Pub Date : 2025-12-22DOI: 10.1016/j.jssc.2025.125793
Le Chen , Wen-Qing Zhang , Lin Nie , Jian-Jun Yin , Qun Chen , Pengxiang Qiu , Ming-Yang He , Zhi-Hui Zhang
Metal-organic aerogels derived from ZIF-8 frameworks were developed for xylene isomer separation, demonstrating unique structural and adsorptive properties. The incorporation of ZIF-8 transformed non-porous agar (AG) aerogel into a hierarchically porous composite, albeit with a reduced surface area compared to pure MOFs. Vapor-phase adsorption and breakthrough experiments revealed exceptional p-xylene selectivity (pX/oX = 19) in ZIF-8/AG composites, though with diminished adsorption capacity relative to pristine ZIF-8. While exhibiting substantial liquid-phase adsorption, the composite showed limited gas-phase selectivity, indicating hydrogen-bonding-mediated adsorption mechanisms. This work highlights the correlation between selectivity and capacity in MOF-based aerogel adsorbents for the separation of aromatics.
{"title":"Hierarchically porous ZIF-8 aerogel composites for selective adsorption and separation of xylene isomers","authors":"Le Chen , Wen-Qing Zhang , Lin Nie , Jian-Jun Yin , Qun Chen , Pengxiang Qiu , Ming-Yang He , Zhi-Hui Zhang","doi":"10.1016/j.jssc.2025.125793","DOIUrl":"10.1016/j.jssc.2025.125793","url":null,"abstract":"<div><div>Metal-organic aerogels derived from ZIF-8 frameworks were developed for xylene isomer separation, demonstrating unique structural and adsorptive properties. The incorporation of ZIF-8 transformed non-porous agar (AG) aerogel into a hierarchically porous composite, albeit with a reduced surface area compared to pure MOFs. Vapor-phase adsorption and breakthrough experiments revealed exceptional <em>p</em>-xylene selectivity (<em>p</em>X/<em>o</em>X = 19) in ZIF-8/AG composites, though with diminished adsorption capacity relative to pristine ZIF-8. While exhibiting substantial liquid-phase adsorption, the composite showed limited gas-phase selectivity, indicating hydrogen-bonding-mediated adsorption mechanisms. This work highlights the correlation between selectivity and capacity in MOF-based aerogel adsorbents for the separation of aromatics.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"355 ","pages":"Article 125793"},"PeriodicalIF":3.5,"publicationDate":"2025-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145837031","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 : 2025-12-22DOI: 10.1016/j.jssc.2025.125790
Haixiao Kang , Haifeng Yuan , Haidong Zhang , Xianghua Kong , Yuquan Wang , Siying Zhang , Jiamei Liu
Doping and heterophase junctions are known to improve TiO2 photocatalysts, but their synergistic effect is not fully understood. In this work, we use in-situ XPS and ATR-FTIR to directly observe this synergy in Ce-doped TiO2, revealing how charge separation and the degradation pathway are enhanced. The obtained catalyst demonstrated good performance in the photocatalytic degradation of methyl orange (MO). Comprehensive characterization techniques, including XRD, Raman, XPS, and TEM, confirmed the successful formation of heterophase junctions and the incorporation of Ce ions into the TiO2 lattice. The findings also indicate that this process induced lattice expansion and modified the surface electronic structure. The optimized catalyst with 0.1 wt% Ce doping (Ce0·1Ti) exhibited superior photocatalytic activity, achieving 84 % degradation of MO within 60 min under UV light. Its catalytic rate was found to be three times higher than that of undoped TiO2 catalysts. Meanwhile, the catalyst demonstrated excellent cycling stability. The enhancement of catalytic activity can be attributed to the cooperative effect between the TiO2 A/R heterophase junctions and Ce3+/Ce4+ redox electron pair, which promotes the separation and migration of photogenerated carriers. In-situ XPS analysis directly confirmed this mechanism. Furthermore, in-situ ATR-FTIR analysis revealed the possible degradation pathway of MO, including cleavage of azo bonds and subsequent oxidation steps for intermediates. This study provides a strategic design of doped heterophase junctions for high-performance photocatalytic applications.
{"title":"Enhanced charge separation in Ce-doped TiO2 heterophase junctions: Mechanistic insights from in-situ XPS and ATR-FTIR studies","authors":"Haixiao Kang , Haifeng Yuan , Haidong Zhang , Xianghua Kong , Yuquan Wang , Siying Zhang , Jiamei Liu","doi":"10.1016/j.jssc.2025.125790","DOIUrl":"10.1016/j.jssc.2025.125790","url":null,"abstract":"<div><div>Doping and heterophase junctions are known to improve TiO<sub>2</sub> photocatalysts, but their synergistic effect is not fully understood. In this work, we use <em>in-situ</em> XPS and ATR-FTIR to directly observe this synergy in Ce-doped TiO<sub>2</sub>, revealing how charge separation and the degradation pathway are enhanced. The obtained catalyst demonstrated good performance in the photocatalytic degradation of methyl orange (MO). Comprehensive characterization techniques, including XRD, Raman, XPS, and TEM, confirmed the successful formation of heterophase junctions and the incorporation of Ce ions into the TiO<sub>2</sub> lattice. The findings also indicate that this process induced lattice expansion and modified the surface electronic structure. The optimized catalyst with 0.1 wt% Ce doping (Ce<sub>0</sub><sub>·</sub><sub>1</sub>Ti) exhibited superior photocatalytic activity, achieving 84 % degradation of MO within 60 min under UV light. Its catalytic rate was found to be three times higher than that of undoped TiO<sub>2</sub> catalysts. Meanwhile, the catalyst demonstrated excellent cycling stability. The enhancement of catalytic activity can be attributed to the cooperative effect between the TiO<sub>2</sub> A/R heterophase junctions and Ce<sup>3+</sup>/Ce<sup>4+</sup> redox electron pair, which promotes the separation and migration of photogenerated carriers. <em>In-situ</em> XPS analysis directly confirmed this mechanism. Furthermore, <em>in-situ</em> ATR-FTIR analysis revealed the possible degradation pathway of MO, including cleavage of azo bonds and subsequent oxidation steps for intermediates. This study provides a strategic design of doped heterophase junctions for high-performance photocatalytic applications.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"355 ","pages":"Article 125790"},"PeriodicalIF":3.5,"publicationDate":"2025-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145836972","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 : 2025-12-18DOI: 10.1016/j.jssc.2025.125785
Ruiqi Liu , Xiangwen Yan , Yunzhou Guan , Jincheng Ji , Changxin Li
The cooling rate is a critical processing parameter that determines the microstructure and macroscopic properties of metallic glasses, therefore, molecular dynamics simulations were employed to investigate the effects of cooling rate on the microstructure evolution and mechanical properties of Mg-Zn-Ca metallic glass in this work. The structural analysis results indicate that Mg-Zn-Ca melt could form metallic glass with uniformly distributed atoms at different cooling rates, and the Zn-centered clusters exhibited a more regular arrangement. Voronoi analysis reveals that the total content of icosahedral-like clusters is the highest, followed by mixed clusters, and crystal-like clusters is the lowest. Notably, the content of ⟨0,0,12,0⟩-type cluster centered by Zn is always higher than that centered by other types of atoms, indicating that Zn atoms have a stronger tendency to form perfect icosahedral structures. The uniaxial tensile simulation results show that the elastic modulus of Mg-Zn-Ca metallic glass decreases with the increase of cooling rate, and this aligns with the variation trend of the content of icosahedral-like clusters in the system. The underlying mechanism is attributed to the fact that the regularity of icosahedral structures can effectively alleviate local stress concentration, thereby enhancing the elastic modulus of metallic glass. This study provides theoretical support for the design and performance regulation of new metallic glass components.
{"title":"Structural properties of Mg-Zn-Ca metallic glass induced by cooling rates studied by molecular dynamics simulations","authors":"Ruiqi Liu , Xiangwen Yan , Yunzhou Guan , Jincheng Ji , Changxin Li","doi":"10.1016/j.jssc.2025.125785","DOIUrl":"10.1016/j.jssc.2025.125785","url":null,"abstract":"<div><div>The cooling rate is a critical processing parameter that determines the microstructure and macroscopic properties of metallic glasses, therefore, molecular dynamics simulations were employed to investigate the effects of cooling rate on the microstructure evolution and mechanical properties of Mg-Zn-Ca metallic glass in this work. The structural analysis results indicate that Mg-Zn-Ca melt could form metallic glass with uniformly distributed atoms at different cooling rates, and the Zn-centered clusters exhibited a more regular arrangement. Voronoi analysis reveals that the total content of icosahedral-like clusters is the highest, followed by mixed clusters, and crystal-like clusters is the lowest. Notably, the content of ⟨0,0,12,0⟩-type cluster centered by Zn is always higher than that centered by other types of atoms, indicating that Zn atoms have a stronger tendency to form perfect icosahedral structures. The uniaxial tensile simulation results show that the elastic modulus of Mg-Zn-Ca metallic glass decreases with the increase of cooling rate, and this aligns with the variation trend of the content of icosahedral-like clusters in the system. The underlying mechanism is attributed to the fact that the regularity of icosahedral structures can effectively alleviate local stress concentration, thereby enhancing the elastic modulus of metallic glass. This study provides theoretical support for the design and performance regulation of new metallic glass components.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"355 ","pages":"Article 125785"},"PeriodicalIF":3.5,"publicationDate":"2025-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787434","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 : 2025-12-18DOI: 10.1016/j.jssc.2025.125787
Cristina Sanchez Cereceda, Yuncheng Du
Controlling solvent composition provides an effective strategy to tune the structural and functional characteristics of metal–organic frameworks (MOFs). This study systematically investigates the effect of methanol–water mixtures on zeolitic imidazolate framework-8 (ZIF-8) synthesis to elucidate solvent-mediated nucleation and growth behavior. ZIF-8 was synthesized using mixed solvent with methanol volume ratio ranging from 0 % to 100 % and characterized by several techniques including transmission electron microscopy (TEM), X-ray diffraction (XRD), nitrogen (N2) and carbon dioxide (CO2) adsorption, and thermogravimetric analysis (TGA). These results suggest complex correlations between solvent composition and particle morphology, crystallinity, porosity, and yield. Particle size decreases from ∼123 nm in water to ∼50 nm in methanol, accompanied by a transition from rounded to faceted rhombic dodecahedra. XRD analysis shows that crystallite size decreases with increasing methanol content, whereas a 50:50 methanol-water mixture produces the highest Brunauer–Emmett–Teller (BET) surface area (∼1465 m2/g) and a balanced micro-to mesoporosity. Yield calculation suggests a trade-off between productivity and structural characteristics: water-rich mixtures achieve higher yields (∼92 %), while methanol-rich conditions yield smaller, more defective crystallites but promote enhanced textural porosity. These findings suggest that co-solvent system provides a tunable physicochemical environment that governs nucleation kinetics and particle growth, establishing a rational framework for optimizing scalable, high-quality ZIF-8 production.
{"title":"Solvent-mediated control of ZIF-8 morphology, crystallinity, and yield: Insights from methanol-water synthesis","authors":"Cristina Sanchez Cereceda, Yuncheng Du","doi":"10.1016/j.jssc.2025.125787","DOIUrl":"10.1016/j.jssc.2025.125787","url":null,"abstract":"<div><div>Controlling solvent composition provides an effective strategy to tune the structural and functional characteristics of metal–organic frameworks (MOFs). This study systematically investigates the effect of methanol–water mixtures on zeolitic imidazolate framework-8 (ZIF-8) synthesis to elucidate solvent-mediated nucleation and growth behavior. ZIF-8 was synthesized using mixed solvent with methanol volume ratio ranging from 0 % to 100 % and characterized by several techniques including transmission electron microscopy (TEM), X-ray diffraction (XRD), nitrogen (N<sub>2</sub>) and carbon dioxide (CO<sub>2</sub>) adsorption, and thermogravimetric analysis (TGA). These results suggest complex correlations between solvent composition and particle morphology, crystallinity, porosity, and yield. Particle size decreases from ∼123 nm in water to ∼50 nm in methanol, accompanied by a transition from rounded to faceted rhombic dodecahedra. XRD analysis shows that crystallite size decreases with increasing methanol content, whereas a 50:50 methanol-water mixture produces the highest Brunauer–Emmett–Teller (BET) surface area (∼1465 m<sup>2</sup>/g) and a balanced micro-to mesoporosity. Yield calculation suggests a trade-off between productivity and structural characteristics: water-rich mixtures achieve higher yields (∼92 %), while methanol-rich conditions yield smaller, more defective crystallites but promote enhanced textural porosity. These findings suggest that co-solvent system provides a tunable physicochemical environment that governs nucleation kinetics and particle growth, establishing a rational framework for optimizing scalable, high-quality ZIF-8 production.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"355 ","pages":"Article 125787"},"PeriodicalIF":3.5,"publicationDate":"2025-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787517","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 : 2025-12-17DOI: 10.1016/j.jssc.2025.125786
Chengliang Qiu , Shuhong Liu , Xiangyang Yin , Juan Chen , Wei Zhai , Yong Du
Based on the available experimental data reported in the literature, the Y–Nd, Y–Tb and Tb–Nd systems were re-assessed thermodynamically using the CALPHAD (CALculation of PHAse Diagram) method in this work. The calculated phase diagrams of the three binary systems are well consistent with the experimental results. Based on the calculated phase diagrams, 9 solid-solid diffusion couples in hcp phase region were prepared and annealed at 900, 1000, and 1100 °C. The concentration distributions were measured using Electron Probe Microanalysis (EPMA), and the interdiffusion coefficients at different temperatures were evaluated through the Sauer–Freise approach. Subsequently, the CALTPP (CALculation of Thermo-Physical Properties) software was applied to optimize the atomic mobilities as functions of both temperature and composition by integrating the thermodynamic assessment with the experimental diffusion data. The simulated diffusion behavior exhibited good consistency with the experimental results, confirming the reliability of the optimized mobility parameters.
{"title":"Thermodynamics and interdiffusion of the Y–Nd, Y–Tb and Tb–Nd systems","authors":"Chengliang Qiu , Shuhong Liu , Xiangyang Yin , Juan Chen , Wei Zhai , Yong Du","doi":"10.1016/j.jssc.2025.125786","DOIUrl":"10.1016/j.jssc.2025.125786","url":null,"abstract":"<div><div>Based on the available experimental data reported in the literature, the Y–Nd, Y–Tb and Tb–Nd systems were re-assessed thermodynamically using the CALPHAD (CALculation of PHAse Diagram) method in this work. The calculated phase diagrams of the three binary systems are well consistent with the experimental results. Based on the calculated phase diagrams, 9 solid-solid diffusion couples in hcp phase region were prepared and annealed at 900, 1000, and 1100 °C. The concentration distributions were measured using Electron Probe Microanalysis (EPMA), and the interdiffusion coefficients at different temperatures were evaluated through the Sauer–Freise approach. Subsequently, the CALTPP (CALculation of Thermo-Physical Properties) software was applied to optimize the atomic mobilities as functions of both temperature and composition by integrating the thermodynamic assessment with the experimental diffusion data. The simulated diffusion behavior exhibited good consistency with the experimental results, confirming the reliability of the optimized mobility parameters.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"355 ","pages":"Article 125786"},"PeriodicalIF":3.5,"publicationDate":"2025-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787435","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 : 2025-12-16DOI: 10.1016/j.jssc.2025.125782
Mingguang Zhu , Yulin Duan , Lingyuan Li , Jiamin Chen , Shunyan Wang , Lihui Yang , Meihui Chen , Yaohui You
Fluorochromic organic materials capable of changing emitting color were attractive in intelligent material applications but how to carry out large-scale production in an easy and efficient manner remained a challenge. Here we presented a pair of Schiff bases, in which 2-hydroxy-4-methoxybenzophenone hydrazone was decorated with 4-nitrobenzaldehyde and 2,4-dinitrobenzaldehyde, respectively. Although both of them did not undergo excited state intramolecular proton transfer (ESIPT) process in EtOH solvent upon photoexcitation, introduction of electron-withdrawing –NO2 group endowed them with J-type aggregation-induced emission (AIE) features in the EtOH/water binary mixtures, emitting pink and cyan-blue fluorescence with the maximum emission peaks at around 627 and 538 nm, respectively. Notably, although they had the same molecular framework, the differences in the number and position of nitro substituents played a key role in tuning molecular packing arrangement in the solid state, showing vivid red and dull red emission color, respectively. Importantly, crystallizing 4-nitrobenzaldehyde-functionalized Schiff base in pure EtOH and EtOH/water mixtures (v/v, 1/1) afforded red and yellow fluorescence solids with different fluorescence efficiencies because the varying degrees of J-aggregation during the self-assembly in pure EtOH and EtOH/water mixtures (v/v, 1/1) resulted in different crystal sizes. This study provided a significative method for construction of strong long-wavelength emissive J-aggregates based on Schiff base structure and realizing large-scale and simple preparation of controllable solid fluorescence at the single-molecule level.
{"title":"Schiff base with J-aggregation-induced emission and controllable solid fluorescence","authors":"Mingguang Zhu , Yulin Duan , Lingyuan Li , Jiamin Chen , Shunyan Wang , Lihui Yang , Meihui Chen , Yaohui You","doi":"10.1016/j.jssc.2025.125782","DOIUrl":"10.1016/j.jssc.2025.125782","url":null,"abstract":"<div><div>Fluorochromic organic materials capable of changing emitting color were attractive in intelligent material applications but how to carry out large-scale production in an easy and efficient manner remained a challenge. Here we presented a pair of Schiff bases, in which 2-hydroxy-4-methoxybenzophenone hydrazone was decorated with 4-nitrobenzaldehyde and 2,4-dinitrobenzaldehyde, respectively. Although both of them did not undergo excited state intramolecular proton transfer (ESIPT) process in EtOH solvent upon photoexcitation, introduction of electron-withdrawing –NO<sub>2</sub> group endowed them with <em>J</em>-type aggregation-induced emission (AIE) features in the EtOH/water binary mixtures, emitting pink and cyan-blue fluorescence with the maximum emission peaks at around 627 and 538 nm, respectively. Notably, although they had the same molecular framework, the differences in the number and position of nitro substituents played a key role in tuning molecular packing arrangement in the solid state, showing vivid red and dull red emission color, respectively. Importantly, crystallizing 4-nitrobenzaldehyde-functionalized Schiff base in pure EtOH and EtOH/water mixtures (v/v, 1/1) afforded red and yellow fluorescence solids with different fluorescence efficiencies because the varying degrees of <em>J</em>-aggregation during the self-assembly in pure EtOH and EtOH/water mixtures (v/v, 1/1) resulted in different crystal sizes. This study provided a significative method for construction of strong long-wavelength emissive <em>J</em>-aggregates based on Schiff base structure and realizing large-scale and simple preparation of controllable solid fluorescence at the single-molecule level.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"355 ","pages":"Article 125782"},"PeriodicalIF":3.5,"publicationDate":"2025-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787516","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 presents a multifunctional MIL-125/Ti3C2Tx@SrTiO3 hybrid device, which was strategically designed to simultaneously boost effectiveness in energy storage systems and the hydrogen evolution reaction (HER). The strategic configuration of the titanium-based metal organic framework (MOF) MIL-125, due to its huge amount of electron donor configuration, the high electrical conductivity nature of 2D titanium carbide MXene (Ti3C2Tx) as electron transfer mediator, and perovskite strontium titanate (SrTiO3) enables a unique nanocomposite to provide multi-organic active sites, high electrical conductivity, and high electrochemically active surface area. The composite material demonstrated a specific capacity (Qs) of 260 C/g, an energy density (Ed) of 65.76 Wh/kg, and a power density (Pd) of 1250 W/kg, while retaining cycling stability over 1000 charge-discharge cycles. The electrochemical impedance spectroscopy (EIS) results also demonstrate a low charge transfer resistance of 42 Ω, indicating efficient ion and electron transport. The MIL-125/Ti3C2Tx@SrTiO3 exhibited significant HER overpotential and Tafel slope, indicating rapid hydrogen evolution kinetics and catalytic stability. MIL-125/Ti3C2Tx@SrTiO3 underscores bifunctional electrochemical performance, which confirms it as an advanced material platform for next-generation integrated energy storage and hydrogen generation technologies.
{"title":"Rational design of a metal–organic framework-based hybrid with titanium carbide and strontium titanate for high-performance energy storage","authors":"Muhammad Ashraf , M.W. Iqbal , Soumaya Gouadria , Manoj Kumar , Abhinav Kumar","doi":"10.1016/j.jssc.2025.125777","DOIUrl":"10.1016/j.jssc.2025.125777","url":null,"abstract":"<div><div>This study presents a multifunctional MIL-125/Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub>@SrTiO<sub>3</sub> hybrid device, which was strategically designed to simultaneously boost <strong>effectiveness</strong> in energy storage systems and the hydrogen evolution reaction (HER). The strategic configuration of the titanium-based metal organic framework (MOF) MIL-125, due to its huge amount of electron donor configuration, the high electrical conductivity nature of 2D titanium carbide MXene (Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub>) as electron transfer mediator, and perovskite strontium titanate (SrTiO<sub>3</sub>) enables a unique nanocomposite to provide multi-organic active sites, high electrical conductivity, and high electrochemically active surface area. The composite material demonstrated a specific capacity (<em>Qs</em>) of 260 C/g, an energy density (<em>E</em><sub><em>d</em></sub>) of 65.76 Wh/kg, and a power density (<em>P</em><sub><em>d</em></sub>) of 1250 W/kg, while retaining cycling stability over 1000 charge-discharge cycles. The electrochemical impedance spectroscopy (EIS) results also demonstrate a low charge transfer resistance of 42 Ω, indicating efficient ion and electron transport. The MIL-125/Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub>@SrTiO<sub>3</sub> exhibited significant HER overpotential and Tafel slope, indicating rapid hydrogen evolution kinetics and catalytic stability. MIL-125/Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub>@SrTiO<sub>3</sub> underscores bifunctional electrochemical performance, which confirms it as an advanced material platform for next-generation integrated energy storage and hydrogen generation technologies.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"355 ","pages":"Article 125777"},"PeriodicalIF":3.5,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145836974","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 : 2025-12-15DOI: 10.1016/j.jssc.2025.125783
Yang Yan, Xianglan Zhang, Guangtai Ding
This computational study systematically investigates CH4/N2 separation in six distinct MOFs-MIL-53-Al, Cu-BTC, ZIF-8, Ni-DOBDC, ZSTU-5, and Co3(C4O4)2(OH)2 using GCMC simulations and IAST. By correlating simulated adsorption data with structural properties, we establish clear structure-performance relationships and identify optimal materials for specific operating conditions. MIL-53-Al exhibits the highest CH4 saturation capacity (10.5 mmol/g at 35 bar), governed by its unique structural flexibility and host-guest interactions from the organic linkers, making it ideal for high-pressure storage. In contrast, Co3(C4O4)2(OH)2 demonstrates superior low-pressure (1 bar) CH4 uptake (1.83 mmol/g) and the highest CH4/N2 selectivity (12.8), driven by strong affinity from accessible polar sites within narrow micropores (∼0.7 nm). For practical separation applications, the evaluation of working capacity under swing adsorption conditions suggests ZIF-8 as a robust candidate due to its stable, size-sieving-based selectivity and proven scalability. This work goes beyond simple performance comparison and emphasizes the crucial role of structure in selecting optimal materials, with operating pressure also being a significant factor in achieving optimal performance.
{"title":"Grand canonical Monte Carlo (GCMC) study and the ideal adsorbed solution theory (IAST) on adsorption performance of metal organic frameworks (MOFs) for CH4/N2 separation","authors":"Yang Yan, Xianglan Zhang, Guangtai Ding","doi":"10.1016/j.jssc.2025.125783","DOIUrl":"10.1016/j.jssc.2025.125783","url":null,"abstract":"<div><div>This computational study systematically investigates CH<sub>4</sub>/N<sub>2</sub> separation in six distinct MOFs-MIL-53-Al, Cu-BTC, ZIF-8, Ni-DOBDC, ZSTU-5, and Co<sub>3</sub>(C<sub>4</sub>O<sub>4</sub>)<sub>2</sub>(OH)<sub>2</sub> using GCMC simulations and IAST. By correlating simulated adsorption data with structural properties, we establish clear structure-performance relationships and identify optimal materials for specific operating conditions. MIL-53-Al exhibits the highest CH<sub>4</sub> saturation capacity (10.5 mmol/g at 35 bar), governed by its unique structural flexibility and host-guest interactions from the organic linkers, making it ideal for high-pressure storage. In contrast, Co<sub>3</sub>(C<sub>4</sub>O<sub>4</sub>)<sub>2</sub>(OH)<sub>2</sub> demonstrates superior low-pressure (1 bar) CH<sub>4</sub> uptake (1.83 mmol/g) and the highest CH<sub>4</sub>/N<sub>2</sub> selectivity (12.8), driven by strong affinity from accessible polar sites within narrow micropores (∼0.7 nm). For practical separation applications, the evaluation of working capacity under swing adsorption conditions suggests ZIF-8 as a robust candidate due to its stable, size-sieving-based selectivity and proven scalability. This work goes beyond simple performance comparison and emphasizes the crucial role of structure in selecting optimal materials, with operating pressure also being a significant factor in achieving optimal performance.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"355 ","pages":"Article 125783"},"PeriodicalIF":3.5,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145836973","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 : 2025-12-13DOI: 10.1016/j.jssc.2025.125775
Asmaa Zaraq , Duncan H. Gregory , Doriano Brogioli , Fabio La Mantia , Thorsten M. Gesing
The double perovskite series Sr2(Co1-xZnx)TeO6 (x = 0, 0.25, 0.50, 0.75, 1) has been synthesized and systematically investigated to establish the correlations between structure, optical response, and dielectric behavior. Powder X-ray diffraction and Rietveld refinement confirm that Sr2CoTeO6 crystallizes in the monoclinic P21/n structure, Sr2ZnTeO6 in I2/m, and the intermediate compositions in I2/m as well. Structural refinements reveal opposite compositional trends in Co/Zn–O and Te–O bond lengths, directly influencing the vibrational dynamics: Raman spectra display progressive blue-shifts of Te–O stretching modes, particularly near 750 cm−1. Optical diffuse reflectance measurements, analyzed via Tauc and derivative absorption spectroscopy fitting, show a systematic widening of the band gap from 3.21 eV (x = 0) to 4.13 eV (x = 1), consistent with the reduction of Co2+ contributions near the band edge. Dielectric spectroscopy further highlights a strong dependence on composition. While Zn-rich members exhibit insulating behavior with stable permittivity and low loss over 100 Hz–1 MHz, the Co-rich end member Sr2CoTeO6 displays an anomalous dispersion with a crossover from Maxwell–Wagner interfacial polarization to dipolar polarization at ∼300 kHz, as confirmed by Cole–Cole analysis (εs ≈ 320, τ ≈ 3.3 μs). This unusually high transition frequency stabilizes the dielectric response over a broad frequency window. Taken together, these results demonstrate clear structure–optical–dielectric correlations across the Sr2(Co1-xZnx)TeO6 series. The Co-rich composition combines a high permittivity and frequency stability, underscoring its potential for dielectric capacitor applications, while Zn substitution tunes the material toward wider band gaps and enhanced optical insulation.
{"title":"Structure–optical–dielectric correlations in ordered double perovskites Sr2(Co1-xZnx)TeO6 (0 ≤ x ≤ 1)","authors":"Asmaa Zaraq , Duncan H. Gregory , Doriano Brogioli , Fabio La Mantia , Thorsten M. Gesing","doi":"10.1016/j.jssc.2025.125775","DOIUrl":"10.1016/j.jssc.2025.125775","url":null,"abstract":"<div><div>The double perovskite series Sr<sub>2</sub>(Co<sub><em>1-x</em></sub>Zn<sub><em>x</em></sub>)TeO<sub>6</sub> (<em>x</em> = <em>0, 0.25, 0.50, 0.75, 1</em>) has been synthesized and systematically investigated to establish the correlations between structure, optical response, and dielectric behavior. Powder X-ray diffraction and Rietveld refinement confirm that Sr<sub>2</sub>CoTeO<sub>6</sub> crystallizes in the monoclinic <em>P</em>2<sub>1</sub>/<em>n</em> structure, Sr<sub>2</sub>ZnTeO<sub>6</sub> in I2/m, and the intermediate compositions in <em>I</em>2/<em>m</em> as well. Structural refinements reveal opposite compositional trends in Co/Zn–O and Te–O bond lengths, directly influencing the vibrational dynamics: Raman spectra display progressive blue-shifts of Te–O stretching modes, particularly near 750 cm<sup>−1</sup>. Optical diffuse reflectance measurements, analyzed via Tauc and derivative absorption spectroscopy fitting, show a systematic widening of the band gap from 3.21 eV (<em>x</em> = <em>0</em>) to 4.13 eV (<em>x</em> = <em>1</em>), consistent with the reduction of Co<sup>2+</sup> contributions near the band edge. Dielectric spectroscopy further highlights a strong dependence on composition. While Zn-rich members exhibit insulating behavior with stable permittivity and low loss over 100 Hz–1 MHz, the Co-rich end member Sr<sub>2</sub>CoTeO<sub>6</sub> displays an anomalous dispersion with a crossover from Maxwell–Wagner interfacial polarization to dipolar polarization at ∼300 kHz, as confirmed by Cole–Cole analysis (ε<sub>s</sub> ≈ 320, τ ≈ 3.3 μs). This unusually high transition frequency stabilizes the dielectric response over a broad frequency window. Taken together, these results demonstrate clear structure–optical–dielectric correlations across the Sr<sub>2</sub>(Co<sub><em>1-x</em></sub>Zn<sub><em>x</em></sub>)TeO<sub>6</sub> series. The Co-rich composition combines a high permittivity and frequency stability, underscoring its potential for dielectric capacitor applications, while Zn substitution tunes the material toward wider band gaps and enhanced optical insulation.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"355 ","pages":"Article 125775"},"PeriodicalIF":3.5,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787518","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 : 2025-12-13DOI: 10.1016/j.jssc.2025.125780
P. Vinothkumar , S. Praveenkumar , S. Joyal Isac , Paul Dhinakaran A.
A new tellurite-based ceramic system activated by Ce3+, with the compositions [50TeO2-30.25B2O3–10SnO2–5MgO–4CuO-0.75Ce2O3(wt%) - TBSMCCe0.75], and [50TeO2–29B2O3–10SnO2–5MgO–5CuO–1Ce2O3(wt%)- TBSMCCe1] was created using a solid-state process, and its multipurpose applications in photonics and radiation shielding were thoroughly examined. Highly crystalline CuO phases were verified by structural investigation, with typical crystallite sizes ranging from 33.9 to 34.3 nm. Te–O and B–O vibrational modes were detected in Fourier Transform Infrared spectra, confirming the development of a stable oxide framework. Strong Ce3+-related absorption with a direct bandgap of 2.6–2.8 eV was observed by UV–Visible spectroscopy, although Photoluminescence spectra displayed wide visible emission peaking at about 350 nm. The color chromaticity coordinates for the Ce1-doped ceramic changed from 0.2087, 0.1947 for Ce0.75 to 0.2245, 0.1948 for Ce1, both of which were in the blue-cyan area and had color purities of 55.9 % and 51.3 %, respectively. This indicated a greater luminescence intensity. Electron Paramagnetic Resonance evidence confirmed the presence of elevated Ce3+ and oxygen vacancy centers, indicating that the thermoluminescence glow curves displayed a pronounced peak at approximately 260 °C with greater intensity for Ce1. With a mean free path ranging from 0.2 cm (0.015 MeV) to 12 cm (10 MeV) and a mass attenuation coefficient of 1.20 cm2/g at 0.015 MeV, decreasing with energy, radiation shielding investigations demonstrated superior performance for Ce1. In order to prove effective attenuation, the half-value layer was as low as 0.25 cm at 0.05 MeV and approximately 4.5 cm at 5 MeV. around higher energies, the effective atomic number stabilized around about 15–18, after peaking at about 36 in the photoelectric region. Both the energy absorption buildup factor and the exposure buildup factor peaked at about 1 MeV (130–140 at 40 MFP), but steadily decreased for Ce1, suggesting less photon accumulation. For integrated photonic and nuclear shielding applications, TBSMCCe1 is a viable lead-free substitute due to its improved multifunctionality, as shown by the combined optical and shielding findings.
{"title":"Synergistic role of Ce3+ in tellurite–borate–stannate ceramics: Dual functional photonic response and high-energy photon attenuation","authors":"P. Vinothkumar , S. Praveenkumar , S. Joyal Isac , Paul Dhinakaran A.","doi":"10.1016/j.jssc.2025.125780","DOIUrl":"10.1016/j.jssc.2025.125780","url":null,"abstract":"<div><div>A new tellurite-based ceramic system activated by Ce<sup>3+</sup>, with the compositions [50TeO<sub>2</sub>-30.25B<sub>2</sub>O<sub>3</sub>–10SnO<sub>2</sub>–5MgO–4CuO-0.75Ce<sub>2</sub>O<sub>3</sub>(wt%) - TBSMCCe<sub>0.75</sub>], and [50TeO<sub>2</sub>–29B<sub>2</sub>O<sub>3</sub>–10SnO<sub>2</sub>–5MgO–5CuO–1Ce<sub>2</sub>O<sub>3</sub>(wt%)- TBSMCCe<sub>1</sub>] was created using a solid-state process, and its multipurpose applications in photonics and radiation shielding were thoroughly examined. Highly crystalline CuO phases were verified by structural investigation, with typical crystallite sizes ranging from 33.9 to 34.3 nm. Te–O and B–O vibrational modes were detected in Fourier Transform Infrared spectra, confirming the development of a stable oxide framework. Strong Ce<sup>3+</sup>-related absorption with a direct bandgap of 2.6–2.8 eV was observed by UV–Visible spectroscopy, although Photoluminescence spectra displayed wide visible emission peaking at about 350 nm. The color chromaticity coordinates for the Ce<sub>1</sub>-doped ceramic changed from 0.2087, 0.1947 for Ce<sub>0.75</sub> to 0.2245, 0.1948 for Ce<sub>1</sub>, both of which were in the blue-cyan area and had color purities of 55.9 % and 51.3 %, respectively. This indicated a greater luminescence intensity. Electron Paramagnetic Resonance evidence confirmed the presence of elevated Ce<sup>3+</sup> and oxygen vacancy centers, indicating that the thermoluminescence glow curves displayed a pronounced peak at approximately 260 °C with greater intensity for Ce<sub>1</sub>. With a mean free path ranging from 0.2 cm (0.015 MeV) to 12 cm (10 MeV) and a mass attenuation coefficient of 1.20 cm<sup>2</sup>/g at 0.015 MeV, decreasing with energy, radiation shielding investigations demonstrated superior performance for Ce<sub>1</sub>. In order to prove effective attenuation, the half-value layer was as low as 0.25 cm at 0.05 MeV and approximately 4.5 cm at 5 MeV. around higher energies, the effective atomic number stabilized around about 15–18, after peaking at about 36 in the photoelectric region. Both the energy absorption buildup factor and the exposure buildup factor peaked at about 1 MeV (130–140 at 40 MFP), but steadily decreased for Ce<sub>1</sub>, suggesting less photon accumulation. For integrated photonic and nuclear shielding applications, TBSMCCe<sub>1</sub> is a viable lead-free substitute due to its improved multifunctionality, as shown by the combined optical and shielding findings.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"355 ","pages":"Article 125780"},"PeriodicalIF":3.5,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787515","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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