Pub Date : 2025-11-20DOI: 10.1016/j.jssc.2025.125744
Rajalekshmi T.R. , Suraj T.S. , Mahima M. Kurian , Ramachandra Rao M.S. , Sethupathi K.
Complex magnetic ordering in 3 transition metal oxides and their dynamics in terms of hyperfine interactions are promising avenues for fundamental researchers to look for novel phenomena in these materials. The present study report on a comprehensive specific heat and electron spin resonance analysis to understand the hyperfine interactions in orthochromites. Among the lanthanides series, the electronic configuration of La is characterized by the absence of f-electrons in its valence shell (), making LaCrO an ideal system to investigate hyperfine splitting related to the magnetic interactions of Cr ions. Furthermore, substituting Cr with Ga, which is having completely filled d-orbital allows to study the weakening of CrOCr exchange interaction and gives a comprehensive picture of interactions involved. Using Ga dilution technique, we showed that the non-negligible hyperfine contribution mainly arises from CrOCr antiferromagnetic coupling rooted in superexchange mechanism. These findings provide a deeper understanding of hyperfine phenomena in orthochromites, motivating future fundamental research and applications.
{"title":"A comprehensive investigation on the role of hyperfine interactions in LaCrO3","authors":"Rajalekshmi T.R. , Suraj T.S. , Mahima M. Kurian , Ramachandra Rao M.S. , Sethupathi K.","doi":"10.1016/j.jssc.2025.125744","DOIUrl":"10.1016/j.jssc.2025.125744","url":null,"abstract":"<div><div>Complex magnetic ordering in 3<span><math><mi>d</mi></math></span> transition metal oxides and their dynamics in terms of hyperfine interactions are promising avenues for fundamental researchers to look for novel phenomena in these materials. The present study report on a comprehensive specific heat and electron spin resonance analysis to understand the hyperfine interactions in orthochromites. Among the lanthanides series, the electronic configuration of La is characterized by the absence of f-electrons in its valence shell (<span><math><msup><mrow><mi>f</mi></mrow><mrow><mn>0</mn></mrow></msup></math></span>), making LaCrO<span><math><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub></math></span> an ideal system to investigate hyperfine splitting related to the magnetic interactions of Cr ions. Furthermore, substituting Cr with Ga, which is having completely filled d-orbital allows to study the weakening of Cr<span><math><mo>−</mo></math></span>O<span><math><mo>−</mo></math></span>Cr exchange interaction and gives a comprehensive picture of interactions involved. Using Ga dilution technique, we showed that the non-negligible hyperfine contribution mainly arises from Cr<span><math><mo>−</mo></math></span>O<span><math><mo>−</mo></math></span>Cr antiferromagnetic coupling rooted in superexchange mechanism. These findings provide a deeper understanding of hyperfine phenomena in orthochromites, motivating future fundamental research and applications.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"354 ","pages":"Article 125744"},"PeriodicalIF":3.5,"publicationDate":"2025-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145614494","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 : 2025-11-20DOI: 10.1016/j.jssc.2025.125748
Xiaoqin Huang , Heng Zhao , Hailun Zhang , Duohua Jiang , Panpan Ren , Zhongguo Liu , Wei Zhu , Gang Li , Shouzhi Pu
Given the growing environmental pollution and resource waste caused by wastewater containing both rare earth elements and dyes, developing highly efficient multifunctional adsorbents is critically important. In this study, a phosphate-functionalized zirconium-based metal-organic framework material (UiO-66-PMIDA) was successfully synthesized via a post-synthesis modification strategy. The grafting of N-(phosphonomethyl)iminodiacetic acid (PMIDA) ligands onto UiO-66-NH2 introduced abundant phosphonate and carboxyl groups, enabling simultaneous and efficient adsorption of La3+, Gd3+, Lu3+, and methylene blue (MB). The adsorbent exhibited excellent capacity across a broad pH range, high selectivity, and good regenerability. Kinetic and isotherm analyses revealed that the adsorption follows pseudo-second-order kinetics and the Langmuir model, indicating monolayer chemisorption. Thermodynamic studies confirmed a spontaneous and endothermic process. Mechanism analysis indicates that rare earth ions are primarily adsorbed via electrostatic interactions and chelation, while MB adsorption involves electrostatic attraction, hydrogen bonding, and π-π stacking. In summary, this study provides novel insights for developing multifunctional MOF materials adaptable to treating diverse pollutants.
{"title":"Construction of bifunctional MOFs via a post-synthetic modification strategy: A systematic study on rare earth element recovery and dye removal","authors":"Xiaoqin Huang , Heng Zhao , Hailun Zhang , Duohua Jiang , Panpan Ren , Zhongguo Liu , Wei Zhu , Gang Li , Shouzhi Pu","doi":"10.1016/j.jssc.2025.125748","DOIUrl":"10.1016/j.jssc.2025.125748","url":null,"abstract":"<div><div>Given the growing environmental pollution and resource waste caused by wastewater containing both rare earth elements and dyes, developing highly efficient multifunctional adsorbents is critically important. In this study, a phosphate-functionalized zirconium-based metal-organic framework material (UiO-66-PMIDA) was successfully synthesized via a post-synthesis modification strategy. The grafting of N-(phosphonomethyl)iminodiacetic acid (PMIDA) ligands onto UiO-66-NH<sub>2</sub> introduced abundant phosphonate and carboxyl groups, enabling simultaneous and efficient adsorption of La<sup>3+</sup>, Gd<sup>3+</sup>, Lu<sup>3+</sup>, and methylene blue (MB). The adsorbent exhibited excellent capacity across a broad pH range, high selectivity, and good regenerability. Kinetic and isotherm analyses revealed that the adsorption follows pseudo-second-order kinetics and the Langmuir model, indicating monolayer chemisorption. Thermodynamic studies confirmed a spontaneous and endothermic process. Mechanism analysis indicates that rare earth ions are primarily adsorbed via electrostatic interactions and chelation, while MB adsorption involves electrostatic attraction, hydrogen bonding, and π-π stacking. In summary, this study provides novel insights for developing multifunctional MOF materials adaptable to treating diverse pollutants.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"354 ","pages":"Article 125748"},"PeriodicalIF":3.5,"publicationDate":"2025-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145569357","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 : 2025-11-19DOI: 10.1016/j.jssc.2025.125746
Hua-Jun Zhao
The thioantimonate hosted by La/Cl 3D cationic framework, namely La2Cl3[SbS3] has been prepared by conventional solid-state reactions. It crystallizes in space group Pnma (No. 62) with a = 7.779(3) Å, b = 12.893(5) Å, c = 8.905(4) Å, V = 893.2(6) Å3 and Z = 4. Its composite framework is made up of two sublattices of [La2Cl3]3+ 3D cationic network and covalent SbS3 molecular anions. The 3D [La2Cl3]3+ are formed by the 2D layers of edge- and corner-shared Cl1La3 trigonal pyramids propagating in (010) plane and “v’’ shaped Cl2La2 units via corner-sharing. The isolated SbS3 trigonal-pyramidal units are arranged in (010) plane and sandwiched by the 2D layers of Cl1La3 trigonal pyramids. Moreover, the optical gap of 1.93 eV for La2Cl3[SbS3] was derived, showing a red shift with respect to that of La3S2Cl2[SbS3], [La2SCl2][La3S2Cl][SbS3]2, and La3OSCl2[SbS3], which can be attributed to its lower La/Sb ratios.
采用常规固相反应制备了以La/Cl三维阳离子骨架为载体的硫代锑酸盐La2Cl3[SbS3]。结晶在空间群Pnma(62号)= 7.779 (3)a, b = 12.893 (5) a, c = 8.905 (4), V = 893.2 (6) A3和Z = 4。其复合骨架由[La2Cl3]3+三维阳离子网络和共价SbS3分子阴离子两个亚晶格组成。三维[La2Cl3]3+是由沿（010）平面传播的沿边角共享的二维Cl1La3三角形金字塔层和沿边角共享的“v”形Cl2La2单元组成的。孤立的SbS3三角锥体单元排列在（010）平面上，并被Cl1La3三角锥体的二维层夹在中间。此外，La2Cl3[SbS3]的光隙为1.93 eV，相对于La3S2Cl2[SbS3]、[La2SCl2][La3S2Cl][SbS3]2和La3OSCl2[SbS3]的光隙出现了红移，这可归因于其较低的La/Sb比。
{"title":"Synthesis, crystal structure, and optical property of La2Cl3[SbS3]","authors":"Hua-Jun Zhao","doi":"10.1016/j.jssc.2025.125746","DOIUrl":"10.1016/j.jssc.2025.125746","url":null,"abstract":"<div><div>The thioantimonate hosted by La/Cl 3D cationic framework, namely La<sub>2</sub>Cl<sub>3</sub>[SbS<sub>3</sub>] has been prepared by conventional solid-state reactions. It crystallizes in space group <em>Pnma</em> (No. 62) with <em>a</em> = 7.779(3) Å, <em>b</em> = 12.893(5) Å, <em>c</em> = 8.905(4) Å, <em>V</em> = 893.2(6) Å<sup>3</sup> and Z = 4. Its composite framework is made up of two sublattices of [La<sub>2</sub>Cl<sub>3</sub>]<sup>3+</sup> 3D cationic network and covalent SbS<sub>3</sub> molecular anions. The 3D [La<sub>2</sub>Cl<sub>3</sub>]<sup>3+</sup> are formed by the 2D layers of edge- and corner-shared Cl1La<sub>3</sub> trigonal pyramids propagating in (010) plane and “v’’ shaped Cl2La<sub>2</sub> units via corner-sharing. The isolated SbS<sub>3</sub> trigonal-pyramidal units are arranged in (010) plane and sandwiched by the 2D layers of Cl1La<sub>3</sub> trigonal pyramids. Moreover, the optical gap of 1.93 eV for La<sub>2</sub>Cl<sub>3</sub>[SbS<sub>3</sub>] was derived, showing a red shift with respect to that of La<sub>3</sub>S<sub>2</sub>Cl<sub>2</sub>[SbS<sub>3</sub>], [La<sub>2</sub>SCl<sub>2</sub>][La<sub>3</sub>S<sub>2</sub>Cl][SbS<sub>3</sub>]<sub>2</sub>, and La<sub>3</sub>OSCl<sub>2</sub>[SbS<sub>3</sub>], which can be attributed to its lower La/Sb ratios.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"354 ","pages":"Article 125746"},"PeriodicalIF":3.5,"publicationDate":"2025-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145614991","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 : 2025-11-19DOI: 10.1016/j.jssc.2025.125747
Guojian Ji , Chenyu Chu , Jiahua Cheng , Linya Fei , Anqi Xu , Tianle Zhang , Zhihui Zhang , Le Chen , Qunfeng Zou , Chuan Jiang
Metal-organic frameworks (MOFs) are advantageous for hydrogen storage owing to their tunable porosity. Two independent series were constructed: (i) MIL-101(Cr) functionalized with –NH2 or –OH, and (ii) Li+-doped MIL-101 at controlled loadings. All samples retained their framework integrity. Textural analysis reveals a concentration-dependent, non-monotonic effect of Li+: at 0.015 wt%, Li+ acts as an entrance unblocking (window reopening) effect, markedly increasing SBET and Vtotal and strengthening the 1–2 nm window population; at 0.036 wt%, an optimal balance between reopened windows and accessible microporosity yields a peak H2 uptake of 3.00 wt% (77 K, 100 kPa), surpassing both the parent framework and the –NH2 derivative (2.37 wt%); at 0.296 wt%, partial occupation of cages/windows reduces accessibility. GCMC density maps and isosteric-heat data further corroborate that –NH2 enhances polarity and strengthens host-guest interactions, whereas –OH blocks ultramicropores; moderate Li+ simultaneously improves pore accessibility and introduces polarized adsorption sites. Overall, H2 storage correlates more strongly with the coupling between accessible microporosity and pore-surface polarity than with SBET alone, highlighting dopant concentration as a key lever for optimizing MOF-based hydrogen storage.
{"title":"Tailoring MIL-101 for enhanced hydrogen storage via functional group introduction and Li+ doping","authors":"Guojian Ji , Chenyu Chu , Jiahua Cheng , Linya Fei , Anqi Xu , Tianle Zhang , Zhihui Zhang , Le Chen , Qunfeng Zou , Chuan Jiang","doi":"10.1016/j.jssc.2025.125747","DOIUrl":"10.1016/j.jssc.2025.125747","url":null,"abstract":"<div><div>Metal-organic frameworks (MOFs) are advantageous for hydrogen storage owing to their tunable porosity. Two independent series were constructed: (i) MIL-101(Cr) functionalized with –NH<sub>2</sub> or –OH, and (ii) Li<sup>+</sup>-doped MIL-101 at controlled loadings. All samples retained their framework integrity. Textural analysis reveals a concentration-dependent, non-monotonic effect of Li<sup>+</sup>: at 0.015 wt%, Li<sup>+</sup> acts as an entrance unblocking (window reopening) effect, markedly increasing S<sub>BET</sub> and V<sub>total</sub> and strengthening the 1–2 nm window population; at 0.036 wt%, an optimal balance between reopened windows and accessible microporosity yields a peak H<sub>2</sub> uptake of 3.00 wt% (77 K, 100 kPa), surpassing both the parent framework and the –NH<sub>2</sub> derivative (2.37 wt%); at 0.296 wt%, partial occupation of cages/windows reduces accessibility. GCMC density maps and isosteric-heat data further corroborate that –NH<sub>2</sub> enhances polarity and strengthens host-guest interactions, whereas –OH blocks ultramicropores; moderate Li<sup>+</sup> simultaneously improves pore accessibility and introduces polarized adsorption sites. Overall, H<sub>2</sub> storage correlates more strongly with the coupling between accessible microporosity and pore-surface polarity than with S<sub>BET</sub> alone, highlighting dopant concentration as a key lever for optimizing MOF-based hydrogen storage.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"354 ","pages":"Article 125747"},"PeriodicalIF":3.5,"publicationDate":"2025-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145569360","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 : 2025-11-19DOI: 10.1016/j.jssc.2025.125745
Ritobroto Sikdar, Dundappa Mumbaraddi, Pritam Das, Arthur Mar
To classify ternary rare-earth silicides REM2Si2 and germanides REM2Ge2 adopting the ThCr2Si2-type structure, a two-dimensional map based on radius ratios and valence electron counts was developed. This map suggested that the transition metal M plays a dominant role, which was confirmed independently by applying a machine learning algorithm called the sure independence screening and sparsifying operator (SISSO) method. In this way, a simple one-dimensional descriptor based solely on properties of the metal component M was identified in which ThCr2Si2-type phases are more likely to be formed if this descriptor meets a minimum threshold of 1.68 for silicides and 2.27 for germanides. Although arc-melting is typically used to prepare these compounds, it does not usually afford suitably sized crystals for further characterization. Flux growth of ternary germanides was investigated, with the use of indium yielding crystals of RECo2Ge2 (RE = Ce, Eu, Yb) and other compounds.
{"title":"Structure maps and crystal growth of ternary ThCr2Si2-type rare-earth transition-metal silicides and germanides","authors":"Ritobroto Sikdar, Dundappa Mumbaraddi, Pritam Das, Arthur Mar","doi":"10.1016/j.jssc.2025.125745","DOIUrl":"10.1016/j.jssc.2025.125745","url":null,"abstract":"<div><div>To classify ternary rare-earth silicides <em>REM</em><sub>2</sub>Si<sub>2</sub> and germanides <em>REM</em><sub>2</sub>Ge<sub>2</sub> adopting the ThCr<sub>2</sub>Si<sub>2</sub>-type structure, a two-dimensional map based on radius ratios and valence electron counts was developed. This map suggested that the transition metal <em>M</em> plays a dominant role, which was confirmed independently by applying a machine learning algorithm called the sure independence screening and sparsifying operator (SISSO) method. In this way, a simple one-dimensional descriptor <span><math><mrow><msub><mi>n</mi><mtext>valence</mtext></msub><mo>/</mo><msqrt><mi>ρ</mi></msqrt></mrow></math></span> based solely on properties of the metal component <em>M</em> was identified in which ThCr<sub>2</sub>Si<sub>2</sub>-type phases are more likely to be formed if this descriptor meets a minimum threshold of 1.68 for silicides and 2.27 for germanides. Although arc-melting is typically used to prepare these compounds, it does not usually afford suitably sized crystals for further characterization. Flux growth of ternary germanides was investigated, with the use of indium yielding crystals of <em>RE</em>Co<sub>2</sub>Ge<sub>2</sub> (<em>RE</em> = Ce, Eu, Yb) and other compounds.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"354 ","pages":"Article 125745"},"PeriodicalIF":3.5,"publicationDate":"2025-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145569361","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 : 2025-11-18DOI: 10.1016/j.jssc.2025.125738
Gizem Ozge Kayan, Ipek Akin
This study presents a novel sol-gel-based synthesis route for Ti–Al–C MAX phase raw materials in which alkoxide-derived gels not only provide homogeneous mixing of elements but also serve as an internal carbon source. Such a molecular-level control over precursor chemistry, together with the application of a controlled heat treatment, represents the first reported sol–gel-based route for Ti3AlC2 formation. Among the various precursor ratios investigated, the mixture with a Ti-/Al-alkoxide/C/Pr4NOH (aq) molar ratio of 3.0:1.0:10:6.0 showed the best results for MAX phase formation. FTIR, XRD and TG analyses confirmed the presence of alkoxide groups, which also act as a carbon source necessary for the synthesis of the MAX phase, and the existence of Ti–O–Al bonds. The sol-gel raw materials were heated under argon atmosphere between 1150 and 1400 °C at a rate of 2 °C/min, held at these temperatures for 30–60 min, and then cooled in a controlled manner. As the temperature increased, the Ti2AlC phase appeared first and at higher temperatures, especially around 1300–1350 °C, the Ti3AlC2 phase formed. At 1400 °C, decomposition of the MAX phases was observed. The highest purity of MAX phase (97 %) was obtained at 1300 °C with a 90 min dwell time. XRD and EDS results also showed small amounts of aluminum oxide (Al2O3) as secondary phase. Additional analyses using Raman, XPS, SEM, DSC, and TEM confirmed the successful synthesis of layered Ti3AlC2 with typical MAX phase structure.
{"title":"Sol–gel synthesis of Ti2AlC and Ti3AlC2 MAX phases and their sinterability via spark plasma sintering","authors":"Gizem Ozge Kayan, Ipek Akin","doi":"10.1016/j.jssc.2025.125738","DOIUrl":"10.1016/j.jssc.2025.125738","url":null,"abstract":"<div><div>This study presents a novel sol-gel-based synthesis route for Ti–Al–C MAX phase raw materials in which alkoxide-derived gels not only provide homogeneous mixing of elements but also serve as an internal carbon source. Such a molecular-level control over precursor chemistry, together with the application of a controlled heat treatment, represents the first reported sol–gel-based route for Ti<sub>3</sub>AlC<sub>2</sub> formation. Among the various precursor ratios investigated, the mixture with a Ti-/Al-alkoxide/C/Pr<sub>4</sub>NOH (aq) molar ratio of 3.0:1.0:10:6.0 showed the best results for MAX phase formation. FTIR, XRD and TG analyses confirmed the presence of alkoxide groups, which also act as a carbon source necessary for the synthesis of the MAX phase, and the existence of Ti–<em>O</em>–Al bonds. The sol-gel raw materials were heated under argon atmosphere between 1150 and 1400 °C at a rate of 2 °C/min, held at these temperatures for 30–60 min, and then cooled in a controlled manner. As the temperature increased, the Ti<sub>2</sub>AlC phase appeared first and at higher temperatures, especially around 1300–1350 °C, the Ti<sub>3</sub>AlC<sub>2</sub> phase formed. At 1400 °C, decomposition of the MAX phases was observed. The highest purity of MAX phase (97 %) was obtained at 1300 °C with a 90 min dwell time. XRD and EDS results also showed small amounts of aluminum oxide (Al<sub>2</sub>O<sub>3</sub>) as secondary phase. Additional analyses using Raman, XPS, SEM, DSC, and TEM confirmed the successful synthesis of layered Ti<sub>3</sub>AlC<sub>2</sub> with typical MAX phase structure.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"354 ","pages":"Article 125738"},"PeriodicalIF":3.5,"publicationDate":"2025-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145569355","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 : 2025-11-18DOI: 10.1016/j.jssc.2025.125742
Kangli Zhang, Wen Jiang, Ke Zhao, Jiantang Li, Dongmei Wang
Metal-organic frameworks (MOFs), as an emerging class of porous materials, have garnered extensive attention in the field of gas separation due to their tunable porosity and structural diversity. In particular, the separation of acetylene and carbon dioxide presents considerable challenges and practical significance, given their comparable molecular dimensions and similar physicochemical characteristics. In this work, H4IIPA was designed and synthesized via a mixed-ligand strategy. Using divalent cadmium (Cd2+) as the metal node, a ZJNU-410 was successfully constructed under solvothermal conditions. Experimental results indicate that at 298 K and 100 kPa, the adsorption capacities of the ZJNU-410 for C2H2 and CO2 are 0.71 mmol g−1 and 0.54 mmol g−1, respectively. The stronger interaction between the framework and C2H2 compared to CO2 is further reflected in the isosteric adsorption heats (Qst), which are 52.9 kJ mol−1 and 48.5 kJ mol−1, respectively. Notably, the material exhibits excellent chemical stability and recyclability, highlighting its promising potential for industrial applications in C2H2/CO2 separation processes.
{"title":"Metal-organic frameworks constructed from an imidazole-functionalized tetracarboxylic acid for C2H2/CO2 separation","authors":"Kangli Zhang, Wen Jiang, Ke Zhao, Jiantang Li, Dongmei Wang","doi":"10.1016/j.jssc.2025.125742","DOIUrl":"10.1016/j.jssc.2025.125742","url":null,"abstract":"<div><div>Metal-organic frameworks (MOFs), as an emerging class of porous materials, have garnered extensive attention in the field of gas separation due to their tunable porosity and structural diversity. In particular, the separation of acetylene and carbon dioxide presents considerable challenges and practical significance, given their comparable molecular dimensions and similar physicochemical characteristics. In this work, H<sub>4</sub>IIPA was designed and synthesized via a mixed-ligand strategy. Using divalent cadmium (Cd<sup>2+</sup>) as the metal node, a <strong>ZJNU-410</strong> was successfully constructed under solvothermal conditions. Experimental results indicate that at 298 K and 100 kPa, the adsorption capacities of the <strong>ZJNU-410</strong> for C<sub>2</sub>H<sub>2</sub> and CO<sub>2</sub> are 0.71 mmol g<sup>−1</sup> and 0.54 mmol g<sup>−1</sup>, respectively. The stronger interaction between the framework and C<sub>2</sub>H<sub>2</sub> compared to CO<sub>2</sub> is further reflected in the isosteric adsorption heats (<em>Q</em><sub>st</sub>), which are 52.9 kJ mol<sup>−1</sup> and 48.5 kJ mol<sup>−1</sup>, respectively. Notably, the material exhibits excellent chemical stability and recyclability, highlighting its promising potential for industrial applications in C<sub>2</sub>H<sub>2</sub>/CO<sub>2</sub> separation processes.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"354 ","pages":"Article 125742"},"PeriodicalIF":3.5,"publicationDate":"2025-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145569356","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 : 2025-11-17DOI: 10.1016/j.jssc.2025.125743
Yuanyuan Xie, Junhui Guo, Yufeng He, Yaping Zhang, Rongmin Wang
In this study, we developed a novel MIL100(Fe)@MMT composite adsorbent by in-situ growth of eco-friendly nano MIL-100(Fe) onto montmorillonite (MMT) layers. Comprehensive characterization, such as SEM, FT-IR, XRD, and TGA, verified the uniform anchoring of MIL-100(Fe) nanoparticles on the MMT substrate. The composite demonstrated synergistic enhancement in Rhodamine B (RhB) adsorption, exhibiting capacities 4.00-fold and 1.24-fold higher than pristine MMT and pure MIL-100(Fe), respectively. Rapid adsorption kinetics achieved 95 % equilibrium within 10 min, following a pseudo-second-order model (R2 > 0.95), indicative of chemisorption - dominated mechanisms. Freundlich isotherm analysis (R2 = 0.97) revealed multilayer adsorption on heterogeneous active sites. Notably, MIL-100(Fe)/MMT maintained stable performance across a broad pH range from 1 to 10 due to the synergistic interaction between MMT interlayer cation exchanged and MIL-100(Fe) coordinatively unsaturated metal sites. The composite design concurrently addresses MOFs environmental instability while enhancing adsorption kinetics (k2 = 0.016 g mg−1 min−1) and capacity (qe = 506.5 mg/g), offering a promising strategy for dye-laden wastewater remediation.
{"title":"Nano-FeMOFs stabilized by montmorillonite for rapid removing dyes in aqueous systems","authors":"Yuanyuan Xie, Junhui Guo, Yufeng He, Yaping Zhang, Rongmin Wang","doi":"10.1016/j.jssc.2025.125743","DOIUrl":"10.1016/j.jssc.2025.125743","url":null,"abstract":"<div><div>In this study, we developed a novel MIL100(Fe)@MMT composite adsorbent by in-situ growth of eco-friendly nano MIL-100(Fe) onto montmorillonite (MMT) layers. Comprehensive characterization, such as SEM, FT-IR, XRD, and TGA, verified the uniform anchoring of MIL-100(Fe) nanoparticles on the MMT substrate. The composite demonstrated synergistic enhancement in Rhodamine B (RhB) adsorption, exhibiting capacities 4.00-fold and 1.24-fold higher than pristine MMT and pure MIL-100(Fe), respectively. Rapid adsorption kinetics achieved 95 % equilibrium within 10 min, following a pseudo-second-order model (R<sup>2</sup> > 0.95), indicative of chemisorption - dominated mechanisms. Freundlich isotherm analysis (R<sup>2</sup> = 0.97) revealed multilayer adsorption on heterogeneous active sites. Notably, MIL-100(Fe)/MMT maintained stable performance across a broad pH range from 1 to 10 due to the synergistic interaction between MMT interlayer cation exchanged and MIL-100(Fe) coordinatively unsaturated metal sites. The composite design concurrently addresses MOFs environmental instability while enhancing adsorption kinetics (k<sub>2</sub> = 0.016 g mg<sup>−1</sup> min<sup>−1</sup>) and capacity (q<sub>e</sub> = 506.5 mg/g), offering a promising strategy for dye-laden wastewater remediation.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"354 ","pages":"Article 125743"},"PeriodicalIF":3.5,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145569359","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 : 2025-11-17DOI: 10.1016/j.jssc.2025.125741
Minhong Li , Xingliang Chen , Jingran Zhong, Chengjie Liao, Yun An, Jin Lu, Hao Fu, Zhiqiang Jiang
Presented here is a novel design and synthesis strategy for low-pH stable MOFs was introduced, which involved incorporating multiple metal active sites and multiple hydrogen bonds. One Cu-MOF (PZH-3), stable across a pH range of 0–12, was successfully synthesized. When appropriately cobalt-doped, it exhibited remarkable catalytic activity in the hydrogen evolution reaction (HER), with an overpotential of only 240 mV at a current density of 10 mA cm−2. This work not only successfully designed and synthesized a new class of electrocatalytic MOFs but also provided a new approach for creating low-pH stable, HER-active MOFs.
本文介绍了一种新的低ph稳定mof的设计和合成策略，该策略涉及到多个金属活性位点和多个氢键。成功合成了一种pH值在0-12范围内稳定的Cu-MOF （PZH-3）。当适当的钴掺杂时，它在析氢反应（HER）中表现出显著的催化活性，在电流密度为10 mA cm−2时，过电位仅为240 mV。这项工作不仅成功地设计和合成了一类新型的电催化MOFs，而且为制备低ph稳定的her活性MOFs提供了新的途径。
{"title":"The design and synthesis of a MOF for HER, stabilized at low pH values based on multiple H-bonds","authors":"Minhong Li , Xingliang Chen , Jingran Zhong, Chengjie Liao, Yun An, Jin Lu, Hao Fu, Zhiqiang Jiang","doi":"10.1016/j.jssc.2025.125741","DOIUrl":"10.1016/j.jssc.2025.125741","url":null,"abstract":"<div><div>Presented here is a novel design and synthesis strategy for low-pH stable MOFs was introduced, which involved incorporating multiple metal active sites and multiple hydrogen bonds. One Cu-MOF (PZH-3), stable across a pH range of 0–12, was successfully synthesized. When appropriately cobalt-doped, it exhibited remarkable catalytic activity in the hydrogen evolution reaction (HER), with an overpotential of only 240 mV at a current density of 10 mA cm<sup>−2</sup>. This work not only successfully designed and synthesized a new class of electrocatalytic MOFs but also provided a new approach for creating low-pH stable, HER-active MOFs.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"354 ","pages":"Article 125741"},"PeriodicalIF":3.5,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145569363","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 : 2025-11-15DOI: 10.1016/j.jssc.2025.125739
Gang Yang , Jun Li , KangShuai Li , YingJie Xia , WenPing Zhu , Kun liu , XingHua Chang , Zi He , ShengMing Jin
Yttria-stabilized bismuth oxide ((Bi2O3)1-x(Y2O3)x, YSB) electrolytes with varying Y2O3 doping levels (x = 0.10–0.37) were synthesized via a solid-state method, and their structural evolution, microstructural characteristics, and electrochemical performance were systematically investigated. X-ray diffraction and Rietveld refinement confirm the stabilization of the cubic δ-phase across the entire doping range, accompanied by two-stage lattice contraction and peak broadening at higher doping levels, suggesting increased local distortion and potential oxygen vacancy ordering. EBSD and kernel average misorientation (KAM) analyses reveal that moderate doping (x ≈ 0.20) yields the largest grain size and lowest residual lattice strain, supporting enhanced oxygen ion mobility. The optimized 20YSB sample exhibits the highest ionic conductivity (0.1987 S cm−1 at 800 °C), lowest activation energy, and excellent long-term stability (<1.2 % degradation over 200 h at 800 °C). Site occupancy analysis shows that ionic conductivity strongly correlates with the redistribution of oxygen from high-symmetry O1/O2 sites to less favorable O3 sites at high doping levels, which introduces kinetic traps and impedes conduction. A five-factor, four-level orthogonal design further identifies calcination temperature and milling speed as the most influential parameters affecting densification and conductivity. These results establish a robust structure–property–process relationship in YSB electrolytes and offer practical strategies for the scalable preparation of high-performance materials for intermediate-temperature solid oxide fuel cells (IT-SOFCs).
{"title":"Structure optimization and ionic conductivity behavior of yttria-stabilized Bi2O3 electrolytes for intermediate-temperature SOFCs","authors":"Gang Yang , Jun Li , KangShuai Li , YingJie Xia , WenPing Zhu , Kun liu , XingHua Chang , Zi He , ShengMing Jin","doi":"10.1016/j.jssc.2025.125739","DOIUrl":"10.1016/j.jssc.2025.125739","url":null,"abstract":"<div><div>Yttria-stabilized bismuth oxide ((Bi<sub>2</sub>O<sub>3</sub>)<sub>1-x</sub>(Y<sub>2</sub>O<sub>3</sub>)<sub>x</sub>, YSB) electrolytes with varying Y<sub>2</sub>O<sub>3</sub> doping levels (x = 0.10–0.37) were synthesized via a solid-state method, and their structural evolution, microstructural characteristics, and electrochemical performance were systematically investigated. X-ray diffraction and Rietveld refinement confirm the stabilization of the cubic δ-phase across the entire doping range, accompanied by two-stage lattice contraction and peak broadening at higher doping levels, suggesting increased local distortion and potential oxygen vacancy ordering. EBSD and kernel average misorientation (KAM) analyses reveal that moderate doping (x ≈ 0.20) yields the largest grain size and lowest residual lattice strain, supporting enhanced oxygen ion mobility. The optimized 20YSB sample exhibits the highest ionic conductivity (0.1987 S cm<sup>−1</sup> at 800 °C), lowest activation energy, and excellent long-term stability (<1.2 % degradation over 200 h at 800 °C). Site occupancy analysis shows that ionic conductivity strongly correlates with the redistribution of oxygen from high-symmetry O1/O2 sites to less favorable O3 sites at high doping levels, which introduces kinetic traps and impedes conduction. A five-factor, four-level orthogonal design further identifies calcination temperature and milling speed as the most influential parameters affecting densification and conductivity. These results establish a robust structure–property–process relationship in YSB electrolytes and offer practical strategies for the scalable preparation of high-performance materials for intermediate-temperature solid oxide fuel cells (IT-SOFCs).</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"354 ","pages":"Article 125739"},"PeriodicalIF":3.5,"publicationDate":"2025-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145569358","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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