Pub Date : 2024-11-12DOI: 10.1016/j.progsolidstchem.2024.100496
Zuo-Bei Wang , Xin Ye , Jie Yang , Yong-Hui Zhang , Zi-Ang Nan , Yi-Fan Wang , You-Gui Huang , Wei Wang
Excess phosphate contents in water bodies triggers eutrophication, which posts significant challenges to the aquatic ecosystem. Lanthanum-carbonate based adsorbents exhibit excellent phosphate binding properties for remediating eutrophication. However, they suffer from significant adsorption-capacity loss (>85 %) at high pH. Little has been done on understanding this behavior for improving the phosphorus adsorption of lanthanum-carbonate adsorbents in alkaline environments (e.g. eutrophic water bodies). Here, we discover that La2(CO3)3·8H2O, when produced by a conversion reaction from NaLa(CO3)2·xH2O, exhibits high phosphate adsorption capacity in a wide pH window. Under alkaline conditions (e.g. pH = 10), its adsorption capacity decreases by only 8 % compared to the value under neutral pH. By isolating three different lanthanum-carbonate based compounds and analyzing their molecular structures, we find that the trace amount of Na+ residual in our La2(CO3)3·8H2O alters the chemical environment surrounding the La3+ ions, which may significantly boost the phosphate uptake at high pH. Our results provide molecular insights for further tuning the material structure of phosphate adsorbents to achieve robust performances.
{"title":"Boosting the phosphorus uptake of La2(CO3)3·8H2O based adsorbents via sodium addition: Relationship between crystal structure and adsorption capacity","authors":"Zuo-Bei Wang , Xin Ye , Jie Yang , Yong-Hui Zhang , Zi-Ang Nan , Yi-Fan Wang , You-Gui Huang , Wei Wang","doi":"10.1016/j.progsolidstchem.2024.100496","DOIUrl":"10.1016/j.progsolidstchem.2024.100496","url":null,"abstract":"<div><div>Excess phosphate contents in water bodies triggers eutrophication, which posts significant challenges to the aquatic ecosystem. Lanthanum-carbonate based adsorbents exhibit excellent phosphate binding properties for remediating eutrophication. However, they suffer from significant adsorption-capacity loss (>85 %) at high pH. Little has been done on understanding this behavior for improving the phosphorus adsorption of lanthanum-carbonate adsorbents in alkaline environments (<em>e.g.</em> eutrophic water bodies). Here, we discover that La<sub>2</sub>(CO<sub>3</sub>)<sub>3</sub>·8H<sub>2</sub>O, when produced by a conversion reaction from NaLa(CO<sub>3</sub>)<sub>2</sub>·xH<sub>2</sub>O, exhibits high phosphate adsorption capacity in a wide pH window. Under alkaline conditions (<em>e.g.</em> pH = 10), its adsorption capacity decreases by only 8 % compared to the value under neutral pH. By isolating three different lanthanum-carbonate based compounds and analyzing their molecular structures, we find that the trace amount of Na<sup>+</sup> residual in our La<sub>2</sub>(CO<sub>3</sub>)<sub>3</sub>·8H<sub>2</sub>O alters the chemical environment surrounding the La<sup>3+</sup> ions, which may significantly boost the phosphate uptake at high pH. Our results provide molecular insights for further tuning the material structure of phosphate adsorbents to achieve robust performances.</div></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":"76 ","pages":"Article 100496"},"PeriodicalIF":9.1,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142654389","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-09DOI: 10.1016/j.progsolidstchem.2024.100495
Y. Feng , K.B. Tan , S.K. Chang , Y. Sulaiman , H.N. Lim , M. Lu , Y. Wang
Herein we report the structural, dielectric and electrochemical properties of Ba1-xSrx(Zn1/3Nb2/3)O3 (BSZN, 0 ≤ x ≤ 1) solid solution synthesised by solid-state reaction. A complete substitutional solid solution was obtained, wherein the BSZN cubic perovskites of the space group of Pmm were obtained at x ≤ 0.6 while the pseudo-cubic phases were discernible at x > 0.6. The nano-sized crystallites, as determined by both Scherrer and Williamson-Hall analyses, supported the claim of large polyhedral grains of 0.1–0.3 μm by FE-SEM. Both ε′ and tan δ were found to vary consistently with increasing dopant concentration, except for an anomalous observation for the composition, x = 0.6 with the lowest tan δ of 0.0783 and the highest ε′ of 27.5. Such phenomenon could be attributed to the combined effects of larger grain size, higher relative density and stronger polarisation per molar volume. The impedance analysis revealed that these BSZN perovskites were of the negative temperature coefficient of resistance (NTCR) type. The combined plots of imaginary modulus (M″) and impedance (Z″) against frequency showed the short-range movement of localised charge carriers, suggesting a non-Debye-type relaxation process.
在此，我们报告了通过固态反应合成的 Ba1-xSrx(Zn1/3Nb2/3)O3（BSZN，0 ≤ x ≤ 1）固溶体的结构、介电和电化学特性。在 x ≤ 0.6 时，获得了空间群为 Pm 3‾m 的 BSZN 立方包晶，而在 x > 0.6 时，则可以看到假立方相。通过舍勒分析和威廉森-霍尔分析确定的纳米级结晶支持了通过 FE-SEM 确定的 0.1-0.3 μm 大多面体晶粒的说法。随着掺杂剂浓度的增加，ε′和tan δ都发生了一致的变化，除了成分 x = 0.6 的异常观察，其最低的 tan δ为 0.0783，最高的ε′为 27.5。这种现象可归因于较大的晶粒尺寸、较高的相对密度和单位摩尔体积较强极化的综合影响。阻抗分析表明，这些 BSZN 包晶属于负温度系数电阻（NTCR）类型。假想模量（M″）和阻抗（Z″）与频率的组合图显示了局部电荷载流子的短程运动，表明这是一种非德拜型弛豫过程。
{"title":"Investigation of Sr-substituted Ba1-xSrx(Zn1/3Nb2/3)O3 complex perovskites: Structural, electrical and electrochemical properties","authors":"Y. Feng , K.B. Tan , S.K. Chang , Y. Sulaiman , H.N. Lim , M. Lu , Y. Wang","doi":"10.1016/j.progsolidstchem.2024.100495","DOIUrl":"10.1016/j.progsolidstchem.2024.100495","url":null,"abstract":"<div><div>Herein we report the structural, dielectric and electrochemical properties of Ba<sub>1-x</sub>Sr<sub>x</sub>(Zn<sub>1/3</sub>Nb<sub>2/3</sub>)O<sub>3</sub> (BSZN, 0 ≤ x ≤ 1) solid solution synthesised by solid-state reaction. A complete substitutional solid solution was obtained, wherein the BSZN cubic perovskites of the space group of <em>Pm</em> <span><math><mrow><mover><mn>3</mn><mo>‾</mo></mover></mrow></math></span> <em>m</em> were obtained at x ≤ 0.6 while the pseudo-cubic phases were discernible at x > 0.6. The nano-sized crystallites, as determined by both Scherrer and Williamson-Hall analyses, supported the claim of large polyhedral grains of 0.1–0.3 μm by FE-SEM. Both <em>ε</em>′ and tan δ were found to vary consistently with increasing dopant concentration, except for an anomalous observation for the composition, x = 0.6 with the lowest tan δ of 0.0783 and the highest <em>ε</em>′ of 27.5. Such phenomenon could be attributed to the combined effects of larger grain size, higher relative density and stronger polarisation per molar volume. The impedance analysis revealed that these BSZN perovskites were of the negative temperature coefficient of resistance (NTCR) type. The combined plots of imaginary modulus (<em>M</em>″) and impedance (<em>Z</em>″) against frequency showed the short-range movement of localised charge carriers, suggesting a non-Debye-type relaxation process.</div></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":"76 ","pages":"Article 100495"},"PeriodicalIF":9.1,"publicationDate":"2024-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142654388","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-08DOI: 10.1016/j.progsolidstchem.2024.100494
Yu-An Huang , Jun Li , Arthur P. Ramirez , M.A. Subramanian
Hexaferrites are a family of complex iron oxides with hexagonal structures. Novel compositions with the R-type hexaferrite structure, BaFe4-xMxM’2O11 (M = In, Sc; M’ = Ti, Sn; x = 0.0–1.8), are synthesized and characterized. Structural analyses using powder neutron diffraction reveal that trivalent iron cations are distributed among all the available M sites (octahedral and trigonal bipyramidal sites), with site preference varying with the composition. Ferrimagnetic behavior is observed for all the compounds, and the observed magnetic hysteresis loop indicates that the compounds are soft magnets. The color of the new solid solution can be tuned from dark reddish brown to reddish-orange and yellowish-orange as In or Sc substitutions increase. The origin of colors in these ferrite-based solid solutions results from the combination of ligand-to-metal charge transfer and electron-pair transitions across the face-shared octahedra, as seen in the hematite (Fe2O3). Reducing Fe content in the parent compound improves the diffuse reflectance in the near-infrared range, suggesting potential applications as cool pigments.
六铁氧体是一种具有六角形结构的复杂铁氧化物。本文合成并表征了具有 R 型六铁氧体结构的新型成分 BaFe4-xMxM'2O11（M = In、Sc；M' = Ti、Sn；x = 0.0-1.8）。利用粉末中子衍射进行的结构分析表明，三价铁阳离子分布在所有可用的 M 位点（八面体和三叉双锥位点）上，位点偏好随成分而变化。所有化合物都具有铁磁性，观察到的磁滞回线表明这些化合物是软磁体。随着 In 或 Sc 取代度的增加，新固溶体的颜色可从深红棕色调整为橘红色和橘黄色。这些铁基固溶体的颜色来源于配体到金属的电荷转移和面共八面体上的电子对跃迁，赤铁矿（Fe2O3）中就有这种现象。降低母体化合物中的铁含量可提高近红外范围的漫反射率，这表明它们有可能被用作冷颜料。
{"title":"New solid solutions with the R-type hexaferrite structure, BaFe4-xMxM’2O11 (M = In, Sc; M’ = Ti, Sn)","authors":"Yu-An Huang , Jun Li , Arthur P. Ramirez , M.A. Subramanian","doi":"10.1016/j.progsolidstchem.2024.100494","DOIUrl":"10.1016/j.progsolidstchem.2024.100494","url":null,"abstract":"<div><div>Hexaferrites are a family of complex iron oxides with hexagonal structures. Novel compositions with the <em>R</em>-type hexaferrite structure, BaFe<sub>4-<em>x</em></sub><em>M</em><sub><em>x</em></sub><em>M’</em><sub>2</sub>O<sub>11</sub> (<em>M</em> = In, Sc; <em>M’</em> = Ti, Sn; <em>x</em> = 0.0–1.8), are synthesized and characterized. Structural analyses using powder neutron diffraction reveal that trivalent iron cations are distributed among all the available <em>M</em> sites (octahedral and trigonal bipyramidal sites), with site preference varying with the composition. Ferrimagnetic behavior is observed for all the compounds, and the observed magnetic hysteresis loop indicates that the compounds are soft magnets. The color of the new solid solution can be tuned from dark reddish brown to reddish-orange and yellowish-orange as In or Sc substitutions increase. The origin of colors in these ferrite-based solid solutions results from the combination of ligand-to-metal charge transfer and electron-pair transitions across the face-shared octahedra, as seen in the hematite (Fe<sub>2</sub>O<sub>3</sub>). Reducing Fe content in the parent compound improves the diffuse reflectance in the near-infrared range, suggesting potential applications as cool pigments.</div></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":"76 ","pages":"Article 100494"},"PeriodicalIF":9.1,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142654386","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In recent years, second near-infrared window emitting phosphors have gained widespread research interest due to their excellent tissue penetration and high imaging accuracy. In this work, a new type of Ba2Ti1-xMnxO4+x/2 (0.02 ≤ x ≤ 0.10) phosphors were successfully prepared by high-temperature solid-phase method and their potential in luminescence thermometry is evaluated. PL and PLE spectral analysis prove that the optimal Mn doping concentration is x = 0.03. The as-synthesized phosphors exhibit a broad excitation band of 550–1000 nm and a narrow emission band of 1170–1220 nm. The electronic structures of the original Ba2TiO4 and Mn-doped Ba2TiO4 were calculated and analyzed using the DFT + U method, which facilitates a better understanding of the impact of Mn doping on the luminescent properties of Ba2TiO4. The luminescence decay lifetime is measured to be 101.44 μs at room temperature, which is a giant enhancement compared to conventional nanosecond lifetime phosphor, indicating a progress in imaging accuracy. In addition, the as-synthesized phosphors maintain over 75 % of the maximum luminescence intensity within the physiological temperature range. The potential applications in luminescence temperature measurement were also analyzed by the LIR ratio method, and the relative sensitivity could reach 2.31 %K−1 at 283 K, which is a relatively high value in the second near-infrared window. Therefore, the as-synthesized Ba2Ti1-xMnxO4+x/2 (0.02 ≤ x ≤ 0.10) phosphors demonstrate great potential in NIR applications such as biological imaging and luminescent thermometry.
近年来，第二种近红外窗口发射荧光粉因其出色的组织穿透性和高成像精度而获得了广泛的研究兴趣。本研究采用高温固相法成功制备了一种新型 Ba2Ti1-xMnxO4+x/2 （0.02 ≤ x ≤ 0.10）荧光粉，并评估了其在发光测温中的应用潜力。PL 和 PLE 光谱分析证明，最佳锰掺杂浓度为 x = 0.03。合成的荧光粉显示出 550-1000 纳米的宽激发带和 1170-1220 纳米的窄发射带。利用 DFT + U 方法计算并分析了原始 Ba2TiO4 和掺杂锰的 Ba2TiO4 的电子结构，从而更好地理解了掺杂锰对 Ba2TiO4 发光特性的影响。室温下测得的发光衰减寿命为 101.44 μs，与传统的纳秒寿命荧光粉相比有了大幅提高，这表明成像精度有了进步。此外，合成的荧光粉在生理温度范围内能保持 75% 以上的最大发光强度。我们还利用 LIR 比值法分析了发光温度测量的潜在应用，在 283 K 时，相对灵敏度可达 2.31 %K-1，这在第二近红外窗口中是一个相对较高的值。因此，合成的 Ba2Ti1-xMnxO4+x/2 （0.02 ≤ x ≤ 0.10）荧光粉在生物成像和发光测温等近红外应用领域具有很大的潜力。
{"title":"Novel Mn5+-activated Ba2TiO4 phosphor emitting in the second near-infrared biological window","authors":"Hang Zhao , Xin Xin , Liangsheng Tian , Theeranun Siritanon , Suwit Suthirakun , Wongsathorn Kaewraung , Menghang Qi , Ruoxiu Xiao , Jingyi Ren , Peng Jiang","doi":"10.1016/j.progsolidstchem.2024.100493","DOIUrl":"10.1016/j.progsolidstchem.2024.100493","url":null,"abstract":"<div><div>In recent years, second near-infrared window emitting phosphors have gained widespread research interest due to their excellent tissue penetration and high imaging accuracy. In this work, a new type of Ba<sub>2</sub>Ti<sub>1-<em>x</em></sub>Mn<sub><em>x</em></sub>O<sub>4+<em>x</em>/2</sub> (0.02 ≤ <em>x</em> ≤ 0.10) phosphors were successfully prepared by high-temperature solid-phase method and their potential in luminescence thermometry is evaluated. PL and PLE spectral analysis prove that the optimal Mn doping concentration is <em>x</em> = 0.03. The as-synthesized phosphors exhibit a broad excitation band of 550–1000 nm and a narrow emission band of 1170–1220 nm. The electronic structures of the original Ba<sub>2</sub>TiO<sub>4</sub> and Mn-doped Ba<sub>2</sub>TiO<sub>4</sub> were calculated and analyzed using the DFT + U method, which facilitates a better understanding of the impact of Mn doping on the luminescent properties of Ba<sub>2</sub>TiO<sub>4</sub>. The luminescence decay lifetime is measured to be 101.44 μs at room temperature, which is a giant enhancement compared to conventional nanosecond lifetime phosphor, indicating a progress in imaging accuracy. In addition, the as-synthesized phosphors maintain over 75 % of the maximum luminescence intensity within the physiological temperature range. The potential applications in luminescence temperature measurement were also analyzed by the LIR ratio method, and the relative sensitivity could reach 2.31 %K<sup>−1</sup> at 283 K, which is a relatively high value in the second near-infrared window. Therefore, the as-synthesized Ba<sub>2</sub>Ti<sub>1-<em>x</em></sub>Mn<sub><em>x</em></sub>O<sub>4+<em>x</em>/2</sub> (0.02 ≤ <em>x</em> ≤ 0.10) phosphors demonstrate great potential in NIR applications such as biological imaging and luminescent thermometry.</div></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":"76 ","pages":"Article 100493"},"PeriodicalIF":9.1,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142654387","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-16DOI: 10.1016/j.progsolidstchem.2024.100492
Samir F. Matar
Mechanisms of changes from 2D to 3D (D = dimensionality) involving 2D C(sp2) trigonal paving to C(sp3) tetrahedral stacking are proposed through puckering of the 2D layers on one hand and interlayer insertion of extra C on the other hand. Such transformations, led to 3D hexagonal C12 and C18 allotropes respectively characterized by lon and bac topologies. Using density functional theory DFT calculations, the two allotropes were found cohesive and stable both mechanically (elastic properties) and dynamically (phonons). Comparisons of the physical properties with known uni C6 were established letting identify ranges of large Vickers hardness: HV (uni C6) = 89 GPa, HV (lon C12) = 97 GPa, and HV (bac C18) = 70 GPa. Whilst C6 was identified with acoustic phonons instability, C12 and C18 were found stable dynamically throughout the acoustic and optic frequency ranges. Furthering on the thermal properties the allotropes were characterized with a temperature dependence curve of the specific heat CV close to experimental data of diamond with best fit for novel C18. The electronic band structures reveal a small band gap of 1 eV for uni C6 and larger direct band gap of 3 eV for the two other 3D allotropes. Such modulations of the electronic and physical properties should open scopes of carbon research.
{"title":"From layered 2D carbon to 3D tetrahedral allotropes C12 and C18 with physical properties related to diamond: Crystal chemistry and DFT investigations","authors":"Samir F. Matar","doi":"10.1016/j.progsolidstchem.2024.100492","DOIUrl":"10.1016/j.progsolidstchem.2024.100492","url":null,"abstract":"<div><div>Mechanisms of changes from 2D to 3D (D = dimensionality) involving 2D C(sp<sup>2</sup>) trigonal paving to C(sp<sup>3</sup>) tetrahedral stacking are proposed through puckering of the 2D layers on one hand and interlayer insertion of extra C on the other hand. Such transformations, led to 3D hexagonal C<sub>12</sub> and C<sub>18</sub> allotropes respectively characterized by <strong>lon</strong> and <strong>bac</strong> topologies. Using density functional theory DFT calculations, the two allotropes were found cohesive and stable both mechanically (elastic properties) and dynamically (phonons). Comparisons of the physical properties with known <strong>uni</strong> C<sub>6</sub> were established letting identify ranges of large Vickers hardness: H<sub>V</sub> (<strong>uni</strong> C<sub>6</sub>) = 89 GPa, H<sub>V</sub> (<strong>lon</strong> C<sub>12</sub>) = 97 GPa, and H<sub>V</sub> (<strong>bac</strong> C<sub>18</sub>) = 70 GPa. Whilst C<sub>6</sub> was identified with acoustic phonons instability, C<sub>12</sub> and C<sub>18</sub> were found stable dynamically throughout the acoustic and optic frequency ranges. Furthering on the thermal properties the allotropes were characterized with a temperature dependence curve of the specific heat C<sub>V</sub> close to experimental data of diamond with best fit for novel C<sub>18</sub>. The electronic band structures reveal a small band gap of 1 eV for <strong>uni</strong> C<sub>6</sub> and larger direct band gap of 3 eV for the two other 3D allotropes. Such modulations of the electronic and physical properties should open scopes of carbon research.</div></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":"76 ","pages":"Article 100492"},"PeriodicalIF":9.1,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142535872","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-09DOI: 10.1016/j.progsolidstchem.2024.100491
Xiuyuan Li , Zihuan Peng , Chongwen Jiang , Nan Li , Jun Zhang , Changqing Jin , Chuan Xiao
High pressure technique can greatly enrich the chemistry research by innovating the traditional research paradigm. Recently, tremendous attentions have been paid to the high-pressure behavior of low-Z molecules, such as CO, CO2, N2, O2 and mixtures. These molecules tend to polymerize into extended solids at the pressure of 1–100 GPa, but the structures and polymerization mechanisms are still poorly understood. Herein, as a research model, high pressure polymerization process of carbon monoxide (CO) is studied in detail both experimentally and theoretically. The in-situ Raman spectra and angle-resolved X-ray diffraction experiments prove the successful synthesis of p-CO and its amorphous structure. The theoretical simulations reveal that two CO molecules dimerize into the ethylenedione (OCCO) diradical with spin-polarized singlet state firstly, then the OCCO diradical induces the subsequent chain elongation, ring closure and chain crosslinking reactions, leading to formation of the amorphous 3D network. The multiple basic units, hybrid coordination of C/O atoms and complex connecting styles in p-CO are revealed. Based on the polymerization mechanisms, the fundamental principles governing the character (amorphous or crystalline) of extended solids under high pressure are elucidated. Due to the small dipole moment and the head-to-tail disorder of CO molecules, it is reasonable to speculate that crystalline p-CO may exist under more rigorous conditions than 110 GPa and 2000 K, at which the isoelectronic nitrogen (N2) molecules polymerize into a single-bonded cubic form of nitrogen. Our study provides a profound insight into the polymerization mechanism and structures of low-Z CO molecules under compression, contributes to the diversified chemical researches and has a generally scientific implications for the interior dynamics of planets.
高压技术创新了传统的研究范式，极大地丰富了化学研究。近年来，人们对 CO、CO2、N2、O2 和混合物等低 Z 值分子的高压行为给予了极大关注。这些分子往往会在 1-100 GPa 的压力下聚合成扩展固体，但人们对其结构和聚合机制仍知之甚少。本文以一氧化碳（CO）的高压聚合过程为研究模型，从实验和理论两方面进行了详细研究。原位拉曼光谱和角分辨 X 射线衍射实验证明了 p-CO 的成功合成及其无定形结构。理论模拟揭示了两个 CO 分子首先二聚为具有自旋极化单重态的乙烯二酮（OCCO）二元对偶体，然后 OCCO 二元对偶体诱导了后续的链伸长、闭环和链交联反应，从而形成了非晶态三维网络。揭示了 p-CO 中的多个基本单元、C/O 原子的混合配位和复杂的连接方式。根据聚合机理，阐明了高压下扩展固体特性（无定形或结晶）的基本原理。由于一氧化碳分子的偶极矩小且头尾无序，我们有理由推测结晶对一氧化碳可能存在于比 110 GPa 和 2000 K 更严格的条件下，在此条件下，等电子氮（N2）分子聚合成单键立方氮形式。我们的研究深刻揭示了低Z CO分子在压缩条件下的聚合机理和结构，有助于开展多元化的化学研究，并对行星内部动力学具有普遍的科学意义。
{"title":"Insights into the structure and polymerization mechanisms of CO molecules under pressure","authors":"Xiuyuan Li , Zihuan Peng , Chongwen Jiang , Nan Li , Jun Zhang , Changqing Jin , Chuan Xiao","doi":"10.1016/j.progsolidstchem.2024.100491","DOIUrl":"10.1016/j.progsolidstchem.2024.100491","url":null,"abstract":"<div><div>High pressure technique can greatly enrich the chemistry research by innovating the traditional research paradigm. Recently, tremendous attentions have been paid to the high-pressure behavior of low-Z molecules, such as CO, CO<sub>2</sub>, N<sub>2</sub>, O<sub>2</sub> and mixtures. These molecules tend to polymerize into extended solids at the pressure of 1–100 GPa, but the structures and polymerization mechanisms are still poorly understood. Herein, as a research model, high pressure polymerization process of carbon monoxide (CO) is studied in detail both experimentally and theoretically. The in-situ Raman spectra and angle-resolved X-ray diffraction experiments prove the successful synthesis of p-CO and its amorphous structure. The theoretical simulations reveal that two CO molecules dimerize into the ethylenedione (OCCO) diradical with spin-polarized singlet state firstly, then the OCCO diradical induces the subsequent chain elongation, ring closure and chain crosslinking reactions, leading to formation of the amorphous 3D network. The multiple basic units, hybrid coordination of C/O atoms and complex connecting styles in p-CO are revealed. Based on the polymerization mechanisms, the fundamental principles governing the character (amorphous or crystalline) of extended solids under high pressure are elucidated. Due to the small dipole moment and the head-to-tail disorder of CO molecules, it is reasonable to speculate that crystalline p-CO may exist under more rigorous conditions than 110 GPa and 2000 K, at which the isoelectronic nitrogen (N<sub>2</sub>) molecules polymerize into a single-bonded cubic form of nitrogen. Our study provides a profound insight into the polymerization mechanism and structures of low-Z CO molecules under compression, contributes to the diversified chemical researches and has a generally scientific implications for the interior dynamics of planets.</div></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":"76 ","pages":"Article 100491"},"PeriodicalIF":9.1,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142434494","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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.progsolidstchem.2024.100490
Devika Rajan Sajitha , Beauno Stephen , Atsushi Nakamura , Manickam Selvaraj , Shyju Thankaraj Salammal , Shamima Hussain
This paper aims to provide a comprehensive overview of the recent advancements in chalcogenide-based solar absorber materials and their potential to revolutionize solar energy conversion. Researchers are focused on chalcogenide materials due to their distinctive properties, aiming to harness solar energy efficiently in response to the increasing demand for sustainable energy sources. The application of chalcogenide absorbers with zinc blende and chalcopyrite structures, such as CdTe and Cu(In, Ga)Se2 (CIGSe) has resulted in considerable advances in thin film photovoltaic performance at both the laboratory and commercial scales. However, concerns persist about toxicity and the scarcity of constituent elements in CIGSe/CdTe absorbers remains. Cu2ZnSn(S, Se)4 (CZTS, Se) materials based on the kesterite structure have emerged as appealing alternatives, promising non-toxicity and an abundance of constituent metals. CZTS, Se solar cells have a lower record power conversion efficiency of 14.9 % when compared to CIGSe (22.6 %), CdTe (22.1 %), and CIS (20 %) devices. This research highlights the emergence of chalcogenides as a promising material class for flexible thin-film solar absorbers.
{"title":"The emergence of chalcogenides: A new era for thin film solar absorbers","authors":"Devika Rajan Sajitha , Beauno Stephen , Atsushi Nakamura , Manickam Selvaraj , Shyju Thankaraj Salammal , Shamima Hussain","doi":"10.1016/j.progsolidstchem.2024.100490","DOIUrl":"10.1016/j.progsolidstchem.2024.100490","url":null,"abstract":"<div><div>This paper aims to provide a comprehensive overview of the recent advancements in chalcogenide-based solar absorber materials and their potential to revolutionize solar energy conversion. Researchers are focused on chalcogenide materials due to their distinctive properties, aiming to harness solar energy efficiently in response to the increasing demand for sustainable energy sources. The application of chalcogenide absorbers with zinc blende and chalcopyrite structures, such as CdTe and Cu(In, Ga)Se<sub>2</sub> (CIGSe) has resulted in considerable advances in thin film photovoltaic performance at both the laboratory and commercial scales. However, concerns persist about toxicity and the scarcity of constituent elements in CIGSe/CdTe absorbers remains. Cu<sub>2</sub>ZnSn(S, Se)<sub>4</sub> (CZTS, Se) materials based on the kesterite structure have emerged as appealing alternatives, promising non-toxicity and an abundance of constituent metals. CZTS, Se solar cells have a lower record power conversion efficiency of 14.9 % when compared to CIGSe (22.6 %), CdTe (22.1 %), and CIS (20 %) devices. This research highlights the emergence of chalcogenides as a promising material class for flexible thin-film solar absorbers.</div></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":"76 ","pages":"Article 100490"},"PeriodicalIF":9.1,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142421712","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-12DOI: 10.1016/j.progsolidstchem.2024.100489
Gajiram Murmu , Tamanna Harihar Panigrahi , Sumit Saha
Polyoxometalates (POMs) and their composites have emerged as promising candidates for degrading toxic chemical dyes in wastewater remediation. POMs, with their tunable structures and redox properties, exhibit high catalytic activity towards various organic pollutants, including dyes. The integration of POMs into composite materials creates a synergistic effect that enhances endurance and efficiency during dye degradation. POMs are classified based on metal composition and structure, highlighting their roles in dye removal processes. Categories include molybdenum-based, tungsten-based, vanadium-based, and mixed metal-based POMs, each with distinct properties affecting dye elimination efficacy. The application of POMs and their composites in degrading specific chemical dyes, including cationic, anionic, and azo dyes, is elaborately described. Various mechanisms for dye removal from aqueous media, such as photocatalysis, adsorption, Fenton-like reactions, and electrochemical processes, underscore the crucial role of POMs and their composites in toxic chemical dye degradation. The factors influencing dye-POM interactions, such as pH, temperature, POM composition, and dye structure, are analyzed to understand their impact on removal efficiency. The review discusses the influence of metal type, POM structure, and solution conditions on dye removal efficacy, providing insights into how specific metal-based POMs interact with different dye molecules. Challenges and future perspectives for implementing POM-based materials in dye wastewater treatment are outlined, emphasizing the need for further research to optimize performance and ensure practical feasibility in large-scale applications.
{"title":"Recent advances in the development of polyoxometalates and their composites for the degradation of toxic chemical dyes","authors":"Gajiram Murmu , Tamanna Harihar Panigrahi , Sumit Saha","doi":"10.1016/j.progsolidstchem.2024.100489","DOIUrl":"10.1016/j.progsolidstchem.2024.100489","url":null,"abstract":"<div><p>Polyoxometalates (POMs) and their composites have emerged as promising candidates for degrading toxic chemical dyes in wastewater remediation. POMs, with their tunable structures and redox properties, exhibit high catalytic activity towards various organic pollutants, including dyes. The integration of POMs into composite materials creates a synergistic effect that enhances endurance and efficiency during dye degradation. POMs are classified based on metal composition and structure, highlighting their roles in dye removal processes. Categories include molybdenum-based, tungsten-based, vanadium-based, and mixed metal-based POMs, each with distinct properties affecting dye elimination efficacy. The application of POMs and their composites in degrading specific chemical dyes, including cationic, anionic, and azo dyes, is elaborately described. Various mechanisms for dye removal from aqueous media, such as photocatalysis, adsorption, Fenton-like reactions, and electrochemical processes, underscore the crucial role of POMs and their composites in toxic chemical dye degradation. The factors influencing dye-POM interactions, such as pH, temperature, POM composition, and dye structure, are analyzed to understand their impact on removal efficiency. The review discusses the influence of metal type, POM structure, and solution conditions on dye removal efficacy, providing insights into how specific metal-based POMs interact with different dye molecules. Challenges and future perspectives for implementing POM-based materials in dye wastewater treatment are outlined, emphasizing the need for further research to optimize performance and ensure practical feasibility in large-scale applications.</p></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":"76 ","pages":"Article 100489"},"PeriodicalIF":9.1,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142239249","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-02DOI: 10.1016/j.progsolidstchem.2024.100478
L. Gowsalya , C. Jesica Anjeline , P. Devi , P. Murugan , N. Lakshminarasimhan
<div><p><span><math><mrow><mtext>BaBi</mtext><msub><mi>O</mi><mn>3</mn></msub></mrow></math></span> (BBO), a charge-ordered perovskite with mixed-valent states of Bi (Bi<sup>3+</sup> and Bi<sup>5+</sup>), is known for its charge density wave (CDW) semiconducting and topological insulating properties. BBO has been extensively investigated for its superconducting, electrical, and photocatalytic properties. The present study aims to understand the alterations in the CDW and electronic properties of <span><math><mrow><mtext>Ba</mtext><msubsup><mtext>Bi</mtext><mn>0.5</mn><mrow><mn>3</mn><mo>+</mo></mrow></msubsup><msubsup><mtext>Bi</mtext><mn>0.5</mn><mrow><mn>5</mn><mo>+</mo></mrow></msubsup><msub><mi>O</mi><mn>3</mn></msub></mrow></math></span> by valence-selective substitution of Bi<sup>3+</sup> and Bi<sup>5+</sup> with La<sup>3+</sup> and Nb<sup>5+</sup>, respectively, in the solid solutions <span><math><mrow><mtext>Ba</mtext><msubsup><mtext>Bi</mtext><mrow><mn>0.5</mn><mo>−</mo><mi>x</mi></mrow><mrow><mn>3</mn><mo>+</mo></mrow></msubsup><msubsup><mrow><msub><mtext>La</mtext><mi>x</mi></msub><mtext>Bi</mtext></mrow><mn>0.5</mn><mrow><mn>5</mn><mo>+</mo></mrow></msubsup><msub><mi>O</mi><mn>3</mn></msub></mrow></math></span> and <span><math><mrow><mtext>Ba</mtext><msubsup><mtext>Bi</mtext><mn>0.5</mn><mrow><mn>3</mn><mo>+</mo></mrow></msubsup><msubsup><mtext>Bi</mtext><mrow><mn>0.5</mn><mo>−</mo><mi>y</mi></mrow><mrow><mn>5</mn><mo>+</mo></mrow></msubsup><msub><mtext>Nb</mtext><mi>y</mi></msub><msub><mi>O</mi><mn>3</mn></msub></mrow></math></span> (x = y = 0.0, 0.1, 0.3, and 0.5). The samples synthesized <em>via</em> high-temperature solid-state reaction method were characterized by powder X-ray diffraction and various spectroscopic techniques (FT-IR, Laser Raman, EPR, XPS, and UPS). Impedance analysis revealed an upsurge in total impedance with the substitution of Bi<sup>3+</sup>/Bi<sup>5+</sup> by La<sup>3+</sup>/Nb<sup>5+</sup> indicating the blocking of electron/hole hopping by disruption of the charge ordering of redox pair Bi<sup>3+</sup> and Bi<sup>5+</sup>. The valence-selective substitution of Bi<sup>3+</sup>/Bi<sup>5+</sup> in BaBiO<sub>3</sub> resulted in an alteration of the electronic structure and changes in the bandwidth of <span><math><mrow><mtext>Ba</mtext><msubsup><mtext>Bi</mtext><mrow><mn>0.5</mn><mo>−</mo><mi>x</mi></mrow><mrow><mn>3</mn><mo>+</mo></mrow></msubsup><msubsup><mrow><msub><mtext>La</mtext><mi>x</mi></msub><mtext>Bi</mtext></mrow><mn>0.5</mn><mrow><mn>5</mn><mo>+</mo></mrow></msubsup><msub><mi>O</mi><mn>3</mn></msub></mrow></math></span> and <span><math><mrow><mtext>Ba</mtext><msubsup><mtext>Bi</mtext><mn>0.5</mn><mrow><mn>3</mn><mo>+</mo></mrow></msubsup><msubsup><mtext>Bi</mtext><mrow><mn>0.5</mn><mo>−</mo><mi>y</mi></mrow><mrow><mn>5</mn><mo>+</mo></mrow></msubsup><msub><mtext>Nb</mtext><mi>y</mi></msub><msub><mi>O</mi><mn>3</mn></msub></mrow></math></span> (x = y = 0.0, 0.1, 0.3, and 0.5) solid solutions, which
{"title":"Impeding conduction by breaking the charge carrier hopping in charge-ordered perovskite BaBiO3 (BaBi0.53+Bi0.55+O3): Experimental and theoretical electronic structural correlations","authors":"L. Gowsalya , C. Jesica Anjeline , P. Devi , P. Murugan , N. Lakshminarasimhan","doi":"10.1016/j.progsolidstchem.2024.100478","DOIUrl":"10.1016/j.progsolidstchem.2024.100478","url":null,"abstract":"<div><p><span><math><mrow><mtext>BaBi</mtext><msub><mi>O</mi><mn>3</mn></msub></mrow></math></span> (BBO), a charge-ordered perovskite with mixed-valent states of Bi (Bi<sup>3+</sup> and Bi<sup>5+</sup>), is known for its charge density wave (CDW) semiconducting and topological insulating properties. BBO has been extensively investigated for its superconducting, electrical, and photocatalytic properties. The present study aims to understand the alterations in the CDW and electronic properties of <span><math><mrow><mtext>Ba</mtext><msubsup><mtext>Bi</mtext><mn>0.5</mn><mrow><mn>3</mn><mo>+</mo></mrow></msubsup><msubsup><mtext>Bi</mtext><mn>0.5</mn><mrow><mn>5</mn><mo>+</mo></mrow></msubsup><msub><mi>O</mi><mn>3</mn></msub></mrow></math></span> by valence-selective substitution of Bi<sup>3+</sup> and Bi<sup>5+</sup> with La<sup>3+</sup> and Nb<sup>5+</sup>, respectively, in the solid solutions <span><math><mrow><mtext>Ba</mtext><msubsup><mtext>Bi</mtext><mrow><mn>0.5</mn><mo>−</mo><mi>x</mi></mrow><mrow><mn>3</mn><mo>+</mo></mrow></msubsup><msubsup><mrow><msub><mtext>La</mtext><mi>x</mi></msub><mtext>Bi</mtext></mrow><mn>0.5</mn><mrow><mn>5</mn><mo>+</mo></mrow></msubsup><msub><mi>O</mi><mn>3</mn></msub></mrow></math></span> and <span><math><mrow><mtext>Ba</mtext><msubsup><mtext>Bi</mtext><mn>0.5</mn><mrow><mn>3</mn><mo>+</mo></mrow></msubsup><msubsup><mtext>Bi</mtext><mrow><mn>0.5</mn><mo>−</mo><mi>y</mi></mrow><mrow><mn>5</mn><mo>+</mo></mrow></msubsup><msub><mtext>Nb</mtext><mi>y</mi></msub><msub><mi>O</mi><mn>3</mn></msub></mrow></math></span> (x = y = 0.0, 0.1, 0.3, and 0.5). The samples synthesized <em>via</em> high-temperature solid-state reaction method were characterized by powder X-ray diffraction and various spectroscopic techniques (FT-IR, Laser Raman, EPR, XPS, and UPS). Impedance analysis revealed an upsurge in total impedance with the substitution of Bi<sup>3+</sup>/Bi<sup>5+</sup> by La<sup>3+</sup>/Nb<sup>5+</sup> indicating the blocking of electron/hole hopping by disruption of the charge ordering of redox pair Bi<sup>3+</sup> and Bi<sup>5+</sup>. The valence-selective substitution of Bi<sup>3+</sup>/Bi<sup>5+</sup> in BaBiO<sub>3</sub> resulted in an alteration of the electronic structure and changes in the bandwidth of <span><math><mrow><mtext>Ba</mtext><msubsup><mtext>Bi</mtext><mrow><mn>0.5</mn><mo>−</mo><mi>x</mi></mrow><mrow><mn>3</mn><mo>+</mo></mrow></msubsup><msubsup><mrow><msub><mtext>La</mtext><mi>x</mi></msub><mtext>Bi</mtext></mrow><mn>0.5</mn><mrow><mn>5</mn><mo>+</mo></mrow></msubsup><msub><mi>O</mi><mn>3</mn></msub></mrow></math></span> and <span><math><mrow><mtext>Ba</mtext><msubsup><mtext>Bi</mtext><mn>0.5</mn><mrow><mn>3</mn><mo>+</mo></mrow></msubsup><msubsup><mtext>Bi</mtext><mrow><mn>0.5</mn><mo>−</mo><mi>y</mi></mrow><mrow><mn>5</mn><mo>+</mo></mrow></msubsup><msub><mtext>Nb</mtext><mi>y</mi></msub><msub><mi>O</mi><mn>3</mn></msub></mrow></math></span> (x = y = 0.0, 0.1, 0.3, and 0.5) solid solutions, which ","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":"76 ","pages":"Article 100478"},"PeriodicalIF":9.1,"publicationDate":"2024-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142164824","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Currently, the development of single-phase white emitters is an interesting research topic. Researchers have paid much attention to tune white-emitting of Dy3+-activated phosphors via Tm3+ sensitization strategy. However, the role of Tm3+ sensitization on luminescence thermostability was usually underestimated. Herein, color-tunable germanate phosphors Ba2Y2Ge4O13 (BYGO):Tm3+,Dy3+ were prepared. The white light emission is achieved due to the effective energy transfer from Tm3+ to Dy3+. A BYGO:Tm3+,Dy3+-based w-LED exhibits warm white-emitting. Moreover, the back-energy transfer of Dy3+→Tm3+ contributes to the improvement of luminescence thermal stability. Meanwhile, the difference of temperature-dependent Tm3+ and Dy3+ emissions realizes satisfactory temperature sensing properties. This work provides a deep understanding for the role of Tm3+ sensitization strategy on color tuning and thermostable improvement, promoting multifunctional utilizations of Dy3+-activated phosphors.
{"title":"Unusual Tm3+ sensitization-induced white-emitting and thermostable improvement in Ba2Y2Ge4O13:Dy3+ phosphor for solid-state lighting and optical thermometry","authors":"Huan Tang, Xiaoyang Zhao, Yue Qin, Shanlin Liu, Hongzhi Zhang, Hong Li, Conglin Liu, Jing Zhu","doi":"10.1016/j.progsolidstchem.2024.100477","DOIUrl":"10.1016/j.progsolidstchem.2024.100477","url":null,"abstract":"<div><p>Currently, the development of single-phase white emitters is an interesting research topic. Researchers have paid much attention to tune white-emitting of Dy<sup>3+</sup>-activated phosphors via Tm<sup>3+</sup> sensitization strategy. However, the role of Tm<sup>3+</sup> sensitization on luminescence thermostability was usually underestimated. Herein, color-tunable germanate phosphors Ba<sub>2</sub>Y<sub>2</sub>Ge<sub>4</sub>O<sub>13</sub> (BYGO):Tm<sup>3+</sup>,Dy<sup>3+</sup> were prepared. The white light emission is achieved due to the effective energy transfer from Tm<sup>3+</sup> to Dy<sup>3+</sup>. A BYGO:Tm<sup>3+</sup>,Dy<sup>3+</sup>-based w-LED exhibits warm white-emitting. Moreover, the back-energy transfer of Dy<sup>3+</sup>→Tm<sup>3+</sup> contributes to the improvement of luminescence thermal stability. Meanwhile, the difference of temperature-dependent Tm<sup>3+</sup> and Dy<sup>3+</sup> emissions realizes satisfactory temperature sensing properties. This work provides a deep understanding for the role of Tm<sup>3+</sup> sensitization strategy on color tuning and thermostable improvement, promoting multifunctional utilizations of Dy<sup>3+</sup>-activated phosphors.</p></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":"75 ","pages":"Article 100477"},"PeriodicalIF":9.1,"publicationDate":"2024-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142097276","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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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