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}
Pub Date : 2025-11-12DOI: 10.1016/j.jssc.2025.125733
Rachita Newar , Nasrin Sultana , Arabinda Baruah
The uncontrolled release of CO2 gas and synthetic dyes severely threatens environmental quality, demanding the need for sustainable remediation strategies. Activated carbon (AC), distinguished by its high surface area, abundant active sites, and robust structural stability, demonstrates excellent capacity for adsorbing CO2 and dye molecules. In this study, a novel silica-impregnated activated carbon (SiO2@AC) composite was synthesized from waste rice (WR) via synergistic chemical activation using Na2CO3 and KOH. The composite exhibited a high surface area of ∼400 m2/g with uniform microporous structure (average pore size of 1.71 nm), as confirmed by XPS, PXRD, FTIR, SEM, EDAX, RAMAN and BET analyses. CO2 adsorption capacity reached 72 cm3/g at 280 K and 1 bar, with negative ΔHads values ranging from 83.51 to 1.48 kJ/mol, indicating physisorption. Dye adsorption experiments revealed maximum capacities of 66.04 mg/g for crystal violet (CV) and 78.23 mg/g for methylene blue (MB), fitting well with the Langmuir isotherm model for CV and the Temkin isotherm model for MB. Kinetic analyses confirmed a predominantly physisorption-driven mechanism with weak chemical interactions for both CV and MB. Collectively, these findings demonstrate that rice-waste-derived SiO2@AC is a multifunctional, sustainable adsorbent, aligning with circular economy principles by valorizing agricultural residues for environmental remediation.
{"title":"Nanoarchitectonics of waste rice derived SiO2@Activated carbon composite for high-performance adsorptive removal of CO2 and cationic dyes","authors":"Rachita Newar , Nasrin Sultana , Arabinda Baruah","doi":"10.1016/j.jssc.2025.125733","DOIUrl":"10.1016/j.jssc.2025.125733","url":null,"abstract":"<div><div>The uncontrolled release of CO<sub>2</sub> gas and synthetic dyes severely threatens environmental quality, demanding the need for sustainable remediation strategies. Activated carbon (AC), distinguished by its high surface area, abundant active sites, and robust structural stability, demonstrates excellent capacity for adsorbing CO<sub>2</sub> and dye molecules. In this study, a novel silica-impregnated activated carbon (SiO<sub>2</sub>@AC) composite was synthesized from waste rice (WR) via synergistic chemical activation using Na<sub>2</sub>CO<sub>3</sub> and KOH. The composite exhibited a high surface area of ∼400 m<sup>2</sup>/g with uniform microporous structure (average pore size of 1.71 nm), as confirmed by XPS, PXRD, FTIR, SEM, EDAX, RAMAN and BET analyses. CO<sub>2</sub> adsorption capacity reached 72 cm<sup>3</sup>/g at 280 K and 1 bar, with negative ΔH<sub>ads</sub> values ranging from 83.51 to 1.48 kJ/mol, indicating physisorption. Dye adsorption experiments revealed maximum capacities of 66.04 mg/g for crystal violet (CV) and 78.23 mg/g for methylene blue (MB), fitting well with the Langmuir isotherm model for CV and the Temkin isotherm model for MB. Kinetic analyses confirmed a predominantly physisorption-driven mechanism with weak chemical interactions for both CV and MB. Collectively, these findings demonstrate that rice-waste-derived SiO<sub>2</sub>@AC is a multifunctional, sustainable adsorbent, aligning with circular economy principles by valorizing agricultural residues for environmental remediation.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"354 ","pages":"Article 125733"},"PeriodicalIF":3.5,"publicationDate":"2025-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145517555","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 : 2025-11-12DOI: 10.1016/j.jssc.2025.125734
Jie Duan , Yang Wang , Wei-Li Zhai , Xian Wang , Zhou-Cao Ye , Qing Li , Wei Zhu
The monitoring of Cr(VI) ions presents extremely high standards in the hydrolysis/acid-base stability, detection sensitivity, anti-interference capability and accuracy of MOFs-based probes. Immobilization of rare earth ions (Ln3+) onto a stable luminescent Zr-MOF for dual fluorescence signals offered organic modules and Ln3+ sites, constitutes a feasible yet challenging strategy for efficient ratio fluorescence detection of Cr(VI). Herein, a novel Tb@Zr-MOF with dual emission signals (I391, I426 from Zr-MOF, I490, I546, I586, I622 from Tb3+) was fabricated by anchoring Tb3+ ions into a Zr-MOF inherently possesses bright blue fluorescence, utilizing the principles of antenna effect and photo-induced electron transfer (PET). Subsequently, it was deployed for effectively identification and quantitative detection of Cr2O72− and CrO42− analytes, utilizing the stable intensity ratio relationship of fluorescence signals (I391–I546) originated from Zr-MOF (I391) and Tb3+ (I546). Notably, the detection accuracy for Cr(VI) ions has been significantly improved due to the inherent cooperative quenching response mechanism associated with its dual fluorescence emission centers. It was determined that Tb@Zr-MOF exhibited a highly sensitive response towards both Cr2O72− and CrO42−, achieving fairly low detection limits (DL) of 6.77 ppb and 4.74 ppb, and the corresponding notably high quenching constants (Ksv) of 3.95 × 105 M−1 and 7.91 × 104 M−1, respectively. More ingeniously, even within an aqueous environment containing complex cations and anions or acidic and basic components (pH = 2–13), it still exhibited a reliable fluorescence quenching response towards the target analytes. This study offers a highly viable reference for the design of innovative and efficient ratio fluorescence responsive typed MOFs-based photochemical sensors.
{"title":"A novel Tb@Zr-MOF photochemical probe via anchoring Tb3+ onto a luminescent Zr-MOF platform for highly efficient ratio fluorescence sensing of Cr(VI) ions","authors":"Jie Duan , Yang Wang , Wei-Li Zhai , Xian Wang , Zhou-Cao Ye , Qing Li , Wei Zhu","doi":"10.1016/j.jssc.2025.125734","DOIUrl":"10.1016/j.jssc.2025.125734","url":null,"abstract":"<div><div>The monitoring of Cr(VI) ions presents extremely high standards in the hydrolysis/acid-base stability, detection sensitivity, anti-interference capability and accuracy of MOFs-based probes. Immobilization of rare earth ions (Ln<sup>3+</sup>) onto a stable luminescent Zr-MOF for dual fluorescence signals offered organic modules and Ln<sup>3+</sup> sites, constitutes a feasible yet challenging strategy for efficient ratio fluorescence detection of Cr(VI). Herein, a novel Tb@Zr-MOF with dual emission signals (I<sub>391</sub>, I<sub>426</sub> from Zr-MOF, I<sub>490</sub>, I<sub>546</sub>, I<sub>586</sub>, I<sub>622</sub> from Tb<sup>3+</sup>) was fabricated by anchoring Tb<sup>3+</sup> ions into a Zr-MOF inherently possesses bright blue fluorescence, utilizing the principles of antenna effect and photo-induced electron transfer (PET). Subsequently, it was deployed for effectively identification and quantitative detection of Cr<sub>2</sub>O<sub>7</sub><sup>2−</sup> and CrO<sub>4</sub><sup>2−</sup> analytes, utilizing the stable intensity ratio relationship of fluorescence signals (I<sub>391</sub>–I<sub>546</sub>) originated from Zr-MOF (I<sub>391</sub>) and Tb<sup>3+</sup> (I<sub>546</sub>). Notably, the detection accuracy for Cr(VI) ions has been significantly improved due to the inherent cooperative quenching response mechanism associated with its dual fluorescence emission centers. It was determined that Tb@Zr-MOF exhibited a highly sensitive response towards both Cr<sub>2</sub>O<sub>7</sub><sup>2−</sup> and CrO<sub>4</sub><sup>2−</sup>, achieving fairly low detection limits (DL) of 6.77 ppb and 4.74 ppb, and the corresponding notably high quenching constants (K<sub>sv</sub>) of 3.95 × 10<sup>5</sup> M<sup>−1</sup> and 7.91 × 10<sup>4</sup> M<sup>−1</sup>, respectively. More ingeniously, even within an aqueous environment containing complex cations and anions or acidic and basic components (pH = 2–13), it still exhibited a reliable fluorescence quenching response towards the target analytes. This study offers a highly viable reference for the design of innovative and efficient ratio fluorescence responsive typed MOFs-based photochemical sensors.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"354 ","pages":"Article 125734"},"PeriodicalIF":3.5,"publicationDate":"2025-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145517558","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 : 2025-11-11DOI: 10.1016/j.jssc.2025.125737
Vladimir B. Nalbandyan , Igor L. Shukaev , Maria A. Evstigneeva , Yuri V. Popov , Alexander N. Vasiliev , Tatyana M. Vasilchikova
Hexagonal layered Na2T2TeO6 (T = Co1/3Ni1/3Cu1/3) and Na2Z2TeO6 (Z = Co1/4Ni1/4Cu1/4Zn1/4) have been prepared by solid-state reactions. According to the X-ray Rietveld refinement, Na2Z2TeO6 is isostructural with its honeycomb-ordered constituents Na2M2TeO6 (M = Co, Zn), space group P6322. For Na2T2TeO6, however, only subcell (ignoring T/Te ordering) could be successfully refined despite presence of weak superstructure reflection. This is attributed to intergrowth of two packing modes with similar lattice parameters: P63/mcm (characteristic of Na2Ni2TeO6) and P6322. According to magnetic susceptibility and heat capacity measurements, both materials undergo antiferromagnetic ordering at low temperatures with negative Weiss temperatures of −38 and −26 K for the T- and Z-compositions, respectively. The Néel point of Na2T2TeO6, 16.9 K, is considerably lower than those of its Ni and Co constituents (both being about 27 K), in contrast to the sister system, monoclinic Na3T2SbO6, where TN is intermediate between those of Ni and Co constituents. Further lowering of the Néel point in Na2Z2TeO6, 8.6 K, is attributed to the diamagnetic dilution with Zn2+.
{"title":"Effect of multiple cationic substitutions on structure and magnetism of honeycomb-layered hexagonal tellurates Na2M2TeO6 (M = Co, Ni, Cu, Zn)","authors":"Vladimir B. Nalbandyan , Igor L. Shukaev , Maria A. Evstigneeva , Yuri V. Popov , Alexander N. Vasiliev , Tatyana M. Vasilchikova","doi":"10.1016/j.jssc.2025.125737","DOIUrl":"10.1016/j.jssc.2025.125737","url":null,"abstract":"<div><div>Hexagonal layered Na<sub>2</sub><em>T</em><sub>2</sub>TeO<sub>6</sub> (<em>T</em> = Co<sub>1/3</sub>Ni<sub>1/3</sub>Cu<sub>1/3</sub>) and Na<sub>2</sub><em>Z</em><sub>2</sub>TeO<sub>6</sub> (<em>Z</em> = Co<sub>1/4</sub>Ni<sub>1/4</sub>Cu<sub>1/4</sub>Zn<sub>1/4</sub>) have been prepared by solid-state reactions. According to the X-ray Rietveld refinement, Na<sub>2</sub><em>Z</em><sub>2</sub>TeO<sub>6</sub> is isostructural with its honeycomb-ordered constituents Na<sub>2</sub><em>M</em><sub>2</sub>TeO<sub>6</sub> (<em>M</em> = Co, Zn), space group <em>P</em>6<sub>3</sub>22. For Na<sub>2</sub><em>T</em><sub>2</sub>TeO<sub>6</sub>, however, only subcell (ignoring <em>T</em>/Te ordering) could be successfully refined despite presence of weak superstructure reflection. This is attributed to intergrowth of two packing modes with similar lattice parameters: <em>P</em>6<sub>3</sub>/<em>mcm</em> (characteristic of Na<sub>2</sub>Ni<sub>2</sub>TeO<sub>6</sub>) and <em>P</em>6<sub>3</sub>22. According to magnetic susceptibility and heat capacity measurements, both materials undergo antiferromagnetic ordering at low temperatures with negative Weiss temperatures of −38 and −26 K for the <em>T</em>- and <em>Z</em>-compositions, respectively. The Néel point of Na<sub>2</sub><em>T</em><sub>2</sub>TeO<sub>6</sub>, 16.9 K, is considerably lower than those of its Ni and Co constituents (both being about 27 K), in contrast to the sister system, monoclinic Na<sub>3</sub><em>T</em><sub>2</sub>SbO<sub>6</sub>, where <em>T</em><sub>N</sub> is intermediate between those of Ni and Co constituents. Further lowering of the Néel point in Na<sub>2</sub><em>Z</em><sub>2</sub>TeO<sub>6</sub>, 8.6 K, is attributed to the diamagnetic dilution with Zn<sup>2+</sup>.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"354 ","pages":"Article 125737"},"PeriodicalIF":3.5,"publicationDate":"2025-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145517559","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 : 2025-11-08DOI: 10.1016/j.jssc.2025.125736
Zhang Huan , Han Bing , Qin Changyu , Fan Xuxin , Huang Yiyong , Yu Xianglin , Li Junbo
Using solar energy to produce hydrogen and oxygen through photocatalytic decomposition of water is an ideal way to deal with energy crisis and environmental pollution. In this research, a new one-dimensional covalent organic framework (1D COF) was designed and synthesized through Schiff base condensation reaction between 4,4′,4″,4‴-(porphyrin-5,10,15,20-tetrayl) tetraaniline (TP) and 4,4'-(pyrimidine-4,6-diyl) dibenzaldehyde (PA), which simultaneously incorporates pyrimidine-based hydrogen evolution units and porphyrin-based oxygen evolution units. Experimental data confirmed that the as-prepared TP-PA-COF exhibited excellent bifunctional catalytic performance of photocatalytic hydrogen and oxygen production under visible light illumination. Its performance advantages mainly come from the material's highly ordered crystal structure, large specific surface area and excellent pore characteristics. Specifically, the pyrimidine units, acting as electron acceptors and active sites for hydrogen evolution reaction (HER), promote the accumulation of electrons and accelerate the proton reduction reaction; the porphyrin units, serving as electron donors and active sites for oxygen evolution reaction (OER), efficiently enhance visible light harvesting and accelerate the migration of photoinduced electrons. This synergistic effect enables TP-PA-COF to achieve hydrogen production rate of 37.4 mmol g−1·h−1 and oxygen production rate of 7.4 mmol g−1·h−1 in photocatalytic reactions, respectively. Furthermore, the material maintains good stability after three cycle tests. This research provides new insights for constructing efficient and stable COF-based bifunctional photocatalysts and realizing visible light-driven overall water splitting.
{"title":"Construction of porphyrin-pyrimidine 1D covalent organic framework (1D-COF) with dual photocatalytic hydrogen and oxygen evolution","authors":"Zhang Huan , Han Bing , Qin Changyu , Fan Xuxin , Huang Yiyong , Yu Xianglin , Li Junbo","doi":"10.1016/j.jssc.2025.125736","DOIUrl":"10.1016/j.jssc.2025.125736","url":null,"abstract":"<div><div>Using solar energy to produce hydrogen and oxygen through photocatalytic decomposition of water is an ideal way to deal with energy crisis and environmental pollution. In this research, a new one-dimensional covalent organic framework (1D COF) was designed and synthesized through Schiff base condensation reaction between 4,4′,4″,4‴-(porphyrin-5,10,15,20-tetrayl) tetraaniline (TP) and 4,4'-(pyrimidine-4,6-diyl) dibenzaldehyde (PA), which simultaneously incorporates pyrimidine-based hydrogen evolution units and porphyrin-based oxygen evolution units. Experimental data confirmed that the as-prepared TP-PA-COF exhibited excellent bifunctional catalytic performance of photocatalytic hydrogen and oxygen production under visible light illumination. Its performance advantages mainly come from the material's highly ordered crystal structure, large specific surface area and excellent pore characteristics. Specifically, the pyrimidine units, acting as electron acceptors and active sites for hydrogen evolution reaction (HER), promote the accumulation of electrons and accelerate the proton reduction reaction; the porphyrin units, serving as electron donors and active sites for oxygen evolution reaction (OER), efficiently enhance visible light harvesting and accelerate the migration of photoinduced electrons. This synergistic effect enables TP-PA-COF to achieve hydrogen production rate of 37.4 mmol g<sup>−1</sup>·h<sup>−1</sup> and oxygen production rate of 7.4 mmol g<sup>−1</sup>·h<sup>−1</sup> in photocatalytic reactions, respectively. Furthermore, the material maintains good stability after three cycle tests. This research provides new insights for constructing efficient and stable COF-based bifunctional photocatalysts and realizing visible light-driven overall water splitting.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"354 ","pages":"Article 125736"},"PeriodicalIF":3.5,"publicationDate":"2025-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145517556","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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