Pub Date : 2025-11-06DOI: 10.1016/j.jssc.2025.125731
Abdelazeem S. Eltaweil , Esraa Talaat , Eman M. Abd El-Monaem , Gehan M. El-Subruiti
{"title":"Corrigendum to “Photocatalytic removal of o-Nitro phenol using phyto-assisted synthesized NiO/CdS@g-GO catalyst” [J. Solid State Chem. 343 (2025) 125159 10.1016/j.jssc.2024.125159]","authors":"Abdelazeem S. Eltaweil , Esraa Talaat , Eman M. Abd El-Monaem , Gehan M. El-Subruiti","doi":"10.1016/j.jssc.2025.125731","DOIUrl":"10.1016/j.jssc.2025.125731","url":null,"abstract":"","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"354 ","pages":"Article 125731"},"PeriodicalIF":3.5,"publicationDate":"2025-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145680953","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 : 2025-11-06DOI: 10.1016/j.jssc.2025.125735
Vaishnavi B. Hubale , Ankita N. Dalvi , Omkar S. Nille , Govind B. Kolekar , Vaishali A. Sawant
In this study, two novel one-dimensional coordination polymers (CPs), [Zn2(bib)(3F-PAA)4]n (1) and [Cd(bib)(3F-PAA)2]n (2), were synthesized using a solvothermal method involving a mixed-ligand strategy with 1,4-bis(imidazole)butane (bib) and 3-fluorophenylacrylic acid (3F-PAA). Structural analysis via single-crystal X-ray diffraction revealed square pyramidal geometry around Zn(II) in 1 and distorted octahedral coordination geometry around Cd(II) in 2. The CPs exhibit excellent water dispersibility, high thermal stability, and strong photoluminescence, making them suitable candidates for sensing. Both CPs demonstrated high selectivity and sensitivity in the fluorescence detection of Fe3+, Cr2O72−, and folic acid (FA) in aqueous media. The detection limits achieved are remarkably low, with values of Fe3+: 0.031 μM (1), 0.026 μM (2); Cr2O72−: 0.018 μM (1), 0.019 μM (2); FA: 0.014 μM (1), 0.017 μM (2), highlighting the potential of these CPs as efficient, multifunctional fluorescent sensors for environmental and biomedical applications.
{"title":"Multifunctional Zn(II)/Cd(II) coordination polymers for the selective fluorescence detection of Fe3+, Cr2O72−, and folic acid","authors":"Vaishnavi B. Hubale , Ankita N. Dalvi , Omkar S. Nille , Govind B. Kolekar , Vaishali A. Sawant","doi":"10.1016/j.jssc.2025.125735","DOIUrl":"10.1016/j.jssc.2025.125735","url":null,"abstract":"<div><div>In this study, two novel one-dimensional coordination polymers (CPs), <strong>[Zn<sub>2</sub>(bib)(3F-PAA)<sub>4</sub>]</strong><strong><sub>n</sub></strong> (<strong>1</strong>) and <strong>[Cd(bib)(3F-PAA)<sub>2</sub>]</strong><sub>n</sub> (<strong>2</strong>), were synthesized using a solvothermal method involving a mixed-ligand strategy with 1,4-bis(imidazole)butane (<strong>bib</strong>) and 3-fluorophenylacrylic acid (<strong>3F-PAA</strong>). Structural analysis via single-crystal X-ray diffraction revealed square pyramidal geometry around Zn(II) in <strong>1</strong> and distorted octahedral coordination geometry around Cd(II) in <strong>2</strong>. The CPs exhibit excellent water dispersibility, high thermal stability, and strong photoluminescence, making them suitable candidates for sensing. Both CPs demonstrated high selectivity and sensitivity in the fluorescence detection of Fe<sup>3+</sup>, Cr<sub>2</sub>O<sub>7</sub><sup>2−</sup>, and folic acid (FA) in aqueous media. The detection limits achieved are remarkably low, with values of Fe<sup>3+</sup>: 0.031 μM (<strong>1</strong>), 0.026 μM (<strong>2</strong>); Cr<sub>2</sub>O<sub>7</sub><sup>2−</sup>: 0.018 μM (<strong>1</strong>), 0.019 μM (<strong>2</strong>); FA: 0.014 μM (<strong>1</strong>), 0.017 μM (<strong>2</strong>), highlighting the potential of these CPs as efficient, multifunctional fluorescent sensors for environmental and biomedical applications.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"354 ","pages":"Article 125735"},"PeriodicalIF":3.5,"publicationDate":"2025-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145569362","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 : 2025-11-04DOI: 10.1016/j.jssc.2025.125732
Gleb M. Zirnik , Yaroslav V. Boleiko , Ibrohimi A. Solizoda , Lev S. Avvakumov , Daniil A. Uchaev , Gelena M. Boleiko , Konstantin V. Matveev , Аlexander S. Chernukha , Svetlana A. Gudkova , Nataly A. Cherkasova , Denis A. Vinnik
The use of new semiconductor oxide materials is one of the modern directions of printed electronics. In the article, a new approach to the synthesis of InGaZn3O6 by the method of combustion of nitrate-glycol gel is proposed. It is shown that it is possible to obtain powder material both in amorphous and crystalline states. The kinetic patterns of particle growth are studied by XRD, SEM and TEM methods. The sigmoidal nature of particle growth is found.
{"title":"Synthesis and phase-formation kinetic of InGaZn3O6 nano-powder","authors":"Gleb M. Zirnik , Yaroslav V. Boleiko , Ibrohimi A. Solizoda , Lev S. Avvakumov , Daniil A. Uchaev , Gelena M. Boleiko , Konstantin V. Matveev , Аlexander S. Chernukha , Svetlana A. Gudkova , Nataly A. Cherkasova , Denis A. Vinnik","doi":"10.1016/j.jssc.2025.125732","DOIUrl":"10.1016/j.jssc.2025.125732","url":null,"abstract":"<div><div>The use of new semiconductor oxide materials is one of the modern directions of printed electronics. In the article, a new approach to the synthesis of InGaZn<sub>3</sub>O<sub>6</sub> by the method of combustion of nitrate-glycol gel is proposed. It is shown that it is possible to obtain powder material both in amorphous and crystalline states. The kinetic patterns of particle growth are studied by XRD, SEM and TEM methods. The sigmoidal nature of particle growth is found.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"354 ","pages":"Article 125732"},"PeriodicalIF":3.5,"publicationDate":"2025-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145464307","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.jssc.2025.125729
Feixiang Yang , Boyu Xiao , Wenliang Wu , Chenglan Huang , Junxiang Ding , Bingyan Qu , Lei Wang
The development of non-toxic, highly biocompatible, and eco-friendly red-emitting materials, with emission spectra matching plant pigment absorption (notably phytochrome red, Pr, and phytochrome far-red, Pfr), is highly promising for plant cultivation applications. In this work, a series of Fe-doped LiAlSiO4 and LiGaSiO4 luminescent materials were successfully synthesized. Under excitation at 297 nm, LiAlSiO4:Fe3+ shows a broad red emission band ranging from 600 to 805 nm with a peak at 670 nm. Similarly, LiGaSiO4:Fe3+ exhibits a broad emission from 600 to 890 nm, peaking at 707 nm when excited at 285 nm. Both materials demonstrate good thermal stability at elevated temperatures. Notably, their emission spectra align well with the absorption spectra of Pr and Pfr, indicating strong potential for use in plant growth lighting systems. This work offers new perspectives for designing novel red-emitting luminescent materials.
{"title":"Development of novel red broadband luminescent materials based on tetrahedrally coordinated Fe3+ activated LiAlSiO4 and LiGaSiO4 for multifunctional pc-LEDs","authors":"Feixiang Yang , Boyu Xiao , Wenliang Wu , Chenglan Huang , Junxiang Ding , Bingyan Qu , Lei Wang","doi":"10.1016/j.jssc.2025.125729","DOIUrl":"10.1016/j.jssc.2025.125729","url":null,"abstract":"<div><div>The development of non-toxic, highly biocompatible, and eco-friendly red-emitting materials, with emission spectra matching plant pigment absorption (notably phytochrome red, Pr, and phytochrome far-red, Pfr), is highly promising for plant cultivation applications. In this work, a series of Fe-doped LiAlSiO<sub>4</sub> and LiGaSiO<sub>4</sub> luminescent materials were successfully synthesized. Under excitation at 297 nm, LiAlSiO<sub>4</sub>:Fe<sup>3+</sup> shows a broad red emission band ranging from 600 to 805 nm with a peak at 670 nm. Similarly, LiGaSiO<sub>4</sub>:Fe<sup>3+</sup> exhibits a broad emission from 600 to 890 nm, peaking at 707 nm when excited at 285 nm. Both materials demonstrate good thermal stability at elevated temperatures. Notably, their emission spectra align well with the absorption spectra of Pr and Pfr, indicating strong potential for use in plant growth lighting systems. This work offers new perspectives for designing novel red-emitting luminescent materials.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"354 ","pages":"Article 125729"},"PeriodicalIF":3.5,"publicationDate":"2025-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145464297","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}
The development of efficient electrocatalysts for oxygen evolution reaction (OER) is crucial for advancing sustainable energy technologies. In this work, we present a facile solid-state grinding approach to encapsulate the Anderson-type polyoxometalate [NiMo6O24H6]4- (denoted as NiMo6) into the pores of the robust metal-organic framework (MOF) MIL-101(Fe), forming a series of NiMo6@MIL composites with varying mass ratios. Among these, NiMo6@MIL-1 demonstrated superior OER performance under alkaline conditions with a low overpotential of 392 mV and a Tafel slope of 89 mV/dec at a current density of 10 mA/cm2. NiMo6@MIL-1 composite exhibited enhanced electrocatalytic activity compared to its individual components, along with excellent stability over a 4-h period. Notably, comparative studies on OER and hydrogen evolution reaction (HER) performance across composites constructed by isostructural Anderson-type anions with different heteroatoms revealed that the feature of the central atom plays a crucial role in the electrocatalytic behavior of the composite materials. The reaction mechanism of NiMo6@MIL-1 composite for electrocatalytic OER is also discussed.
{"title":"Regulated Anderson-type polyoxometalate-based composites with MIL-101(Fe) for enhanced electrocatalytic oxygen evolution reaction","authors":"Xinyi Xu, Hongji Kang, Dandan Qiu, Wanrou Shi, Lu Yang, Daopeng Zhang, Zhen Zhou","doi":"10.1016/j.jssc.2025.125730","DOIUrl":"10.1016/j.jssc.2025.125730","url":null,"abstract":"<div><div>The development of efficient electrocatalysts for oxygen evolution reaction (OER) is crucial for advancing sustainable energy technologies. In this work, we present a facile solid-state grinding approach to encapsulate the Anderson-type polyoxometalate [NiMo<sub>6</sub>O<sub>24</sub>H<sub>6</sub>]<sup>4-</sup> (denoted as NiMo<sub>6</sub>) into the pores of the robust metal-organic framework (MOF) MIL-101(Fe), forming a series of NiMo<sub>6</sub>@MIL composites with varying mass ratios. Among these, NiMo<sub>6</sub>@MIL-1 demonstrated superior OER performance under alkaline conditions with a low overpotential of 392 mV and a Tafel slope of 89 mV/dec at a current density of 10 mA/cm<sup>2</sup>. NiMo<sub>6</sub>@MIL-1 composite exhibited enhanced electrocatalytic activity compared to its individual components, along with excellent stability over a 4-h period. Notably, comparative studies on OER and hydrogen evolution reaction (HER) performance across composites constructed by isostructural Anderson-type anions with different heteroatoms revealed that the feature of the central atom plays a crucial role in the electrocatalytic behavior of the composite materials. The reaction mechanism of NiMo<sub>6</sub>@MIL-1 composite for electrocatalytic OER is also discussed.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"354 ","pages":"Article 125730"},"PeriodicalIF":3.5,"publicationDate":"2025-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145414531","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 : 2025-10-30DOI: 10.1016/j.jssc.2025.125727
Zhihao Wang , Zhanshou Wang , Honglei Han , Guohua Shi , Qiyong Zhao , Shaohua Wu , Hongli Zhao
This study reports a facile and cost-effective atmospheric pressure CVD method for synthesizing high-quality SnSe2 thin films. Utilizing readily available SnCl2 and Se powder precursors, this method enables the growth of highly crystalline (98.56 %) SnSe2 films with a strong (00l) preferred orientation on glass substrates. The resulting films exhibit a direct band gap of 1.51 eV, as determined by optical measurements. This simplified CVD approach presents a promising route for the large-scale production of SnSe2 thin films, with potential applications in optoelectronic devices.
{"title":"Tailoring the properties of SnSe2 thin films via atmospheric pressure CVD: Growth and characterization","authors":"Zhihao Wang , Zhanshou Wang , Honglei Han , Guohua Shi , Qiyong Zhao , Shaohua Wu , Hongli Zhao","doi":"10.1016/j.jssc.2025.125727","DOIUrl":"10.1016/j.jssc.2025.125727","url":null,"abstract":"<div><div>This study reports a facile and cost-effective atmospheric pressure CVD method for synthesizing high-quality SnSe<sub>2</sub> thin films. Utilizing readily available SnCl<sub>2</sub> and Se powder precursors, this method enables the growth of highly crystalline (98.56 %) SnSe<sub>2</sub> films with a strong (00l) preferred orientation on glass substrates. The resulting films exhibit a direct band gap of 1.51 eV, as determined by optical measurements. This simplified CVD approach presents a promising route for the large-scale production of SnSe<sub>2</sub> thin films, with potential applications in optoelectronic devices.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"354 ","pages":"Article 125727"},"PeriodicalIF":3.5,"publicationDate":"2025-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145464305","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 : 2025-10-30DOI: 10.1016/j.jssc.2025.125728
J.H. He , H.P. Song , P.Y. Zhang , L. Yuan , X. Wu
Potassium fluosilicate (K2SiF6) and sodium fluosilicate (Na2SiF6) doped with Mn4+ are promising hexafluoro silicates with efficient emitting luminescent properties. However, the highly symmetric of the cubic crystal structure (space group Fmm) in K2SiF6 limits its applications. To explore their structural properties under pressure, K2SiF6 and Na2SiF6 were investigated using Synchrotron radiation powder X-ray diffraction (XRD), Raman spectroscopy, and density-functional theory (DFT) calculations. Both experimental and theoretical results show K2SiF6 undergoes a phase transition from Fmm to P63mc phase at 1.3 GPa. Experimentally at 12.0 GPa, Na2SiF6 undergoes a phase transition from P321 to a new phase, which is confirmed to be the Fmm phase by DFT calculations. The pressure-volume data of K2SiF6 and Na2SiF6 are fitted to the second-order Birch-Murnaghan equation of state with K0 = 50(3) GPa for P63mc K2SiF6, and K0 = 25.3(7) GPa for P321 Na2SiF6. The difference in phase transition pressures and compressibility of hexafluoro silicates are attributed to the distinct phase transition mechanisms and the radius of metal cations. Notably, the hexagonal K2SiF6 with lower crystal symmetry may offer improved emission efficiency and broaden its practical applicability.
{"title":"Pressure-induced phase transitions and structural stability in K2SiF6 and Na2SiF6","authors":"J.H. He , H.P. Song , P.Y. Zhang , L. Yuan , X. Wu","doi":"10.1016/j.jssc.2025.125728","DOIUrl":"10.1016/j.jssc.2025.125728","url":null,"abstract":"<div><div>Potassium fluosilicate (K<sub>2</sub>SiF<sub>6</sub>) and sodium fluosilicate (Na<sub>2</sub>SiF<sub>6</sub>) doped with Mn<sup>4+</sup> are promising hexafluoro silicates with efficient emitting luminescent properties. However, the highly symmetric of the cubic crystal structure (space group <em>Fm</em> <span><math><mrow><mover><mn>3</mn><mo>‾</mo></mover></mrow></math></span> <em>m</em>) in K<sub>2</sub>SiF<sub>6</sub> limits its applications. To explore their structural properties under pressure, K<sub>2</sub>SiF<sub>6</sub> and Na<sub>2</sub>SiF<sub>6</sub> were investigated using Synchrotron radiation powder X-ray diffraction (XRD), Raman spectroscopy, and density-functional theory (DFT) calculations. Both experimental and theoretical results show K<sub>2</sub>SiF<sub>6</sub> undergoes a phase transition from <em>Fm</em> <span><math><mrow><mover><mn>3</mn><mo>‾</mo></mover></mrow></math></span> <em>m</em> to <em>P</em>6<sub>3</sub><em>mc</em> phase at 1.3 GPa. Experimentally at 12.0 GPa, Na<sub>2</sub>SiF<sub>6</sub> undergoes a phase transition from <em>P</em>321 to a new phase, which is confirmed to be the <em>Fm</em> <span><math><mrow><mover><mn>3</mn><mo>‾</mo></mover></mrow></math></span> <em>m</em> phase by DFT calculations. The pressure-volume data of K<sub>2</sub>SiF<sub>6</sub> and Na<sub>2</sub>SiF<sub>6</sub> are fitted to the second-order Birch-Murnaghan equation of state with <em>K</em><sub>0</sub> = 50(3) GPa for <em>P</em>6<sub>3</sub><em>mc</em> K<sub>2</sub>SiF<sub>6</sub>, and <em>K</em><sub>0</sub> = 25.3(7) GPa for <em>P</em>321 Na<sub>2</sub>SiF<sub>6</sub>. The difference in phase transition pressures and compressibility of hexafluoro silicates are attributed to the distinct phase transition mechanisms and the radius of metal cations. Notably, the hexagonal K<sub>2</sub>SiF<sub>6</sub> with lower crystal symmetry may offer improved emission efficiency and broaden its practical applicability.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"354 ","pages":"Article 125728"},"PeriodicalIF":3.5,"publicationDate":"2025-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145464306","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 : 2025-10-27DOI: 10.1016/j.jssc.2025.125715
Weiping Tang, Yi Dong, Qiuying Huang
Against the global low-carbon energy transition, proton exchange membrane fuel cells (PEMFCs) are pivotal for carbon neutrality, and metal-organic frameworks (MOFs) show promise as PEM materials. Herein, we synthesized a terbium-based MOF ([Tb2(DBTA)3(DMF)2]•DMF, denoted MOF 1) via the solvothermal method using 2,5-dibromoterephthalic acid (H2DBTA) and Tb(NO3)3•6H2O, which was systematically characterized using powder X-ray diffraction (PXRD), Fourier-transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), and other techniques. The results demonstrated that 1 exhibits favorable properties for proton conduction applications, as it maintains good thermal stability and water stability, and has a water contact angle of 46.0° (indicating hydrophilicity). Alternating current (AC) impedance measurements, conducted over a temperature range of 30–100 °C and a relative humidity (RH) range of 68 %–97 %, revealed that the proton conductivity of 1 is strongly dependent on both temperature and humidity. The maximum proton conductivity reached 4.64 × 10−4 S cm−1 under the optimal conditions of 100 °C/97 % RH. Activation energy (Ea) analysis further clarified the proton conduction mechanism: at 97 % RH, the conduction follows the Grotthuss mechanism (Ea = 0.21 eV), while at 68 % RH, a mixed conduction mechanism dominates (Ea = 0.44 eV). This work provides insights for the rational design of MOF-based proton-conductive materials.
{"title":"Preparation and proton-conductive properties of a two-dimensional terbium(III)-organic framework constructed from 2,5-dibromoterephthalic acid","authors":"Weiping Tang, Yi Dong, Qiuying Huang","doi":"10.1016/j.jssc.2025.125715","DOIUrl":"10.1016/j.jssc.2025.125715","url":null,"abstract":"<div><div>Against the global low-carbon energy transition, proton exchange membrane fuel cells (PEMFCs) are pivotal for carbon neutrality, and metal-organic frameworks (MOFs) show promise as PEM materials. Herein, we synthesized a terbium-based MOF ([Tb<sub>2</sub>(DBTA)<sub>3</sub>(DMF)<sub>2</sub>]•DMF, denoted MOF <strong>1</strong>) via the solvothermal method using 2,5-dibromoterephthalic acid (H<sub>2</sub>DBTA) and Tb(NO<sub>3</sub>)<sub>3</sub>•6H<sub>2</sub>O, which was systematically characterized using powder X-ray diffraction (PXRD), Fourier-transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), and other techniques. The results demonstrated that <strong>1</strong> exhibits favorable properties for proton conduction applications, as it maintains good thermal stability and water stability, and has a water contact angle of 46.0° (indicating hydrophilicity). Alternating current (AC) impedance measurements, conducted over a temperature range of 30–100 °C and a relative humidity (RH) range of 68 %–97 %, revealed that the proton conductivity of <strong>1</strong> is strongly dependent on both temperature and humidity. The maximum proton conductivity reached 4.64 × 10<sup>−4</sup> S cm<sup>−1</sup> under the optimal conditions of 100 °C/97 % RH. Activation energy (<em>E</em><sub>a</sub>) analysis further clarified the proton conduction mechanism: at 97 % RH, the conduction follows the Grotthuss mechanism (<em>E</em><sub>a</sub> = 0.21 eV), while at 68 % RH, a mixed conduction mechanism dominates (<em>E</em><sub>a</sub> = 0.44 eV). This work provides insights for the rational design of MOF-based proton-conductive materials.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"354 ","pages":"Article 125715"},"PeriodicalIF":3.5,"publicationDate":"2025-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145414539","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}
We prepared mesoporous carbon materials doped with nitrogen and sulfur and embedded with molybdenum disulfide (MoS2) and molybdenum carbide (Mo2C) using the solid-state synthesis technique. The specific process is as follows: Firstly, thiourea is introduced into the continuous-stirred melamine-formaldehyde solution to achieve uniform mixing of it in the carbon precursor. Then, the introduced molybdenum oxide (MoO3) promotes the in-situ formation of MoS2 on the carbon framework and its uniform dispersion. This synthesis strategy helps to improve the accessibility of active MoS2 sites and promotes the formation of the carbon-coated MoS2 and Mo2C structures, thereby enhancing the electrical conductivity and catalytic activity of the material. The resulting mesoporous carbon composites exhibit superior electrocatalytic performance in the hydrogen evolution reaction (HER). The catalyst 2MF-1.5S–1Mo with a sulfururea doping amount of 1.5g has the best catalytic performance. Under alkaline conditions, when the current density is 10 mA cm−2, 2MF-1.5S–1W has the lowest overpotential of 96 mV. It also has the smallest Tafel slope of 51.83 mV dec−1.
采用固态合成技术制备了掺杂氮和硫，包埋二硫化钼（MoS2）和碳化钼（Mo2C）的介孔碳材料。具体流程如下：首先，将硫脲引入连续搅拌的三聚氰胺-甲醛溶液中，使其与碳前驱体混合均匀。然后，引入的氧化钼（MoO3）促进了MoS2在碳骨架上的原位形成和均匀分散。这种合成策略有助于提高活性MoS2位点的可及性，促进碳包覆MoS2和Mo2C结构的形成，从而提高材料的导电性和催化活性。制备的介孔碳复合材料在析氢反应（HER）中表现出优异的电催化性能。硫脲掺杂量为1.5g时，催化剂2MF-1.5S-1Mo的催化性能最好。在碱性条件下，当电流密度为10 mA cm−2时，2MF-1.5S-1W的过电位最低为96 mV。Tafel斜率最小，为51.83 mV dec−1。
{"title":"A solid-state strategy for synthesizing MoS2/Mo2C-embedded, nitrogen, sulfur Co-doped mesoporous carbons electrocatalysts for hydrogen evolution","authors":"Minghui Hu, Wenting Zhang, Duihai Tang, Shigang Xin, Zhen Zhao","doi":"10.1016/j.jssc.2025.125714","DOIUrl":"10.1016/j.jssc.2025.125714","url":null,"abstract":"<div><div>We prepared mesoporous carbon materials doped with nitrogen and sulfur and embedded with molybdenum disulfide (MoS<sub>2</sub>) and molybdenum carbide (Mo<sub>2</sub>C) using the solid-state synthesis technique. The specific process is as follows: Firstly, thiourea is introduced into the continuous-stirred melamine-formaldehyde solution to achieve uniform mixing of it in the carbon precursor. Then, the introduced molybdenum oxide (MoO<sub>3</sub>) promotes the in-situ formation of MoS<sub>2</sub> on the carbon framework and its uniform dispersion. This synthesis strategy helps to improve the accessibility of active MoS<sub>2</sub> sites and promotes the formation of the carbon-coated MoS<sub>2</sub> and Mo<sub>2</sub>C structures, thereby enhancing the electrical conductivity and catalytic activity of the material. The resulting mesoporous carbon composites exhibit superior electrocatalytic performance in the hydrogen evolution reaction (HER). The catalyst 2MF-1.5S–1Mo with a sulfururea doping amount of 1.5g has the best catalytic performance. Under alkaline conditions, when the current density is 10 mA cm<sup>−2</sup>, 2MF-1.5S–1W has the lowest overpotential of 96 mV. It also has the smallest Tafel slope of 51.83 mV dec<sup>−1</sup>.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"354 ","pages":"Article 125714"},"PeriodicalIF":3.5,"publicationDate":"2025-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145414529","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 : 2025-10-27DOI: 10.1016/j.jssc.2025.125716
Victoria G. Grossman , Maxim S. Molokeev
Ionic conductivity of triple molybdates Tl5A0.5Hf1.5(MoO4)6 (A = Ca, Cd) is studied by the method of impedance spectroscopy in the frequency range from 1 Hz to 1 MHz and in the temperature range of 300–830 K. The molybdates Tl5A0.5Hf1.5(MoO4)6 (A = Ca, Cd) are prepared in the form of fine crystalline powder by solid state synthesis from Tl2MoO4, CaMoO4 (or CdMoO4), and Hf(MoO4)2 at 723–823 K. The conductivity of Tl5Ca0.5Hf1.5(MoO4)6 ceramic samples σ = 2.69‧10−4 S/cm (at 830 K); Tl5Cd0.5Hf1.5(MoO4)6 ‒ 8.5‧10−5 S/cm (at 830 K). The σ vs. T curve demonstrates an anomaly which corresponds to thermal effects in this temperature range. The ionic conductivity of Tl5A0.5Hf1.5(MoO4)6 (A = Ca, Cd) is due to Tl + ions localized in channels of the framework structure. The crystal structures of Tl5A0.5Hf1.5(MoO4)6 (A = Ca, Cd) are obtained by Rietveld method. The following unit cell parameters are calculated for Tl5Ca0.5Hf1.5(MoO4)6: a = 10.68493(26), c = 38.3943(11) Å, V = 3796.13(22) Å3, Z = 6 and for Tl5Cd0.5Hf1.5(MoO4)6: a = 10.66890(17), c = 38.25443(73) Å, V = 3770.96(14) Å3, Z = 6.
用阻抗谱法研究了三钼酸盐Tl5A0.5Hf1.5(MoO4)6 （A = Ca, Cd）在1 Hz ~ 1 MHz频率和300 ~ 830 K温度范围内的离子电导率。以Tl2MoO4、CaMoO4（或CdMoO4）和Hf(MoO4)2为原料，在723 ~ 823 K的温度下，以固态法合成了钼酸盐Tl5A0.5Hf1.5(MoO4)6 （A = Ca, Cd）。Tl5Ca0.5Hf1.5(MoO4)6陶瓷样品的电导率σ = 2.69·10−4 S/cm (830 K)；Tl5Cd0.5Hf1.5(MoO4)6 - 8.5·10−5 S/cm （at 830k）。σ对T曲线显示了一个异常，对应于该温度范围内的热效应。Tl5A0.5Hf1.5(MoO4)6 （A = Ca, Cd）的离子电导率是由于Tl +离子定位在框架结构的通道中。用Rietveld法得到了Tl5A0.5Hf1.5(MoO4)6 （A = Ca, Cd）的晶体结构。计算了Tl5Ca0.5Hf1.5(MoO4)6的单元格参数：a = 10.68493(26), c = 38.3943（11） Å， V = 3796.13（22） Å3, Z = 6; Tl5Cd0.5Hf1.5(MoO4)6的单元格参数：a = 10.66890(17), c = 38.25443（73） Å， V = 3770.96（14） Å3, Z = 6。
{"title":"Synthesis, structural characterization, and conductive properties of new Tl5A0.5Hf1.5(MoO4)6 (A = Ca, Cd) molybdates","authors":"Victoria G. Grossman , Maxim S. Molokeev","doi":"10.1016/j.jssc.2025.125716","DOIUrl":"10.1016/j.jssc.2025.125716","url":null,"abstract":"<div><div>Ionic conductivity of triple molybdates Tl<sub>5</sub><em>A</em><sub>0.5</sub>Hf<sub>1.5</sub>(MoO<sub>4</sub>)<sub>6</sub> (<em>A</em> = Ca, Cd) is studied by the method of impedance spectroscopy in the frequency range from 1 Hz to 1 MHz and in the temperature range of 300–830 K. The molybdates Tl<sub>5</sub><em>A</em><sub>0.5</sub>Hf<sub>1.5</sub>(MoO<sub>4</sub>)<sub>6</sub> (<em>A</em> = Ca, Cd) are prepared in the form of fine crystalline powder by solid state synthesis from Tl<sub>2</sub>MoO<sub>4</sub>, CaMoO<sub>4</sub> (or CdMoO<sub>4</sub>), and Hf(MoO<sub>4</sub>)<sub>2</sub> at 723–823 K. The conductivity of Tl<sub>5</sub>Ca<sub>0.5</sub>Hf<sub>1.5</sub>(MoO<sub>4</sub>)<sub>6</sub> ceramic samples σ = 2.69‧10<sup>−4</sup> S/cm (at 830 K); Tl<sub>5</sub>Cd<sub>0.5</sub>Hf<sub>1.5</sub>(MoO<sub>4</sub>)<sub>6</sub> ‒ 8.5‧10<sup>−5</sup> S/cm (at 830 K). The σ vs. T curve demonstrates an anomaly which corresponds to thermal effects in this temperature range. The ionic conductivity of Tl<sub>5</sub><em>A</em><sub>0.5</sub>Hf<sub>1.5</sub>(MoO<sub>4</sub>)<sub>6</sub> (<em>A</em> = Ca, Cd) is due to Tl <sup>+</sup> ions localized in channels of the framework structure. The crystal structures of Tl<sub>5</sub><em>A</em><sub>0.5</sub>Hf<sub>1.5</sub>(MoO<sub>4</sub>)<sub>6</sub> (<em>A</em> = Ca, Cd) are obtained by Rietveld method. The following unit cell parameters are calculated for Tl<sub>5</sub>Ca<sub>0.5</sub>Hf<sub>1.5</sub>(MoO<sub>4</sub>)<sub>6</sub>: <em>a</em> = 10.68493(26), <em>c</em> = 38.3943(11) Å, <em>V</em> = 3796.13(22) Å<sup>3</sup>, <em>Z</em> = 6 and for Tl<sub>5</sub>Cd<sub>0.5</sub>Hf<sub>1.5</sub>(MoO<sub>4</sub>)<sub>6</sub>: <em>a</em> = 10.66890(17), <em>c</em> = 38.25443(73) Å, <em>V</em> = 3770.96(14) Å<sup>3</sup>, <em>Z</em> = 6.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"354 ","pages":"Article 125716"},"PeriodicalIF":3.5,"publicationDate":"2025-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145414532","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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