Spin crossover complexes represent a fascinating class of molecular materials with potential applications in diverse fields ranging from information storage to molecular electronics. Here using density functional theory, we investigate the properties of the binuclear spin crossover complex Fe()(4phpy)(m-bpypz), which presents the intriguing property that the two step magnetic transition occurs through an intermediate state made of low spin or high spin chains, as seen experimentally. We observe that the different magnetic configurations can be reproduced by our calculations, and that irons ions are coupled antiferromagnetically. This complex transition is further elucidated through nudged elastic band calculations and observation of the magnetization density, and opens the path towards more studies of polynuclear spin crossover complexes.
{"title":"Exploring the two step spin transition of Fe(NCBH3)(4phpy)2(m-bpypz)2 with ab initio calculations","authors":"Koussai Lazaar , Fatma Aouaini , Fatemah H. Alkallas , Haifa Alyousef , Saber Gueddida","doi":"10.1016/j.jssc.2024.125167","DOIUrl":"10.1016/j.jssc.2024.125167","url":null,"abstract":"<div><div>Spin crossover complexes represent a fascinating class of molecular materials with potential applications in diverse fields ranging from information storage to molecular electronics. Here using density functional theory, we investigate the properties of the binuclear spin crossover complex Fe(<span><math><msub><mrow><mtext>NCBH</mtext></mrow><mrow><mn>3</mn></mrow></msub></math></span>)(4phpy)<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>(m-bpypz)<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>, which presents the intriguing property that the two step magnetic transition occurs through an intermediate state made of low spin or high spin chains, as seen experimentally. We observe that the different magnetic configurations can be reproduced by our calculations, and that irons ions are coupled antiferromagnetically. This complex transition is further elucidated through nudged elastic band calculations and observation of the magnetization density, and opens the path towards more studies of polynuclear spin crossover complexes.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"344 ","pages":"Article 125167"},"PeriodicalIF":3.2,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143142684","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 : 2024-12-28DOI: 10.1016/j.jssc.2024.125168
Le Chen, An Xie, Nan Zhang, Jianjun Yin, Qun Chen, Mingyang He, Zhihui Zhang
Zeolitic-Imidazolate Framework 8 (ZIF-8), a porous crystalline absorbent, could be synthesized from the coordination reaction of zinc ions and 2-methylimidazole (2-mIM). ZIF-8 has a large specific surface area and a high adsorption capacity for n-hexane (nHEX). However, ZIF-8 suffers from low selectivity for both linear and mono-chain alkanes. Therefore, ZIF-8 was modified through 2-mIM ligand being partly replaced by 2-nitroimidazole (2-nIM) through Vapor-Phase post-synthesis modification. The modified materials were denoted as ZIF-8-2-nIM-X (X = 24h, 48h, 72h). ZIF-8-2-nIM-X has a higher specific surface area and better thermal stability than ZIF-8. Further thermodynamic and kinetic calculations show that the affinity of hexane isomers on ZIF-8-2-nIM-X is spontaneous physical adsorption combined with an exothermic process. In contrast, kinetic studies show that the adsorption of hexane isomers on ZIF-8-2-nIM-X is a pseudo-second-order kinetic model. The batch and dynamic adsorption and separation properties of ZIF-8-2-nIM-X for hexane isomers were studied. The results of the one-component vapor adsorption equilibrium experiment show that ZIF-8-2-nIM-72h has the best adsorption separation coefficient at 293 K. The adsorption capacity of nHEX and 3-methylpentane (3 MP) were 211.63 mg/g and 33.91 mg/g, respectively. Compared with ZIF-8 (selectivity coefficient: 1.08), the adsorption selectivity coefficient of the modified material is greatly improved. The adsorption selectivity coefficient of nHEX/3 MP is 6.24 (ZIF-8-2-nIM-72h).
{"title":"The effective adsorption separation of n-hexane/3-methylpentane by vapor-phase linker exchange of Zeolitic-imidazolate framework ZIF-8","authors":"Le Chen, An Xie, Nan Zhang, Jianjun Yin, Qun Chen, Mingyang He, Zhihui Zhang","doi":"10.1016/j.jssc.2024.125168","DOIUrl":"10.1016/j.jssc.2024.125168","url":null,"abstract":"<div><div>Zeolitic-Imidazolate Framework 8 (ZIF-8), a porous crystalline absorbent, could be synthesized from the coordination reaction of zinc ions and 2-methylimidazole (2-mIM). ZIF-8 has a large specific surface area and a high adsorption capacity for <em>n</em>-hexane (<em>n</em>HEX). However, ZIF-8 suffers from low selectivity for both linear and mono-chain alkanes. Therefore, ZIF-8 was modified through 2-mIM ligand being partly replaced by 2-nitroimidazole (2-nIM) through Vapor-Phase post-synthesis modification. The modified materials were denoted as ZIF-8-2-nIM-X (X = 24h, 48h, 72h). ZIF-8-2-nIM-X has a higher specific surface area and better thermal stability than ZIF-8. Further thermodynamic and kinetic calculations show that the affinity of hexane isomers on ZIF-8-2-nIM-X is spontaneous physical adsorption combined with an exothermic process. In contrast, kinetic studies show that the adsorption of hexane isomers on ZIF-8-2-nIM-X is a pseudo-second-order kinetic model. The batch and dynamic adsorption and separation properties of ZIF-8-2-nIM-X for hexane isomers were studied. The results of the one-component vapor adsorption equilibrium experiment show that ZIF-8-2-nIM-72h has the best adsorption separation coefficient at 293 K. The adsorption capacity of <em>n</em>HEX and 3-methylpentane (3 MP) were 211.63 mg/g and 33.91 mg/g, respectively. Compared with ZIF-8 (selectivity coefficient: 1.08), the adsorption selectivity coefficient of the modified material is greatly improved. The adsorption selectivity coefficient of <em>n</em>HEX/3 MP is 6.24 (ZIF-8-2-nIM-72h).</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"343 ","pages":"Article 125168"},"PeriodicalIF":3.2,"publicationDate":"2024-12-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143149995","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 : 2024-12-27DOI: 10.1016/j.jssc.2024.125164
Zhen Yang, Chang-Qing Lin, Chun-Yang Pan
In this study, Rb ion and Cl ion co-doping were employed to prepare Rb0.5Cs0.5PbCl1.5Br1.5 QDs, achieving high PLQY with deep blue emission. The doping of A-site cation Rb+ induces distortion of [PbX6]4- octahedra, leading to a more stable crystal structure, suppressing defect formation, and enhancing resistance to external environments. Simultaneously, Cl− doping at the halogen site allows for tuning of the emission spectrum, resulting in deep blue emission at ∼460 nm. The final blue quantum dots (Rb0.5Cs0.5PbCl1.5Br1.5 QDs) exhibit a PLQY of 61.90 %, a significant improvement compared to the undoped CsPbCl1.5Br1.5 QDs (27.12 %). By encapsulating QDs with hydrophobic polymer PCL, this encapsulation process isolates the QDs from the surrounding environment, significantly enhancing their stability. After placing Rb0.5Cs0.5PbCl1.5Br1.5/PCL in water for a period of time, the PL intensity remains almost unchanged. These quantum dots were then coated onto a commercial 365 nm GaN LED chip to create a blue LED, with color coordinates of (0.1428, 0.0522). The strategy proposed in this paper holds great promise for various potential applications in blue LEDs and backlight displays.
{"title":"Rb and Cl co-doped CsPbBr3 QDs for bright blue light emitting diode","authors":"Zhen Yang, Chang-Qing Lin, Chun-Yang Pan","doi":"10.1016/j.jssc.2024.125164","DOIUrl":"10.1016/j.jssc.2024.125164","url":null,"abstract":"<div><div>In this study, Rb ion and Cl ion co-doping were employed to prepare Rb<sub>0.5</sub>Cs<sub>0.5</sub>PbCl<sub>1.5</sub>Br<sub>1.5</sub> QDs, achieving high PLQY with deep blue emission. The doping of A-site cation Rb<sup>+</sup> induces distortion of [PbX<sub>6</sub>]<sup>4-</sup> octahedra, leading to a more stable crystal structure, suppressing defect formation, and enhancing resistance to external environments. Simultaneously, Cl<sup>−</sup> doping at the halogen site allows for tuning of the emission spectrum, resulting in deep blue emission at ∼460 nm. The final blue quantum dots (Rb<sub>0.5</sub>Cs<sub>0.5</sub>PbCl<sub>1.5</sub>Br<sub>1.5</sub> QDs) exhibit a PLQY of 61.90 %, a significant improvement compared to the undoped CsPbCl<sub>1.5</sub>Br<sub>1.5</sub> QDs (27.12 %). By encapsulating QDs with hydrophobic polymer PCL, this encapsulation process isolates the QDs from the surrounding environment, significantly enhancing their stability. After placing Rb<sub>0.5</sub>Cs<sub>0.5</sub>PbCl<sub>1.5</sub>Br<sub>1.5</sub>/PCL in water for a period of time, the PL intensity remains almost unchanged. These quantum dots were then coated onto a commercial 365 nm GaN LED chip to create a blue LED, with color coordinates of (0.1428, 0.0522). The strategy proposed in this paper holds great promise for various potential applications in blue LEDs and backlight displays.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"343 ","pages":"Article 125164"},"PeriodicalIF":3.2,"publicationDate":"2024-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143098257","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 : 2024-12-26DOI: 10.1016/j.jssc.2024.125172
Petr S. Sokolov , Andrey N. Baranov , Evgeny P. Skipetrov , Vladimir L. Solozhenko
Metastable cubic Fe1-xZnxO solid solutions (0 < x ≤ 0.5) with a rock salt structure (Fm-3m) have been synthesized by a solid-phase reaction between wurtzite ZnO and cubic FeO at 7.7 GPa and 1500 K. The magnetic and transport properties of these solid solutions were studied at ambient pressure over the temperature range of 4.2–300 K, and the presence of antiferromagnetic order has been revealed with a decrease of the Néel temperature from 112 K for Fe0.7Zn0.3O down to 45 K for Fe0.5Zn0.5O. Synthesized rock salt Fe1-xZnxO solid solutions exhibit semiconducting behavior with low electrical resistivity (at 300 K, from 0.37 Ohm∙cm for x = 0 to 28 Ohm∙cm for x = 0.5) and p-type conductivity due to the presence of a deep defect level with an activation energy of 105–144 meV located above the top of the valence band.
{"title":"Magnetic and transport properties of cubic Fe1-xZnxO solid solutions with a rock salt structure synthesized at high pressure","authors":"Petr S. Sokolov , Andrey N. Baranov , Evgeny P. Skipetrov , Vladimir L. Solozhenko","doi":"10.1016/j.jssc.2024.125172","DOIUrl":"10.1016/j.jssc.2024.125172","url":null,"abstract":"<div><div>Metastable cubic Fe<sub>1-x</sub>Zn<sub>x</sub>O solid solutions (0 < x ≤ 0.5) with a rock salt structure (<em>Fm</em>-3<em>m</em>) have been synthesized by a solid-phase reaction between wurtzite ZnO and cubic FeO at 7.7 GPa and 1500 K. The magnetic and transport properties of these solid solutions were studied at ambient pressure over the temperature range of 4.2–300 K, and the presence of antiferromagnetic order has been revealed with a decrease of the Néel temperature from 112 K for Fe<sub>0.7</sub>Zn<sub>0.3</sub>O down to 45 K for Fe<sub>0.5</sub>Zn<sub>0.5</sub>O. Synthesized rock salt Fe<sub>1-x</sub>Zn<sub>x</sub>O solid solutions exhibit semiconducting behavior with low electrical resistivity (at 300 K, from 0.37 Ohm∙cm for x = 0 to 28 Ohm∙cm for x = 0.5) and p-type conductivity due to the presence of a deep defect level with an activation energy of 105–144 meV located above the top of the valence band.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"343 ","pages":"Article 125172"},"PeriodicalIF":3.2,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143149991","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 : 2024-12-26DOI: 10.1016/j.jssc.2024.125166
Y.L. Leibas , M. Bakhtbidar , A. Kharade , S. Obernberger , A. Tejeda-Cruz , G. Santana , A. Hernandez-Garcia , L. Hamui , J.R. Aguilar-Hernández , G. Contreras-Puente , A. Ruediger , O. de Melo
This study presents the deposition of a Mo5O14/MoO3 composite onto the surface of a pre-grown MoO2 film by exposing the MoO2 surface to MoO3 vapours under low vacuum. Significant surface selectivity was observed, with the formation of a Mo5O14/MoO3 composite occurring exclusively on the MoO2 surface. In contrast, pure MoO3 was deposited directly onto the uncovered part of the used SiO2/Si substrate. The formation of the composite was revealed by X-ray diffraction, Raman spectra, and Energy Dispersive Spectroscopy. The selective deposition of the composite is attributed to the solid-state reaction between MoO3 and MoO2 at their interface, which is facilitated by the porous structure of the MoO2 film (as confirmed by scanning electron microscopy). Thermodynamic considerations support this reaction mechanism and predict the temperature range in which the reaction can occur.
{"title":"Selective deposition of Mo5O14/MoO3 composite onto MoO2 surfaces induced by MoO3/MoO2 interfacial reaction","authors":"Y.L. Leibas , M. Bakhtbidar , A. Kharade , S. Obernberger , A. Tejeda-Cruz , G. Santana , A. Hernandez-Garcia , L. Hamui , J.R. Aguilar-Hernández , G. Contreras-Puente , A. Ruediger , O. de Melo","doi":"10.1016/j.jssc.2024.125166","DOIUrl":"10.1016/j.jssc.2024.125166","url":null,"abstract":"<div><div>This study presents the deposition of a Mo<sub>5</sub>O<sub>14</sub>/MoO<sub>3</sub> composite onto the surface of a pre-grown MoO<sub>2</sub> film by exposing the MoO<sub>2</sub> surface to MoO<sub>3</sub> vapours under low vacuum. Significant surface selectivity was observed, with the formation of a Mo<sub>5</sub>O<sub>14</sub>/MoO<sub>3</sub> composite occurring exclusively on the MoO<sub>2</sub> surface. In contrast, pure MoO<sub>3</sub> was deposited directly onto the uncovered part of the used SiO<sub>2</sub>/Si substrate. The formation of the composite was revealed by X-ray diffraction, Raman spectra, and Energy Dispersive Spectroscopy. The selective deposition of the composite is attributed to the solid-state reaction between MoO<sub>3</sub> and MoO<sub>2</sub> at their interface, which is facilitated by the porous structure of the MoO<sub>2</sub> film (as confirmed by scanning electron microscopy). Thermodynamic considerations support this reaction mechanism and predict the temperature range in which the reaction can occur.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"343 ","pages":"Article 125166"},"PeriodicalIF":3.2,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143149994","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 : 2024-12-25DOI: 10.1016/j.jssc.2024.125170
Cyrille Galven, Marie-Pierre Crosnier-Lopez, Françoise Le Berre
A new tellurate Li2TeO4 (Li2TeO4-LT) was synthesized via a conventional solid-state route from specific precursors, LiOH.H2O and H6TeO6. The cell, initially identified as tetragonal from X-ray powder diffraction at room temperature, was finally found to be orthorhombic thanks to thermal X-ray powder diffraction. The space group, Pbcn, was determined with the help of electron diffraction while the structure was obtained from neutron powder diffraction (a = 5.0106(3), b = 11.5369(8) and c = 5.0057(4) Å. As the tellurate β-Na2TeO4, its structure is built from TeO6 octahedra sharing edges forming thus infinite chains [TeO4]n2n− parallel to the c axis. These chains are separated from each other by Li+ ions in octahedral coordination. Contrary to β-Na2TeO4, Li2TeO4-LT does not capture CO2 and presents a modest ionic conduction (300 °C, T = 1.8 10−8 S cm−1), lower than the tetragonal Li2TeO4 variety (300 °C, ≈10−6 S.cm-1). In addition, a complete solid solution Na2-xLixTeO4 was evidenced.
{"title":"Li2TeO4: Structural characterization and ionic conductivity measurements of a new tellurate","authors":"Cyrille Galven, Marie-Pierre Crosnier-Lopez, Françoise Le Berre","doi":"10.1016/j.jssc.2024.125170","DOIUrl":"10.1016/j.jssc.2024.125170","url":null,"abstract":"<div><div>A new tellurate Li<sub>2</sub>TeO<sub>4</sub> (Li<sub>2</sub>TeO<sub>4</sub>-LT) was synthesized via a conventional solid-state route from specific precursors, LiOH.H<sub>2</sub>O and H<sub>6</sub>TeO<sub>6</sub>. The cell, initially identified as tetragonal from X-ray powder diffraction at room temperature, was finally found to be orthorhombic thanks to thermal X-ray powder diffraction. The space group, <em>Pbcn</em>, was determined with the help of electron diffraction while the structure was obtained from neutron powder diffraction (a = 5.0106(3), b = 11.5369(8) and c = 5.0057(4) Å. As the tellurate β-Na<sub>2</sub>TeO<sub>4</sub>, its structure is built from TeO<sub>6</sub> octahedra sharing edges forming thus infinite chains [TeO<sub>4</sub>]<sub>n</sub><sup>2n−</sup> parallel to the <em>c</em> axis. These chains are separated from each other by Li<sup>+</sup> ions in octahedral coordination. Contrary to β-Na<sub>2</sub>TeO<sub>4</sub><sup>,</sup> Li<sub>2</sub>TeO<sub>4</sub>-LT does not capture CO<sub>2</sub> and presents a modest ionic conduction (300 °C, T = 1.8 10<sup>−8</sup> S cm<sup>−1</sup>), lower than the tetragonal Li<sub>2</sub>TeO<sub>4</sub> variety (300 °C, ≈10<sup>−6</sup> S.cm-<sup>1</sup>). In addition, a complete solid solution Na<sub>2-x</sub>Li<sub>x</sub>TeO<sub>4</sub> was evidenced.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"344 ","pages":"Article 125170"},"PeriodicalIF":3.2,"publicationDate":"2024-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143142791","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-12-25DOI: 10.1016/j.jssc.2024.125171
Xiaochen Zhang , Yu Wang , Tao Bo , Lei Zhang
Single crystals of three new uranyl silicates were grown from mixed alkali fluoride fluxes. Cs1.8K0.2[(UO2)(Si2O6)] crystallizes in the space group C2/c and lattice parameters a = 21.5486(11) Å, b = 15.1071(8) Å, c = 14.8947(14) Å, and β = 129.267(2), which is isostructural to the known α-Cs2[(UO2)(Si2O6)] phase. The new framework K4Sr[(UO2)(Si4O12)] is compared with the related K4SrU3O12, and crystallizes in the tetragonal space group P—4n2 with lattice parameters a = 9.3808(3) Å, b = 9.3808(3) Å, c = 8.5234(4) Å. A new salt-inclusion material (SIMs) [Cs2KF][(UO2)(Si4O10)] is compared and discussed with previously reported SIM [Cs3F][(UO2)(Si4O10)], which crystallizes in the space group I2/c and lattice parameters a = 7.5400(3) Å, b = 12.6143(7) Å, c = 14.9686(8) Å, and β = 93.032(3)°. The Raman spectra of these phases were collected, and bands were assigned according to the existing oxo-silicate and oxo-uranium units. The formation enthalpy, lattice energy and band gap of the salt-inclusion materials were calculated by density functional theory to provide more structural information.
{"title":"Three uranyl silicate framework structures, Cs1.8K0.2[(UO2)(Si2O6)], K4Sr[(UO2)(Si4O12)], and [Cs2KF][(UO2)(Si4O10)], and theoretical calculation of density functional theory for salt-inclusion material","authors":"Xiaochen Zhang , Yu Wang , Tao Bo , Lei Zhang","doi":"10.1016/j.jssc.2024.125171","DOIUrl":"10.1016/j.jssc.2024.125171","url":null,"abstract":"<div><div>Single crystals of three new uranyl silicates were grown from mixed alkali fluoride fluxes. Cs<sub>1.8</sub>K<sub>0.2</sub>[(UO<sub>2</sub>)(Si<sub>2</sub>O<sub>6</sub>)] crystallizes in the space group C2/c and lattice parameters <em>a</em> = 21.5486(11) Å, <em>b</em> = 15.1071(8) Å, <em>c</em> = 14.8947(14) Å, and <em>β</em> = 129.267(2), which is isostructural to the known α-Cs<sub>2</sub>[(UO<sub>2</sub>)(Si<sub>2</sub>O<sub>6</sub>)] phase. The new framework K<sub>4</sub>Sr[(UO<sub>2</sub>)(Si<sub>4</sub>O<sub>12</sub>)] is compared with the related K<sub>4</sub>SrU<sub>3</sub>O<sub>12</sub>, and crystallizes in the tetragonal space group <em>P</em>—4n2 with lattice parameters <em>a</em> = 9.3808(3) Å, <em>b</em> = 9.3808(3) Å, <em>c</em> = 8.5234(4) Å. A new salt-inclusion material (SIMs) [Cs<sub>2</sub>KF][(UO<sub>2</sub>)(Si<sub>4</sub>O<sub>10</sub>)] is compared and discussed with previously reported SIM [Cs<sub>3</sub>F][(UO<sub>2</sub>)(Si<sub>4</sub>O<sub>10</sub>)], which crystallizes in the space group I2/c and lattice parameters <em>a</em> = 7.5400(3) Å, <em>b</em> = 12.6143(7) Å, <em>c</em> = 14.9686(8) Å, and <em>β</em> = 93.032(3)°. The Raman spectra of these phases were collected, and bands were assigned according to the existing oxo-silicate and oxo-uranium units. The formation enthalpy, lattice energy and band gap of the salt-inclusion materials were calculated by density functional theory to provide more structural information.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"343 ","pages":"Article 125171"},"PeriodicalIF":3.2,"publicationDate":"2024-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143097790","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 : 2024-12-24DOI: 10.1016/j.jssc.2024.125169
Laraib Kiran , Muhammad Hammad Ijaz , Zaki I. Zaki , Mohamed E. Khalifa , Zunaira Shafiq , Zeeshan Zubair , Nimra Sultan , Muhammad Ramzan Saeed Ashraf Janjua
The optimization of dyes with high dielectric constant is crucial to perform superior functions in communication electronics, solar cells, and battery technologies. Generally, the approaches to synthesizes compounds require significant time and effort, underlining the importance of computing tools that would help to save time. In this work, machine learning models are used to estimate dielectric constant. Random Forest is best model. yielding the least RMSE of 0.592 and highest R2 of 0.676. Descriptors such as SMR_VSA10 were found from the correlation analysis to be very important. Ten thousand new dye structures were designed and dielectric constants of these dyes were predicted by the Random Forest regressor. Chemical space is visualized through clustering. The results presented here highlight how machine learning methods can be applied in the context of dye chemistry to minimize the time spent conducting experiments and to improve dye synthesis rates.
{"title":"Data driven design of dyes with high dielectric constant for efficient optoelectronics","authors":"Laraib Kiran , Muhammad Hammad Ijaz , Zaki I. Zaki , Mohamed E. Khalifa , Zunaira Shafiq , Zeeshan Zubair , Nimra Sultan , Muhammad Ramzan Saeed Ashraf Janjua","doi":"10.1016/j.jssc.2024.125169","DOIUrl":"10.1016/j.jssc.2024.125169","url":null,"abstract":"<div><div>The optimization of dyes with high dielectric constant is crucial to perform superior functions in communication electronics, solar cells, and battery technologies. Generally, the approaches to synthesizes compounds require significant time and effort, underlining the importance of computing tools that would help to save time. In this work, machine learning models are used to estimate dielectric constant. Random Forest is best model. yielding the least RMSE of 0.592 and highest R<sup>2</sup> of 0.676. Descriptors such as SMR_VSA10 were found from the correlation analysis to be very important. Ten thousand new dye structures were designed and dielectric constants of these dyes were predicted by the Random Forest regressor. Chemical space is visualized through clustering. The results presented here highlight how machine learning methods can be applied in the context of dye chemistry to minimize the time spent conducting experiments and to improve dye synthesis rates.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"343 ","pages":"Article 125169"},"PeriodicalIF":3.2,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143149993","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 : 2024-12-20DOI: 10.1016/j.jssc.2024.125165
Long Han, Yankun Chen, Wenhuai Tian
ZnS:Cu, Al phosphor (P22) has garnered significant attention owing to its unique green light emission properties. Enhancing the luminescence intensity of P22 phosphor can broaden its application in optoelectronic fields, including LEDs and low-light-level image intensifiers. In this study, we employed the solid-phase sintering method to synthesize high-performance P22 phosphors by optimizing the types and ratios of doping salts. Subsequently, we improved the luminescence performance of the phosphors through an acid washing process. We analyzed the effects of doping with halogenated elements on the luminescence and emission peak shape by examining the impact of various doping salt types on the luminescence performance. The spectral analysis revealed that, while doping with halogenated elements augmented the luminescence intensity of the phosphor, its emission peaks exhibited hump characteristics. Furthermore, different doping ratios of Cu–Al could effectively adjust the luminescence intensity without shifting the position of the emission peaks. Additionally, we observed that during sintering, the Zn element in the interstitial position failed to migrate to the grain boundary to combine with the S element in the lattice, leading to a transformation from the cubic phase to the hexagonal phase at a lower temperature. Further results from the acid washing process indicated that the luminescence performance could be substantially enhanced. However, the use of dilute nitric acid also reacted with Cu, resulting in a decrease in the concentration of luminescent centers. Utilizing sieving technology for ultrafine powders can further enhance the luminescence intensity.
{"title":"Preparation and performance study of high-performance ZnS:Cu, Al phosphor","authors":"Long Han, Yankun Chen, Wenhuai Tian","doi":"10.1016/j.jssc.2024.125165","DOIUrl":"10.1016/j.jssc.2024.125165","url":null,"abstract":"<div><div>ZnS:Cu, Al phosphor (P22) has garnered significant attention owing to its unique green light emission properties. Enhancing the luminescence intensity of P22 phosphor can broaden its application in optoelectronic fields, including LEDs and low-light-level image intensifiers. In this study, we employed the solid-phase sintering method to synthesize high-performance P22 phosphors by optimizing the types and ratios of doping salts. Subsequently, we improved the luminescence performance of the phosphors through an acid washing process. We analyzed the effects of doping with halogenated elements on the luminescence and emission peak shape by examining the impact of various doping salt types on the luminescence performance. The spectral analysis revealed that, while doping with halogenated elements augmented the luminescence intensity of the phosphor, its emission peaks exhibited hump characteristics. Furthermore, different doping ratios of Cu–Al could effectively adjust the luminescence intensity without shifting the position of the emission peaks. Additionally, we observed that during sintering, the Zn element in the interstitial position failed to migrate to the grain boundary to combine with the S element in the lattice, leading to a transformation from the cubic phase to the hexagonal phase at a lower temperature. Further results from the acid washing process indicated that the luminescence performance could be substantially enhanced. However, the use of dilute nitric acid also reacted with Cu, resulting in a decrease in the concentration of luminescent centers. Utilizing sieving technology for ultrafine powders can further enhance the luminescence intensity.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"343 ","pages":"Article 125165"},"PeriodicalIF":3.2,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143098258","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 : 2024-12-19DOI: 10.1016/j.jssc.2024.125163
Y.O. Villafañe-Bautista, Ch J. Salas-Juárez, J. Guzmán-Mendoza, I. Garduño-Wilches, T. Rivera-Montalvo
We report the structural and thermoluminescent (TL) properties of Li₂B₄O₇ phosphor synthesized by a solid-state reaction method for radiation dosimetry. The Li₂B₄O₇ was characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) to determine the crystalline structure and morphology. The Li₂B₄O₇ samples were exposed to beta particle irradiation in a dose range from 1 to 1024 Gy. The TL glow curve showed three emission maxima at ∼ 123, 191 and 290 °C. The TL signal increased with increasing dose, with a linear dependence from 1 to 64 Gy. Remarkable reproducibility of the integrated TL response in 10 irradiation cycles was observed for the TL maximum at 191 °C, suggesting that Li₂B₄O₇ samples are reusable, especially for the dosimetric TL peak. The Tm-Tstop and computerized glow curve deconvolution (CGCD) showed that the TL glow curve of Li₂B₄O₇ consists of seven TL peaks, with five peaks showing a first-order trend (peaks 1, 2, 3, 5 and 6) and two peaks showing a second-order trend (peaks 4 and 7). The mass attenuation and energy absorption coefficients show that Li₂B₄O₇ exhibits similar behavior to human tissue when indirectly exposed to ionizing radiation. Li₂B₄O₇ exhibits a wide linearity range and a reliable response to high doses, positioning it as an optimal dosimeter for dosimetric applications where the dosimetric range of commercial dosimeters, such as the TLD-100, has limitations. This novelty is particularly important as Li₂B₄O₇ has an effective atomic number equivalent to that of human tissue. These results suggest that Li₂B₄O₇ phosphor is a promising candidate for clinical dosimetry applications such as radiotherapy and brachytherapy.
{"title":"Li2B4O7 phosphor for beta particle dosimetry: Synthesis, structural and thermoluminescence performance","authors":"Y.O. Villafañe-Bautista, Ch J. Salas-Juárez, J. Guzmán-Mendoza, I. Garduño-Wilches, T. Rivera-Montalvo","doi":"10.1016/j.jssc.2024.125163","DOIUrl":"10.1016/j.jssc.2024.125163","url":null,"abstract":"<div><div>We report the structural and thermoluminescent (TL) properties of Li₂B₄O₇ phosphor synthesized by a solid-state reaction method for radiation dosimetry. The Li₂B₄O₇ was characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) to determine the crystalline structure and morphology. The Li₂B₄O₇ samples were exposed to beta particle irradiation in a dose range from 1 to 1024 Gy. The TL glow curve showed three emission maxima at ∼ 123, 191 and 290 °C. The TL signal increased with increasing dose, with a linear dependence from 1 to 64 Gy. Remarkable reproducibility of the integrated TL response in 10 irradiation cycles was observed for the TL maximum at 191 °C, suggesting that Li₂B₄O₇ samples are reusable, especially for the dosimetric TL peak. The T<sub>m</sub>-T<sub>stop</sub> and computerized glow curve deconvolution (CGCD) showed that the TL glow curve of Li₂B₄O₇ consists of seven TL peaks, with five peaks showing a first-order trend (peaks 1, 2, 3, 5 and 6) and two peaks showing a second-order trend (peaks 4 and 7). The mass attenuation and energy absorption coefficients show that Li₂B₄O₇ exhibits similar behavior to human tissue when indirectly exposed to ionizing radiation. Li₂B₄O₇ exhibits a wide linearity range and a reliable response to high doses, positioning it as an optimal dosimeter for dosimetric applications where the dosimetric range of commercial dosimeters, such as the TLD-100, has limitations. This novelty is particularly important as Li₂B₄O₇ has an effective atomic number equivalent to that of human tissue. These results suggest that Li₂B₄O₇ phosphor is a promising candidate for clinical dosimetry applications such as radiotherapy and brachytherapy.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"343 ","pages":"Article 125163"},"PeriodicalIF":3.2,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143149431","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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