Pub Date : 2024-10-05DOI: 10.1016/j.solidstatesciences.2024.107717
Xiaoling Liu , Meng Wen , Qi Guo , Gang Wang , Pengcheng Hao , Wanyi Liu , Haijuan Zhan , Xiaoyan Chen , Heping Li
The development of photocatalysts with high charge separation and migration efficiencies for environmental remediation using sunlight had been a research priority. In this study, a ternary composite photocatalyst, P-CN/BC/NCDs, was successfully synthesized by thermal condensation and hydrothermal methods, incorporating graphitic carbon nitride (P-CN), biochar (BC), and nitrogen-doped carbon quantum dots (NCDs). Alizarin red S (ARS) was selected as the model pollutant to evaluate the photocatalytic degradation performance. P-CN/BC/NCDs exhibited enhanced photocatalytic degradation performance under visible light irradiation, with a 4.5-fold improvement compared to P-CN alone. The optimally NCDs-loaded P-CN/BC nanocomposites exhibited high visible light absorption and high specific surface area. The increased photocatalytic activity was further confirmed by the increase in photocurrent intensity and the decrease in fluorescence intensity and resistance. XPS and FT-IR tests showed that NCDs, as co-catalysts of P-CN/BC, effectively promoted charge separation through ether bonds and electrostatic interactions. It was experimentally verified by free radical trapping experiments and EPR tests that •O2− was the primary active species in the photocatalytic process, while •OH served as an auxiliary site during the degradation process. Cyclic experiments demonstrated high reusability and excellent stability, with an activity exceeding 93.8 %. Decomposition intermediates and reaction pathways were identified by liquid-quality analysis. Photocatalyst pervasiveness was evaluated by using different pollutants including methyl orange (MO), rhodamine B (Rh B) under similar conditions. This design concept of functional synergistic modification of P-CN materials holds promise for application in various fields.
{"title":"A novel metal-free nanomaterial P-CN/BC/NCDs preparation and its performance of photocatalytic degradation","authors":"Xiaoling Liu , Meng Wen , Qi Guo , Gang Wang , Pengcheng Hao , Wanyi Liu , Haijuan Zhan , Xiaoyan Chen , Heping Li","doi":"10.1016/j.solidstatesciences.2024.107717","DOIUrl":"10.1016/j.solidstatesciences.2024.107717","url":null,"abstract":"<div><div>The development of photocatalysts with high charge separation and migration efficiencies for environmental remediation using sunlight had been a research priority. In this study, a ternary composite photocatalyst, P-CN/BC/NCDs, was successfully synthesized by thermal condensation and hydrothermal methods, incorporating graphitic carbon nitride (P-CN), biochar (BC), and nitrogen-doped carbon quantum dots (NCDs). Alizarin red S (ARS) was selected as the model pollutant to evaluate the photocatalytic degradation performance. P-CN/BC/NCDs exhibited enhanced photocatalytic degradation performance under visible light irradiation, with a 4.5-fold improvement compared to P-CN alone. The optimally NCDs-loaded P-CN/BC nanocomposites exhibited high visible light absorption and high specific surface area. The increased photocatalytic activity was further confirmed by the increase in photocurrent intensity and the decrease in fluorescence intensity and resistance. XPS and FT-IR tests showed that NCDs, as co-catalysts of P-CN/BC, effectively promoted charge separation through ether bonds and electrostatic interactions. It was experimentally verified by free radical trapping experiments and EPR tests that •O<sub>2</sub><sup>−</sup> was the primary active species in the photocatalytic process, while •OH served as an auxiliary site during the degradation process. Cyclic experiments demonstrated high reusability and excellent stability, with an activity exceeding 93.8 %. Decomposition intermediates and reaction pathways were identified by liquid-quality analysis. Photocatalyst pervasiveness was evaluated by using different pollutants including methyl orange (MO), rhodamine B (Rh B) under similar conditions. This design concept of functional synergistic modification of P-CN materials holds promise for application in various fields.</div></div>","PeriodicalId":432,"journal":{"name":"Solid State Sciences","volume":"157 ","pages":"Article 107717"},"PeriodicalIF":3.4,"publicationDate":"2024-10-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142424665","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 : 2024-10-05DOI: 10.1016/j.solidstatesciences.2024.107716
R. Li , J. Zhang , X.J. Zhou , X.T. Pang , X.X. Ji , J.F. Duan , X.Z. Lu , X.M. Chen , J.H. Li , D.W. Zhou
In this paper, the nitrogen doped (N-HPC), nitrogen and phosphorus co-doped hierarchical porous carbon (NP-HPC) are prepared by cross-linking phytic acid and poly pyrrole/aniline precursor, respectively. They are mixed with MgH2 by high-energy ball milling, and then their effects and mechanisms on the hydrogen absorption and desorption properties of MgH2 are investigated. Meanwhile, the hydrogen storage properties of MgH2 added with graphite (G) are also compared. The results show that the additions of NP-HPC, N-HPC, and G all exhibit the catalytic effect on the hydrogen absorption and desorption of MgH2. As for the hydrogen desorption, the catalytic effect is enhanced in the order of N-HPC, G and NP-HPC. Compared with pure MgH2, the hydrogen desorption temperature is reduced by 65.3 °C, 79.6 °C and 91.1 °C, respectively. Among them, the MgH2 + NP-HPC system can release 5.17 wt% hydrogen at 300 °C within 30 min. First-principles calculations reveal that the P-doped and vacancy-containing carbon materials significantly reduce the H2 recombination barrier from the surface of MgH2 and distort the atomic structure of near-surface layer of MgH2, which in turn weakens the Mg-H bond strength. This may be the intrinsic reason for the excellent catalytic effect of NP-HPC and vacancy-containing G on the hydrogen desorption performance of MgH2.
{"title":"Effects of heteroatom-doped hierarchical porous carbon on hydrogen storage properties of MgH2","authors":"R. Li , J. Zhang , X.J. Zhou , X.T. Pang , X.X. Ji , J.F. Duan , X.Z. Lu , X.M. Chen , J.H. Li , D.W. Zhou","doi":"10.1016/j.solidstatesciences.2024.107716","DOIUrl":"10.1016/j.solidstatesciences.2024.107716","url":null,"abstract":"<div><div>In this paper, the nitrogen doped (N-HPC), nitrogen and phosphorus co-doped hierarchical porous carbon (NP-HPC) are prepared by cross-linking phytic acid and poly pyrrole/aniline precursor, respectively. They are mixed with MgH<sub>2</sub> by high-energy ball milling, and then their effects and mechanisms on the hydrogen absorption and desorption properties of MgH<sub>2</sub> are investigated. Meanwhile, the hydrogen storage properties of MgH<sub>2</sub> added with graphite (G) are also compared. The results show that the additions of NP-HPC, N-HPC, and G all exhibit the catalytic effect on the hydrogen absorption and desorption of MgH<sub>2</sub>. As for the hydrogen desorption, the catalytic effect is enhanced in the order of N-HPC, G and NP-HPC. Compared with pure MgH<sub>2</sub>, the hydrogen desorption temperature is reduced by 65.3 °C, 79.6 °C and 91.1 °C, respectively. Among them, the MgH<sub>2</sub> + NP-HPC system can release 5.17 wt% hydrogen at 300 °C within 30 min. First-principles calculations reveal that the P-doped and vacancy-containing carbon materials significantly reduce the H<sub>2</sub> recombination barrier from the surface of MgH<sub>2</sub> and distort the atomic structure of near-surface layer of MgH<sub>2</sub>, which in turn weakens the Mg-H bond strength. This may be the intrinsic reason for the excellent catalytic effect of NP-HPC and vacancy-containing G on the hydrogen desorption performance of MgH<sub>2</sub>.</div></div>","PeriodicalId":432,"journal":{"name":"Solid State Sciences","volume":"157 ","pages":"Article 107716"},"PeriodicalIF":3.4,"publicationDate":"2024-10-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142424667","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 : 2024-09-30DOI: 10.1016/j.solidstatesciences.2024.107714
Sree Sesha Sudha Gayatri B, Madhusudhana Rao N
To examine the effect of rare earth ions on CuS nanostructures, a series of Gadolinium-doped copper sulphide (Cu1-xGdxS) nanostructures were synthesized through the hydrothermal method. These nanostructures were prepared at x = 0, 1, 3, 5, and 7 at. % concentrations. The prepared samples’ structural, optical, and magnetic characteristics were investigated. Powder X-ray diffraction and Raman analysis were performed to examine the structural analysis of the samples and confirm the existence of a covellite phase hexagonal structure. XPS analysis was conducted to study the valence states. Observations of the surface morphology study from FESEM reveal the formation of flower-shaped structures resembling nanospheres, while at lower magnification nanoflakes were observed. Optical reflectance spectra were recorded using UV–Vis spectroscopy, which showed the increase in bandgap as the concentration of Gd rises. The fluorescence spectrophotometer was utilized for the analysis of room-temperature photoluminescence. The prepared samples showed significant emission peaks at 435 nm. Fluorescence lifetime studies were carried out to confirm the fluorescence decay of CuS nanostructures doped with Gd. Magnetic measurements revealed that prepared samples exhibit an unexpected superparamagnetic nature at room temperature.
为了研究稀土离子对 CuS 纳米结构的影响，我们采用水热法合成了一系列掺杂钆的硫化铜（Cu1-xGdxS）纳米结构。这些纳米结构的 x = 0、1、3、5 和 7 的浓度分别为%的浓度下制备了这些纳米结构。研究了所制备样品的结构、光学和磁学特性。粉末 X 射线衍射和拉曼分析用于检查样品的结构分析，并确认了沸石相六方结构的存在。XPS 分析用于研究价态。通过 FESEM 对表面形貌的观察发现，形成了类似纳米球的花形结构，而在较低的放大倍率下则观察到了纳米片。使用紫外可见光谱仪记录的光学反射光谱显示，随着钆浓度的增加，带隙也在增加。荧光分光光度计用于分析室温光致发光。制备的样品在 435 纳米波长处显示出明显的发射峰。荧光寿命研究证实了掺杂钆的 CuS 纳米结构的荧光衰减。磁性测量显示，制备的样品在室温下具有意想不到的超顺磁性。
{"title":"Influence of gadolinium doping on structural, optical, and magnetic properties of CuS nanostructures","authors":"Sree Sesha Sudha Gayatri B, Madhusudhana Rao N","doi":"10.1016/j.solidstatesciences.2024.107714","DOIUrl":"10.1016/j.solidstatesciences.2024.107714","url":null,"abstract":"<div><div>To examine the effect of rare earth ions on CuS nanostructures, a series of Gadolinium-doped copper sulphide (Cu<sub>1-x</sub>Gd<sub>x</sub>S) nanostructures were synthesized through the hydrothermal method. These nanostructures were prepared at x = 0, 1, 3, 5, and 7 at. % concentrations. The prepared samples’ structural, optical, and magnetic characteristics were investigated. Powder X-ray diffraction and Raman analysis were performed to examine the structural analysis of the samples and confirm the existence of a covellite phase hexagonal structure. XPS analysis was conducted to study the valence states. Observations of the surface morphology study from FESEM reveal the formation of flower-shaped structures resembling nanospheres, while at lower magnification nanoflakes were observed. Optical reflectance spectra were recorded using UV–Vis spectroscopy, which showed the increase in bandgap as the concentration of Gd rises. The fluorescence spectrophotometer was utilized for the analysis of room-temperature photoluminescence. The prepared samples showed significant emission peaks at 435 nm. Fluorescence lifetime studies were carried out to confirm the fluorescence decay of CuS nanostructures doped with Gd. Magnetic measurements revealed that prepared samples exhibit an unexpected superparamagnetic nature at room temperature.</div></div>","PeriodicalId":432,"journal":{"name":"Solid State Sciences","volume":"157 ","pages":"Article 107714"},"PeriodicalIF":3.4,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142424663","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}
Sr3Y(PO4)3 (SYPO) is recognized as a highly promising material for dosimetry applications, owing to its dosimetric properties. In this work, we synthesized the SYPO single crystals doped with 0.1, 0.5, 1, and 5 % Dy using the floating zone furnace to evaluate the photoluminescence and thermally stimulated luminescence (TSL) characteristics. All the SYPO single crystals doped with Dy exhibited emission peaks at 480, 580, 670, and 760 nm in PL and TSL spectra. These emission peaks were typical for the 4f–4f transitions of Dy3+ ions. The SYPO single crystal doped with 0.1 % Dy displayed a glow peak in the TSL glow curve at 70 °C. The SYPO single crystals doped with 0.5, 1, and 5 % Dy showed two glow peaks at approximately 70 and 110 °C. The SYPO single crystal doped with 0.5 % Dy exhibited the highest TSL intensity with a lower detection limit of 0.1 mGy. The SYPO single crystal doped with 0.5 % Dy showed a spatial resolution of 50.0 μm after X-ray irradiation of 1Gy.
Sr3Y(PO4)3（SYPO）因其剂量测定特性而被认为是一种极具潜力的剂量测定应用材料。在这项工作中，我们利用浮区炉合成了掺杂 0.1%、0.5%、1% 和 5% Dy 的 SYPO 单晶，并对其光致发光和热激发发光（TSL）特性进行了评估。在 PL 和 TSL 光谱中，所有掺入 Dy 的 SYPO 单晶都在 480、580、670 和 760 纳米波长处显示出发射峰。这些发射峰是典型的 Dy3+ 离子的 4f-4f 转变。掺杂了 0.1 % Dy 的 SYPO 单晶在 70 °C 时的 TSL 辉光曲线中显示出一个辉光峰。掺杂了 0.5%、1% 和 5% Dy 的 SYPO 单晶在大约 70 ℃ 和 110 ℃ 处显示出两个辉光峰。掺入 0.5 % Dy 的 SYPO 单晶显示出最高的 TSL 强度，检测下限为 0.1 mGy。掺入 0.5 % Dy 的 SYPO 单晶体在 1Gy X 射线照射后显示出 50.0 μm 的空间分辨率。
{"title":"Photoluminescence and thermally stimulated luminescence properties of Sr3Y(PO4)3 single crystals doped with dy","authors":"Haruaki Ezawa , Kai Okazaki , Yuma Takebuchi , Takumi Kato , Daisuke Nakauchi , Noriaki Kawaguchi , Takayuki Yanagida","doi":"10.1016/j.solidstatesciences.2024.107715","DOIUrl":"10.1016/j.solidstatesciences.2024.107715","url":null,"abstract":"<div><div>Sr<sub>3</sub>Y(PO<sub>4</sub>)<sub>3</sub> (SYPO) is recognized as a highly promising material for dosimetry applications, owing to its dosimetric properties. In this work, we synthesized the SYPO single crystals doped with 0.1, 0.5, 1, and 5 % Dy using the floating zone furnace to evaluate the photoluminescence and thermally stimulated luminescence (TSL) characteristics. All the SYPO single crystals doped with Dy exhibited emission peaks at 480, 580, 670, and 760 nm in PL and TSL spectra. These emission peaks were typical for the 4f–4f transitions of Dy<sup>3+</sup> ions. The SYPO single crystal doped with 0.1 % Dy displayed a glow peak in the TSL glow curve at 70 °C. The SYPO single crystals doped with 0.5, 1, and 5 % Dy showed two glow peaks at approximately 70 and 110 °C. The SYPO single crystal doped with 0.5 % Dy exhibited the highest TSL intensity with a lower detection limit of 0.1 mGy. The SYPO single crystal doped with 0.5 % Dy showed a spatial resolution of 50.0 μm after X-ray irradiation of 1Gy.</div></div>","PeriodicalId":432,"journal":{"name":"Solid State Sciences","volume":"157 ","pages":"Article 107715"},"PeriodicalIF":3.4,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142424664","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 : 2024-09-26DOI: 10.1016/j.solidstatesciences.2024.107712
Sourav Adak , Luke L. Daemen , Monika Hartl , Aman Kumar Pandey , Heinz Nakotte
Thermal expansion in Prussian Blue Analogs (PBAs) M3[Cr(CN)6]2.nH2O (M = Mn, Fe, Co, Ni; n = 10–16) was studied using powder X-ray diffraction (XRD) as a function of temperature in the range 123–298 K. Standard chemical precipitation was used to prepare the materials and they were characterized using standard characterization techniques XRD, X-ray fluorescence (XRF), thermogravimetric analysis (TGA) and Fourier transform infrared (FTIR) spectroscopy. All materials were found to crystallize in the cubic structure with space group . Strong compositional dependence of thermal expansion is found in this series of PBAs. While Mn3[Cr(CN)6]2.12H2O and Ni3[Cr(CN)6]2.16H2O show positive thermal expansion (PTE) behavior the other two PBAs, Fe3[Cr(CN)6]2.10H2O and Co3[Cr(CN)6]2.14H2O, show strong negative thermal expansion (NTE) behavior with as large coefficient of thermal expansion (CTE) as −19.7 x 10−6 K−1 (for M = Fe) in the temperature range 123–223 K. For the PBAs showing NTE, the magnitude of NTE coefficients can be correlated with the trends for M cation size and cell (or lattice) parameter.
{"title":"Thermal expansion in Prussian Blue analogs M3[Cr(CN)6]2.nH2O (M = Mn, Fe, Co, Ni)","authors":"Sourav Adak , Luke L. Daemen , Monika Hartl , Aman Kumar Pandey , Heinz Nakotte","doi":"10.1016/j.solidstatesciences.2024.107712","DOIUrl":"10.1016/j.solidstatesciences.2024.107712","url":null,"abstract":"<div><div>Thermal expansion in Prussian Blue Analogs (PBAs) M<sub>3</sub>[Cr(CN)<sub>6</sub>]<sub>2</sub>.nH<sub>2</sub>O (M = Mn, Fe, Co, Ni; n = 10–16) was studied using powder X-ray diffraction (XRD) as a function of temperature in the range 123–298 K. Standard chemical precipitation was used to prepare the materials and they were characterized using standard characterization techniques XRD, X-ray fluorescence (XRF), thermogravimetric analysis (TGA) and Fourier transform infrared (FTIR) spectroscopy. All materials were found to crystallize in the cubic structure with space group <span><math><mrow><mi>F</mi><mi>m</mi><mover><mn>3</mn><mo>‾</mo></mover><mi>m</mi></mrow></math></span>. Strong compositional dependence of thermal expansion is found in this series of PBAs. While Mn<sub>3</sub>[Cr(CN)<sub>6</sub>]<sub>2</sub>.12H<sub>2</sub>O and Ni<sub>3</sub>[Cr(CN)<sub>6</sub>]<sub>2</sub>.16H<sub>2</sub>O show positive thermal expansion (PTE) behavior the other two PBAs, Fe<sub>3</sub>[Cr(CN)<sub>6</sub>]<sub>2</sub>.10H<sub>2</sub>O and Co<sub>3</sub>[Cr(CN)<sub>6</sub>]<sub>2</sub>.14H<sub>2</sub>O, show strong negative thermal expansion (NTE) behavior with as large coefficient of thermal expansion (CTE) as −19.7 x 10<sup>−6</sup> K<sup>−1</sup> (for M = Fe) in the temperature range 123–223 K. For the PBAs showing NTE, the magnitude of NTE coefficients can be correlated with the trends for M cation size and cell (or lattice) parameter.</div></div>","PeriodicalId":432,"journal":{"name":"Solid State Sciences","volume":"157 ","pages":"Article 107712"},"PeriodicalIF":3.4,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142357045","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 method was developed for the production of nanosized complex oxides and oxysulfides. The first stage uses supercritical СО2 fluid (SAS – supercritical antisolvent method). This approach makes it possible to obtain precursor-free complex oxides in a narrow nanoscale range. Nanosized rare-earth iron garnets with the general formula R3Fe5O12, where R is a rare earth element, were obtained and studied by physicochemical methods. The resulting samples have a size of less than 100 nm, exhibit ferromagnetic ordering, and can be used as soft magnetic materials. The multi-stage method for the preparation of complex oxysulfides was not previously demonstrated anywhere in the literature. The method involves three stages. At the first stage, a nanosized X-ray amorphous solid solution of the original salts is obtained using the SAS method. Then a nanosized X-ray amorphous component – the oxide phase – is obtained by annealing in a furnace. After this, the resulting oxide phase is mixed with the disulfide of a transition element (Nb, Mo), and high-temperature annealing is performed in an evacuated quartz ampoule. As a result, compact and nanosized phases of the composition Eu3Fe5-3/2xMox□1/2xO12-2xS2x and Eu3Fe5-3/2xNbx□1/2xO12-2xS2x, where x = 0.15, were obtained for the first time. The introduction of the sulfide component, namely NbS2, into the garnet structure increases its magnetic parameters by the factor of 1.5.
我们开发了一种生产纳米级复合氧化物和氧化硫的方法。第一阶段使用超临界 СО2 流体（SAS - 超临界反溶剂法）。这种方法可以在较窄的纳米尺度范围内获得不含前驱体的复合氧化物。我们获得了通式为 R3Fe5O12（其中 R 为稀土元素）的纳米级稀土铁榴石，并通过物理化学方法对其进行了研究。所得样品的尺寸小于 100 纳米，具有铁磁有序性，可用作软磁材料。这种多阶段制备复杂氧化硫的方法在以前的文献中从未出现过。该方法包括三个阶段。第一阶段，使用 SAS 方法获得原始盐类的纳米级 X 射线无定形固溶体。然后，在熔炉中退火，获得纳米级 X 射线无定形成分--氧化物相。之后，将得到的氧化物相与过渡元素（铌、钼）的二硫化物混合，并在抽真空的石英安瓿瓶中进行高温退火。结果，首次获得了成分为 Eu3Fe5-3/2xMox□1/2xO12-2xS2x 和 Eu3Fe5-3/2xNbx□1/2xO12-2xS2x （其中 x = 0.15）的紧凑型纳米级相。在石榴石结构中引入硫化物成分（即 NbS2）后，其磁性参数增加了 1.5 倍。
{"title":"Synthesis of nanosized phases with a garnet structure using supercritical СО2 fluid","authors":"A.I. Kolobanov , V.V. Fomichev , A.S. Sigov , A.S. Kumskov , A.M. Ionov , R.N. Mozhchil","doi":"10.1016/j.solidstatesciences.2024.107710","DOIUrl":"10.1016/j.solidstatesciences.2024.107710","url":null,"abstract":"<div><div>A method was developed for the production of nanosized complex oxides and oxysulfides. The first stage uses supercritical СО<sub>2</sub> fluid (SAS – supercritical antisolvent method). This approach makes it possible to obtain precursor-free complex oxides in a narrow nanoscale range. Nanosized rare-earth iron garnets with the general formula R<sub>3</sub>Fe<sub>5</sub>O<sub>12</sub>, where R is a rare earth element, were obtained and studied by physicochemical methods. The resulting samples have a size of less than 100 nm, exhibit ferromagnetic ordering, and can be used as soft magnetic materials. The multi-stage method for the preparation of complex oxysulfides was not previously demonstrated anywhere in the literature. The method involves three stages. At the first stage, a nanosized X-ray amorphous solid solution of the original salts is obtained using the SAS method. Then a nanosized X-ray amorphous component – the oxide phase – is obtained by annealing in a furnace. After this, the resulting oxide phase is mixed with the disulfide of a transition element (Nb, Mo), and high-temperature annealing is performed in an evacuated quartz ampoule. As a result, compact and nanosized phases of the composition Eu<sub>3</sub>Fe<sub>5-3/2x</sub>Mo<sub>x</sub>□<sub>1/2x</sub>O<sub>12-2x</sub>S<sub>2x</sub> and Eu<sub>3</sub>Fe<sub>5-3/2x</sub>Nb<sub>x</sub>□<sub>1/2x</sub>O<sub>12-2x</sub>S<sub>2x</sub>, where x = 0.15, were obtained for the first time. The introduction of the sulfide component, namely NbS<sub>2</sub>, into the garnet structure increases its magnetic parameters by the factor of 1.5.</div></div>","PeriodicalId":432,"journal":{"name":"Solid State Sciences","volume":"157 ","pages":"Article 107710"},"PeriodicalIF":3.4,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142357044","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 : 2024-09-25DOI: 10.1016/j.solidstatesciences.2024.107713
Fei Ruan, Chonggui Lei, Xi Wu, Jinxiao Bao, Fen Zhou, Jianquan Gao, Guoqi Liu
To further investigate the electrochemical performance of Tm doped CaZrO3 electrolyte, the CaZr1−xTmxO3−α (x = 0, 0.025, 0.05, 0.075 and 0.1) solid electrolyte specimens were prepared by high temperature solid state method. The phase structure and microstructure of the electrolyte samples were analyzed by Raman spectrum, XRD and SEM. The electrical conductivity of the specimen was measured at the temperature of 673∼1373K in hydrogen-rich and oxygen-rich atmosphere by the two-terminal AC impedance spectroscopy method. The H/D isotope effect of the specimen at different temperature was tested to confirm the dominant conducting carrier in predetermined temperature and atmosphere. It is found that proton is the dominant charge carrier both in oxygen-rich and hydrogen-rich atmosphere at the lower temperature below 1073 K. However, at higher temperature above 1073K, the predominant charge carrier seems to be oxygen ion vacancy in hydrogen-rich, whereas to be electron hole in oxygen-rich atmosphere, based on the analysis of the atmospheric dependence of the electrical conductivity. Moreover, partial conductivities of conducting species, the active doping amount of Tm and the standard Gibbs free energy changes for interstitial proton production by dissolution of water and hydrogen in Tm doped electrolyte were estimated based on crystal defect chemistry theory.
{"title":"Research on electrical conductive properties of thulium-doped calcium zirconate solid electrolyte","authors":"Fei Ruan, Chonggui Lei, Xi Wu, Jinxiao Bao, Fen Zhou, Jianquan Gao, Guoqi Liu","doi":"10.1016/j.solidstatesciences.2024.107713","DOIUrl":"10.1016/j.solidstatesciences.2024.107713","url":null,"abstract":"<div><div>To further investigate the electrochemical performance of Tm doped CaZrO<sub>3</sub> electrolyte, the CaZr<sub>1<em>−x</em></sub>Tm<sub><em>x</em></sub>O<sub>3<em>−α</em></sub> (<em>x</em> = 0, 0.025, 0.05, 0.075 and 0.1) solid electrolyte specimens were prepared by high temperature solid state method. The phase structure and microstructure of the electrolyte samples were analyzed by Raman spectrum, XRD and SEM. The electrical conductivity of the specimen was measured at the temperature of 673∼1373K in hydrogen-rich and oxygen-rich atmosphere by the two-terminal AC impedance spectroscopy method. The H/D isotope effect of the specimen at different temperature was tested to confirm the dominant conducting carrier in predetermined temperature and atmosphere. It is found that proton is the dominant charge carrier both in oxygen-rich and hydrogen-rich atmosphere at the lower temperature below 1073 K. However, at higher temperature above 1073K, the predominant charge carrier seems to be oxygen ion vacancy in hydrogen-rich, whereas to be electron hole in oxygen-rich atmosphere, based on the analysis of the atmospheric dependence of the electrical conductivity. Moreover, partial conductivities of conducting species, the active doping amount of Tm and the standard Gibbs free energy changes for interstitial proton production by dissolution of water and hydrogen in Tm doped electrolyte were estimated based on crystal defect chemistry theory.</div></div>","PeriodicalId":432,"journal":{"name":"Solid State Sciences","volume":"157 ","pages":"Article 107713"},"PeriodicalIF":3.4,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142326607","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}
<div><div>Thermoelectric (TE) materials have lately attracted a lot of attention and sparked a flurry of research because of their potential for energy conversion and broad spectrum of applications, including waste heat recovery, thermocouples, sensors, and refrigeration. Additionally, they could potentially be able to offer extremely effective and eco-friendly methods for energy production and harvesting, which might aid in addressing the world's energy concerns. Concerning the advancement in condensed matter physics, although a plethora of research has been devoted to identifying suitable TE materials over the years, there is still scope for the exploration of new materials. This review article strives to project extensive progress in the field of thermoelectricity, commencing with a discussion on various classes of TE materials scrutinized based on TE coefficients such as thermopower, power factor, and thermal conductivity computed within the framework of DFT, combined with an in-depth look at the computational techniques used. A wide range of prospective TE material classes, including chalcogenides, pnictides, oxides, perovskites, transition metal dichalcogenides (TMD), and a few more, are meticulously addressed, stressing the unique characteristics of each class in separate sections and subsections. SrAgChF (Ch = S, Se, Te), with its superlattice structure, boasts high thermopower for both carriers, making it ideal for power generation. Similarly, ThOCh (Ch = S, Se, Te) and NbX<sub>2</sub>Y<sub>2</sub> (X = S, Se, Y = Cl, Br, I) chalcogen materials exhibit significant thermoelectric properties in both bulk and monolayer forms. Fe<sub>2</sub>GeCh<sub>4</sub> (Ch = S, Se, Te) demonstrates exceptional anisotropic TE characteristics, advantageous for device applications. Structurally resembling chalcopyrites, Zn-based pnictides show high efficiency, validated by the analysis of power factor scaled by temperature and relaxation time (<em>S</em><sup>2</sup><em>σT</em>/<em>τ</em>: where S is thermopower, <em>σ</em> is electrical conductivity, <em>S</em><sup>2</sup><em>σ</em> is power factor, T is temperature and <em>τ</em> is the relaxation time). Moreover, CaLiPn (Pn = As, Sb, Bi) emerges as more favorable for TE applications than SrLiAs, displaying low lattice thermal conductivity. Among transition metal dichalcogenides (TMDs), OsX<sub>2</sub> (S, Se, Te) exhibits high thermopower, while FeS<sub>2</sub> displays remarkable thermoelectric properties in both marcasite and pyrite structural phases. In exploring 2D materials akin to graphene, ReS<sub>2</sub>'s TE properties have been scrutinized across various forms, showcasing significant potential, especially when tailored for flexibility. Compounds like CaSrX (X = Si, Ge, Sn, Pb) and ZnGeSb<sub>2</sub> exhibit notable TE features, indicating avenues for strain-engineered modulation of TE properties. Lattice dynamics play a pivotal role in TE efficiency, driving investigations into phonon dispersio
热电（TE）材料因其在能量转换方面的潜力和广泛的应用（包括废热回收、热电偶、传感器和制冷），近来吸引了众多关注和研究热潮。此外，它们还有可能提供极其有效和环保的能源生产和收集方法，从而有助于解决世界能源问题。关于凝聚态物理学的发展，尽管多年来大量研究都致力于确定合适的 TE 材料，但仍有探索新材料的空间。这篇综述文章致力于预测热电领域的广泛进展，首先讨论了基于 TE 系数（如在 DFT 框架内计算的热功率、功率因数和热导率）的各类 TE 材料，并结合所使用的计算技术进行了深入探讨。该书对包括钙钛矿、锑化物、氧化物、过氧化物、过渡金属二钙钛矿 (TMD) 等在内的各种前瞻性 TE 材料类别进行了细致的论述，并在不同的章节和小节中强调了每一类材料的独特性。SrAgChF（Ch = S、Se、Te）具有超晶格结构，对两种载流子都具有很高的热功率，是理想的发电材料。同样，ThOCh（Ch = S、Se、Te）和 NbX2Y2（X = S、Se，Y = Cl、Br、I）铬合金材料在块体和单层形式下都具有显著的热电特性。Fe2GeCh4（Ch = S、Se、Te）显示出卓越的各向异性 TE 特性，有利于器件应用。通过分析功率因数与温度和弛豫时间的比例关系（S2σT/τ：其中 S 为热功率，σ 为电导率，S2σ 为功率因数，T 为温度，τ 为弛豫时间），验证了锌基锑化物与黄铜矿的结构相似，具有很高的效率。此外，CaLiPn（Pn = As、Sb、Bi）显示出较低的晶格热导率，比 SrLiAs 更适合 TE 应用。在过渡金属二卤化物 (TMD) 中，OsX2（S、Se、Te）表现出较高的热功率，而 FeS2 在马氏体和黄铁矿结构相中都表现出显著的热电特性。在探索类似石墨烯的二维材料过程中，ReS2 的 TE 特性在各种形态中都得到了仔细研究，尤其是在进行柔性定制时，显示出巨大的潜力。CaSrX（X = Si、Ge、Sn、Pb）和 ZnGeSb2 等化合物表现出显著的 TE 特性，为应变工程调节 TE 特性提供了途径。晶格动力学在 TE 效率中起着举足轻重的作用，推动着对材料声子色散和热特性的研究。CsAgO 的晶格热导率极低，彰显了其作为 TE 材料的前景。尽管半经典近似很有效，但要准确预测传输参数，就必须考虑散射效应。考虑这些因素对于精确估算热电功勋值（ZT）至关重要。值得注意的是，CsAgO 的低晶格热导率有助于提高其效能，其 ZT 超过 1.4。CuTlX（X = S、Se）等层状化合物的晶格热导率表现出极强的各向异性，在 300 K 时的 ZT 值超过了 1。本综述的结论部分讨论了所研究化合物的优点、TE 材料在设备应用方面的前景、柔性和可穿戴 TE 材料的开发以及改进 TE 参数的策略。
{"title":"Computational advances for energy conversion: Unleashing the potential of thermoelectric materials","authors":"Kanchana Venkatakrishnan, Vineet Kumar Sharma, Sushree Sarita Sahoo","doi":"10.1016/j.solidstatesciences.2024.107707","DOIUrl":"10.1016/j.solidstatesciences.2024.107707","url":null,"abstract":"<div><div>Thermoelectric (TE) materials have lately attracted a lot of attention and sparked a flurry of research because of their potential for energy conversion and broad spectrum of applications, including waste heat recovery, thermocouples, sensors, and refrigeration. Additionally, they could potentially be able to offer extremely effective and eco-friendly methods for energy production and harvesting, which might aid in addressing the world's energy concerns. Concerning the advancement in condensed matter physics, although a plethora of research has been devoted to identifying suitable TE materials over the years, there is still scope for the exploration of new materials. This review article strives to project extensive progress in the field of thermoelectricity, commencing with a discussion on various classes of TE materials scrutinized based on TE coefficients such as thermopower, power factor, and thermal conductivity computed within the framework of DFT, combined with an in-depth look at the computational techniques used. A wide range of prospective TE material classes, including chalcogenides, pnictides, oxides, perovskites, transition metal dichalcogenides (TMD), and a few more, are meticulously addressed, stressing the unique characteristics of each class in separate sections and subsections. SrAgChF (Ch = S, Se, Te), with its superlattice structure, boasts high thermopower for both carriers, making it ideal for power generation. Similarly, ThOCh (Ch = S, Se, Te) and NbX<sub>2</sub>Y<sub>2</sub> (X = S, Se, Y = Cl, Br, I) chalcogen materials exhibit significant thermoelectric properties in both bulk and monolayer forms. Fe<sub>2</sub>GeCh<sub>4</sub> (Ch = S, Se, Te) demonstrates exceptional anisotropic TE characteristics, advantageous for device applications. Structurally resembling chalcopyrites, Zn-based pnictides show high efficiency, validated by the analysis of power factor scaled by temperature and relaxation time (<em>S</em><sup>2</sup><em>σT</em>/<em>τ</em>: where S is thermopower, <em>σ</em> is electrical conductivity, <em>S</em><sup>2</sup><em>σ</em> is power factor, T is temperature and <em>τ</em> is the relaxation time). Moreover, CaLiPn (Pn = As, Sb, Bi) emerges as more favorable for TE applications than SrLiAs, displaying low lattice thermal conductivity. Among transition metal dichalcogenides (TMDs), OsX<sub>2</sub> (S, Se, Te) exhibits high thermopower, while FeS<sub>2</sub> displays remarkable thermoelectric properties in both marcasite and pyrite structural phases. In exploring 2D materials akin to graphene, ReS<sub>2</sub>'s TE properties have been scrutinized across various forms, showcasing significant potential, especially when tailored for flexibility. Compounds like CaSrX (X = Si, Ge, Sn, Pb) and ZnGeSb<sub>2</sub> exhibit notable TE features, indicating avenues for strain-engineered modulation of TE properties. Lattice dynamics play a pivotal role in TE efficiency, driving investigations into phonon dispersio","PeriodicalId":432,"journal":{"name":"Solid State Sciences","volume":"157 ","pages":"Article 107707"},"PeriodicalIF":3.4,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142357046","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 : 2024-09-24DOI: 10.1016/j.solidstatesciences.2024.107711
M.S. Al-Buriahi , Norah Alomayrah , Jamila S. Alzahrani , Sultan Alomairy , Z.A. Alrowaili , I.O. Olarinoye , Amani Alalawi , Alaa Hammoud
The optical quality and compositional flexibility of borate glasses make them attractive materials for optical applications, nuclear waste containment, transparent radiation shields and many other applications in the nuclear and allied industries. This study presents the physical, optical, and gamma transmission data of the sodium borate glass structure: 75B2O3 – 15Na2O – 9.5x – 0.5Nd2O3; for x = Bi2O3 (BiNd), SrO (SrNd), and Li2O (LiNd). The glasses were prepared using the traditional melt-and-quench technique. The influence of Bi2O3, SrO, and Li2O on the physical attributes, optical constants, and gamma radiation interaction coefficients was probed using standard laboratory procedures and software. The density of BiNd, SrNd, and LiNd was 3.32, 2.43, and 2.24 g/cm3, respectively. The molar volume of the glasses followed the trend: BiNd > SrNd > LiNd. The optical constants of the glasses, such as refractive index, metallization criterion, molar refractivity, molar polarizability, reflectance loss, and optical transmission, showed a wide fluctuation with respect to glass composition. The values of the gamma mass attenuation coefficients for 15 keV–15 MeV photons were in the range 0.0316–45.0225 cm2/g for BiNd, 0.0206–5.4940 cm2/g for SrNd, and 0.0184–3.4603 cm2/g for LiNd. Generally, density has a positive correlation with the gamma absorption prowess of the investigated xNd glasses. A correlation between the optical and shielding parameters was highlighted in this study. The xNd glasses, especially SrNd and BiNd, are preferred as transparent radiation protection barriers, in contrast to some conventional Pb-based glasses, from environmental and public health perspectives. This glass composition is therefore unique and its properties are essentially useful in optical and radiation technologies.
{"title":"Optical parameters and gamma shielding quality of sodium-borate glasses: The relative contribution of Bi2O3, SrO, and Li2O","authors":"M.S. Al-Buriahi , Norah Alomayrah , Jamila S. Alzahrani , Sultan Alomairy , Z.A. Alrowaili , I.O. Olarinoye , Amani Alalawi , Alaa Hammoud","doi":"10.1016/j.solidstatesciences.2024.107711","DOIUrl":"10.1016/j.solidstatesciences.2024.107711","url":null,"abstract":"<div><div>The optical quality and compositional flexibility of borate glasses make them attractive materials for optical applications, nuclear waste containment, transparent radiation shields and many other applications in the nuclear and allied industries. This study presents the physical, optical, and gamma transmission data of the sodium borate glass structure: 75B<sub>2</sub>O<sub>3</sub> – 15Na<sub>2</sub>O – 9.5x – 0.5Nd<sub>2</sub>O<sub>3;</sub> for <em>x</em> = Bi<sub>2</sub>O<sub>3</sub> (BiNd), SrO (SrNd), and Li<sub>2</sub>O (LiNd). The glasses were prepared using the traditional melt-and-quench technique. The influence of Bi<sub>2</sub>O<sub>3</sub>, SrO, and Li<sub>2</sub>O on the physical attributes, optical constants, and gamma radiation interaction coefficients was probed using standard laboratory procedures and software. The density of BiNd, SrNd, and LiNd was 3.32, 2.43, and 2.24 g/cm<sup>3</sup>, respectively. The molar volume of the glasses followed the trend: BiNd > SrNd > LiNd. The optical constants of the glasses, such as refractive index, metallization criterion, molar refractivity, molar polarizability, reflectance loss, and optical transmission, showed a wide fluctuation with respect to glass composition. The values of the gamma mass attenuation coefficients for 15 keV–15 MeV photons were in the range 0.0316–45.0225 cm<sup>2</sup>/g for BiNd, 0.0206–5.4940 cm<sup>2</sup>/g for SrNd, and 0.0184–3.4603 cm<sup>2</sup>/g for LiNd. Generally, density has a positive correlation with the gamma absorption prowess of the investigated xNd glasses. A correlation between the optical and shielding parameters was highlighted in this study. The xNd glasses, especially SrNd and BiNd, are preferred as transparent radiation protection barriers, in contrast to some conventional Pb-based glasses, from environmental and public health perspectives. This glass composition is therefore unique and its properties are essentially useful in optical and radiation technologies.</div></div>","PeriodicalId":432,"journal":{"name":"Solid State Sciences","volume":"157 ","pages":"Article 107711"},"PeriodicalIF":3.4,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142322359","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 : 2024-09-21DOI: 10.1016/j.solidstatesciences.2024.107709
M. Všianská , M. Šob
We discuss recent doubts about the true ground-state (GS) structure of the intermetallic compound Fe3Al. It seems that it should be the D03 structure (observed experimentally), but there are some considerations that, perhaps, D03 might be a high-temperature (>400 K) structure and the GS at 0 K might be the L12 structure because there might be a high energy barrier between both structures and, when the temperature is lowered, the system is not able to transform into the (perhaps) lower-energy L12 structure. To elucidate this problem, we re-interpret our recent extended ab initio electronic structure calculations for Fe3Al performed with the help of the VASP code and using various exchange-correlation energies within the generalized gradient approximation (GGA). Regrettably, some calculations provide the L12 and some of them D03 as the GS structure.
To resolve this question, we performed further calculations testing 9 frequently applied metaGGAs, such as TPSS, revTPSS, M06-L, SCAN(-L), rSCAN(-L) and r2SCAN(-L) representing a higher rung of the Jacob's ladder. It turns out that also here some meta-GGAs lead to L12 and some others to D03 GS structure and, again, we cannot decide.
In this way, the present results represent the very first step on the way to understand the energetics of the Fe3Al compound and its ground state. We hope they may motivate future theoretical and experimental work in this direction.
{"title":"What is the true ground state of intermetallic compound Fe3Al?","authors":"M. Všianská , M. Šob","doi":"10.1016/j.solidstatesciences.2024.107709","DOIUrl":"10.1016/j.solidstatesciences.2024.107709","url":null,"abstract":"<div><div>We discuss recent doubts about the true ground-state (GS) structure of the intermetallic compound Fe<sub>3</sub>Al. It seems that it should be the D0<sub>3</sub> structure (observed experimentally), but there are some considerations that, perhaps, D0<sub>3</sub> might be a high-temperature (>400 K) structure and the GS at 0 K might be the L1<sub>2</sub> structure because there might be a high energy barrier between both structures and, when the temperature is lowered, the system is not able to transform into the (perhaps) lower-energy L1<sub>2</sub> structure. To elucidate this problem, we re-interpret our recent extended ab initio electronic structure calculations for Fe<sub>3</sub>Al performed with the help of the VASP code and using various exchange-correlation energies within the generalized gradient approximation (GGA). Regrettably, some calculations provide the L1<sub>2</sub> and some of them D0<sub>3</sub> as the GS structure.</div><div>To resolve this question, we performed further calculations testing 9 frequently applied metaGGAs, such as TPSS, revTPSS, M06-L, SCAN(-L), rSCAN(-L) and r<sup>2</sup>SCAN(-L) representing a higher rung of the Jacob's ladder. It turns out that also here some meta-GGAs lead to L1<sub>2</sub> and some others to D0<sub>3</sub> GS structure and, again, we cannot decide.</div><div>In this way, the present results represent the very first step on the way to understand the energetics of the Fe<sub>3</sub>Al compound and its ground state. We hope they may motivate future theoretical and experimental work in this direction.</div></div>","PeriodicalId":432,"journal":{"name":"Solid State Sciences","volume":"157 ","pages":"Article 107709"},"PeriodicalIF":3.4,"publicationDate":"2024-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142320263","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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