Pub Date : 2025-12-26DOI: 10.1016/j.jssc.2025.125798
Shabnam Feyziyeva , Nathalie Kyritsakas-Gruber , Nizami Israfilov , Benoît Louis
Two new pillared-layer mixed-ligand metal–organic frameworks (MOFs) were synthesized using 2,5-thiophene dicarboxylic acid (TDC) in combination with pyrazine (Pyr) or 1,4-diazabicyclo[2.2.2]octane (DABCO). Copper, positioned between hard and soft acids according to the HSAB theory, was selected as the metal center. Pairing the anionic carboxylate linker with neutral N-donor ligands yielded a 3D framework in the TDC–Pyr system and a 2D architecture in the TDC–DABCO system. Both materials exhibited structural phase transformations at approximately 200 °C. The MOFs were fully characterized by SCXRD, PXRD, FT-IR, TGA, nitrogen physisorption analyses, and CO2 sorption studies. Notably, the 2D Cu-TDC-DABCO framework achieved the highest CO2 uptake, reaching 2.5 mmol g−1 at 273 K and 1.2 bar.
{"title":"A mixed-ligand strategy to enhance MOF stability and functionality: Case study on copper MOFs and CO2 adsorption","authors":"Shabnam Feyziyeva , Nathalie Kyritsakas-Gruber , Nizami Israfilov , Benoît Louis","doi":"10.1016/j.jssc.2025.125798","DOIUrl":"10.1016/j.jssc.2025.125798","url":null,"abstract":"<div><div>Two new pillared-layer mixed-ligand metal–organic frameworks (MOFs) were synthesized using 2,5-thiophene dicarboxylic acid (TDC) in combination with pyrazine (Pyr) or 1,4-diazabicyclo[2.2.2]octane (DABCO). Copper, positioned between hard and soft acids according to the HSAB theory, was selected as the metal center. Pairing the anionic carboxylate linker with neutral N-donor ligands yielded a 3D framework in the TDC–Pyr system and a 2D architecture in the TDC–DABCO system. Both materials exhibited structural phase transformations at approximately 200 °C. The MOFs were fully characterized by SCXRD, PXRD, FT-IR, TGA, nitrogen physisorption analyses, and CO<sub>2</sub> sorption studies. Notably, the 2D Cu-TDC-DABCO framework achieved the highest CO<sub>2</sub> uptake, reaching 2.5 mmol g<sup>−1</sup> at 273 K and 1.2 bar.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"355 ","pages":"Article 125798"},"PeriodicalIF":3.5,"publicationDate":"2025-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145836965","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 : 2025-12-24DOI: 10.1016/j.jssc.2025.125797
Takuji Ikeda, Takako Nagase
A new Cs-containing crystalline layered silicate, named as Cs-LS, (Cs8[Si80O160(OH)8]·8H2O) was synthesized by the hydrothermal conversion of acid-treated layered silicates RUB-18 (H-RUB-18, H8Si32O64(OH)8) or PLS-1 (H-PLS-1, H0.4TMA1.6(OH)2[Si18O34(OH)4]) at 473 K for 5 d. The solvothermal conversion of the same starting materials in ethanol solvent was also attempted at 473 K for 5 d, yielding Cs-containing silicate CsHSiO5 with a ladder-like silicate framework. The crystal structure of Cs-LS was determined by the combination of 3D-ED/microED, powder X-ray diffraction, and solid-state NMR experiments. The space group, lattice constants, and unit-cell volume were determined as P21/n, a = 1.00363(2) nm, b = 1.06402(3) nm, c = 3.62537(9) nm, β = 94.253(2)°, and V = 3.8605(2) nm3. The robust-looking silicate layer, consisting of 4-, 5-, 7-, and 8-rings, was identical to the clay mineral kenyaite and was about 1.6 nm thick. The layer surface had semi-cylindrical depressions along the [110] direction, and Cs+ ions and water molecules were alternately distributed in the depressions. The structure of the Cs-LS layer is partially similar to H-RUB-18 but quite different from H-PLS-1, suggesting that Cs+ ions acted as a structure-directing agent. Cs-LS exhibited water vapor adsorption ability due to hydroxyl groups on the layer surface, and its specific surface area was estimated to be 97.4 m2 g−1.
{"title":"Synthesis and crystal structure of a new Cs-containing layered silicate by the hydrothermal conversion of H-RUB-18","authors":"Takuji Ikeda, Takako Nagase","doi":"10.1016/j.jssc.2025.125797","DOIUrl":"10.1016/j.jssc.2025.125797","url":null,"abstract":"<div><div>A new Cs-containing crystalline layered silicate, named as Cs-LS, (Cs<sub>8</sub>[Si<sub>80</sub>O<sub>160</sub>(OH)<sub>8</sub>]·8H<sub>2</sub>O) was synthesized by the hydrothermal conversion of acid-treated layered silicates RUB-18 (H-RUB-18, H<sub>8</sub>Si<sub>32</sub>O<sub>64</sub>(OH)<sub>8</sub>) or PLS-1 (H-PLS-1, H<sub>0.4</sub>TMA<sub>1.6</sub>(OH)<sub>2</sub>[Si<sub>18</sub>O<sub>34</sub>(OH)<sub>4</sub>]) at 473 K for 5 d. The solvothermal conversion of the same starting materials in ethanol solvent was also attempted at 473 K for 5 d, yielding Cs-containing silicate CsHSiO<sub>5</sub> with a ladder-like silicate framework. The crystal structure of Cs-LS was determined by the combination of 3D-ED/microED, powder X-ray diffraction, and solid-state NMR experiments. The space group, lattice constants, and unit-cell volume were determined as <em>P</em>2<sub>1</sub>/<em>n</em>, <em>a</em> = 1.00363(2) nm, <em>b</em> = 1.06402(3) nm, <em>c</em> = 3.62537(9) nm, <em>β</em> = 94.253(2)°, and <em>V</em> = 3.8605(2) nm<sup>3</sup>. The robust-looking silicate layer, consisting of 4-, 5-, 7-, and 8-rings, was identical to the clay mineral kenyaite and was about 1.6 nm thick. The layer surface had semi-cylindrical depressions along the [110] direction, and Cs<sup>+</sup> ions and water molecules were alternately distributed in the depressions. The structure of the Cs-LS layer is partially similar to H-RUB-18 but quite different from H-PLS-1, suggesting that Cs<sup>+</sup> ions acted as a structure-directing agent. Cs-LS exhibited water vapor adsorption ability due to hydroxyl groups on the layer surface, and its specific surface area was estimated to be 97.4 m<sup>2</sup> g<sup>−1</sup>.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"356 ","pages":"Article 125797"},"PeriodicalIF":3.5,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145940139","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 : 2025-12-24DOI: 10.1016/j.jssc.2025.125796
Shuaikun Li , Yanhong Wang , Haibo Li , Hang Liu , Yun Lv , Hongcheng Lu
A novel magnetic alkaline-earth chromium fluoroiodate Ba2CrIO3F6 has been successfully synthesized via the hydrothermal method and characterized for its structure and physical properties by single crystal X-ray diffraction, attenuated total reflection (ATR) infrared spectroscopy, UV–vis–NIR spectroscopy, thermal stability, as well as magnetic susceptibility, and specific heat. The compound Ba2CrIO3F6 contains the [CrIO3F6]4- spin chains which are further separated by nonmagnetic Ba2+ cations. The magnetic susceptibility results show no long-range magnetic order down to 2 K, which are further confirmed by specific heat measurement. The positive Weiss temperature and the increase of χT-T curve at low temperature both suggest the magnetic exchange interactions through the Cr3+−IO4F–Cr3+ pathway are unexpectedly ferromagnetic. Our work illustrates that it is promising to use the [IOxFy]n– anion group for the design and construction of novel magnetic materials with ferromagnetic exchange interactions for potential spintronics device applications.
{"title":"Ba2CrIO3F6: a magnetic alkaline-earth chromium fluoroiodate with ferromagnetic exchange interactions","authors":"Shuaikun Li , Yanhong Wang , Haibo Li , Hang Liu , Yun Lv , Hongcheng Lu","doi":"10.1016/j.jssc.2025.125796","DOIUrl":"10.1016/j.jssc.2025.125796","url":null,"abstract":"<div><div>A novel magnetic alkaline-earth chromium fluoroiodate Ba<sub>2</sub>CrIO<sub>3</sub>F<sub>6</sub> has been successfully synthesized via the hydrothermal method and characterized for its structure and physical properties by single crystal X-ray diffraction, attenuated total reflection (ATR) infrared spectroscopy, UV–vis–NIR spectroscopy, thermal stability, as well as magnetic susceptibility, and specific heat. The compound Ba<sub>2</sub>CrIO<sub>3</sub>F<sub>6</sub> contains the [CrIO<sub>3</sub>F<sub>6</sub>]<sup>4-</sup> spin chains which are further separated by nonmagnetic Ba<sup>2+</sup> cations. The magnetic susceptibility results show no long-range magnetic order down to 2 K, which are further confirmed by specific heat measurement. The positive Weiss temperature and the increase of <em>χT</em>-<em>T</em> curve at low temperature both suggest the magnetic exchange interactions through the Cr<sup>3+</sup>−IO<sub>4</sub>F–Cr<sup>3+</sup> pathway are unexpectedly ferromagnetic. Our work illustrates that it is promising to use the [IO<sub><em>x</em></sub>F<sub><em>y</em></sub>]<sup><em>n<sup>–</sup></em></sup> anion group for the design and construction of novel magnetic materials with ferromagnetic exchange interactions for potential spintronics device applications.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"355 ","pages":"Article 125796"},"PeriodicalIF":3.5,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145836976","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 : 2025-12-24DOI: 10.1016/j.jssc.2025.125795
Mingming Huang , Shoushuang Li , Rui Cui , Laura C.J. Pereira , Ambre Theron , Olivier Mentré , Xiedong Cheng , Feifan Li , Hui Shao , Minfeng Lü
Two transition metal selenites Li2Mn2.5(SeO3)4 and Li2Co3(SeO3)4 were synthesized using hydrothermal and solid-state reactions, respectively. Both compounds form similar three-dimensional (3D) frameworks featuring twisted one-dimensional (1D) chains, where transition metal polyhedra connect through shared corners or edges. However, Li2Co3(SeO3)4 and Li2Mn2.5(SeO3)4 exhibit distinct structural features. The former contains one type of [4 + 2] Li, two different CoO6 octahedra, and two SeO3 pyramids. The latter possesses one type of [5 + 1] Li, one Mn3+O6 octahedron, one Mn2+O5 square-pyramid, and two SeO3 pyramids. Consequently, the lithium polyhedron undergoes unusually strong irregular distortions in the cobalt compound, but experiences strong distortions in the manganese compound. Magnetic measurements confirm that Li2Co3(SeO3)4 with a S = 3/2 uniform spin chain structure possess a long-range antiferromagnetic ordering and field-induced spin-flip transition at 2K, where the fitting via the Bonner–Fisher model with interchain mean-field corrections yields Jintra/kB = -4.32(2) K, Jinter/kB = −0.64(10) K, g = 2.34(3). Systematic distortion regularities in central metal cation polyhedra emerge from quantifying the ratio of SeO3 groups to total cation polyhedra within lithium transition metal selenites.
{"title":"Synthesis, structure and magnetic properties of two selenites, Li2Mn2.5(SeO3)4 and Li2Co3(SeO3)4 with a one-dimensional spin-chain","authors":"Mingming Huang , Shoushuang Li , Rui Cui , Laura C.J. Pereira , Ambre Theron , Olivier Mentré , Xiedong Cheng , Feifan Li , Hui Shao , Minfeng Lü","doi":"10.1016/j.jssc.2025.125795","DOIUrl":"10.1016/j.jssc.2025.125795","url":null,"abstract":"<div><div>Two transition metal selenites Li<sub>2</sub>Mn<sub>2.5</sub>(SeO<sub>3</sub>)<sub>4</sub> and Li<sub>2</sub>Co<sub>3</sub>(SeO<sub>3</sub>)<sub>4</sub> were synthesized using hydrothermal and solid-state reactions, respectively. Both compounds form similar three-dimensional (3D) frameworks featuring twisted one-dimensional (1D) chains, where transition metal polyhedra connect through shared corners or edges. However, Li<sub>2</sub>Co<sub>3</sub>(SeO<sub>3</sub>)<sub>4</sub> and Li<sub>2</sub>Mn<sub>2.5</sub>(SeO<sub>3</sub>)<sub>4</sub> exhibit distinct structural features. The former contains one type of [4 + 2] Li, two different CoO<sub>6</sub> octahedra, and two SeO<sub>3</sub> pyramids. The latter possesses one type of [5 + 1] Li, one Mn<sup>3+</sup>O<sub>6</sub> octahedron, one Mn<sup>2+</sup>O<sub>5</sub> square-pyramid, and two SeO<sub>3</sub> pyramids. Consequently, the lithium polyhedron undergoes unusually strong irregular distortions in the cobalt compound, but experiences strong distortions in the manganese compound. Magnetic measurements confirm that Li<sub>2</sub>Co<sub>3</sub>(SeO<sub>3</sub>)<sub>4</sub> with a <em>S</em> = 3/2 uniform spin chain structure possess a long-range antiferromagnetic ordering and field-induced spin-flip transition at 2K, where the fitting via the Bonner–Fisher model with interchain mean-field corrections yields <em>J</em><sub>intra</sub><em>/k</em><sub>B</sub> = -4.32(2) K, <em>J</em><sub>inter</sub><em>/k</em><sub>B</sub> = −0.64(10) K, <em>g</em> = 2.34(3). Systematic distortion regularities in central metal cation polyhedra emerge from quantifying the ratio of SeO<sub>3</sub> groups to total cation polyhedra within lithium transition metal selenites.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"355 ","pages":"Article 125795"},"PeriodicalIF":3.5,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145836963","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The tris(β-keto-hydrazo)-cyclohexane-based porous organic polymers (the TKH-POPs) are a novel type of POPs that can be prepared in 0–5 °C aqueous solution through simple diazo-coupling isomerization reaction. Their synthetic strategy is mild and green, without metal catalyst and high temperature. Nevertheless, there are only a few reports about their application as fluorescent sensors to date. In this study, using anhydrous phloroglucinol, 4,4′-ethylenedianiline, and 4,4′-azodianiline as the aromatic building blocks, we successfully synthesized two novel TKH-POPs ——PEDAN and PHZDA. Spectroscopic analysis proved that their structures are tris(β-keto-hydrazo)-cyclohexane tautomers instead of the azo tautomerides. PEDAN and PHZDA have large BET specific areas of 1441 and 957 m2 g−1 and can sense 2,4-dinitrophenol (DNP) with high sensitivity by fluorescence. The quenching constants (KSV) of PEDAN and PHZDA for DNP are severally 3.40 × 104 and 9.13 × 104 L mol−1. The fluorescent quenching mechanisms of PEDAN and PHZDA by DNP comprise photo-induced electron-transfer process, resonance energy transfer process, absorption competition quenching mechanism, inter filtration effect, and hydrogen bonding interactions.
{"title":"Green synthesis of the tris(β-keto-hydrazo)-cyclohexane-based porous organic polymers applied for fluorescence sensing 2,4-dinitrophenol","authors":"Tong-Mou Geng, Yun-Long Gui, Heng Xu, Yuan-Yuan Jiao","doi":"10.1016/j.jssc.2025.125788","DOIUrl":"10.1016/j.jssc.2025.125788","url":null,"abstract":"<div><div>The tris(β-keto-hydrazo)-cyclohexane-based porous organic polymers (the TKH-POPs) are a novel type of POPs that can be prepared in 0–5 °C aqueous solution through simple diazo-coupling isomerization reaction. Their synthetic strategy is mild and green, without metal catalyst and high temperature. Nevertheless, there are only a few reports about their application as fluorescent sensors to date. In this study, using anhydrous phloroglucinol, 4,4′-ethylenedianiline, and 4,4′-azodianiline as the aromatic building blocks, we successfully synthesized two novel TKH-POPs ——PEDAN and PHZDA. Spectroscopic analysis proved that their structures are tris(β-keto-hydrazo)-cyclohexane tautomers instead of the azo tautomerides. PEDAN and PHZDA have large BET specific areas of 1441 and 957 m<sup>2</sup> g<strong><sup>−</sup></strong><sup>1</sup> and can sense 2,4-dinitrophenol (DNP) with high sensitivity by fluorescence. The quenching constants (K<sub>SV</sub>) of PEDAN and PHZDA for DNP are severally 3.40 × 10<sup>4</sup> and 9.13 × 10<sup>4</sup> L mol<sup>−1</sup>. The fluorescent quenching mechanisms of PEDAN and PHZDA by DNP comprise photo-induced electron-transfer process, resonance energy transfer process, absorption competition quenching mechanism, inter filtration effect, and hydrogen bonding interactions.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"355 ","pages":"Article 125788"},"PeriodicalIF":3.5,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145836971","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}
Orange-red KLa(WO4)2 phosphors co-doped with Sm3+-Gd3+ were synthesized via high-temperature solid-state reaction. Phase purity and crystal structure were confirmed by XRD, while SEM revealed non-uniform particle distribution. XPS verified elemental composition and suggested the chemical states of dopants. Under 403 nm excitation, KLa(WO4)2: Sm3+ exhibited intense orange–red emissions, dominated by the 4G5/2 - 6Hᵢ (i = 5/2, 7/2, 9/2, 11/2) transition from 500 to 750 nm. Substitution by Gd3+ lowers the local symmetry, as evidenced by the increased asymmetry ratio, resulting in a 1.88-fold increase in emission intensity. Notably, the optimized phosphor, KLa0.8Gd0.15(WO4)2:0.05Sm3+, exhibits a high color purity (CP) of 99 % and excellent thermal stability retaining 85 % of its room-temperature emission intensity at 423K. When combined with a 405 nm InGaN chip, the fabricated LED displayed strong spectral overlap with chlorophyll and phytochrome absorption peaks, confirming its potential for plant-growth illumination.
{"title":"Sm3+ -activated KLa(WO4)2 phosphors with Gd3+ Co-doping: Orange-Red emission and thermal stability toward potential plant lighting applications","authors":"Lanwei Qiu , Haochang Ye , Guangting Xiong , Wei Zhang , Yirong Huang , Qiuzhi Liang , Canhui Pan , Jinquan Chen , Zuyong Feng","doi":"10.1016/j.jssc.2025.125784","DOIUrl":"10.1016/j.jssc.2025.125784","url":null,"abstract":"<div><div>Orange-red KLa(WO<sub>4</sub>)<sub>2</sub> phosphors co-doped with Sm<sup>3+</sup>-Gd<sup>3+</sup> were synthesized via high-temperature solid-state reaction. Phase purity and crystal structure were confirmed by XRD, while SEM revealed non-uniform particle distribution. XPS verified elemental composition and suggested the chemical states of dopants. Under 403 nm excitation, KLa(WO<sub>4</sub>)<sub>2</sub>: Sm<sup>3+</sup> exhibited intense orange–red emissions, dominated by the <sup>4</sup>G<sub>5/2</sub> - <sup>6</sup>Hᵢ (i = 5/2, 7/2, 9/2, 11/2) transition from 500 to 750 nm. Substitution by Gd<sup>3+</sup> lowers the local symmetry, as evidenced by the increased asymmetry ratio, resulting in a 1.88-fold increase in emission intensity. Notably, the optimized phosphor, KLa<sub>0.8</sub>Gd<sub>0.15</sub>(WO<sub>4</sub>)<sub>2</sub>:0.05Sm<sup>3+</sup>, exhibits a high color purity (CP) of 99 % and excellent thermal stability retaining 85 % of its room-temperature emission intensity at 423K. When combined with a 405 nm InGaN chip, the fabricated LED displayed strong spectral overlap with chlorophyll and phytochrome absorption peaks, confirming its potential for plant-growth illumination.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"355 ","pages":"Article 125784"},"PeriodicalIF":3.5,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145836975","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 : 2025-12-23DOI: 10.1016/j.jssc.2025.125792
Aïcha Mbarek
A new cadmium sodium ortho-pyrophosphate, Na2.48Cd4.15(P2O7)2PO4, was successfully synthesized and characterized using single-crystal X-ray diffraction, infrared (IR), Raman, and solid-state NMR spectroscopy. The compound crystallizes in the triclinic system, space group P1, with the following unit cell parameters: a = 6.7262(1) Å, b = 9.6660(2) Å, c = 11.5040(2) Å, α = 98.262(1)°, β = 92.165(1)°, γ = 90.583(1)°, and V = 739.55(2) Å3. The crystal structure consists of NaO6, NaO7, and CdO6 polyhedra connected through corners and edges with isolated PO43− tetrahedra and P2O74− pyrophosphate groups, forming a layered framework parallel to the ab plane. Partial cationic substitution between Cd2+ and Na+ was confirmed by crystallographic analysis. IR and Raman spectra exhibit characteristic vibrational modes of both PO43− and P2O74− units. Upon UV excitation, Eu3+-doped samples show intense orange-red photoluminescence, mainly arising from the 5D0 → 7F2 transition at 609 nm. The emission profile indicates that Eu3+ ions occupy a single low-symmetry site, which is corroborated by the presence of one line in the 5D0 → 7F0 transition and three lines in the 5D0 → 7F1 transition. These results show that Na2.48Cd4.15(P2O7)2PO4 is a good host for rare-earth doping, thanks to its stability, flexible structure, and strong luminescence, making it useful for phosphors, lasers, and optoelectronic devices.
{"title":"A new non-stoichiometric orthopyrophosphate Na2.48Cd4.15(P2O7)2(PO4): Crystal structure, defect chemistry and Eu3+-activated luminescence","authors":"Aïcha Mbarek","doi":"10.1016/j.jssc.2025.125792","DOIUrl":"10.1016/j.jssc.2025.125792","url":null,"abstract":"<div><div>A new cadmium sodium <em>ortho</em>-pyrophosphate, Na<sub>2</sub>.<sub>48</sub>Cd<sub>4</sub>.<sub>15</sub>(P<sub>2</sub>O<sub>7</sub>)<sub>2</sub>PO<sub>4</sub>, was successfully synthesized and characterized using single-crystal X-ray diffraction, infrared (IR), Raman, and solid-state NMR spectroscopy. The compound crystallizes in the triclinic system, space group <em>P1</em>, with the following unit cell parameters: <em>a</em> = 6.7262(1) Å, <em>b</em> = 9.6660(2) Å, <em>c</em> = 11.5040(2) Å, α = 98.262(1)°, β = 92.165(1)°, γ = 90.583(1)°, and <em>V</em> = 739.55(2) Å<sup>3</sup>. The crystal structure consists of NaO<sub>6</sub>, NaO<sub>7</sub>, and CdO<sub>6</sub> polyhedra connected through corners and edges with isolated PO<sub>4</sub><sup>3−</sup> tetrahedra and P<sub>2</sub>O<sub>7</sub><sup>4−</sup> pyrophosphate groups, forming a layered framework parallel to the ab plane. Partial cationic substitution between Cd<sup>2+</sup> and Na<sup>+</sup> was confirmed by crystallographic analysis. IR and Raman spectra exhibit characteristic vibrational modes of both PO<sub>4</sub><sup>3−</sup> and P<sub>2</sub>O<sub>7</sub><sup>4−</sup> units. Upon UV excitation, Eu<sup>3+</sup>-doped samples show intense orange-red photoluminescence, mainly arising from the <sup>5</sup>D<sub>0</sub> → <sup>7</sup>F<sub>2</sub> transition at 609 nm. The emission profile indicates that Eu<sup>3+</sup> ions occupy a single low-symmetry site, which is corroborated by the presence of one line in the <sup>5</sup>D<sub>0</sub> → <sup>7</sup>F<sub>0</sub> transition and three lines in the <sup>5</sup>D<sub>0</sub> → <sup>7</sup>F<sub>1</sub> transition. These results show that Na<sub>2</sub>.<sub>48</sub>Cd<sub>4</sub>.<sub>15</sub>(P<sub>2</sub>O<sub>7</sub>)<sub>2</sub>PO<sub>4</sub> is a good host for rare-earth doping, thanks to its stability, flexible structure, and strong luminescence, making it useful for phosphors, lasers, and optoelectronic devices.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"356 ","pages":"Article 125792"},"PeriodicalIF":3.5,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145940143","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 : 2025-12-23DOI: 10.1016/j.jssc.2025.125794
Thamer Adnan Abdullah , Alyaa H. Abdalsalam , Ali A. Ati , Rashed T. Rasheed , Sarmad Al–Anssari , Oday I. Abdullah , Mukhtar Ali Hussein , Mais A. Mohammed , Karol Kułacz , Phuoc-Cuong Le
Heavy metal pollution, particularly lead (Pb2+), poses a significant threat to the environment and human health. In this study, it was synthesized and analyzed a unique nanocomposite by preparing cadmium-cobalt in specific ratios with ferrite nanoparticles on a polymer. This resulted in the nanocomposite (Co0·2Cd0·8Fe2O4/PANi–g–Chitosan), which was used to remove lead ions efficiently. The nanocomposite consists of cobalt and cadmium ferrite nanoparticles with a chitosan and polyaniline polymer matrix, which was synthesized chemically. This novel nanocomposite exhibits exceptional removal efficiency, demonstrating remarkable performance. The properties of the nanocomposite were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and UV–Vis spectroscopy. These tests confirmed the successful fabrication and structural integrity of the nanocomposite. The nanocomposite exhibited high adsorption and purification efficiency, achieving 97.8 % removal of lead ions at pH 5. The adsorption behavior was investigated by studying the reaction kinetics (using a pseudo-second-order reaction model) and analyzing the adsorption curve, providing valuable insights into the reaction mechanisms. Notably, the Taguchi method was employed to optimize the adsorption parameters. This analysis revealed that adsorption time and pH value are significant factors. The optimal conditions were: contact time of 90 min, a pH of 5, and a shaking speed of 200 rpm, based on Taguchi results. The removal of lead ions using this nanocomposite revealed great potential as an effective nanocomposite for purifying water.
重金属污染，特别是铅（Pb2+），对环境和人类健康构成重大威胁。在本研究中，通过在聚合物上制备特定比例的镉钴和铁氧体纳米颗粒，合成并分析了一种独特的纳米复合材料。制备了Co0·2Cd0·8Fe2O4/聚苯胺- g -壳聚糖纳米复合材料，用于高效去除铅离子。采用化学方法合成了以壳聚糖和聚苯胺为基体的钴和镉铁氧体纳米复合材料。这种新型纳米复合材料具有优异的去除效率，表现出卓越的性能。采用x射线衍射（XRD）、扫描电镜（SEM）、傅里叶变换红外光谱（FTIR）和紫外可见光谱（UV-Vis）对纳米复合材料的性能进行了研究。这些测试证实了纳米复合材料的成功制造和结构完整性。在pH为5的条件下，该纳米复合材料对铅离子的去除率达到97.8%。通过研究反应动力学（采用拟二级反应模型）和分析吸附曲线来研究吸附行为，为研究反应机理提供了有价值的见解。值得注意的是，采用田口法优化吸附参数。结果表明，吸附时间和pH值是影响吸附效果的重要因素。根据田口结果，最佳条件为：接触时间90 min， pH = 5，震动速度200 rpm。利用该纳米复合材料去除铅离子显示出作为一种有效的净水纳米复合材料的巨大潜力。
{"title":"Novel CoCdFe2O4/Chitosan–PANi ternary nanocomposite for High-Efficiency Lead Removal","authors":"Thamer Adnan Abdullah , Alyaa H. Abdalsalam , Ali A. Ati , Rashed T. Rasheed , Sarmad Al–Anssari , Oday I. Abdullah , Mukhtar Ali Hussein , Mais A. Mohammed , Karol Kułacz , Phuoc-Cuong Le","doi":"10.1016/j.jssc.2025.125794","DOIUrl":"10.1016/j.jssc.2025.125794","url":null,"abstract":"<div><div>Heavy metal pollution, particularly lead (Pb<sup>2+</sup>), poses a significant threat to the environment and human health. In this study, it was synthesized and analyzed a unique nanocomposite by preparing cadmium-cobalt in specific ratios with ferrite nanoparticles on a polymer. This resulted in the nanocomposite (Co<sub>0·2</sub>Cd<sub>0·8</sub>Fe<sub>2</sub>O<sub>4</sub>/PANi–g–Chitosan), which was used to remove lead ions efficiently. The nanocomposite consists of cobalt and cadmium ferrite nanoparticles with a chitosan and polyaniline polymer matrix, which was synthesized chemically. This novel nanocomposite exhibits exceptional removal efficiency, demonstrating remarkable performance. The properties of the nanocomposite were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and UV–Vis spectroscopy. These tests confirmed the successful fabrication and structural integrity of the nanocomposite. The nanocomposite exhibited high adsorption and purification efficiency, achieving 97.8 % removal of lead ions at pH 5. The adsorption behavior was investigated by studying the reaction kinetics (using a pseudo-second-order reaction model) and analyzing the adsorption curve, providing valuable insights into the reaction mechanisms. Notably, the Taguchi method was employed to optimize the adsorption parameters. This analysis revealed that adsorption time and pH value are significant factors. The optimal conditions were: contact time of 90 min, a pH of 5, and a shaking speed of 200 rpm, based on Taguchi results. The removal of lead ions using this nanocomposite revealed great potential as an effective nanocomposite for purifying water.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"355 ","pages":"Article 125794"},"PeriodicalIF":3.5,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880318","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}
With the growing demand for clean and sustainable energy, efficient and eco-friendly power sources are more crucial than ever. Solar energy, though abundant and renewable, remains underutilized due to limitations in current photovoltaic technologies. Overcoming these limitations calls for innovative semiconductors that can exceed conventional efficiency limits. Defect chalcopyrite semiconductors, particularly ZnGaS have emerged as strong candidate for next-generation intermediate band solar cells (IBSCs). In this study, we employ density functional theory (DFT) to investigate the effects of transition metal (TM) substitutions (Mn, Fe, Co, and Ni) on the structural, electronic and mechanical properties of ZnGaS. Our results show that TM substitution introduces intermediate band (IB) states within the bandgap. Specifically, Co substitution exhibits well-isolated IB states, making it the most promising candidate for IBSC applications. The structural analysis indicates that TM incorporation modifies lattice parameters, with Mn causing unit cell expansion while Fe, Co, and Ni induce lattice contraction. Mechanical stability is confirmed through Born criteria and all of these TM-substituted compounds are found to be ductile in nature. Thermodynamic stability is evaluated via cohesive and formation energy calculations, where Mn-substituted ZnGaS demonstrates the strongest bonding. Additionally, melting temperature analysis indicates ZnNiGaS has the highest thermal stability (1212.387 K), whereas, ZnMnGaS has the lowest (892.856 K). These findings highlight the potential of Co-substituted ZnGaS for next-generation photovoltaic applications.
{"title":"Role of transition metal substitution in ZnGa2S4 for intermediate band solar cells: A DFT-driven route toward sustainable energy applications","authors":"Sambit Jena , Aiswarya Priyambada , Singdha Sagarika Behera , Priyadarshini Parida","doi":"10.1016/j.jssc.2025.125791","DOIUrl":"10.1016/j.jssc.2025.125791","url":null,"abstract":"<div><div>With the growing demand for clean and sustainable energy, efficient and eco-friendly power sources are more crucial than ever. Solar energy, though abundant and renewable, remains underutilized due to limitations in current photovoltaic technologies. Overcoming these limitations calls for innovative semiconductors that can exceed conventional efficiency limits. Defect chalcopyrite semiconductors, particularly ZnGa<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>S<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span> have emerged as strong candidate for next-generation intermediate band solar cells (IBSCs). In this study, we employ density functional theory (DFT) to investigate the effects of transition metal (TM) substitutions (Mn, Fe, Co, and Ni) on the structural, electronic and mechanical properties of ZnGa<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>S<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span>. Our results show that TM substitution introduces intermediate band (IB) states within the bandgap. Specifically, Co substitution exhibits well-isolated IB states, making it the most promising candidate for IBSC applications. The structural analysis indicates that TM incorporation modifies lattice parameters, with Mn causing unit cell expansion while Fe, Co, and Ni induce lattice contraction. Mechanical stability is confirmed through Born criteria and all of these TM-substituted compounds are found to be ductile in nature. Thermodynamic stability is evaluated via cohesive and formation energy calculations, where Mn-substituted ZnGa<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>S<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span> demonstrates the strongest bonding. Additionally, melting temperature analysis indicates ZnNiGa<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>S<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span> has the highest thermal stability (1212.387 K), whereas, ZnMnGa<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>S<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span> has the lowest (892.856 K). These findings highlight the potential of Co-substituted ZnGa<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>S<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span> for next-generation photovoltaic applications.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"356 ","pages":"Article 125791"},"PeriodicalIF":3.5,"publicationDate":"2025-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145876900","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.2025.125789
Fadhil F. Sead , Rafid Kamal Jameel , Ahmed Aldulaimi , Rekha M M , Subhashree Ray , Kattela Chennakesavulu , Renu Sharma , Aashna Sinha , Rafid Jihad Albadr , Mariem Alwan , Aseel Smerat
The rational design of multi-component heterostructures is an effective route to overcome the limitations of pristine metal–organic frameworks (MOFs) in photocatalytic hydrogen evolution. In this work, a naphthalene-functionalized UiO-67 MOF was integrated with graphene oxide (GO) through a one-pot solvothermal method to obtain a UiO-67-naph/GO hybrid photocatalyst. This study introduces a dual-modification strategy that simultaneously tunes the electronic structure of UiO-67 at the molecular level via π-extended naphthalene linkers and enhances interfacial charge transport through conductive GO sheets—representing the first synergistic design of its kind for UiO-based hydrogen evolution systems. Structural analyses confirmed that GO incorporation preserved MOF crystallinity while enhancing conductivity and interfacial charge transport. Optical and photoelectrochemical studies demonstrated extended visible-light absorption, reduced photoluminescence, lower charge-transfer resistance, and stronger photocurrent compared to pristine UiO-67-naph. Under visible-light irradiation (λ > 420 nm), UiO-67-naph/GO achieved a hydrogen evolution rate of 2897.6 μmol g−1 h−1 and the total hydrogen produced (347.7 μmol) over 4 h, far exceeding UiO-67-naph, UiO-67-NH2, and GO alone. Operational studies revealed maximum performance near neutral pH, at an optimal catalyst dosage of ∼30 mg, and temperatures of 25–30 °C. The composite also exhibited excellent stability and reusability. Mechanistic investigations supported a direct Z-scheme heterojunction, where recombination of intermediate carriers preserved highly reducing electrons on GO (−0.9 V) and oxidizing holes on UiO-67-naph (+1.8 V), ensuring strong redox potentials and efficient charge separation. This work highlights the synergistic role of π-conjugated linkers and GO in tailoring MOF-based photocatalysts for sustainable solar hydrogen production.
{"title":"Dual modification of UiO-67 by graphene oxide and naphthalene: A synergistic strategy toward efficient photocatalytic hydrogen evolution","authors":"Fadhil F. Sead , Rafid Kamal Jameel , Ahmed Aldulaimi , Rekha M M , Subhashree Ray , Kattela Chennakesavulu , Renu Sharma , Aashna Sinha , Rafid Jihad Albadr , Mariem Alwan , Aseel Smerat","doi":"10.1016/j.jssc.2025.125789","DOIUrl":"10.1016/j.jssc.2025.125789","url":null,"abstract":"<div><div>The rational design of multi-component heterostructures is an effective route to overcome the limitations of pristine metal–organic frameworks (MOFs) in photocatalytic hydrogen evolution. In this work, a naphthalene-functionalized UiO-67 MOF was integrated with graphene oxide (GO) through a one-pot solvothermal method to obtain a UiO-67-naph/GO hybrid photocatalyst. This study introduces a dual-modification strategy that simultaneously tunes the electronic structure of UiO-67 at the molecular level via π-extended naphthalene linkers and enhances interfacial charge transport through conductive GO sheets—representing the first synergistic design of its kind for UiO-based hydrogen evolution systems. Structural analyses confirmed that GO incorporation preserved MOF crystallinity while enhancing conductivity and interfacial charge transport. Optical and photoelectrochemical studies demonstrated extended visible-light absorption, reduced photoluminescence, lower charge-transfer resistance, and stronger photocurrent compared to pristine UiO-67-naph. Under visible-light irradiation (λ > 420 nm), UiO-67-naph/GO achieved a hydrogen evolution rate of 2897.6 μmol g<sup>−1</sup> h<sup>−1</sup> and the total hydrogen produced (347.7 μmol) over 4 h, far exceeding UiO-67-naph, UiO-67-NH<sub>2</sub>, and GO alone. Operational studies revealed maximum performance near neutral pH, at an optimal catalyst dosage of ∼30 mg, and temperatures of 25–30 °C. The composite also exhibited excellent stability and reusability. Mechanistic investigations supported a direct Z-scheme heterojunction, where recombination of intermediate carriers preserved highly reducing electrons on GO (−0.9 V) and oxidizing holes on UiO-67-naph (+1.8 V), ensuring strong redox potentials and efficient charge separation. This work highlights the synergistic role of π-conjugated linkers and GO in tailoring MOF-based photocatalysts for sustainable solar hydrogen production.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"355 ","pages":"Article 125789"},"PeriodicalIF":3.5,"publicationDate":"2025-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145836977","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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