Pub Date : 2025-02-22DOI: 10.1016/j.solidstatesciences.2025.107869
Qiuyu Cheng , Zhiwei Wang , Ayahisa Okawa , Takuya Hasegawa , Tohru Sekino , Shu Yin
In the present work, solid solutions of Sr2Mg1-xCoxSi2O7 (0.2 ≤ x ≤ 1) with blue coloration and Sr2Mg1-xNixSi2O7 (0.1 ≤ x ≤ 0.5) with purple coloration were successfully synthesized via solid state reactions. Rietveld refinement analysis confirmed the successful substitution of Mg2+ by Co2+/Ni2+, as indicated by corresponding changes in cell volumes. These solid solutions display tunable blue and purple hues, influenced by the doping levels of Co2+/Ni2+. Compared to commercial cobalt blue (CoAl2O4), the synthesized blue oxides significantly lowered Co2+ levels while achieving the desired color properties. The rarity of purple coloration in nickel compounds makes this topic of particular interest. UV–Vis–NIR spectra revealed that the observed blue and purple colors arise from the and transitions of Co2+ and Ni2+ ions at tetrahedral sites, respectively. Furthermore, the thermal stability of the pigments was evaluated. To assess their compatibility with the polymer, 2 wt% of the as-prepared pigments were incorporated into poly(methyl methacrylate) (PMMA) to fabricate blue and purple PMMA composites, and their color properties were subsequently characterized.
{"title":"Optical properties and application of blue and purple inorganic pigment powders based on cobalt/nickel doped Sr2MgSi2O7","authors":"Qiuyu Cheng , Zhiwei Wang , Ayahisa Okawa , Takuya Hasegawa , Tohru Sekino , Shu Yin","doi":"10.1016/j.solidstatesciences.2025.107869","DOIUrl":"10.1016/j.solidstatesciences.2025.107869","url":null,"abstract":"<div><div>In the present work, solid solutions of Sr<sub>2</sub>Mg<sub>1-<em>x</em></sub>Co<sub><em>x</em></sub>Si<sub>2</sub>O<sub>7</sub> (0.2 ≤ <em>x</em> ≤ 1) with blue coloration and Sr<sub>2</sub>Mg<sub>1-<em>x</em></sub>Ni<sub><em>x</em></sub>Si<sub>2</sub>O<sub>7</sub> (0.1 ≤ <em>x</em> ≤ 0.5) with purple coloration were successfully synthesized via solid state reactions. Rietveld refinement analysis confirmed the successful substitution of Mg<sup>2+</sup> by Co<sup>2+</sup>/Ni<sup>2+</sup>, as indicated by corresponding changes in cell volumes. These solid solutions display tunable blue and purple hues, influenced by the doping levels of Co<sup>2+</sup>/Ni<sup>2+</sup>. Compared to commercial cobalt blue (CoAl<sub>2</sub>O<sub>4</sub>), the synthesized blue oxides significantly lowered Co<sup>2+</sup> levels while achieving the desired color properties. The rarity of purple coloration in nickel compounds makes this topic of particular interest. UV–Vis–NIR spectra revealed that the observed blue and purple colors arise from the <span><math><mrow><mmultiscripts><msub><mi>A</mi><mn>2</mn></msub><mprescripts></mprescripts><none></none><mn>4</mn></mmultiscripts><mrow><mo>(</mo><mmultiscripts><mi>F</mi><mprescripts></mprescripts><none></none><mn>4</mn></mmultiscripts><mo>)</mo></mrow><mo>→</mo><mmultiscripts><msub><mi>T</mi><mn>1</mn></msub><mprescripts></mprescripts><none></none><mn>4</mn></mmultiscripts><mrow><mo>(</mo><mmultiscripts><mi>P</mi><mprescripts></mprescripts><none></none><mn>4</mn></mmultiscripts><mo>)</mo></mrow></mrow></math></span> and <span><math><mrow><mmultiscripts><msub><mi>T</mi><mn>1</mn></msub><mprescripts></mprescripts><none></none><mn>3</mn></mmultiscripts><mrow><mo>(</mo><mmultiscripts><mi>F</mi><mprescripts></mprescripts><none></none><mn>3</mn></mmultiscripts><mo>)</mo></mrow><mo>→</mo><mmultiscripts><msub><mi>T</mi><mn>1</mn></msub><mprescripts></mprescripts><none></none><mn>3</mn></mmultiscripts><mrow><mo>(</mo><mmultiscripts><mi>P</mi><mprescripts></mprescripts><none></none><mn>3</mn></mmultiscripts><mo>)</mo></mrow></mrow></math></span> transitions of Co<sup>2+</sup> and Ni<sup>2+</sup> ions at tetrahedral sites, respectively. Furthermore, the thermal stability of the pigments was evaluated. To assess their compatibility with the polymer, 2 wt% of the as-prepared pigments were incorporated into poly(methyl methacrylate) (PMMA) to fabricate blue and purple PMMA composites, and their color properties were subsequently characterized.</div></div>","PeriodicalId":432,"journal":{"name":"Solid State Sciences","volume":"162 ","pages":"Article 107869"},"PeriodicalIF":3.4,"publicationDate":"2025-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143479209","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 : 2025-02-22DOI: 10.1016/j.solidstatesciences.2025.107867
Jianjiao Xin , Yan Jiang , Kun Song , Nan Zhao , Zhuanfang Zhang , Qiushi Li
Nanozymes with peroxidase activity have lower catalytic activity compared to natural enzymes. Therefore, it is of great significance to develop and design artificial enzymes with high catalytic activity. FeS2-doped MoS2 (FeS2-MoS2) nanoflower is synthesized via a hydrothermal method, using Anderson-type polyoxometalates (FeMo6) as precursors. The X-ray photoelectron spectroscopy (XPS) and Raman spectrum of FeS2-MoS2 confirm the presence of the 1T-MoS2 phase. FeS2-MoS2 with different 1T/2H-MoS2 phase ratios are synthesized by controlling the reaction time. As a nanozyme, the obtained FeS2-MoS2 can promote the oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB) to oxTMB, showing peroxidase activity. FeS2-MoS2 at a reaction time of 12 h exhibits higher peroxidase activity compared to samples prepared at other reaction times. The catalytic activity of FeS2-MoS2 is 3 times that of MoS2. The Km value for H2O2 was 110 times that of horseradish peroxidase (HRP), indicating that the FeS2-MoS2 had a better affinity for H2O2. The excellent catalytic activity may be due to the synergistic effect of bimetal, larger specific surface area, the high content of 1T-MoS2 (77.52 %) and defect. As far as we know, the FeS2-MoS2 nanoflower exhibits an exceptionally low detection limit of 0.52 μM for the colorimetric sensing of H2O2. This research presents a novel approach for creating high-performing nanozyme catalysts.
{"title":"FeS2-doped MoS2 nanoflower with the dominant 1T-MoS2 phase for enhanced peroxidase activity","authors":"Jianjiao Xin , Yan Jiang , Kun Song , Nan Zhao , Zhuanfang Zhang , Qiushi Li","doi":"10.1016/j.solidstatesciences.2025.107867","DOIUrl":"10.1016/j.solidstatesciences.2025.107867","url":null,"abstract":"<div><div>Nanozymes with peroxidase activity have lower catalytic activity compared to natural enzymes. Therefore, it is of great significance to develop and design artificial enzymes with high catalytic activity. FeS<sub>2</sub>-doped MoS<sub>2</sub> (<strong>FeS</strong><sub><strong>2</strong></sub><strong>-MoS</strong><sub><strong>2</strong></sub>) nanoflower is synthesized via a hydrothermal method, using Anderson-type polyoxometalates (FeMo<sub>6</sub>) as precursors. The X-ray photoelectron spectroscopy (XPS) and Raman spectrum of <strong>FeS</strong><sub><strong>2</strong></sub><strong>-MoS</strong><sub><strong>2</strong></sub> confirm the presence of the 1T-MoS<sub>2</sub> phase. <strong>FeS</strong><sub><strong>2</strong></sub><strong>-MoS</strong><sub><strong>2</strong></sub> with different 1T/2H-MoS<sub>2</sub> phase ratios are synthesized by controlling the reaction time. As a nanozyme, the obtained <strong>FeS</strong><sub><strong>2</strong></sub><strong>-MoS</strong><sub><strong>2</strong></sub> can promote the oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB) to oxTMB, showing peroxidase activity. <strong>FeS</strong><sub><strong>2</strong></sub><strong>-MoS</strong><sub><strong>2</strong></sub> at a reaction time of 12 h exhibits higher peroxidase activity compared to samples prepared at other reaction times. The catalytic activity of <strong>FeS</strong><sub><strong>2</strong></sub><strong>-MoS</strong><sub><strong>2</strong></sub> is 3 times that of MoS<sub>2</sub>. The K<sub>m</sub> value for H<sub>2</sub>O<sub>2</sub> was 110 times that of horseradish peroxidase (HRP), indicating that the <strong>FeS</strong><sub><strong>2</strong></sub><strong>-MoS</strong><sub><strong>2</strong></sub> had a better affinity for H<sub>2</sub>O<sub>2</sub>. The excellent catalytic activity may be due to the synergistic effect of bimetal, larger specific surface area, the high content of 1T-MoS<sub>2</sub> (77.52 %) and defect. As far as we know, the <strong>FeS</strong><sub><strong>2</strong></sub><strong>-MoS</strong><sub><strong>2</strong></sub> nanoflower exhibits an exceptionally low detection limit of 0.52 μM for the colorimetric sensing of H<sub>2</sub>O<sub>2</sub>. This research presents a novel approach for creating high-performing nanozyme catalysts.</div></div>","PeriodicalId":432,"journal":{"name":"Solid State Sciences","volume":"162 ","pages":"Article 107867"},"PeriodicalIF":3.4,"publicationDate":"2025-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143487751","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-22DOI: 10.1016/j.solidstatesciences.2025.107868
Li Zhang , Junliang Sun , Xianji Qiao
The study of mixed-anion compounds, aimed at combining the advantages of different anions, has been extensively studied. Metal oxyhalides, with a view to combining the benefits of oxides and halides, play a crucial role in numerous advanced scientific and technological fields. Here we present a novel K4CuO2Cl2 compound whose structure was studied via single-crystal X-ray diffraction. The synthesis of the K4CuO2Cl2 compound employs a low-temperature aqueous solution method, in contrast to the high-temperature synthesis of K4Cu4OCl10. The crystal structure of K4CuO2Cl2 crystallizes in space group P42/mnm with tetragonal symmetry. Moreover, the K atom exhibits a tetrahedral coordination whilst Cu atom have a quadrilateral plane coordination in K4CuO2Cl2, in contrast to the exclusively tetrahedral coordination found in K4Cu4OCl10. This unique structural feature is expected to impart distinctive magnetic properties.
{"title":"K4CuO2Cl2: A new alkali metal copper oxyhalide via aqueous solution processes","authors":"Li Zhang , Junliang Sun , Xianji Qiao","doi":"10.1016/j.solidstatesciences.2025.107868","DOIUrl":"10.1016/j.solidstatesciences.2025.107868","url":null,"abstract":"<div><div>The study of mixed-anion compounds, aimed at combining the advantages of different anions, has been extensively studied. Metal oxyhalides, with a view to combining the benefits of oxides and halides, play a crucial role in numerous advanced scientific and technological fields. Here we present a novel K<sub>4</sub>CuO<sub>2</sub>Cl<sub>2</sub> compound whose structure was studied via single-crystal X-ray diffraction. The synthesis of the K<sub>4</sub>CuO<sub>2</sub>Cl<sub>2</sub> compound employs a low-temperature aqueous solution method, in contrast to the high-temperature synthesis of K<sub>4</sub>Cu<sub>4</sub>OCl<sub>10</sub>. The crystal structure of K<sub>4</sub>CuO<sub>2</sub>Cl<sub>2</sub> crystallizes in space group <em>P</em>4<sub>2</sub>/<em>mnm</em> with tetragonal symmetry. Moreover, the K atom exhibits a tetrahedral coordination whilst Cu atom have a quadrilateral plane coordination in K<sub>4</sub>CuO<sub>2</sub>Cl<sub>2</sub>, in contrast to the exclusively tetrahedral coordination found in K<sub>4</sub>Cu<sub>4</sub>OCl<sub>10</sub>. This unique structural feature is expected to impart distinctive magnetic properties.</div></div>","PeriodicalId":432,"journal":{"name":"Solid State Sciences","volume":"162 ","pages":"Article 107868"},"PeriodicalIF":3.4,"publicationDate":"2025-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143487750","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-20DOI: 10.1016/j.solidstatesciences.2025.107866
Caique D.A. Lima , Thais C.V. de Carvalho , Cesar D. Mendoza , Marcelo E.H. Maia da Costa , Gardênia de S. Pinheiro , Cleânio Luz-Lima , Bruno G. Silva , Rubem L. Sommer , Jefferson F.D. F. Araujo
This study examines the transition from paramagnetic to diamagnetic response in MoO3, a phenomenon previously documented in the literature where the magnetic response of MoO3 varies with the applied field, changing from paramagnetic at low fields to diamagnetic at high fields. MoO3 samples were synthesized with controlled Mo6+/Mo5+ ratios while maintaining high crystallinity to elucidate this phenomenon. The samples were prepared in a chemical vapor deposition (CVD) furnace under an oxygen environment at two different temperatures, 550 and 650 °C, and two annealing times, 4 and 8 h. The resulting samples were subjected to characterization using powder X-ray diffraction (XRD), Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and vibrating sample magnetometry (VSM). The XRD results demonstrated the formation of highly crystalline MoO3 in all samples, which is confirmed by Raman and FTIR. The XPS results demonstrate the concentration of Mo5+ and Mo6+ present in each sample. The results of the VSM experiments demonstrated that the observed change in the magnetic response of MoO3 is due to the intensity of the material's response being comparable to that of the sample holder's response. Moreover, vibrating sample magnetometry and X-ray photoelectron spectroscopy analysis revealed that MoO3 can exhibit both paramagnetic and diamagnetic behavior, depending on the quantity of Mo5+ present in the sample.
{"title":"Magnetic transition in MoO3: Influence of Mo5+/Mo6+ ratios on paramagnetic to diamagnetic behavior","authors":"Caique D.A. Lima , Thais C.V. de Carvalho , Cesar D. Mendoza , Marcelo E.H. Maia da Costa , Gardênia de S. Pinheiro , Cleânio Luz-Lima , Bruno G. Silva , Rubem L. Sommer , Jefferson F.D. F. Araujo","doi":"10.1016/j.solidstatesciences.2025.107866","DOIUrl":"10.1016/j.solidstatesciences.2025.107866","url":null,"abstract":"<div><div>This study examines the transition from paramagnetic to diamagnetic response in MoO<sub>3</sub>, a phenomenon previously documented in the literature where the magnetic response of MoO<sub>3</sub> varies with the applied field, changing from paramagnetic at low fields to diamagnetic at high fields. MoO<sub>3</sub> samples were synthesized with controlled Mo<sup>6+</sup>/Mo<sup>5+</sup> ratios while maintaining high crystallinity to elucidate this phenomenon. The samples were prepared in a chemical vapor deposition (CVD) furnace under an oxygen environment at two different temperatures, 550 and 650 °C, and two annealing times, 4 and 8 h. The resulting samples were subjected to characterization using powder X-ray diffraction (XRD), Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and vibrating sample magnetometry (VSM). The XRD results demonstrated the formation of highly crystalline MoO<sub>3</sub> in all samples, which is confirmed by Raman and FTIR. The XPS results demonstrate the concentration of Mo<sup>5+</sup> and Mo<sup>6+</sup> present in each sample. The results of the VSM experiments demonstrated that the observed change in the magnetic response of MoO<sub>3</sub> is due to the intensity of the material's response being comparable to that of the sample holder's response. Moreover, vibrating sample magnetometry and X-ray photoelectron spectroscopy analysis revealed that MoO<sub>3</sub> can exhibit both paramagnetic and diamagnetic behavior, depending on the quantity of Mo<sup>5+</sup> present in the sample.</div></div>","PeriodicalId":432,"journal":{"name":"Solid State Sciences","volume":"162 ","pages":"Article 107866"},"PeriodicalIF":3.4,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143464940","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-18DOI: 10.1016/j.solidstatesciences.2025.107865
Elena A. Asabina , Anna I. Zhukova , Vladislav A. Sedov , Vladimir I. Pet'kov , Diana A. Osaulenko , Ekaterina B. Markova , Diana G. Fukina , Vitalii A. Koshkin
The study is dedicated to the investigation of the catalytic properties of Ti2(PO4)3 (M − La, Sm, Dy) phosphates in ethanol conversion reactions. The powder samples of the NASICON-type phosphates were synthesized by the Pechini technique. Their phase purity and structure characterization were performed using XRD, IR spectroscopy, SEM, BET and BJH methods. Structural data indicated that the transition from La to Dy was accompanied by a decrease in M − O bond lengths, which is compensated by longer neighboring Ti–O bonds, ultimately leading to greater distortion of the surrounding octahedra. The catalytic activity of M0.33Ti2(PO4)3 (M − La, Sm, Dy) phosphates has been studied in ethanol reforming reactions in the temperature range of 240–400 °C. The regularities of changes in the catalytic properties in the La→Sm→Dy series have been traced. The selectivity of ethanol conversion was found to depend on the phosphate composition. The best alcohol conversion was achieved on Dy-phosphate at 400 °C with an ethylene selectivity of 66 %.
{"title":"Catalytic characteristics of NASICON-type phosphates with rare earth elements in ethanol conversion","authors":"Elena A. Asabina , Anna I. Zhukova , Vladislav A. Sedov , Vladimir I. Pet'kov , Diana A. Osaulenko , Ekaterina B. Markova , Diana G. Fukina , Vitalii A. Koshkin","doi":"10.1016/j.solidstatesciences.2025.107865","DOIUrl":"10.1016/j.solidstatesciences.2025.107865","url":null,"abstract":"<div><div>The study is dedicated to the investigation of the catalytic properties of <span><math><mrow><msubsup><mi>M</mi><mn>0.33</mn><mrow><mn>3</mn><mo>+</mo></mrow></msubsup></mrow></math></span> Ti<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> (M − La, Sm, Dy) phosphates in ethanol conversion reactions. The powder samples of the NASICON-type phosphates were synthesized by the Pechini technique. Their phase purity and structure characterization were performed using XRD, IR spectroscopy, SEM, BET and BJH methods. Structural data indicated that the transition from La to Dy was accompanied by a decrease in M − O bond lengths, which is compensated by longer neighboring Ti–O bonds, ultimately leading to greater distortion of the surrounding octahedra. The catalytic activity of M<sub>0.33</sub>Ti<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> (M − La, Sm, Dy) phosphates has been studied in ethanol reforming reactions in the temperature range of 240–400 °C. The regularities of changes in the catalytic properties in the La→Sm→Dy series have been traced. The selectivity of ethanol conversion was found to depend on the phosphate composition. The best alcohol conversion was achieved on Dy-phosphate at 400 °C with an ethylene selectivity of 66 %.</div></div>","PeriodicalId":432,"journal":{"name":"Solid State Sciences","volume":"162 ","pages":"Article 107865"},"PeriodicalIF":3.4,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143445392","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-14DOI: 10.1016/j.solidstatesciences.2025.107864
Tingting Yan, Han Li, Dongyang Xi, Linan Liu, Dinghan Jin, Lei Sun
We synthesized the energetic molecular perovskite DAI-1 (C48H112I24N16Na8O96) and investigated its behavior under high pressure using high-pressure Raman spectroscopy. DAI-1 exhibits an ABX3 cubic perovskite structure, with significant changes in its Raman spectrum occurring between 4.3 and 7.1 GPa, signaling a phase transition. Releasing the pressure after applying it up to 12.3 GPa showed that the Raman spectrum did not return to its original state, indicating an irreversible phase transition. Furthermore, we conducted simulations to analyze the trend of changes in the crystal structure under pressure. This study serves as a reference for in-depth research on the high-pressure behavior of DAI-1 and other related substances.
{"title":"Synthesis and pressure-induced structural phase transition of energetic molecular perovskite DAI-1","authors":"Tingting Yan, Han Li, Dongyang Xi, Linan Liu, Dinghan Jin, Lei Sun","doi":"10.1016/j.solidstatesciences.2025.107864","DOIUrl":"10.1016/j.solidstatesciences.2025.107864","url":null,"abstract":"<div><div>We synthesized the energetic molecular perovskite DAI-1 (C<sub>48</sub>H<sub>112</sub>I<sub>24</sub>N<sub>16</sub>Na<sub>8</sub>O<sub>96</sub>) and investigated its behavior under high pressure using high-pressure Raman spectroscopy. DAI-1 exhibits an ABX<sub>3</sub> cubic perovskite structure, with significant changes in its Raman spectrum occurring between 4.3 and 7.1 GPa, signaling a phase transition. Releasing the pressure after applying it up to 12.3 GPa showed that the Raman spectrum did not return to its original state, indicating an irreversible phase transition. Furthermore, we conducted simulations to analyze the trend of changes in the crystal structure under pressure. This study serves as a reference for in-depth research on the high-pressure behavior of DAI-1 and other related substances.</div></div>","PeriodicalId":432,"journal":{"name":"Solid State Sciences","volume":"162 ","pages":"Article 107864"},"PeriodicalIF":3.4,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143429086","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-13DOI: 10.1016/j.solidstatesciences.2025.107863
Raul Oliveira , Cláudio Remédios
In the present work, the crystal of L-asparagine monohydrate (C4H8N2O3.H2O) was studied at high temperatures by thermal analysis and synchrotron X-ray diffraction. Two structural transformations (dehydration and decomposition) are briefly discussed. L-asparagine monohydrate exhibits anisotropic thermal expansion, as it is more intense along the b-axis. This crystal has an even more interesting effect, a negative thermal expansion along the a-axis in the range of 311–358 K. Thermal expansions were analyzed from the anisotropic atomic displacement parameters using the rigid body model. The behavior of the translation and libration tensors indicate positive expansions along the hydrogen bonds that connect the molecular chains in the b x c plane, as well as a negative thermal expansion along the hydrogen bond transverse to the this plane.
{"title":"L-asparagine monohydrate at high temperatures: transformations and negative thermal expansion. A study by thermal analysis and synchrotron X-ray diffraction","authors":"Raul Oliveira , Cláudio Remédios","doi":"10.1016/j.solidstatesciences.2025.107863","DOIUrl":"10.1016/j.solidstatesciences.2025.107863","url":null,"abstract":"<div><div>In the present work, the crystal of L-asparagine monohydrate (C<sub>4</sub>H<sub>8</sub>N<sub>2</sub>O<sub>3</sub>.H<sub>2</sub>O) was studied at high temperatures by thermal analysis and synchrotron X-ray diffraction. Two structural transformations (dehydration and decomposition) are briefly discussed. L-asparagine monohydrate exhibits anisotropic thermal expansion, as it is more intense along the b-axis. This crystal has an even more interesting effect, a negative thermal expansion along the a-axis in the range of 311–358 K. Thermal expansions were analyzed from the anisotropic atomic displacement parameters using the rigid body model. The behavior of the translation and libration tensors indicate positive expansions along the hydrogen bonds that connect the molecular chains in the <em>b x c</em> plane, as well as a negative thermal expansion along the hydrogen bond transverse to the this plane.</div></div>","PeriodicalId":432,"journal":{"name":"Solid State Sciences","volume":"162 ","pages":"Article 107863"},"PeriodicalIF":3.4,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143429085","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}
Carbon nanocages (CNCs) are promising materials for catalysis, filtration and electrochemistry. This work is devoted to the experimental and theoretical study of the magnetic properties of both pure CNCs and those encapsulated by transition metals Ni and Co. This study presents high-resolution transmission electron microscopy (HR-TEM) images of the homogeneous composite consisting of Co particles with a diameter of 3–5 nm coated with one or more layers of graphitized carbon. We also present HR-TEM images of hollow nanocages obtained after the complete etching of the metal with acid. The coercivity of the homogeneous composites (Ni and Co encapsulated) exhibited a rapid decrease below 50 K, while in the temperature range of 50–350 K, pronounced superparamagnetic properties are observed. On the other hand, in the etched material consisting of hollow carbon cages, the contribution of the diamagnetism of the carbon fraction increases with temperature. Theoretical estimates of saturation magnetization of metal nanoparticles and the electronic diamagnetic susceptibility of the carbon spheres are consistent with the experimental results.
{"title":"Magnetic properties of carbon nanocages: Pure and with the Ni or Co inclusions","authors":"K.B. Tsiberkin , A.V. Sosunov , V.V. Govorina , D.S. Neznakhin , V.K. Henner , G. Sumanasekera","doi":"10.1016/j.solidstatesciences.2025.107862","DOIUrl":"10.1016/j.solidstatesciences.2025.107862","url":null,"abstract":"<div><div>Carbon nanocages (CNCs) are promising materials for catalysis, filtration and electrochemistry. This work is devoted to the experimental and theoretical study of the magnetic properties of both pure CNCs and those encapsulated by transition metals Ni and Co. This study presents high-resolution transmission electron microscopy (HR-TEM) images of the homogeneous composite consisting of Co particles with a diameter of 3–5 nm coated with one or more layers of graphitized carbon. We also present HR-TEM images of hollow nanocages obtained after the complete etching of the metal with acid. The coercivity of the homogeneous composites (Ni and Co encapsulated) exhibited a rapid decrease below 50 K, while in the temperature range of 50–350 K, pronounced superparamagnetic properties are observed. On the other hand, in the etched material consisting of hollow carbon cages, the contribution of the diamagnetism of the carbon fraction increases with temperature. Theoretical estimates of saturation magnetization of metal nanoparticles and the electronic diamagnetic susceptibility of the carbon spheres are consistent with the experimental results.</div></div>","PeriodicalId":432,"journal":{"name":"Solid State Sciences","volume":"162 ","pages":"Article 107862"},"PeriodicalIF":3.4,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143445393","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-12DOI: 10.1016/j.solidstatesciences.2025.107861
Anil Kumar , A. Dahshan , Neeraj Mehta
Micro-indentations were made on new samples of the Se100(AgX)0 and Se95(AgX)5 (where X = Cl, Br, & I) systems to perform hardness measurement studies at different loads. Numerous models and methodologies, such as Meyer's law, the elastic/plastic deformation theory, Hays-Kendall's method, and the energy balance model, were used to assess the gathered Vickers microhardness data. DSC techniques were used to identify events related to thermal glass transition. Essential mechanical qualities that have been assessed include several thermos-mechanical parameters, such as the modulus of elasticity (E), the least micro-void formation energy (Eh), the micro-void volume (Vh), etc. Furthermore, a variety of physicochemical characteristics have been theoretically computed, such as the average coordination number (<r>), average heat of atomization (Hs), total constraints per atom (Nc), and the axial (nβ) and radial (nα) strength of the bonds.
The findings highlight that the various thermo-mechanical parameters examined in this work reach their optimized values in the case of the Se95(AgBr)5 sample. Furthermore, molar volume (Vm), compactness (δ), and density (ρ) have been computed both theoretically and experimentally.
{"title":"Thermo-mechanical and physicochemical features in Pseudo-binary Se-AgX chalcogenide glassy system","authors":"Anil Kumar , A. Dahshan , Neeraj Mehta","doi":"10.1016/j.solidstatesciences.2025.107861","DOIUrl":"10.1016/j.solidstatesciences.2025.107861","url":null,"abstract":"<div><div>Micro-indentations were made on new samples of the Se<sub>100</sub>(AgX)<sub>0</sub> and Se<sub>95</sub>(AgX)<sub>5</sub> (where X = Cl, Br, & I) systems to perform hardness measurement studies at different loads. Numerous models and methodologies, such as Meyer's law, the elastic/plastic deformation theory, Hays-Kendall's method, and the energy balance model, were used to assess the gathered Vickers microhardness data. DSC techniques were used to identify events related to thermal glass transition. Essential mechanical qualities that have been assessed include several thermos-mechanical parameters, such as the modulus of elasticity (<em>E</em>), the least micro-void formation energy (<em>E</em><sub><em>h</em></sub>), the micro-void volume (<em>V</em><sub><em>h</em></sub>), etc. Furthermore, a variety of physicochemical characteristics have been theoretically computed, such as the average coordination number (<<em>r</em>>), average heat of atomization (<em>H</em><sub><em>s</em></sub>), total constraints per atom (<em>N</em><sub><em>c</em></sub>), and the axial (<em>n</em><sub><em>β</em></sub>) and radial (<em>n</em><sub><em>α</em></sub>) strength of the bonds.</div><div>The findings highlight that the various thermo-mechanical parameters examined in this work reach their optimized values in the case of the Se<sub>95</sub>(AgBr)<sub>5</sub> sample. Furthermore, molar volume (<em>V</em><sub><em>m</em></sub>), compactness (<em>δ</em>), and density (<em>ρ</em>) have been computed both theoretically and experimentally.</div></div>","PeriodicalId":432,"journal":{"name":"Solid State Sciences","volume":"162 ","pages":"Article 107861"},"PeriodicalIF":3.4,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143437154","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-12DOI: 10.1016/j.solidstatesciences.2025.107860
Shutian Lin , Xinli Zhang , Yingzhi Chen , Yuanhong Zhong , Gao Cheng , Lin Yu
The Fe-N-C catalyst was synthesized using loofah sponge-derived carbon and applied for peroxymonosulfate (PMS) activation to degrade organic pollutants. The catalyst, featuring highly dispersed single-atom Fe on the N-C framework, showed outstanding activity for phenol degradation across a wide pH range. The incorporation of Fe significantly boosted the catalytic performance, achieving rapid degradation of phenol at 20 mg L−1 within 10 min, using 0.5 mmol L‒1 of PMS and 0.2 g L−1 of catalyst. Electron paramagnetic resonance (EPR) and reactive oxygen quenching experiments identified the singlet oxygen (1O2) and superoxide radical (O2•‒) as the main reactive oxygen species, with the former playing a key role. It has been demonstrated that the Fe-Nx structures were the active sites that facilitated the generation of 1O2, thereby enhancing the catalytic activity of the Fe-N-C materials. The catalyst also effectively addressed pollutants like Rhodamine B and climbazole, indicating its potential for environmental remediation. The synthesis approach for Fe-N-C is applicable to other transition metals, such as Mn, Co, Ni, Cu, and Zn, providing valuable insights for the development of highly efficient and durable M-N-C catalysts.
{"title":"High-dispersed single-atom Fe on N-doped biochar for efficient degradation of organic contaminants by activating peroxymonosulfate","authors":"Shutian Lin , Xinli Zhang , Yingzhi Chen , Yuanhong Zhong , Gao Cheng , Lin Yu","doi":"10.1016/j.solidstatesciences.2025.107860","DOIUrl":"10.1016/j.solidstatesciences.2025.107860","url":null,"abstract":"<div><div>The Fe-N-C catalyst was synthesized using loofah sponge-derived carbon and applied for peroxymonosulfate (PMS) activation to degrade organic pollutants. The catalyst, featuring highly dispersed single-atom Fe on the N-C framework, showed outstanding activity for phenol degradation across a wide pH range. The incorporation of Fe significantly boosted the catalytic performance, achieving rapid degradation of phenol at 20 mg L<sup>−1</sup> within 10 min, using 0.5 mmol L<sup>‒</sup><sup>1</sup> of PMS and 0.2 g L<sup>−1</sup> of catalyst. Electron paramagnetic resonance (EPR) and reactive oxygen quenching experiments identified the singlet oxygen (<sup>1</sup>O<sub>2</sub>) and superoxide radical (O<sub>2</sub><sup>•‒</sup>) as the main reactive oxygen species, with the former playing a key role. It has been demonstrated that the Fe-N<sub><em>x</em></sub> structures were the active sites that facilitated the generation of <sup>1</sup>O<sub>2</sub>, thereby enhancing the catalytic activity of the Fe-N-C materials. The catalyst also effectively addressed pollutants like Rhodamine B and climbazole, indicating its potential for environmental remediation. The synthesis approach for Fe-N-C is applicable to other transition metals, such as Mn, Co, Ni, Cu, and Zn, providing valuable insights for the development of highly efficient and durable M-N-C catalysts.</div></div>","PeriodicalId":432,"journal":{"name":"Solid State Sciences","volume":"162 ","pages":"Article 107860"},"PeriodicalIF":3.4,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143437248","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}