This study presents a machine learning-assisted approach for the designing of conjugated organic chromophores. 10 machine learning models are trained to predict exciton binding energy, random forest has appeared as best model (R-squared = 0.723). A database of new chromophores is generated and exciton binding energy of chromophores is predicted. 30 organic chromophores with low exciton binding energy values are identified. Clustering and chemical similarity analyses, based on chemical fingerprints, are conducted on the selected chromophores. Additionally, the synthetic accessibility scores of the newly designed chromophores are evaluated. This approach enables rapid screening of organic chromophores for use in organic solar cells. The proposed framework provides a strategic and efficient pathway for discovering optimal materials for organic solar cell applications.
{"title":"Data-driven designing of conjugated organic chromophores: Chemical space generation and property prediction","authors":"Numan Khan , Mahmoud A.A. Ibrahim , Shaban R.M. Sayed , Rashid Iqbal","doi":"10.1016/j.jssc.2025.125201","DOIUrl":"10.1016/j.jssc.2025.125201","url":null,"abstract":"<div><div>This study presents a machine learning-assisted approach for the designing of conjugated organic chromophores. 10 machine learning models are trained to predict exciton binding energy, random forest has appeared as best model (R-squared = 0.723). A database of new chromophores is generated and exciton binding energy of chromophores is predicted. 30 organic chromophores with low exciton binding energy values are identified. Clustering and chemical similarity analyses, based on chemical fingerprints, are conducted on the selected chromophores. Additionally, the synthetic accessibility scores of the newly designed chromophores are evaluated. This approach enables rapid screening of organic chromophores for use in organic solar cells. The proposed framework provides a strategic and efficient pathway for discovering optimal materials for organic solar cell applications.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"344 ","pages":"Article 125201"},"PeriodicalIF":3.2,"publicationDate":"2025-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143142325","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 : 2025-01-10DOI: 10.1016/j.jssc.2025.125193
Yingxia Ma , Miaoshi Li , Tianze Li , Haijun Yang , Ruilin Zhang , Xiaofei Ye , Wenli Meng , Xiaojun Chai , Cuixia Li
Industrial wastewater containing heavy metal Ag(I) causes irreversible harm to human health through food chain, necessitating effective removal methods. According to hard-soft acids-bases (HSAB) theory, nitrogen (N) and sulfur (S) functional groups form stable chelates with Ag(I). In this study, 2-amino-5-sulfanyl-1,3,4-thiadiazole (AST) with three N and two S groups served as organic ligand, and zinc nitrate hexahydrate provided metal center, novel amorphous metal-organic framework (Zn-AST) rich in N and S groups was synthesized via a one-pot solvothermal method. Batch experiments assessed the Zn-AST adsorption properties for Ag(I) in aqueous solutions. In addition, density-functional theory, frontier orbital theory, and molecular electrostatic surface potential analyses were used to elucidate the synthesis and adsorption mechanisms. The maximum adsorption capacity of Zn-AST for Ag(I) was 2932.91 mg/g. The Zn-AST exhibited good selectivity in the presence of Cu(II), Co(II), Ni(II), and Pb(II) ions, the removal rate for Ag(I) was 98.28 %, which was far higher than the values of other ions (all less than 10 %). The main adsorption mechanisms of Ag(I) by the Zn-AST involved electrostatic interactions, the formation of Ag–S bonds, and chelation between Ag and nitrogen functional groups. This study offers a viable strategy for developing unique adsorbents for Ag(I) removal from wastewater.
{"title":"Synthesis of a novel amorphous metal-organic framework containing rich N and S groups for efficient adsorption of Ag(I) in aqueous solutions","authors":"Yingxia Ma , Miaoshi Li , Tianze Li , Haijun Yang , Ruilin Zhang , Xiaofei Ye , Wenli Meng , Xiaojun Chai , Cuixia Li","doi":"10.1016/j.jssc.2025.125193","DOIUrl":"10.1016/j.jssc.2025.125193","url":null,"abstract":"<div><div>Industrial wastewater containing heavy metal Ag(I) causes irreversible harm to human health through food chain, necessitating effective removal methods. According to hard-soft acids-bases (HSAB) theory, nitrogen (N) and sulfur (S) functional groups form stable chelates with Ag(I). In this study, 2-amino-5-sulfanyl-1,3,4-thiadiazole (AST) with three N and two S groups served as organic ligand, and zinc nitrate hexahydrate provided metal center, novel amorphous metal-organic framework (Zn-AST) rich in N and S groups was synthesized via a one-pot solvothermal method. Batch experiments assessed the Zn-AST adsorption properties for Ag(I) in aqueous solutions. In addition, density-functional theory, frontier orbital theory, and molecular electrostatic surface potential analyses were used to elucidate the synthesis and adsorption mechanisms. The maximum adsorption capacity of Zn-AST for Ag(I) was 2932.91 mg/g. The Zn-AST exhibited good selectivity in the presence of Cu(II), Co(II), Ni(II), and Pb(II) ions, the removal rate for Ag(I) was 98.28 %, which was far higher than the values of other ions (all less than 10 %). The main adsorption mechanisms of Ag(I) by the Zn-AST involved electrostatic interactions, the formation of Ag–S bonds, and chelation between Ag and nitrogen functional groups. This study offers a viable strategy for developing unique adsorbents for Ag(I) removal from wastewater.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"344 ","pages":"Article 125193"},"PeriodicalIF":3.2,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143142320","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 : 2025-01-10DOI: 10.1016/j.jssc.2025.125200
Luyu Wang , Jia Song , Chunyang Yu
Cadaverine, a compound produced during biological decomposition, possesses a degree of acute toxicity to humans and poses risks to aquatic life. As the need for cadaverine detection intensifies, quartz crystal microbalance (QCM) technology stands out due to its exceptional sensitivity and consistent performance. In this research, we synthesized sulfonic acid-functionalized UIO-66 (UIO-66-SO3H) octahedrons employing a solvothermal approach. These UIO-66-SO3H octahedrons served as the sensing element in a QCM sensor specifically designed for detecting cadaverine in water. Notably, the sensor demonstrated the ability to detect cadaverine at a concentration of 1 part per billion (ppb), with a frequency shift of approximately 48 Hz within 300 s. Furthermore, we conducted a comprehensive analysis of the sensor's continuous response, selectivity, and resistance to interference. Our findings suggest that this cadaverine detection method is swift, economical, and potentially adaptable to diverse water pollution inspection scenarios resulting from biological decomposition.
{"title":"Sulfonic functionalized UIO-66 octahedrons for detecting ppb level cadaverine in water","authors":"Luyu Wang , Jia Song , Chunyang Yu","doi":"10.1016/j.jssc.2025.125200","DOIUrl":"10.1016/j.jssc.2025.125200","url":null,"abstract":"<div><div>Cadaverine, a compound produced during biological decomposition, possesses a degree of acute toxicity to humans and poses risks to aquatic life. As the need for cadaverine detection intensifies, quartz crystal microbalance (QCM) technology stands out due to its exceptional sensitivity and consistent performance. In this research, we synthesized sulfonic acid-functionalized UIO-66 (UIO-66-SO<sub>3</sub>H) octahedrons employing a solvothermal approach. These UIO-66-SO<sub>3</sub>H octahedrons served as the sensing element in a QCM sensor specifically designed for detecting cadaverine in water. Notably, the sensor demonstrated the ability to detect cadaverine at a concentration of 1 part per billion (ppb), with a frequency shift of approximately 48 Hz within 300 s. Furthermore, we conducted a comprehensive analysis of the sensor's continuous response, selectivity, and resistance to interference. Our findings suggest that this cadaverine detection method is swift, economical, and potentially adaptable to diverse water pollution inspection scenarios resulting from biological decomposition.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"344 ","pages":"Article 125200"},"PeriodicalIF":3.2,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143142323","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 : 2025-01-10DOI: 10.1016/j.jssc.2025.125202
Peixun Wang , Zilin Yu , Peicheng Mo , Jun Zhang , Yi Wu , Chao Chen
High-entropy ceramics (HECs) have gained significant attention in ceramics research due to their unique single-crystal structure, extensive composition range, and exceptional physicochemical properties. In this study, TiN0.3 with anionic vacancies was prepared using mechanical alloying, while high-entropy nitride ceramics (Ti0.25V0.25Cr0.25Nb0.25)N0.825 were synthesized using the Spark Plasma Sintering (SPS) process, utilizing TiN0.3 as a sintering aid. The microstructure and mechanical properties of the high-entropy nitride ceramics at different sintering temperatures were thoroughly investigated. The results indicate that (1) non-stoichiometric TiN0.3 was formed after 48 h of high-energy ball milling of Ti and TiN due to the concentration gradient, (2) single-phase Face-Centered Cubic (FCC) structured high-entropy nitride ceramics (Ti0.25V0.25Cr0.25Nb0.25)N0.825 were synthesized using TiN0.3 as a sintering accelerator, and (3) the maximum values of flexural strength (925 ± 46 MPa), hardness (16.88 ± 1.50 GPa), and fracture toughness (3.02 ± 0.15 MPa m1/2) of the high-entropy nitride ceramics (Ti0.25V0.25Cr0.25Nb0.25)N0.825 were achieved at a temperature of 1700 °C. This paper presents an innovative approach that combines vacancies with high-entropy ceramics, providing a novel synthetic pathway for high-entropy nitride ceramics. This new synthesis method opens up opportunities for exploring fresh directions in the research and application of ceramic materials, holding significant scientific importance and promising application prospects.
{"title":"The effect of N vacancy on the synthesis and properties of high-entropy nitride ceramics (Ti0.25V0.25Cr0.25Nb0.25)N0.825","authors":"Peixun Wang , Zilin Yu , Peicheng Mo , Jun Zhang , Yi Wu , Chao Chen","doi":"10.1016/j.jssc.2025.125202","DOIUrl":"10.1016/j.jssc.2025.125202","url":null,"abstract":"<div><div>High-entropy ceramics (HECs) have gained significant attention in ceramics research due to their unique single-crystal structure, extensive composition range, and exceptional physicochemical properties. In this study, TiN<sub>0.3</sub> with anionic vacancies was prepared using mechanical alloying, while high-entropy nitride ceramics (Ti<sub>0.25</sub>V<sub>0.25</sub>Cr<sub>0.25</sub>Nb<sub>0.25</sub>)N<sub>0.825</sub> were synthesized using the Spark Plasma Sintering (SPS) process, utilizing TiN<sub>0.3</sub> as a sintering aid. The microstructure and mechanical properties of the high-entropy nitride ceramics at different sintering temperatures were thoroughly investigated. The results indicate that (1) non-stoichiometric TiN<sub>0.3</sub> was formed after 48 h of high-energy ball milling of Ti and TiN due to the concentration gradient, (2) single-phase Face-Centered Cubic (FCC) structured high-entropy nitride ceramics (Ti<sub>0.25</sub>V<sub>0.25</sub>Cr<sub>0.25</sub>Nb<sub>0.25</sub>)N<sub>0.825</sub> were synthesized using TiN<sub>0.3</sub> as a sintering accelerator, and (3) the maximum values of flexural strength (925 ± 46 MPa), hardness (16.88 ± 1.50 GPa), and fracture toughness (3.02 ± 0.15 MPa m<sup>1/2</sup>) of the high-entropy nitride ceramics (Ti<sub>0.25</sub>V<sub>0.25</sub>Cr<sub>0.25</sub>Nb<sub>0.25</sub>)N<sub>0.825</sub> were achieved at a temperature of 1700 °C. This paper presents an innovative approach that combines vacancies with high-entropy ceramics, providing a novel synthetic pathway for high-entropy nitride ceramics. This new synthesis method opens up opportunities for exploring fresh directions in the research and application of ceramic materials, holding significant scientific importance and promising application prospects.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"344 ","pages":"Article 125202"},"PeriodicalIF":3.2,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143142321","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 : 2025-01-09DOI: 10.1016/j.jssc.2025.125198
Yinghao Lv , Jiaqi He , Yajie Yang , Meilin Huang , Dawei He , Yongsheng Wang
Supercapacitors are gaining traction in the energy storage sector due to their high power and energy density. MnO2 is identified as a promising supercapacitors electrode material due to its reversible Faraday reaction and great theoretical specific capacitance. However, its practical performance is hindered by poor electrical conductivity and structural instability. By incorporating Ti3C2Tx, a 2D MXene material known for its high conductivity and functional groups, the electrochemical behavior of the MnO2 composite is expected to be enhanced. This study introduces a novel method for synthesizing MnO2@Ti3C2Tx self-assembled electrodes (1, 3, 6, 9-MnO2@Ti3C2Tx composite electrodes) via a simple solution immersion technique at room temperature and ambient pressure. The state of manganese dioxide deposition can be influenced by varying the number of operations of the solution immersion technique. Among them, 6-MnO2@Ti3C2Tx has the largest specific surface area and achieves the best specific capacitance of 324.1 F g−1. When the current density is increased to 10 A g−1, the specific capacitance retention of 6-MnO2@Ti3C2Tx is 67.11 %. Furthermore, the 6-MnO2@Ti3C2Tx//Ti3C2Tx asymmetric capacitor demonstrated a maximum energy density of 30.8 W h kg−1 and a power density of 7493.3 W kg−1, maintaining a capacitance retention rate of 95.98 % (from 74.6 to 71.6F g−1) after 2000 charge-discharge cycles. This study presents an effective and scalable synthesis strategy for MnO2 composite electrodes, highlighting their potential for future energy storage applications.
{"title":"Facile synthesis of MnO2@Ti3C2Tx composite electrodes for superior performance supercapacitor","authors":"Yinghao Lv , Jiaqi He , Yajie Yang , Meilin Huang , Dawei He , Yongsheng Wang","doi":"10.1016/j.jssc.2025.125198","DOIUrl":"10.1016/j.jssc.2025.125198","url":null,"abstract":"<div><div>Supercapacitors are gaining traction in the energy storage sector due to their high power and energy density. MnO<sub>2</sub> is identified as a promising supercapacitors electrode material due to its reversible Faraday reaction and great theoretical specific capacitance. However, its practical performance is hindered by poor electrical conductivity and structural instability. By incorporating Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub>, a 2D MXene material known for its high conductivity and functional groups, the electrochemical behavior of the MnO<sub>2</sub> composite is expected to be enhanced. This study introduces a novel method for synthesizing MnO<sub>2</sub>@Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub> self-assembled electrodes (1, 3, 6, 9-MnO<sub>2</sub>@Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub> composite electrodes) via a simple solution immersion technique at room temperature and ambient pressure. The state of manganese dioxide deposition can be influenced by varying the number of operations of the solution immersion technique. Among them, 6-MnO<sub>2</sub>@Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub> has the largest specific surface area and achieves the best specific capacitance of 324.1 F g<sup>−1</sup>. When the current density is increased to 10 A g<sup>−1</sup>, the specific capacitance retention of 6-MnO<sub>2</sub>@Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub> is 67.11 %. Furthermore, the 6-MnO<sub>2</sub>@Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub>//Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub> asymmetric capacitor demonstrated a maximum energy density of 30.8 W h kg<sup>−1</sup> and a power density of 7493.3 W kg<sup>−1</sup>, maintaining a capacitance retention rate of 95.98 % (from 74.6 to 71.6F g<sup>−1</sup>) after 2000 charge-discharge cycles. This study presents an effective and scalable synthesis strategy for MnO<sub>2</sub> composite electrodes, highlighting their potential for future energy storage applications.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"344 ","pages":"Article 125198"},"PeriodicalIF":3.2,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143142328","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 : 2025-01-08DOI: 10.1016/j.jssc.2025.125178
Shuaiqi Zhao , Yujie Chen , Yumeng Ge , Hongbin Zhang , Kai Yang , Shiqing Xu , Xiaolei Yang , Gongxun Bai
Multicolor phosphors are crucial components in various applications such as screen displays, lighting fixtures, and color imaging technologies. Despite their widespread use, they still encounter some obstacles in multicolored luminescence. Here, we synthesized a series of Gd2ZnTiO6 phosphors doped with Tb3+ and Eu3+ using a high-temperature solid-state reaction method. By employing Reisfeld's approximation theory and Dexter's multipolar interaction theory, we analyzed the energy transfer mechanism from Tb3+ to Eu3+. Our findings indicate that the Tb3+ to Eu3+ energy transfer is facilitated by quadrupole-quadrupole interactions. Additionally, we assessed the thermal stability of Gd2ZnTiO6:Tb3+, Eu3+ using temperature-variable emission spectroscopy across a temperature range of 303–463 K. The Gd2ZnTiO6 phosphors exhibited polychromatic luminescence ranging from green (0.3632, 0.61033) to red (0.6521, 0.3481) under 381 nm excitation by adjusting the content of Eu3+ and Tb3+. Consequently, the Gd2ZnTiO6:Tb3+, Eu3+ phosphors exhibit excellent luminescence performance coupled with remarkable thermal stability, offering a valuable reference for the advancement of novel and robust luminescent materials.
{"title":"Multicolored luminescence in double perovskite Gd2ZnTiO6 phosphors with Tb3+/Eu3+ codoping and energy transfer","authors":"Shuaiqi Zhao , Yujie Chen , Yumeng Ge , Hongbin Zhang , Kai Yang , Shiqing Xu , Xiaolei Yang , Gongxun Bai","doi":"10.1016/j.jssc.2025.125178","DOIUrl":"10.1016/j.jssc.2025.125178","url":null,"abstract":"<div><div>Multicolor phosphors are crucial components in various applications such as screen displays, lighting fixtures, and color imaging technologies. Despite their widespread use, they still encounter some obstacles in multicolored luminescence. Here, we synthesized a series of Gd<sub>2</sub>ZnTiO<sub>6</sub> phosphors doped with Tb<sup>3+</sup> and Eu<sup>3+</sup> using a high-temperature solid-state reaction method. By employing Reisfeld's approximation theory and Dexter's multipolar interaction theory, we analyzed the energy transfer mechanism from Tb<sup>3+</sup> to Eu<sup>3+</sup>. Our findings indicate that the Tb<sup>3+</sup> to Eu<sup>3+</sup> energy transfer is facilitated by quadrupole-quadrupole interactions. Additionally, we assessed the thermal stability of Gd<sub>2</sub>ZnTiO<sub>6</sub>:Tb<sup>3+</sup>, Eu<sup>3+</sup> using temperature-variable emission spectroscopy across a temperature range of 303–463 K. The Gd<sub>2</sub>ZnTiO<sub>6</sub> phosphors exhibited polychromatic luminescence ranging from green (0.3632, 0.61033) to red (0.6521, 0.3481) under 381 nm excitation by adjusting the content of Eu<sup>3+</sup> and Tb<sup>3+</sup>. Consequently, the Gd<sub>2</sub>ZnTiO<sub>6</sub>:Tb<sup>3+</sup>, Eu<sup>3+</sup> phosphors exhibit excellent luminescence performance coupled with remarkable thermal stability, offering a valuable reference for the advancement of novel and robust luminescent materials.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"344 ","pages":"Article 125178"},"PeriodicalIF":3.2,"publicationDate":"2025-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143142682","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 : 2025-01-07DOI: 10.1016/j.jssc.2025.125184
Daniel S. Tortorella, Kowsik Ghosh, Svilen Bobev
Reported in this article are results from comprehensive crystallographic studies of the Zintl phase Mg3–xZnxP2, which exists with a rather wide stoichiometry breadth. Through systematic syntheses carried out via the Sn-flux method, single crystals of the title compounds were grown. Structural work done with the aid of powder X-ray diffraction and single-crystal X-ray diffraction methods confirmed that Mg3–xZnxP2 crystallizes in a trigonal crystal system with the space group Pm1 (anti-La2O3 structure type, Pearson symbol hP5). The refined chemical formulae indicate a compositional range of 0.9 < x < 2.0. Therefore, Mg3–xZnxP2 is an intermediate solid solution and not a simple admixture of Mg3P2 and Zn3P2, as the end members and the title phase all have different crystal structures. In addition to the crystallographic analyses, the electronic structures of two idealized structure models, MgZn2P2 and Mg2ZnP2, were also considered as a part of this study. Electronic band structure calculations show the Zn–P interactions to be more covalent than the respective Mg–P ones. There exists an indirect bandgap of 0.6 eV in MgZn2P2 and a wider direct bandgap of 1.0 eV in Mg2ZnP2. These results indicate that precise tuning of the Zn|Mg distribution could be a viable synthetic tool to control the transport properties.
{"title":"Realization of a trigonal Mg3–xZnxP2 intermediate solid solution between the binary cubic Mg3P2 and tetragonal Zn3P2 end members","authors":"Daniel S. Tortorella, Kowsik Ghosh, Svilen Bobev","doi":"10.1016/j.jssc.2025.125184","DOIUrl":"10.1016/j.jssc.2025.125184","url":null,"abstract":"<div><div>Reported in this article are results from comprehensive crystallographic studies of the Zintl phase Mg<sub>3–<em>x</em></sub>Zn<sub><em>x</em></sub>P<sub>2</sub>, which exists with a rather wide stoichiometry breadth. Through systematic syntheses carried out via the Sn-flux method, single crystals of the title compounds were grown. Structural work done with the aid of powder X-ray diffraction and single-crystal X-ray diffraction methods confirmed that Mg<sub>3–<em>x</em></sub>Zn<sub><em>x</em></sub>P<sub>2</sub> crystallizes in a trigonal crystal system with the space group <em>P</em> <span><math><mrow><mover><mn>3</mn><mo>‾</mo></mover></mrow></math></span> <em>m</em>1 (<em>anti</em>-La<sub>2</sub>O<sub>3</sub> structure type, Pearson symbol <em>hP</em>5). The refined chemical formulae indicate a compositional range of 0.9 < <em>x</em> < 2.0. Therefore, Mg<sub>3–<em>x</em></sub>Zn<sub><em>x</em></sub>P<sub>2</sub> is an intermediate solid solution and not a simple admixture of Mg<sub>3</sub>P<sub>2</sub> and Zn<sub>3</sub>P<sub>2</sub>, as the end members and the title phase all have different crystal structures. In addition to the crystallographic analyses, the electronic structures of two idealized structure models, MgZn<sub>2</sub>P<sub>2</sub> and Mg<sub>2</sub>ZnP<sub>2</sub>, were also considered as a part of this study. Electronic band structure calculations show the Zn–P interactions to be more covalent than the respective Mg–P ones. There exists an indirect bandgap of 0.6 eV in MgZn<sub>2</sub>P<sub>2</sub> and a wider direct bandgap of 1.0 eV in Mg<sub>2</sub>ZnP<sub>2</sub>. These results indicate that precise tuning of the Zn|Mg distribution could be a viable synthetic tool to control the transport properties.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"344 ","pages":"Article 125184"},"PeriodicalIF":3.2,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143142330","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 : 2025-01-07DOI: 10.1016/j.jssc.2025.125181
Guiming Chen , Wei Liu , Qing Li , Yanxia Wang , Lingmin Sun , Jiangshan Zhao , Jibin Dong , Shenbao Xu , Xihao Yu , Min Wang , Weiwei Li , Zhigang Wang
This study focused on the adsorption mechanism of six aliphatic VOCs (cyclohexane, n-hexane, methyl-cyclopentane, n-butanol, butyl-acetate, and methyl-methacrylate) on industrial ZSM-5 zeolites with different Si/Al ratios (20, 50, 300) by combining experiment with theoretical approach. Meanwhile, the effects of flow rate, initial concentration of n-butanol, and temperature for ZSM-5-300 zeolite were investigated. The interaction energy and distribution of the centroid of VOCs on ZSM-5 zeolites were calculated using Material Studio software. The experimental results showed that adsorption capacities of ZSM-5 zeolites for oxygenated VOCs of highly-polarity (n-butanol, methyl-methacrylate, butyl-acetate) were significantly higher than low-polarity VOCs without oxygen (cyclohexane, methyl-cyclopentane, n-hexane). The adsorption efficiency was improved at low temperature, high initial VOCs concentration, and flow rate. The adsorption processes of VOCs on ZSM-5 zeolites were suited to the Freundlich isotherm model and the pseudo-first-order kinetic model. The calculation results revealed that the adsorption capacity increases from about 31 mg/g to 85 mg/g for low-polar VOCs as the adsorption energy decreases from −14.40 kJ/mol to −20.80 kJ/mol. The interaction energy curves of highly-polar VOCs show multiple peaks as the Si/Al ratio decreases, due to they were absorbed in both the intersection and zigzag channels of ZSM-5 framework. The adsorption site distribution indicated that the adsorption preferences were affected by the compatibility between pore geometry and VOCs structure. The ring-structured VOCs were mainly in the intersection channels, and chain-structured VOCs spread across all channels.
{"title":"Adsorption mechanism and quantum chemical calculation of six aliphatic VOCs on industrial ZSM-5 zeolites","authors":"Guiming Chen , Wei Liu , Qing Li , Yanxia Wang , Lingmin Sun , Jiangshan Zhao , Jibin Dong , Shenbao Xu , Xihao Yu , Min Wang , Weiwei Li , Zhigang Wang","doi":"10.1016/j.jssc.2025.125181","DOIUrl":"10.1016/j.jssc.2025.125181","url":null,"abstract":"<div><div>This study focused on the adsorption mechanism of six aliphatic VOCs (cyclohexane, n-hexane, methyl-cyclopentane, n-butanol, butyl-acetate, and methyl-methacrylate) on industrial ZSM-5 zeolites with different Si/Al ratios (20, 50, 300) by combining experiment with theoretical approach. Meanwhile, the effects of flow rate, initial concentration of n-butanol, and temperature for ZSM-5-300 zeolite were investigated. The interaction energy and distribution of the centroid of VOCs on ZSM-5 zeolites were calculated using Material Studio software. The experimental results showed that adsorption capacities of ZSM-5 zeolites for oxygenated VOCs of highly-polarity (n-butanol, methyl-methacrylate, butyl-acetate) were significantly higher than low-polarity VOCs without oxygen (cyclohexane, methyl-cyclopentane, n-hexane). The adsorption efficiency was improved at low temperature, high initial VOCs concentration, and flow rate. The adsorption processes of VOCs on ZSM-5 zeolites were suited to the Freundlich isotherm model and the pseudo-first-order kinetic model. The calculation results revealed that the adsorption capacity increases from about 31 mg/g to 85 mg/g for low-polar VOCs as the adsorption energy decreases from −14.40 kJ/mol to −20.80 kJ/mol. The interaction energy curves of highly-polar VOCs show multiple peaks as the Si/Al ratio decreases, due to they were absorbed in both the intersection and zigzag channels of ZSM-5 framework. The adsorption site distribution indicated that the adsorption preferences were affected by the compatibility between pore geometry and VOCs structure. The ring-structured VOCs were mainly in the intersection channels, and chain-structured VOCs spread across all channels.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"344 ","pages":"Article 125181"},"PeriodicalIF":3.2,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143142324","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 : 2025-01-06DOI: 10.1016/j.jssc.2025.125182
Shengming Liu, Yun Zhang, Shihua Ding, Tianxiu Song
V cation was introduced at Nb-site in CoTiNb2O8 for the purpose of tuning the defects concentration. XRD analysis indicated that no secondary phase developed over the whole composition range. The sintering temperature decreased to 1150 °C in current work, compared with pure CoTiNb2O8 ceramic (∼1250 °C). V-introduction inhibited grain growth and benefited grain homogenization. The decreased molecular dielectric polarizability and blue shift of Raman A1g mode both made lower εr from 59.2 to 41.8. Based on the X-ray photoelectron spectroscopy (XPS), V doping decreased the oxygen vacancy concentration and tuned the Co valence state. The defects compensation by oxygen and Co vacancies significantly improved Q × f up to 38,012 GHz, accompanied with a 50 % rise. The slight increase in τf was attributed to the Nb–O bond energy reduction. The CoTi(Nb0.97V0.03)2O8 had a high εr of 54.6 with good Q × f of about 38,012 GHz and τf = 96.47 ppm/°C. Enhanced Q × f and low sintering temperature were achieved simultaneously.
{"title":"Enhanced Q×f in CoTi(Nb1-xVx)2O8 ceramics by tuning oxygen vacancy concentration and Co valence state","authors":"Shengming Liu, Yun Zhang, Shihua Ding, Tianxiu Song","doi":"10.1016/j.jssc.2025.125182","DOIUrl":"10.1016/j.jssc.2025.125182","url":null,"abstract":"<div><div>V cation was introduced at Nb-site in CoTiNb<sub>2</sub>O<sub>8</sub> for the purpose of tuning the defects concentration. XRD analysis indicated that no secondary phase developed over the whole composition range. The sintering temperature decreased to 1150 °C in current work, compared with pure CoTiNb<sub>2</sub>O<sub>8</sub> ceramic (∼1250 °C). V-introduction inhibited grain growth and benefited grain homogenization. The decreased molecular dielectric polarizability and blue shift of Raman A<sub>1g</sub> mode both made lower <em>ε</em><sub>r</sub> from 59.2 to 41.8. Based on the X-ray photoelectron spectroscopy (XPS), V doping decreased the oxygen vacancy concentration and tuned the Co valence state. The defects compensation by oxygen and Co vacancies significantly improved <em>Q</em> × <em>f</em> up to 38,012 GHz, accompanied with a 50 % rise. The slight increase in <em>τ</em><sub><em>f</em></sub> was attributed to the Nb–O bond energy reduction. The CoTi(Nb<sub>0.97</sub>V<sub>0.03</sub>)<sub>2</sub>O<sub>8</sub> had a high <em>ε</em><sub>r</sub> of 54.6 with good <em>Q</em> × <em>f</em> of about 38,012 GHz and <em>τ</em><sub><em>f</em></sub> = 96.47 ppm/°C. Enhanced <em>Q</em> × <em>f</em> and low sintering temperature were achieved simultaneously.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"344 ","pages":"Article 125182"},"PeriodicalIF":3.2,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143142681","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 series of single crystals of solid solutions KTi1-xZrxOAsO4(x = 0.025, 0.05, 0.075, 0.1) have been grown by the Czochralski method. The structural analysis of this series of samples showed that at titanium partial substitution (0.025 ≤ x ≤ 0.1) Zr4+ occupies the T1 position of the Ti1O6 octahedron, as well as the T2 position of the Ti2O6 octahedron, at the same time the volume of octahedra increases. But at 0.05 ≤ x ≤ 0.1 the volume of the Ti1O6 octahedron stops growing, and only the volume of Ti2O6 increases, consequently, at x = 0.05 Zr saturation is observed at position Ti1. The Raman spectrum of a pure KTA crystal is very different from the spectra of the entire range of solid solutions. In the transmission spectrum of samples with partial substitution of titanium atoms by zirconium atoms, there is practically no wide absorption band at 3.5–4 μm typical for pure KTA, the maximum crystal transparency in this region is achieved for x = 0.075. It was found that the introduction of large Zr ions into the KTiOAsO4 structure leads to a distortion of the lattice and an increase of the band gap.
{"title":"Structure and properties of KTi1-xZrxOAsO4 (x=0.025, 0.05, 0.075, 0.1) crystals","authors":"K.E. Korzhneva , A.P. Yelisseyev , S.A. Zhurkov , M.S. Molokeev , L.I. Isaenko","doi":"10.1016/j.jssc.2025.125183","DOIUrl":"10.1016/j.jssc.2025.125183","url":null,"abstract":"<div><div>A series of single crystals of solid solutions KTi<sub>1-x</sub>Zr<sub>x</sub>OAsO<sub>4</sub> <strong>(</strong>x = 0.025, 0.05, 0.075, 0.1) have been grown by the Czochralski method. The structural analysis of this series of samples showed that at titanium partial substitution (0.025 ≤ x ≤ 0.1) Zr<sup>4+</sup> occupies the T1 position of the Ti1O<sub>6</sub> octahedron, as well as the T2 position of the Ti2O<sub>6</sub> octahedron, at the same time the volume of octahedra increases. But at 0.05 ≤ x ≤ 0.1 the volume of the Ti1O<sub>6</sub> octahedron stops growing, and only the volume of Ti2O<sub>6</sub> increases, consequently, at x = 0.05 Zr saturation is observed at position Ti1. The Raman spectrum of a pure KTA crystal is very different from the spectra of the entire range of solid solutions. In the transmission spectrum of samples with partial substitution of titanium atoms by zirconium atoms, there is practically no wide absorption band at 3.5–4 μm typical for pure KTA, the maximum crystal transparency in this region is achieved for x = 0.075. It was found that the introduction of large Zr ions into the KTiOAsO<sub>4</sub> structure leads to a distortion of the lattice and an increase of the band gap.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"344 ","pages":"Article 125183"},"PeriodicalIF":3.2,"publicationDate":"2025-01-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143142683","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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