Pub Date : 2025-11-03DOI: 10.1016/j.solidstatesciences.2025.108129
E.P. Arévalo-López , J. Pilo , H. Muñoz , J.M. Cervantes , L. Huerta , J.E. Antonio , R. Valerio-Méndez , J. Vargas-Bustamante , E. Benitez-Flores , Claire Minaud , C. Cosio-Castañeda , R. Escamilla , M. Romero
In this work, the solid solution of the double spinel LiFe1-xGaxCr4O8 was synthesized and characterized by X-ray diffraction, magnetic susceptibility measurements, UV–Vis–NIR spectroscopy, and X-ray photoelectron spectroscopy (XPS). Rietveld refinements show that the crystal structure is cubic with space group F 3m (No. 216), which is maintained as Fe is gradually substituted by Ga. The lattice parameter a and unit cell volume V decrease consistently due to the smaller ionic radius of Ga compared to Fe. Magnetic susceptibility data indicate that increasing Ga content reduces ferrimagnetic behavior while enhancing the antiferromagnetic component. From Density Functional Theory (DFT) calculations and using Hubbard-corrected Local Spin Density Approximation (LSDA + U) we observe that LiGaCr4O8 has a direct electronic band gap (Eg) of 1.73 eV at the Γ point. Additionally, UV–Vis–NIR spectroscopy reveals an increasing of the direct optical band gap (Eg) with increasing Ga concentration, from 1.43 eV at x = 0.25–1.54 eV at x = 1.00. XPS analysis of Li 1s, Fe 3p, Ga 3d, Cr 3p, and O 1s core levels, together with the valence band (VB), reveals through detailed spectral deconvolution that the oxidation states of Li1+, Fe3+, Ga3+, and Cr3+ remain constant throughout the solid solution.
{"title":"Magnetic and electronic properties of LiFe1-xGaxCr4O8 double spinel by Ga doping","authors":"E.P. Arévalo-López , J. Pilo , H. Muñoz , J.M. Cervantes , L. Huerta , J.E. Antonio , R. Valerio-Méndez , J. Vargas-Bustamante , E. Benitez-Flores , Claire Minaud , C. Cosio-Castañeda , R. Escamilla , M. Romero","doi":"10.1016/j.solidstatesciences.2025.108129","DOIUrl":"10.1016/j.solidstatesciences.2025.108129","url":null,"abstract":"<div><div>In this work, the solid solution of the double spinel LiFe<sub>1-x</sub>Ga<sub>x</sub>Cr<sub>4</sub>O<sub>8</sub> was synthesized and characterized by X-ray diffraction, magnetic susceptibility measurements, UV–Vis–NIR spectroscopy, and X-ray photoelectron spectroscopy (XPS). Rietveld refinements show that the crystal structure is cubic with space group F <span><math><mrow><mover><mn>4</mn><mo>‾</mo></mover></mrow></math></span> 3m (No. 216), which is maintained as Fe is gradually substituted by Ga. The lattice parameter <em>a</em> and unit cell volume <em>V</em> decrease consistently due to the smaller ionic radius of Ga compared to Fe. Magnetic susceptibility data indicate that increasing Ga content reduces ferrimagnetic behavior while enhancing the antiferromagnetic component. From Density Functional Theory (DFT) calculations and using Hubbard-corrected Local Spin Density Approximation (LSDA + U) we observe that LiGaCr<sub>4</sub>O<sub>8</sub> has a direct electronic band gap (E<sub>g</sub>) of 1.73 eV at the Γ point. Additionally, UV–Vis–NIR spectroscopy reveals an increasing of the direct optical band gap (E<sub>g</sub>) with increasing Ga concentration, from 1.43 eV at <em>x</em> = 0.25–1.54 eV at <em>x</em> = 1.00. XPS analysis of Li <em>1s</em>, Fe <em>3p</em>, Ga <em>3d</em>, Cr <em>3p</em>, and O <em>1s</em> core levels, together with the valence band (VB), reveals through detailed spectral deconvolution that the oxidation states of Li<sup>1+</sup>, Fe<sup>3+</sup>, Ga<sup>3+</sup>, and Cr<sup>3+</sup> remain constant throughout the solid solution.</div></div>","PeriodicalId":432,"journal":{"name":"Solid State Sciences","volume":"170 ","pages":"Article 108129"},"PeriodicalIF":3.3,"publicationDate":"2025-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145463972","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 : 2025-11-03DOI: 10.1016/j.solidstatesciences.2025.108109
Bin He , Haihua Hu , Xiaolong Feng , Claudia Felser
Bi-Sb based topological insulators garnered significant research interest due to their role as a platform for investigating the topological surfaces states and achieving a high thermoelectric figure of merit at and below room temperature. However, electronic transport measurements yield contradictory results, particularly above nitrogen temperature. While zero-field transport exhibits a clear two-carrier signature, field-dependent transport reveals only a single-carrier signature. In this study, we systematically investigated the temperature and field dependent transport properties of Bi88Sb12 including p-type doped crystals. A distinct p-n transition is observed above 60 K, with the crystals exhibiting n-type behavior above 100 K regardless of doping. We propose that Bi88Sb12 is intrinsically close to an n-type semiconductor, a characteristic attributed to heavy T-holes that induce an asymmetric electronic structure between the conduction and valence bands.
{"title":"The influence of heavy valence band in Bi88Sb12","authors":"Bin He , Haihua Hu , Xiaolong Feng , Claudia Felser","doi":"10.1016/j.solidstatesciences.2025.108109","DOIUrl":"10.1016/j.solidstatesciences.2025.108109","url":null,"abstract":"<div><div>Bi-Sb based topological insulators garnered significant research interest due to their role as a platform for investigating the topological surfaces states and achieving a high thermoelectric figure of merit at and below room temperature. However, electronic transport measurements yield contradictory results, particularly above nitrogen temperature. While zero-field transport exhibits a clear two-carrier signature, field-dependent transport reveals only a single-carrier signature. In this study, we systematically investigated the temperature and field dependent transport properties of Bi<sub>88</sub>Sb<sub>12</sub> including <em>p</em>-type doped crystals. A distinct <em>p-n</em> transition is observed above 60 K, with the crystals exhibiting <em>n</em>-type behavior above 100 K regardless of doping. We propose that Bi<sub>88</sub>Sb<sub>12</sub> is intrinsically close to an <em>n</em>-type semiconductor, a characteristic attributed to heavy T-holes that induce an asymmetric electronic structure between the conduction and valence bands.</div></div>","PeriodicalId":432,"journal":{"name":"Solid State Sciences","volume":"170 ","pages":"Article 108109"},"PeriodicalIF":3.3,"publicationDate":"2025-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145517383","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 : 2025-11-01DOI: 10.1016/j.solidstatesciences.2025.108009
F.F. Alharbi , Salma Aman , Naseeb Ahmad , Muhammad Abdullah , Abdul Ghafoor Abid , Sumaira Manzoor , Sergei Trukhanov , M.I. Sayyed , Daria Tishkevich , Alex Trukhanov
{"title":"Corrigendum to ‘Investigation of photoreduction of Cr (VI) and electrocatalytic properties of hydrothermally produced novel CoFe2O4/ZnO nanostructure’ [Solid State Sci. Volume 143, September 2023, 107278]","authors":"F.F. Alharbi , Salma Aman , Naseeb Ahmad , Muhammad Abdullah , Abdul Ghafoor Abid , Sumaira Manzoor , Sergei Trukhanov , M.I. Sayyed , Daria Tishkevich , Alex Trukhanov","doi":"10.1016/j.solidstatesciences.2025.108009","DOIUrl":"10.1016/j.solidstatesciences.2025.108009","url":null,"abstract":"","PeriodicalId":432,"journal":{"name":"Solid State Sciences","volume":"169 ","pages":"Article 108009"},"PeriodicalIF":3.3,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145412530","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 : 2025-11-01DOI: 10.1016/j.solidstatesciences.2025.108113
Mehrnoosh Bitaraf , Ali Amoozadeh
Forming heterostructures is a promising approach to develop visible-light-responsive photocatalysts. However, facile separation and recyclability of the photocatalyst remains an issue. Here, a novel magnetic photocatalyst is rationally designed and synthesized via covalent linkage of magnetite Fe3O4 nano-particles to n-TiO2-P25 and n-WO3. According to its reduced band gap (2.45 eV compared to 3.2 eV for n-TiO2-P25), the as-prepared photocatalyst shows an extended absorption edge in the visible region, which expands its application compared to ultraviolet absorption in titanium dioxide. Its photocatalytic activity is investigated through selective oxidation of benzyl alcohol under visible light (blue, green, and red LEDs) in the presence of nitrate as oxidant, yielding notable results and >99 % selectivity within 8 h. Various characterization techniques confirm the structure and enhanced properties of the magnetic nanoparticles. Magnetic property of photocatalyst, n-Fe3O4@ECH@n-TiO2/WO3, enables easy separation and reusability of nanoparticles for at least four consecutive runs without significant loss of activity. The formed heterojunction between n-TiO2-P25 and n-WO3, not only improves light absorption and photocatalytic efficiency, but also overcomes the drawbacks associated with recovering and long-term stability, offering outstanding potential for advanced applications and future studies.
{"title":"A covalently engineered magnetically recyclable TiO2/WO3 heterojunction for visible-light-driven selective photooxidation","authors":"Mehrnoosh Bitaraf , Ali Amoozadeh","doi":"10.1016/j.solidstatesciences.2025.108113","DOIUrl":"10.1016/j.solidstatesciences.2025.108113","url":null,"abstract":"<div><div>Forming heterostructures is a promising approach to develop visible-light-responsive photocatalysts. However, facile separation and recyclability of the photocatalyst remains an issue. Here, a novel magnetic photocatalyst is rationally designed and synthesized via covalent linkage of magnetite Fe<sub>3</sub>O<sub>4</sub> nano-particles to n-TiO<sub>2</sub>-P25 and n-WO<sub>3</sub>. According to its reduced band gap (2.45 eV compared to 3.2 eV for n-TiO<sub>2</sub>-P25), the as-prepared photocatalyst shows an extended absorption edge in the visible region, which expands its application compared to ultraviolet absorption in titanium dioxide. Its photocatalytic activity is investigated through selective oxidation of benzyl alcohol under visible light (blue, green, and red LEDs) in the presence of nitrate as oxidant, yielding notable results and >99 % selectivity within 8 h. Various characterization techniques confirm the structure and enhanced properties of the magnetic nanoparticles. Magnetic property of photocatalyst, n-Fe<sub>3</sub>O<sub>4</sub>@ECH@n-TiO<sub>2</sub>/WO<sub>3</sub>, enables easy separation and reusability of nanoparticles for at least four consecutive runs without significant loss of activity. The formed heterojunction between n-TiO<sub>2</sub>-P25 and n-WO<sub>3</sub>, not only improves light absorption and photocatalytic efficiency, but also overcomes the drawbacks associated with recovering and long-term stability, offering outstanding potential for advanced applications and future studies.</div></div>","PeriodicalId":432,"journal":{"name":"Solid State Sciences","volume":"171 ","pages":"Article 108113"},"PeriodicalIF":3.3,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145622742","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 : 2025-11-01DOI: 10.1016/j.solidstatesciences.2025.108018
Özge Balcı-Çağıran (Executive Guest Editor) , Onuralp Yücel (Co-Guest Editor) , Mehmet Somer (Co-GuestEditor)
{"title":"Editorial on: 22nd International Symposium on Boron, Borides and related materials (ISBB 2024)","authors":"Özge Balcı-Çağıran (Executive Guest Editor) , Onuralp Yücel (Co-Guest Editor) , Mehmet Somer (Co-GuestEditor)","doi":"10.1016/j.solidstatesciences.2025.108018","DOIUrl":"10.1016/j.solidstatesciences.2025.108018","url":null,"abstract":"","PeriodicalId":432,"journal":{"name":"Solid State Sciences","volume":"169 ","pages":"Article 108018"},"PeriodicalIF":3.3,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145412527","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 : 2025-10-31DOI: 10.1016/j.solidstatesciences.2025.108127
Sebastiano Caravati , Dario Baratella , Paolo Fantini , Marco Bernasconi
GeAsSe alloys are of interest for application in selector devices in combination with both phase change and resistive memories. In this work, we compute the electronic properties of GeAsSe alloys at several compositions and of a Si-doped GeAsSe alloy within Density Functional Theory (DFT). The analysis of the amorphous models generated by quenching from the melt within DFT molecular dynamics aims at gaining information on in-gap states that are believed to control the functional properties of these alloys exploited in the selector devices, namely the switching threshold voltage, its dependence on the preparation conditions of the amorphous material, and its drift with time. The simulations reveal that localized empty in-gap states (electron traps) are mostly related to homopolar GeGe, AsAs and GeAs bonds, while the most localized filled states (hole traps) are mostly related to SeSe bonds and are particularly evident in Se-rich compositions.
{"title":"In-gap electronic states of GeAsSe and SiGeAsSe alloys for selector devices from atomistic simulations","authors":"Sebastiano Caravati , Dario Baratella , Paolo Fantini , Marco Bernasconi","doi":"10.1016/j.solidstatesciences.2025.108127","DOIUrl":"10.1016/j.solidstatesciences.2025.108127","url":null,"abstract":"<div><div>GeAsSe alloys are of interest for application in selector devices in combination with both phase change and resistive memories. In this work, we compute the electronic properties of GeAsSe alloys at several compositions and of a Si-doped GeAsSe alloy within Density Functional Theory (DFT). The analysis of the amorphous models generated by quenching from the melt within DFT molecular dynamics aims at gaining information on in-gap states that are believed to control the functional properties of these alloys exploited in the selector devices, namely the switching threshold voltage, its dependence on the preparation conditions of the amorphous material, and its drift with time. The simulations reveal that localized empty in-gap states (electron traps) are mostly related to homopolar Ge<img>Ge, As<img>As and Ge<img>As bonds, while the most localized filled states (hole traps) are mostly related to Se<img>Se bonds and are particularly evident in Se-rich compositions.</div></div>","PeriodicalId":432,"journal":{"name":"Solid State Sciences","volume":"170 ","pages":"Article 108127"},"PeriodicalIF":3.3,"publicationDate":"2025-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145463969","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}
Bi2MoO6, a Bi-based semiconductor catalyst, exhibits effective degradation of organic pollutants. Nevertheless, its photocatalytic performance is constrained by several limitations, such as inadequate sunlight absorption, poor charge mobility, and fast charge carrier recombination upon photoexcitation. In this research, we successfully synthesized a Bi2MoO6 composite modified with carbon quantum dots (CQDs), which demonstrates a significant improvement in photocatalytic performance. A series of characterizations and photocatalytic experiments were performed on the synthesized CQDs/Bi2MoO6 samples. Degradation experiments revealed that under simulated sunlight, the CQDs/Bi2MoO6 composite achieved a 95 % degradation rate for Rhodamine B (RhB) within 70 min, with a kinetic constant of 0.03994 min−1. In comparison, the undoped Bi2MoO6 sample degraded only 46 % of RhB under the same conditions, exhibiting a kinetic constant of 0.00658 min−1. The primary reactive species, ·O2− and h+, were unequivocally identified through combined ESR spectroscopy and radical scavenging experiments as the drivers of pollutant degradation. Furthermore, after four consecutive reaction cycles, the catalyst maintained 90.05 % of its initial activity, confirming its high stability. In summary, this study successfully developed a CQDs-doped Bi2MoO6 composite photocatalyst, offering a promising strategy for advancing photocatalysis research.
Bi2MoO6是一种铋基半导体催化剂，对有机污染物具有较好的降解效果。然而，它的光催化性能受到一些限制，如阳光吸收不足，电荷迁移率差，光激发后电荷载流子重组快。在本研究中，我们成功地合成了碳量子点（CQDs）修饰的Bi2MoO6复合材料，其光催化性能得到了显著改善。对合成的CQDs/Bi2MoO6样品进行了一系列表征和光催化实验。降解实验表明，在模拟阳光下，CQDs/Bi2MoO6复合材料在70 min内对Rhodamine B （RhB）的降解率达到95%，降解动力学常数为0.03994 min−1。相比之下，未掺杂的Bi2MoO6样品在相同条件下仅降解了46%的RhB，其动力学常数为0.00658 min−1。通过ESR光谱和自由基清除实验，我们明确地确定了主要的活性物质·O2−和h+是污染物降解的驱动因素。在连续4个反应周期后，催化剂的活性仍保持在初始活性的90.05%，证明了催化剂的高稳定性。综上所述，本研究成功开发了cqds掺杂Bi2MoO6复合光催化剂，为推进光催化研究提供了一个有前景的策略。
{"title":"Fabrication of carbon quantum dot-decorated Bi2MoO6 composites via a hydrothermal method for enhanced photocatalytic degradation of Rhodamine B","authors":"Huadong Liu, Xiaoyu Sun, Jingliang Cheng, Zhonghao Zhao, Cong Zhang","doi":"10.1016/j.solidstatesciences.2025.108108","DOIUrl":"10.1016/j.solidstatesciences.2025.108108","url":null,"abstract":"<div><div>Bi<sub>2</sub>MoO<sub>6</sub>, a Bi-based semiconductor catalyst, exhibits effective degradation of organic pollutants. Nevertheless, its photocatalytic performance is constrained by several limitations, such as inadequate sunlight absorption, poor charge mobility, and fast charge carrier recombination upon photoexcitation. In this research, we successfully synthesized a Bi<sub>2</sub>MoO<sub>6</sub> composite modified with carbon quantum dots (CQDs), which demonstrates a significant improvement in photocatalytic performance. A series of characterizations and photocatalytic experiments were performed on the synthesized CQDs/Bi<sub>2</sub>MoO<sub>6</sub> samples. Degradation experiments revealed that under simulated sunlight, the CQDs/Bi<sub>2</sub>MoO<sub>6</sub> composite achieved a 95 % degradation rate for Rhodamine B (RhB) within 70 min, with a kinetic constant of 0.03994 min<sup>−1</sup>. In comparison, the undoped Bi<sub>2</sub>MoO<sub>6</sub> sample degraded only 46 % of RhB under the same conditions, exhibiting a kinetic constant of 0.00658 min<sup>−1</sup>. The primary reactive species, ·O<sub>2</sub><sup>−</sup> and h<sup>+</sup>, were unequivocally identified through combined ESR spectroscopy and radical scavenging experiments as the drivers of pollutant degradation. Furthermore, after four consecutive reaction cycles, the catalyst maintained 90.05 % of its initial activity, confirming its high stability. In summary, this study successfully developed a CQDs-doped Bi<sub>2</sub>MoO<sub>6</sub> composite photocatalyst, offering a promising strategy for advancing photocatalysis research.</div></div>","PeriodicalId":432,"journal":{"name":"Solid State Sciences","volume":"170 ","pages":"Article 108108"},"PeriodicalIF":3.3,"publicationDate":"2025-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145463970","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}
This study reports the development of a sensitive and reliable electrochemical sensor based on a zinc oxide nanoparticle-modified graphitic carbon nitride (ZnO@g-C3N4) nanocomposite for the individual and simultaneous determination of Pb2+ and Hg2+ ions. Three different weight ratio of nanocomposites were prepared and characterized by spectroscopic techniques like UV–Vis spectroscopy, Fourier-transform infrared (FT-IR) spectroscopy, X-Ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and microscopic techniques such as scanning electron microscope (SEM), transmission electron microscopy (TEM) and Atomic Force Microscopy (AFM). Thermogravimetric analysis (TGA) was also performed to assess the thermal stability and decomposition behaviour of the prepared samples. The ZnO@g-C3N4 nanocomposite modified GCE was successfully fabricated on electrode surface to determine Pb2+ and Hg2+ simultaneously using differential pulse voltammetry (DPV). Under optimized conditions, the anodic current exhibited a linear relationship with metal ion concentration, covering 0.1–100 μM for Pb2+ with a detection limit of 5.17 nM (S/N = 3), and 0.1–10 μM for Hg2+ with a detection limit of 7.9 nM (S/N = 3). Finally, the effective application of this novel electrode material allowed for the simultaneous determination of Pb2+ and Hg2+ in real water samples, cosmetics, and fish tissues, yielding satisfactory recovery results.
{"title":"Advanced ZnO-g-C3N4 nanocomposite: A highly sensitive electrochemical sensor for simultaneous determination of lead and mercury ions","authors":"Vikas Jangra , Harpreet Kaur , Narvdeshwar Kumar , Anand Ratnam , Lal Bahadur Prasad , Piyush Kumar Sonkar","doi":"10.1016/j.solidstatesciences.2025.108116","DOIUrl":"10.1016/j.solidstatesciences.2025.108116","url":null,"abstract":"<div><div>This study reports the development of a sensitive and reliable electrochemical sensor based on a zinc oxide nanoparticle-modified graphitic carbon nitride (ZnO@g-C<sub>3</sub>N<sub>4</sub>) nanocomposite for the individual and simultaneous determination of Pb<sup>2+</sup> and Hg<sup>2+</sup> ions. Three different weight ratio of nanocomposites were prepared and characterized by spectroscopic techniques like UV–Vis spectroscopy, Fourier-transform infrared (FT-IR) spectroscopy, X-Ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and microscopic techniques such as scanning electron microscope (SEM), transmission electron microscopy (TEM) and Atomic Force Microscopy (AFM). Thermogravimetric analysis (TGA) was also performed to assess the thermal stability and decomposition behaviour of the prepared samples. The ZnO@g-C<sub>3</sub>N<sub>4</sub> nanocomposite modified GCE was successfully fabricated on electrode surface to determine Pb<sup>2+</sup> and Hg<sup>2+</sup> simultaneously using differential pulse voltammetry (DPV). Under optimized conditions, the anodic current exhibited a linear relationship with metal ion concentration, covering 0.1–100 μM for Pb<sup>2+</sup> with a detection limit of 5.17 nM (S/N = 3), and 0.1–10 μM for Hg<sup>2+</sup> with a detection limit of 7.9 nM (S/N = 3). Finally, the effective application of this novel electrode material allowed for the simultaneous determination of Pb<sup>2+</sup> and Hg<sup>2+</sup> in real water samples, cosmetics, and fish tissues, yielding satisfactory recovery results.</div></div>","PeriodicalId":432,"journal":{"name":"Solid State Sciences","volume":"170 ","pages":"Article 108116"},"PeriodicalIF":3.3,"publicationDate":"2025-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145414893","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 : 2025-10-28DOI: 10.1016/j.solidstatesciences.2025.108115
R.A. Kadam , S.B. Madake , M.A. Yewale , A.A. Jadhawar , S.A. Alshehri , R. Venkatesan , D.K. Shin , Minjae Kim
In this study, hierarchical ZnFe2O4 nanostructures were synthesized via a hydrothermal method using ammonium fluoride (NH4F) as a morphology-directing agent. By varying NH4F concentrations (30–120 mM), we successfully modulated the material morphology from agglomerated nanoparticles to highly ordered flower-like architectures. Comprehensive structural and morphological analyses confirmed the formation of phase-pure spinel ZnFe2O4 with tailored crystal orientation and reduced lattice strain. Among the samples, the ZF-AF-120mM nanostructure, composed of radially assembled nanosheets, exhibited outstanding photoelectrochemical (PEC) performance for solar water splitting. It delivered a peak photocurrent density of 6.25 mA cm−2 at 1.3 V vs. Ag/AgCl and an applied bias photon-to-current efficiency (ABPE) of 0.45 %, along with excellent stability (61.1 % retention over 2h). Electrochemical impedance spectroscopy revealed the lowest charge transfer resistance (Rct = 16.09 Ω) for ZF-AF-120mM, indicating enhanced charge transport and reduced recombination. The exceptional PEC activity is attributed to the hierarchical nanoflower morphology, which promotes superior light harvesting, increased surface area, and efficient charge carrier dynamics. These results underscore the crucial role of NH4F-mediated morphology engineering in optimizing spinel ferrite photoanodes for efficient and durable solar-driven hydrogen generation.
本研究以氟化铵（NH4F）为形态导向剂，通过水热法制备了具有层次结构的ZnFe2O4纳米结构。通过改变NH4F浓度（30-120 mM），我们成功地将材料形态从凝聚的纳米颗粒调节为高度有序的花状结构。综合结构和形态分析证实，形成了取向定制、晶格应变减小的相纯尖晶石ZnFe2O4。其中，由径向组装纳米片组成的ZF-AF-120mM纳米结构在太阳能水分解中表现出优异的光电化学（PEC）性能。在1.3 V vs. Ag/AgCl下，它的峰值光电流密度为6.25 mA cm−2，应用偏压光子电流效率（ABPE）为0.45%，具有优异的稳定性（2h内保持率为61.1%）。电化学阻抗谱显示ZF-AF-120mM的电荷转移电阻最低（Rct = 16.09 Ω），表明电荷传输增强，复合减少。特殊的PEC活性归因于分层纳米花的形态，它促进了优越的光收集，增加了表面积，以及有效的载流子动力学。这些结果强调了nh4f介导的形态学工程在优化尖晶石铁氧体光阳极以实现高效耐用的太阳能制氢方面的关键作用。
{"title":"Hierarchical flower-like zinc ferrite photoanode for enhanced photoelectrocatalytic water splitting effect of ammonium fluoride-assisted morphological control","authors":"R.A. Kadam , S.B. Madake , M.A. Yewale , A.A. Jadhawar , S.A. Alshehri , R. Venkatesan , D.K. Shin , Minjae Kim","doi":"10.1016/j.solidstatesciences.2025.108115","DOIUrl":"10.1016/j.solidstatesciences.2025.108115","url":null,"abstract":"<div><div>In this study, hierarchical ZnFe<sub>2</sub>O<sub>4</sub> nanostructures were synthesized via a hydrothermal method using ammonium fluoride (NH<sub>4</sub>F) as a morphology-directing agent. By varying NH<sub>4</sub>F concentrations (30–120 mM), we successfully modulated the material morphology from agglomerated nanoparticles to highly ordered flower-like architectures. Comprehensive structural and morphological analyses confirmed the formation of phase-pure spinel ZnFe<sub>2</sub>O<sub>4</sub> with tailored crystal orientation and reduced lattice strain. Among the samples, the ZF-AF-120mM nanostructure, composed of radially assembled nanosheets, exhibited outstanding photoelectrochemical (PEC) performance for solar water splitting. It delivered a peak photocurrent density of 6.25 mA cm<sup>−2</sup> at 1.3 V vs. Ag/AgCl and an applied bias photon-to-current efficiency (ABPE) of 0.45 %, along with excellent stability (61.1 % retention over 2h). Electrochemical impedance spectroscopy revealed the lowest charge transfer resistance (R<sub>ct</sub> = 16.09 Ω) for ZF-AF-120mM, indicating enhanced charge transport and reduced recombination. The exceptional PEC activity is attributed to the hierarchical nanoflower morphology, which promotes superior light harvesting, increased surface area, and efficient charge carrier dynamics. These results underscore the crucial role of NH<sub>4</sub>F-mediated morphology engineering in optimizing spinel ferrite photoanodes for efficient and durable solar-driven hydrogen generation.</div></div>","PeriodicalId":432,"journal":{"name":"Solid State Sciences","volume":"170 ","pages":"Article 108115"},"PeriodicalIF":3.3,"publicationDate":"2025-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145463971","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 : 2025-10-28DOI: 10.1016/j.solidstatesciences.2025.108117
Gianluca Tesi , Chiara Coppi , Lorenzo Fornari , Francesco Mezzadri , Giovanna Trevisi , Elena Del Canale , Edmondo Gilioli , Davide Delmonte
Silica, valued for its unique properties and abundance, is widely studied and applied in various fields. Quartz, the most stable polymorph at ambient conditions, can be obtained from amorphous silica through calcination. However, achieving this transformation without mineralizers such as alkaline salts is extremely challenging, since metastable phases like cristobalite often form even at temperatures where quartz is the thermodynamically stable phase. In this work, an optimized calcination strategy is proposed to selectively obtain polycrystalline α-quartz from amorphous silica pellets by varying process parameters such as target temperature, dwell time, and cooling rates. Quantitative analyses by X-ray powder diffraction and scanning electron microscopy reveal that the initial density of the precursors significantly influences both the thermodynamics and kinetics of the structural phase transformation. A phenomenological explanation of these findings is proposed, considering initial density and morphology of amorphous silica as key driving factors in the process. Additional experiments performed under high-pressure/high-temperature conditions underline the complementary roles of thermodynamics and kinetics in the formation of the target phase.
{"title":"Thermodynamic, kinetic, and density-driven pathways in the selective transformation of amorphous silica to α-quartz","authors":"Gianluca Tesi , Chiara Coppi , Lorenzo Fornari , Francesco Mezzadri , Giovanna Trevisi , Elena Del Canale , Edmondo Gilioli , Davide Delmonte","doi":"10.1016/j.solidstatesciences.2025.108117","DOIUrl":"10.1016/j.solidstatesciences.2025.108117","url":null,"abstract":"<div><div>Silica, valued for its unique properties and abundance, is widely studied and applied in various fields. Quartz, the most stable polymorph at ambient conditions, can be obtained from amorphous silica through calcination. However, achieving this transformation without mineralizers such as alkaline salts is extremely challenging, since metastable phases like cristobalite often form even at temperatures where quartz is the thermodynamically stable phase. In this work, an optimized calcination strategy is proposed to selectively obtain polycrystalline α-quartz from amorphous silica pellets by varying process parameters such as target temperature, dwell time, and cooling rates. Quantitative analyses by X-ray powder diffraction and scanning electron microscopy reveal that the initial density of the precursors significantly influences both the thermodynamics and kinetics of the structural phase transformation. A phenomenological explanation of these findings is proposed, considering initial density and morphology of amorphous silica as key driving factors in the process. Additional experiments performed under high-pressure/high-temperature conditions underline the complementary roles of thermodynamics and kinetics in the formation of the target phase.</div></div>","PeriodicalId":432,"journal":{"name":"Solid State Sciences","volume":"170 ","pages":"Article 108117"},"PeriodicalIF":3.3,"publicationDate":"2025-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145463973","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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