into the possible catalytic mechanism suggested that metal oxides, generated from the decomposition of metal complexes, may facilitate charge transfer and enhance the desorption of NH3 during the high-temperature decomposition stage of AP. This study highlights the importance of experimental and theoretical analysis, providing a fresh perspective for the development of complexes in the field of energetic materials.
{"title":"Thermal decomposition catalytic properties of ammonium perchlorate with three new energetic complexes on the basis of metal centre regulation","authors":"Shoufeng Fu, Jiawei Liang, Bing Li, Yanhong Yang, Chenxi Yang, Hongyan Wu, Jiaxing He, Jiayan Guo, Chenghao Wang, Xiaoyan Chen, Jianlin Ren","doi":"10.1016/j.jssc.2025.125376","DOIUrl":"10.1016/j.jssc.2025.125376","url":null,"abstract":"<div><div>Due to the diverse structural configurations and exceptional thermal stability, energetic complexes have been extensively utilized as catalysts for the thermal decomposition of ammonium perchlorate (AP). Nevertheless, enhancing the catalytic activity of these energetic complexes remains a significant challenge. In this study, three nitrogen-rich heterocyclic complexes, M(Hapza)<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub> (M = Co, Zn, and Cd), were successfully synthesized by the hydrothermal method using 3-aminopyrazole-4-carboxylic acid (H<sub>2</sub>apza) as an energetic ligand. Single-crystal X-ray diffraction analysis revealed that the three complexes are single-nucleated and isomorphic, forming thermally stable three-dimensional supramolecular structures through extensive hydrogen bonding networks. The incorporation of these complexes significantly advanced the high decomposition peak of AP by 26.9–51.4 °C and reduced the activation energy (<em>E</em><sub>a</sub>) by 41.19–52.99 kJ mol<sup>−1</sup>, demonstrating their remarkable catalytic effect on AP. The detonation properties of the complexes were evaluated using the <em>Kamlet-Jacobs</em> equation, revealing that these complexes possess higher detonation velocities (8.9–9.4 km s<sup>−1</sup>) and detonation pressures (36.1–42.4 GPa) compared to traditional energetic materials. Further investigation into the possible catalytic mechanism suggested that metal oxides, generated from the decomposition of metal complexes, may facilitate charge transfer and enhance the desorption of NH<sub>3</sub> during the high-temperature decomposition stage of AP. This study highlights the importance of experimental and theoretical analysis, providing a fresh perspective for the development of complexes in the field of energetic materials.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"348 ","pages":"Article 125376"},"PeriodicalIF":3.2,"publicationDate":"2025-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143839018","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 : 2025-04-11DOI: 10.1016/j.jssc.2025.125378
Yao Wang , Jiang-Feng Song , Rui-Sha Zhou
Reducing the concentration of F− in water is crucial, given that excessive fluoride poses a threat to both the environment and human health. In this study, amorphous alumina (AlOx) was prepared using solvothermal method and the surface hydroxyl content of calcined AlOx was enhanced using H2O2 (0–5 wt%) to improve its defluoridation rate. The produced materials were gradually transformed from the amorphous form to the crystalline state. The crystalline calcined AlOx modified with 0.5 % H2O2 exhibits a rapid increase in defluoridation rate, from 76.4 % to 94 %, in just 5 min at the initial fluoride concentration of 10 mg/L. Furthermore, it shows effective fluoride removal across the pH range of 3–10. The pseudo-second-order model and the Langmuir model provided an accurate representation of the kinetics and isotherms associated with adsorption, suggesting that the process is characterized by chemisorption and occurs in a monolayer. The adsorption mechanism, primarily the ion exchange between F− and hydroxyl groups, is discussed. The 0.5 % H2O2/AlOx adsorbent regenerated through aluminum sulfate solution showed good reusability performance, and its defluoridation rate was maintained at 79.9 % after five cycles. This indicates that enhancing hydroxyl groups content on the surface of the adsorbent enhances its defluoridation performance which is promising for practical mine water treatment.
{"title":"Hydrogen peroxide induces the transition of amorphous to crystalline structure of AlOx and enhanced fluoride removal efficiency in coal mine wastewater","authors":"Yao Wang , Jiang-Feng Song , Rui-Sha Zhou","doi":"10.1016/j.jssc.2025.125378","DOIUrl":"10.1016/j.jssc.2025.125378","url":null,"abstract":"<div><div>Reducing the concentration of F<sup>−</sup> in water is crucial, given that excessive fluoride poses a threat to both the environment and human health. In this study, amorphous alumina (AlO<sub>x</sub>) was prepared using solvothermal method and the surface hydroxyl content of calcined AlO<sub>x</sub> was enhanced using H<sub>2</sub>O<sub>2</sub> (0–5 wt%) to improve its defluoridation rate. The produced materials were gradually transformed from the amorphous form to the crystalline state. The crystalline calcined AlO<sub>x</sub> modified with 0.5 % H<sub>2</sub>O<sub>2</sub> exhibits a rapid increase in defluoridation rate, from 76.4 % to 94 %, in just 5 min at the initial fluoride concentration of 10 mg/L. Furthermore, it shows effective fluoride removal across the pH range of 3–10. The pseudo-second-order model and the Langmuir model provided an accurate representation of the kinetics and isotherms associated with adsorption, suggesting that the process is characterized by chemisorption and occurs in a monolayer. The adsorption mechanism, primarily the ion exchange between F<sup>−</sup> and hydroxyl groups, is discussed. The 0.5 % H<sub>2</sub>O<sub>2</sub>/AlO<sub>x</sub> adsorbent regenerated through aluminum sulfate solution showed good reusability performance, and its defluoridation rate was maintained at 79.9 % after five cycles. This indicates that enhancing hydroxyl groups content on the surface of the adsorbent enhances its defluoridation performance which is promising for practical mine water treatment.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"348 ","pages":"Article 125378"},"PeriodicalIF":3.2,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143820757","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 : 2025-04-11DOI: 10.1016/j.jssc.2025.125377
Hongwei Zhao , Guojun Lu , Mingxin Yu , Xuanting Chen , Wang Yao , Chunyan Cao , An Xie
A series of Y2(WO4)3·3H2O:xmol%Eu3+ (YWO:xEu) red phosphors were prepared. The structure, morphology, composition, photoluminescent (PL) characteristics, and thermal stability were systematically investigated. The samples underwent a structural phase transformation from the orthorhombic to the monoclinic phase with increasing x from 0 to 70 mol%. Due to the transformation in the crystalline phase of the phosphors, the bandgap energy (Eg), the PL intensity, and the fluorescence decay lifetime exhibited significant change. The YWO:5Eu and YWO:20Eu phosphors exhibited thermal enhancing of luminescence (TEL) at 175 °C. Under the monitoring of 5D0→7F2 transition, the maximum excitation intensities reached 7.28 and 4.46 times of those at room temperature. With CTB excitation, the maximum emission intensities were 7.13 and 5.10 times of the corresponding initial emission intensities. In contrast, YWO:50Eu displayed thermal quenching of luminescence (TQL). Combined with in situ X-ray diffraction (XRD) patterns, Rietveld refinement results, thermogravimetric (TG) analyses, and X-ray photoelectron spectroscopy (XPS) data, the mechanism of TEL can be explained by the release of H2O molecules and the negative thermal expansion (NTE) of Y2(WO4)3. This study provides guidance for exploring efficient red phosphors with thermal stability.
{"title":"Exploring thermal enhancing of luminescence in Y2(WO4)3·3H2O:xmol%Eu3+ phosphors","authors":"Hongwei Zhao , Guojun Lu , Mingxin Yu , Xuanting Chen , Wang Yao , Chunyan Cao , An Xie","doi":"10.1016/j.jssc.2025.125377","DOIUrl":"10.1016/j.jssc.2025.125377","url":null,"abstract":"<div><div>A series of Y<sub>2</sub>(WO<sub>4</sub>)<sub>3</sub>·3H<sub>2</sub>O:<em>x</em>mol%Eu<sup>3+</sup> (YWO:<em>x</em>Eu) red phosphors were prepared. The structure, morphology, composition, photoluminescent (PL) characteristics, and thermal stability were systematically investigated. The samples underwent a structural phase transformation from the orthorhombic to the monoclinic phase with increasing <em>x</em> from 0 to 70 mol%. Due to the transformation in the crystalline phase of the phosphors, the bandgap energy (<em>E</em><sub>g</sub>), the PL intensity, and the fluorescence decay lifetime exhibited significant change. The YWO:5Eu and YWO:20Eu phosphors exhibited thermal enhancing of luminescence (TEL) at 175 °C. Under the monitoring of <sup>5</sup>D<sub>0</sub>→<sup>7</sup>F<sub>2</sub> transition, the maximum excitation intensities reached 7.28 and 4.46 times of those at room temperature. With CTB excitation, the maximum emission intensities were 7.13 and 5.10 times of the corresponding initial emission intensities. In contrast, YWO:50Eu displayed thermal quenching of luminescence (TQL). Combined with in situ X-ray diffraction (XRD) patterns, Rietveld refinement results, thermogravimetric (TG) analyses, and X-ray photoelectron spectroscopy (XPS) data, the mechanism of TEL can be explained by the release of H<sub>2</sub>O molecules and the negative thermal expansion (NTE) of Y<sub>2</sub>(WO<sub>4</sub>)<sub>3</sub>. This study provides guidance for exploring efficient red phosphors with thermal stability.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"348 ","pages":"Article 125377"},"PeriodicalIF":3.2,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143825993","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 : 2025-04-11DOI: 10.1016/j.jssc.2025.125375
M. Rudysh , O. Khyzhun , V.I. Sabov , T.A. Malakhovska , A.I. Pogodin , I.E. Barchiy , L. Bychto , A.O. Fedorchuk , P. Brągiel , B. Andriyevsky , M. Piasecki
We report on successful synthesis by the Bridgman technique of a large TlInP2Se6 single crystal and studies of its electronic, optical and vibrational properties. In particular, centimeter size dimensions of the TlInP2Se6 crystal allow its practical use in optical devices. The crystal was characterized by DTA, SEM, EDS, XPS, XES techniques which reveal its high optical quality, single-phase composition and stoichiometry. The present refinements of the crystal structure of TlInP2Se6 bring the following unit-cell constants: a = 6.4494(4) Å, b = 7.5423(5) Å, c = 12.1669(9) Å, α = 100.784(4)°, β = 93.622(4)°, γ = 113.331(3)°, and V = 527.8(2) Å3. The experimental optical reflection spectrum of the crystal was measured in the far-infrared spectral range 30–500 cm−1 using the synchrotron radiation. Furthermore, we employed first-principles computations within a density functional theory (DFT) formalism to elucidate peculiarities of filling the valence-band and conduction-band regions and the nature of semiconducting gap. The DFT calculations confirm the existing measurements that the TlInP2Se6 crystal is an indirect semiconductor (maximum of the valence band and minimum of the conduction band are positioned at high-symmetry F and Z points of the Brillouin zone, respectively), and the principal contributors to the valence band are Se 4p states filling mainly its top and also the bottom of the conduction band. The DFT calculations explain observed highly anisotropic properties (layered structure) by strong differentiation of calculated real and imaginary parts of complex dielectric function in the y direction, with relation to x and z directions for the TlInP2Se6 compound. The vibrational properties of the TlInP2Se6 crystal were also investigated both experimentally by Raman measurements and theoretically using the DFPT method.
{"title":"TlInP2Se6 single crystal: Electronic, optical and vibrational properties","authors":"M. Rudysh , O. Khyzhun , V.I. Sabov , T.A. Malakhovska , A.I. Pogodin , I.E. Barchiy , L. Bychto , A.O. Fedorchuk , P. Brągiel , B. Andriyevsky , M. Piasecki","doi":"10.1016/j.jssc.2025.125375","DOIUrl":"10.1016/j.jssc.2025.125375","url":null,"abstract":"<div><div>We report on successful synthesis by the Bridgman technique of a large TlInP<sub>2</sub>Se<sub>6</sub> single crystal and studies of its electronic, optical and vibrational properties. In particular, centimeter size dimensions of the TlInP<sub>2</sub>Se<sub>6</sub> crystal allow its practical use in optical devices. The crystal was characterized by DTA, SEM, EDS, XPS, XES techniques which reveal its high optical quality, single-phase composition and stoichiometry. The present refinements of the crystal structure of TlInP<sub>2</sub>Se<sub>6</sub> bring the following unit-cell constants: a = 6.4494(4) Å, b = 7.5423(5) Å, c = 12.1669(9) Å, α = 100.784(4)°, β = 93.622(4)°, γ = 113.331(3)°, and V = 527.8(2) Å<sup>3</sup>. The experimental optical reflection spectrum of the crystal was measured in the far-infrared spectral range 30–500 cm<sup>−1</sup> using the synchrotron radiation. Furthermore, we employed first-principles computations within a density functional theory (DFT) formalism to elucidate peculiarities of filling the valence-band and conduction-band regions and the nature of semiconducting gap. The DFT calculations confirm the existing measurements that the TlInP<sub>2</sub>Se<sub>6</sub> crystal is an indirect semiconductor (maximum of the valence band and minimum of the conduction band are positioned at high-symmetry F and Z points of the Brillouin zone, respectively), and the principal contributors to the valence band are Se 4p states filling mainly its top and also the bottom of the conduction band. The DFT calculations explain observed highly anisotropic properties (layered structure) by strong differentiation of calculated real and imaginary parts of complex dielectric function in the <em>y</em> direction, with relation to <em>x</em> and <em>z</em> directions for the TlInP<sub>2</sub>Se<sub>6</sub> compound. The vibrational properties of the TlInP<sub>2</sub>Se<sub>6</sub> crystal were also investigated both experimentally by Raman measurements and theoretically using the DFPT method.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"348 ","pages":"Article 125375"},"PeriodicalIF":3.2,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143851682","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}
Metal–organic frameworks (MOFs) with high proton–conductive behavior have attracted great attention. Here, by using the organic phosphonic acid ligand H5L (4–{[bis(phosphonomethyl)amino]methyl}benzoic acid) and auxiliary ligand oxalic acid (H2C2O4), two Ce–MOFs with different structures, namely, Ce[(H3L)(C2O4)0.5(H2O)]·0.5H2O (1) and Ce[(H4L)(H3L)(H2O)]·2H2O (2), have been hydrothermally synthesized. Due to the existence of hydrogen–bond interactions among uncoordinated carboxyl groups, free water molecules, and protonated N atoms in the framework structures as well as their good stabilities, which provide possibilities in proton conduction. The alternating–current (AC) impedance measurements indicate that the proton conductivities of both 1 and 2 increase with the increasing of the humidity and temperature. Expectedly, the maximum proton conductivity of 1 (1.22 × 10−3 S cm−1) is nearly 2 times higher than that of 2 (6.51 × 10−4 S cm−1). The proton conduction mechanism was clarified by analyzing the structures of 1 and 2, the activation energy (Ea), water vapor and nitrogen adsorption tests. Meanwhile, the structural–activity relationship between structure and proton conductivity has also been analyzed and discussed. Proton conductive composite membrane of 1 and 2 have also been successfully prepared and investigated. This work provides more options for the design and construction of high proton–conductive materials.
{"title":"Two stable proton–conductive Cerium (III)–organic frameworks with high–density carboxylic groups","authors":"Xin Li, Jia-Hui Yu, Lu-Yang Sun, Yi-Fan Xing, Xu Zhang, Cheng-Qi Jiao, Han-Wen Zheng, Yan-Yu Zhu, Zhen-Gang Sun","doi":"10.1016/j.jssc.2025.125367","DOIUrl":"10.1016/j.jssc.2025.125367","url":null,"abstract":"<div><div>Metal–organic frameworks (MOFs) with high proton–conductive behavior have attracted great attention. Here, by using the organic phosphonic acid ligand H<sub>5</sub>L (4–{[bis(phosphonomethyl)amino]methyl}benzoic acid) and auxiliary ligand oxalic acid (H<sub>2</sub>C<sub>2</sub>O<sub>4</sub>), two Ce–MOFs with different structures, namely, Ce[(H<sub>3</sub>L)(C<sub>2</sub>O<sub>4</sub>)<sub>0.5</sub>(H<sub>2</sub>O)]·0.5H<sub>2</sub>O (<strong>1</strong>) and Ce[(H<sub>4</sub>L)(H<sub>3</sub>L)(H<sub>2</sub>O)]·2H<sub>2</sub>O (<strong>2</strong>), have been hydrothermally synthesized. Due to the existence of hydrogen–bond interactions among uncoordinated carboxyl groups, free water molecules, and protonated N atoms in the framework structures as well as their good stabilities, which provide possibilities in proton conduction. The alternating–current (AC) impedance measurements indicate that the proton conductivities of both <strong>1</strong> and <strong>2</strong> increase with the increasing of the humidity and temperature. Expectedly, the maximum proton conductivity of <strong>1</strong> (1.22 × 10<sup>−3</sup> S cm<sup>−1</sup>) is nearly 2 times higher than that of <strong>2</strong> (6.51 × 10<sup>−4</sup> S cm<sup>−1</sup>). The proton conduction mechanism was clarified by analyzing the structures of <strong>1</strong> and <strong>2</strong>, the activation energy (<em>E</em><sub>a</sub>), water vapor and nitrogen adsorption tests. Meanwhile, the structural–activity relationship between structure and proton conductivity has also been analyzed and discussed. Proton conductive composite membrane of <strong>1</strong> and <strong>2</strong> have also been successfully prepared and investigated. This work provides more options for the design and construction of high proton–conductive materials.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"348 ","pages":"Article 125367"},"PeriodicalIF":3.2,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143820756","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 : 2025-04-09DOI: 10.1016/j.jssc.2025.125368
Swaita Devi, Charanjeet Sen, Nidhi Bhagat, Niharika, Haq Nawaz Sheikh
The accumulation of industrial contaminants in aquatic environments, particularly metal ions and organic pollutants, poses significant risks to human health and the ecosystem globally. This has led to the development of multifunctional nanoparticles with dual capabilities: luminescent detection and photocatalytic degradation of hazardous contaminants. In this study, we present the development of Sm3+/Eu3+ co-doped AgGd(MoO4)2 and AgGd(WO4)2 (Sm3+ = 5 %, Eu3+ = 7 %) nanomaterials, synthesized via a hydrothermal method, and assessed their performance in luminescence-based detection of MnO4− anions and photocatalytic degradation of antibiotics in water. The luminescent properties of AgGd(MoO4)2:Sm3+/Eu3+ demonstrated exceptional sensitivity and selectivity for detecting MnO4− anions in aqueous solutions, with a significant quenching of the emission band at 620 nm upon the introduction of varying concentrations of MnO4−. The nanosensor achieved limit of detection of 0.43 ppm and exhibited a Stern-Volmer (Ksv) quenching constant of 3.61 × 104 M−1 for MnO4− anions, showcasing its excellent selectivity and sensitivity toward MnO4− detection. Additionally, AgGd(WO4)2:Sm3+/Eu3+ nanoparticles exhibited superior photocatalytic activity in the degradation of amoxicillin (AMX) in an aqueous environment. UV–Vis spectroscopy data suggested that the AgGd(WO4)2:Sm3+/Eu3+ nanoparticles outperform AgGd(MoO4)2:Sm3+/Eu3+ nanoparticles as nanocatalysts. The AgGd(WO4)2:Sm3+/Eu3+ nanomaterial achieved an efficiency of approximately 94.8 % in degrading AMX under 90 min of UV light exposure, and demonstrated remarkable stability after five consecutive catalytic cycles. This work introduces a novel approach to simultaneous luminescent detection and photocatalytic degradation by utilizing Sm3+/Eu3+ co-doped AgGd(MoO4)2 and AgGd(WO4)2 nanomaterials, highlighting their unique potential for environmental monitoring and remediation. The combination of high sensitivity for MnO4− detection and superior photocatalytic degradation of antibiotics represents a significant advancement in multifunctional nanomaterials, providing a dual-function solution to address critical environmental contamination challenges.
{"title":"Sm3+/Eu3+ Co-doped AgGd(MoO4)2 and AgGd(WO4)2: Multifunctional platforms for luminescent sensing of MnO4− and amoxicillin degradation in water","authors":"Swaita Devi, Charanjeet Sen, Nidhi Bhagat, Niharika, Haq Nawaz Sheikh","doi":"10.1016/j.jssc.2025.125368","DOIUrl":"10.1016/j.jssc.2025.125368","url":null,"abstract":"<div><div>The accumulation of industrial contaminants in aquatic environments, particularly metal ions and organic pollutants, poses significant risks to human health and the ecosystem globally. This has led to the development of multifunctional nanoparticles with dual capabilities: luminescent detection and photocatalytic degradation of hazardous contaminants. In this study, we present the development of Sm<sup>3+</sup>/Eu<sup>3+</sup> co-doped AgGd(MoO<sub>4</sub>)<sub>2</sub> and AgGd(WO<sub>4</sub>)<sub>2</sub> (Sm<sup>3+</sup> = 5 %, Eu<sup>3+</sup> = 7 %) nanomaterials, synthesized <em>via</em> a hydrothermal method, and assessed their performance in luminescence-based detection of MnO<sub>4</sub><sup>−</sup> anions and photocatalytic degradation of antibiotics in water. The luminescent properties of AgGd(MoO<sub>4</sub>)<sub>2</sub>:Sm<sup>3+</sup>/Eu<sup>3+</sup> demonstrated exceptional sensitivity and selectivity for detecting MnO<sub>4</sub><sup>−</sup> anions in aqueous solutions, with a significant quenching of the emission band at 620 nm upon the introduction of varying concentrations of MnO<sub>4</sub><sup>−</sup>. The nanosensor achieved limit of detection of 0.43 ppm and exhibited a Stern-Volmer (K<sub>sv</sub>) quenching constant of 3.61 × 10<sup>4</sup> M<sup>−1</sup> for MnO<sub>4</sub><sup>−</sup> anions, showcasing its excellent selectivity and sensitivity toward MnO<sub>4</sub><sup>−</sup> detection. Additionally, AgGd(WO<sub>4</sub>)<sub>2</sub>:Sm<sup>3+</sup>/Eu<sup>3+</sup> nanoparticles exhibited superior photocatalytic activity in the degradation of amoxicillin (AMX) in an aqueous environment. UV–Vis spectroscopy data suggested that the AgGd(WO<sub>4</sub>)<sub>2</sub>:Sm<sup>3+</sup>/Eu<sup>3+</sup> nanoparticles outperform AgGd(MoO<sub>4</sub>)<sub>2</sub>:Sm<sup>3+</sup>/Eu<sup>3+</sup> nanoparticles as nanocatalysts. The AgGd(WO<sub>4</sub>)<sub>2</sub>:Sm<sup>3+</sup>/Eu<sup>3+</sup> nanomaterial achieved an efficiency of approximately 94.8 % in degrading AMX under 90 min of UV light exposure, and demonstrated remarkable stability after five consecutive catalytic cycles. This work introduces a novel approach to simultaneous luminescent detection and photocatalytic degradation by utilizing Sm<sup>3+</sup>/Eu<sup>3+</sup> co-doped AgGd(MoO<sub>4</sub>)<sub>2</sub> and AgGd(WO<sub>4</sub>)<sub>2</sub> nanomaterials, highlighting their unique potential for environmental monitoring and remediation. The combination of high sensitivity for MnO<sub>4</sub><sup>−</sup> detection and superior photocatalytic degradation of antibiotics represents a significant advancement in multifunctional nanomaterials, providing a dual-function solution to address critical environmental contamination challenges.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"348 ","pages":"Article 125368"},"PeriodicalIF":3.2,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143839017","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}
Luminescent metal-organic frameworks (LMOFs) demonstrate promising applications in the field of fluorescence sensing. In this study, two isomorphic MOFs, [Cd4 (MTPTC)2 (DMF)4]·5DMF·2H2O (Compound 1) and [Mn2 (MTPTC) (DMF)2]·DMF (Compound 2) were constructed using Cd(NO3)2·4H2O and Mn(CH3COO)2·4H2O as metal sources with 5,5’-(5-Methylbenzene-1,3-diyl) diisophthalic acid (H4MTPTC). Topological analysis reveals that both Compounds 1 and 2 possess novel 3,3,4-c connected topologies with vertex symbols [6.82][62.83.10][62.8]. It is considered that the d10 Cd(II)-based MOF shows a better response in the field of nitroaromatic explosive sensing compared with the d5 Mn-based MOF, which may possess lower electron density on the conjugated building blocks. Fluorescence sensing experiments for metal cations, nitroaromatic explosives (NAEs), and sulfonamide antibiotics (SAs) show that Compound 1 exhibits excellent detection capabilities and recyclability for Fe3+, 4-nitrophenol (4-NP), and sulfadiazine (SDZ). The Ksv values (quenching constant) of Compound 1 for Fe3+, 4-NP, and SDZ are 1.30 × 105 M−1, 4.10 × 105 M−1, and 1.36 × 105 M−1. Compound 1 prove to be ideal fluorescence sensing materials for the detection of metal cations, NAEs, and SAs.
{"title":"Two isomorphic Cd/Mn(II) MOFs based on V-shaped carboxylic acid ligands-synthesis and application in fluorescence detection of Fe3+, nitroaromatic explosives and sulfonamide antibiotics","authors":"Xinxin Jia , Wenzhuo Zhang , Shi-Tong Zhang , Xiaolong Luo","doi":"10.1016/j.jssc.2025.125366","DOIUrl":"10.1016/j.jssc.2025.125366","url":null,"abstract":"<div><div>Luminescent metal-organic frameworks (LMOFs) demonstrate promising applications in the field of fluorescence sensing. In this study, two isomorphic MOFs, [Cd<sub>4</sub> (MTPTC)<sub>2</sub> (DMF)<sub>4</sub>]·5DMF·2H<sub>2</sub>O (Compound <strong>1</strong>) and [Mn<sub>2</sub> (MTPTC) (DMF)<sub>2</sub>]·DMF (Compound <strong>2</strong>) were constructed using Cd(NO<sub>3</sub>)<sub>2</sub>·4H<sub>2</sub>O and Mn(CH<sub>3</sub>COO)<sub>2</sub>·4H<sub>2</sub>O as metal sources with 5,5’-(5-Methylbenzene-1,3-diyl) diisophthalic acid (H<sub>4</sub>MTPTC). Topological analysis reveals that both Compounds <strong>1</strong> and <strong>2</strong> possess novel 3,3,4-c connected topologies with vertex symbols [6.8<sup>2</sup>][6<sup>2</sup>.8<sup>3</sup>.10][6<sup>2</sup>.8]. It is considered that the d<sup>10</sup> Cd(II)-based MOF shows a better response in the field of nitroaromatic explosive sensing compared with the d<sup>5</sup> Mn-based MOF, which may possess lower electron density on the conjugated building blocks. Fluorescence sensing experiments for metal cations, nitroaromatic explosives (NAEs), and sulfonamide antibiotics (SAs) show that Compound <strong>1</strong> exhibits excellent detection capabilities and recyclability for Fe<sup>3+</sup>, 4-nitrophenol (4-NP), and sulfadiazine (SDZ). The <em>K</em><sub>sv</sub> values (quenching constant) of Compound <strong>1</strong> for Fe<sup>3+</sup>, 4-NP, and SDZ are 1.30 × 10<sup>5</sup> M<sup>−1</sup>, 4.10 × 10<sup>5</sup> M<sup>−1</sup>, and 1.36 × 10<sup>5</sup> M<sup>−1</sup>. Compound <strong>1</strong> prove to be ideal fluorescence sensing materials for the detection of metal cations, NAEs, and SAs.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"348 ","pages":"Article 125366"},"PeriodicalIF":3.2,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143808650","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}