Pub Date : 2025-04-23DOI: 10.1021/acs.inorgchem.5c01287
Zhining Yuan, Yehong Wan, Ling Zhang, Ke Jiang
Chemodynamic therapy (CDT), which regulates oxidative stress in tumor tissues, has emerged as a promising alternative. However, the efficiency of MOF-based Fenton catalysts for CDT still needs improvement. This study presents a strategy to improve the Fenton catalytic performance of ZnCo-ZIF by depositing Au nanoparticles on its surface. Monodisperse ZnCo-ZIF particles (≤200 nm) were prepared by optimizing the Zn/Co ratio, and Au deposition enhanced electron transfer between Au and Co, increasing the charge density around Co atoms. This resulted in a 2.28-fold improvement in Fenton activity under acidic conditions and mild near-infrared (NIR) light. Loading the system with the natural product naringin (NA) molecule further demonstrated synergistic anticancer effects in vitro. This work offers insights into enhancing MOF-based catalysts for cancer therapy.
{"title":"Au Deposition Enhanced Fenton-like Chemistry within a Metal–Organic Framework","authors":"Zhining Yuan, Yehong Wan, Ling Zhang, Ke Jiang","doi":"10.1021/acs.inorgchem.5c01287","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01287","url":null,"abstract":"Chemodynamic therapy (CDT), which regulates oxidative stress in tumor tissues, has emerged as a promising alternative. However, the efficiency of MOF-based Fenton catalysts for CDT still needs improvement. This study presents a strategy to improve the Fenton catalytic performance of ZnCo-ZIF by depositing Au nanoparticles on its surface. Monodisperse ZnCo-ZIF particles (≤200 nm) were prepared by optimizing the Zn/Co ratio, and Au deposition enhanced electron transfer between Au and Co, increasing the charge density around Co atoms. This resulted in a 2.28-fold improvement in Fenton activity under acidic conditions and mild near-infrared (NIR) light. Loading the system with the natural product naringin (NA) molecule further demonstrated synergistic anticancer effects in vitro. This work offers insights into enhancing MOF-based catalysts for cancer therapy.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"91 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866460","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-23DOI: 10.1021/acs.inorgchem.5c00618
Michelle P Duarte, Clara V. Diniz, Hudson A. Bicalho, Rafik Naccache, Ashlee J. Howarth
CAU-28 (CAU = Christian-Albrechts-University) is a zirconium-based metal–organic framework (MOF) that features a bio-renewable linker (furan-2,5-dicarboxylic acid) and can be obtained through a green synthesis. In this work, we report an optimized synthesis of CAU-28, substantially enhancing the yield from 2 to 53 %. Moreover, taking advantage of the high thermal and chemical stability of CAU-28 as well as the MOF’s surface area (> 1000 m2 g–1), porosity, and four open metal sites per Zr6-cluster, we have demonstrated the high potential of CAU-28 as a green catalyst to produce biodiesel through esterification reactions. Under optimized catalytic conditions, CAU-28 is able to convert oleic acid to its fatty acid methyl ester counterpart with high selectivity, using a catalyst loading of only 5 wt % and 1:24 molar ratio of oleic acid:methanol, at 90 °C for 90 min. Furthermore, the catalyst also shows high stability, maintaining its activity for three reaction cycles.
{"title":"A Zirconium-Based Metal–Organic Framework as an Effective Green Catalyst for the Synthesis of Biodiesel","authors":"Michelle P Duarte, Clara V. Diniz, Hudson A. Bicalho, Rafik Naccache, Ashlee J. Howarth","doi":"10.1021/acs.inorgchem.5c00618","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00618","url":null,"abstract":"CAU-28 (CAU = Christian-Albrechts-University) is a zirconium-based metal–organic framework (MOF) that features a bio-renewable linker (furan-2,5-dicarboxylic acid) and can be obtained through a green synthesis. In this work, we report an optimized synthesis of CAU-28, substantially enhancing the yield from 2 to 53 %. Moreover, taking advantage of the high thermal and chemical stability of CAU-28 as well as the MOF’s surface area (> 1000 m<sup>2</sup> g<sup>–1</sup>), porosity, and four open metal sites per Zr<sub>6</sub>-cluster, we have demonstrated the high potential of CAU-28 as a green catalyst to produce biodiesel through esterification reactions. Under optimized catalytic conditions, CAU-28 is able to convert oleic acid to its fatty acid methyl ester counterpart with high selectivity, using a catalyst loading of only 5 wt % and 1:24 molar ratio of oleic acid:methanol, at 90 °C for 90 min. Furthermore, the catalyst also shows high stability, maintaining its activity for three reaction cycles.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"5 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866418","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-23DOI: 10.1021/acs.inorgchem.5c00130
Yu-Chia Su, Li Chu Tseng, Wei-Tao Peng, Chao-Ping Hsu, Yi-Cheun Yeh
Integrating luminescent nanomaterials into hydrogels provides unique optical properties and improves their mechanical features for various applications. It is challenging but highly desirable to develop a versatile luminescent nanocomposite hydrogel system with tunable structures and properties to expand the potential uses of luminescent materials. Here, multiple amine-functionalized lanthanide-containing hydroxyapatites are synthesized as tailored nanomaterial cross-linkers to interact with polydextran aldehyde through imine bonds. The microstructure, gelation time, luminescence, rheological behavior, mechanical properties, thermal stability, degradation, and swelling capability of the luminescent lanthanide-containing nanocomposite hydrogels are systematically investigated. This study reveals that the strong binding affinity between surface metal ions and capping ligands of the nanomaterial cross-linkers contributes to the densest network and the highest mechanical properties of the nanocomposite hydrogels. In addition, these nanocomposite hydrogels possess dynamic features of self-healing, shear-thinning, and injectability, improving their suitability for advanced applications. The luminescent lanthanide-containing nanocomposite lyophilized hydrogels are also demonstrated in the differentiation of volatile organic compounds. Taken together, the adjustable microstructures and characteristics of this lanthanide-containing nanocomposite hydrogel system highlight its potential for offering guidance in producing diverse luminescent materials with definable performances across various fields.
{"title":"Tailoring Nanomaterial Cross-Linkers through Lanthanide–Ligand Pairs: Guidance for Fine-Tuning the Structures and Properties of Luminescent Nanocomposite Hydrogels","authors":"Yu-Chia Su, Li Chu Tseng, Wei-Tao Peng, Chao-Ping Hsu, Yi-Cheun Yeh","doi":"10.1021/acs.inorgchem.5c00130","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00130","url":null,"abstract":"Integrating luminescent nanomaterials into hydrogels provides unique optical properties and improves their mechanical features for various applications. It is challenging but highly desirable to develop a versatile luminescent nanocomposite hydrogel system with tunable structures and properties to expand the potential uses of luminescent materials. Here, multiple amine-functionalized lanthanide-containing hydroxyapatites are synthesized as tailored nanomaterial cross-linkers to interact with polydextran aldehyde through imine bonds. The microstructure, gelation time, luminescence, rheological behavior, mechanical properties, thermal stability, degradation, and swelling capability of the luminescent lanthanide-containing nanocomposite hydrogels are systematically investigated. This study reveals that the strong binding affinity between surface metal ions and capping ligands of the nanomaterial cross-linkers contributes to the densest network and the highest mechanical properties of the nanocomposite hydrogels. In addition, these nanocomposite hydrogels possess dynamic features of self-healing, shear-thinning, and injectability, improving their suitability for advanced applications. The luminescent lanthanide-containing nanocomposite lyophilized hydrogels are also demonstrated in the differentiation of volatile organic compounds. Taken together, the adjustable microstructures and characteristics of this lanthanide-containing nanocomposite hydrogel system highlight its potential for offering guidance in producing diverse luminescent materials with definable performances across various fields.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"47 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866459","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In this work, Dy(NO3)3·6H2O and o-vanillin reacted under “one-pot” conditions, achieving for the first time four efficient condensations of o-vanillin and obtaining a pair of chiral hexanuclear clusters R/S-Dy6. The four Dy(III) ions in the structure of R/S-Dy6 are arranged in a planar quadrilateral with a Dy(III) ion derived from each of the upper and lower ends, forming a shape similar to a “chair”. The complex chiral ligands H4LR1 and H4LS1 were obtained from simple o-vanillin through a multistep tandem reaction. Their formation process involved a series of reaction steps, including a free radical coupling reaction to form pinacol and an in situ tandem reaction of pinacol and o-vanillin. Magnetic studies show that the Dy(III) ions in R/S-Dy6 have magnetic anisotropy and/or low excited states. In addition, R/S-Dy6 has an outstanding ability to produce reactive oxygen species under low-power light irradiation and shows excellent photodynamic sterilization. The inhibition zones against Escherichia coli are about 2.09 and 2.99 cm, and the inhibition zones against Staphylococcus aureus are about 2.51 and 2.93 cm, respectively. This work not only provides a vivid example for the synthesis of complex chiral organic products but also promotes the progress of lanthanide clusters’ crystal engineering.
{"title":"In Situ Coordination-Catalyzed o-Vanillin Underwent a One-Pot Tandem Reaction to Construct Complex Chiral Tetrameric Isomer-Based Hexanuclear Clusters","authors":"Ru-Yan Li, Ju-Fen Ai, Jia-Yi Tao, Zhong-Hong Zhu, Hua-Hong Zou, Hai-Ling Wang","doi":"10.1021/acs.inorgchem.5c00046","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00046","url":null,"abstract":"In this work, Dy(NO<sub>3</sub>)<sub>3</sub>·6H<sub>2</sub>O and <i>o</i>-vanillin reacted under “one-pot” conditions, achieving for the first time four efficient condensations of <i>o</i>-vanillin and obtaining a pair of chiral hexanuclear clusters <i>R</i>/<i>S</i>-<b>Dy</b><sub><b>6</b></sub>. The four Dy(III) ions in the structure of <i>R</i>/<i>S</i>-<b>Dy</b><sub><b>6</b></sub> are arranged in a planar quadrilateral with a Dy(III) ion derived from each of the upper and lower ends, forming a shape similar to a “chair”. The complex chiral ligands H<sub>4</sub>L<sub>R</sub><sup>1</sup> and H<sub>4</sub>L<sub>S</sub><sup>1</sup> were obtained from simple <i>o</i>-vanillin through a multistep tandem reaction. Their formation process involved a series of reaction steps, including a free radical coupling reaction to form pinacol and an in situ tandem reaction of pinacol and <i>o</i>-vanillin. Magnetic studies show that the Dy(III) ions in <i>R</i>/<i>S</i>-<b>Dy</b><sub><b>6</b></sub> have magnetic anisotropy and/or low excited states. In addition, <i>R</i>/<i>S</i>-<b>Dy</b><sub><b>6</b></sub> has an outstanding ability to produce reactive oxygen species under low-power light irradiation and shows excellent photodynamic sterilization. The inhibition zones against <i>Escherichia coli</i> are about 2.09 and 2.99 cm, and the inhibition zones against <i>Staphylococcus aureus</i> are about 2.51 and 2.93 cm, respectively. This work not only provides a vivid example for the synthesis of complex chiral organic products but also promotes the progress of lanthanide clusters’ crystal engineering.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"18 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862246","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-23DOI: 10.1021/acs.inorgchem.5c00461
Marina V. Kirillova, Adrián Pastor, Alexander M. Kirillov
Layered double hydroxides (LDHs) represent a promising class of inexpensive and tunable inorganic materials with growing applications in diverse areas. In this study, we applied an aqueous miscible organic solvent treatment (AMOST) to prepare a novel series of highly dispersed LDHs containing up to four different metal centers (Mg, Cu, Al, and Fe). These AMO-LDHs were fully characterized and employed as precatalysts for the mild oxidative functionalization of cyclic and gaseous alkanes with aqueous H2O2 to give the corresponding alcohols, ketones, and carboxylic acids. Cyclohexane and propane were used as model substrates. The oxidation reactions, occurring under mild conditions (30–50 °C), demonstrated good efficiency with total product yields up to 40% and catalyst turnover numbers up to 370 when using a tetra-heterometallic AMO-LDH precatalyst (AMO-MgCuAlFe). Its enhanced catalytic activity is likely associated with the synergic effect of different metal centers (Cu, Fe, and Al─all having a recognized function in oxidation catalysis). Substrate scope, selectivity, and the influence of the reaction parameters were also investigated. This work offers a novel, easy, and more sustainable path to advance the application of AMO-LDHs in oxidation catalysis, opening up the use of this type of catalytic systems in the mild oxidation of alkanes.
{"title":"Multimetal Layered Double Hydroxides: Synthesis, Characterization, and Synergic Effect in Mild Catalytic Oxidation of Alkanes","authors":"Marina V. Kirillova, Adrián Pastor, Alexander M. Kirillov","doi":"10.1021/acs.inorgchem.5c00461","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00461","url":null,"abstract":"Layered double hydroxides (LDHs) represent a promising class of inexpensive and tunable inorganic materials with growing applications in diverse areas. In this study, we applied an aqueous miscible organic solvent treatment (AMOST) to prepare a novel series of highly dispersed LDHs containing up to four different metal centers (Mg, Cu, Al, and Fe). These AMO-LDHs were fully characterized and employed as precatalysts for the mild oxidative functionalization of cyclic and gaseous alkanes with aqueous H<sub>2</sub>O<sub>2</sub> to give the corresponding alcohols, ketones, and carboxylic acids. Cyclohexane and propane were used as model substrates. The oxidation reactions, occurring under mild conditions (30–50 °C), demonstrated good efficiency with total product yields up to 40% and catalyst turnover numbers up to 370 when using a tetra-heterometallic AMO-LDH precatalyst (AMO-MgCuAlFe). Its enhanced catalytic activity is likely associated with the synergic effect of different metal centers (Cu, Fe, and Al─all having a recognized function in oxidation catalysis). Substrate scope, selectivity, and the influence of the reaction parameters were also investigated. This work offers a novel, easy, and more sustainable path to advance the application of AMO-LDHs in oxidation catalysis, opening up the use of this type of catalytic systems in the mild oxidation of alkanes.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"32 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862247","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Two square planar Ni(II) azido complexes [Ni(N3)(L1)] and [Ni(N3)(L2)] (where L1 = N-phenyl-2-(pyridin-2-ylmethylene)hydrazine-1-carbothioamide; L2 = (E)-1-(((2-(diethylamino)ethyl)imino)methyl)naphthalen-2-olato) were used to study the effect of auxiliary ligands on the [3+2] cycloaddition reactions with different dipolarophiles. The reactivity of the complex [Ni(N3)(L1)] was greater than that of the complex [Ni(N3)(L2)]. [Ni(N3)(L1)] gives an N2-triazolato product with an electron-deficient alkyne R1─C≡C─R2 with R1 = R2 = COOCH3, COOEt, or R1 = CF3, R2 = COOEt while [Ni(N3)(L2)] gives a homobimetallic bis(μ-NN’-triazolato) bridged product only with F3C─C≡C─COOEt. The complex [Ni(N3)(L2)] reacts with dialkyl acetylene-dicarboxylate alkyne, yielding N1-triazolato products under strictly anhydrous conditions, whereas the same reaction under ambient conditions yielded a new unexpected octahedral complex in which the alkyne is converted into a novel O, O donor bidentate ligand. The nature of the predominant triazolato isomer (N1/N2) was experimentally confirmed by single-crystal X-ray diffraction analysis and also verified by DFT calculations. [Ni(N3)(L1)] gives a homobimetallic bis(μ-tetrazolato) bridged product by the [3+2] cycloaddition reaction of 2-cyanopyridine and 2-cyanopyrimidine. [Ni(N3)(L1)] also underwent a 1,3-dipolar cycloaddition with phenyl isothiocyanate at room temperature, giving the corresponding tetrazolato-thione complex, while the same reaction with [Ni(N3)(L2)] does not proceed. Both complexes give Ni(II) isothiocyanate complexes by the reaction of carbon disulfide. The catalytic activities of all the Ni(II) complexes were evaluated for the synthesis of 2-amino-3-cyano-4H-pyran derivatives. [Ni(triazolateCOOMe,COOMe–N2)(L1)] (complex 3) emerged as a highly efficient catalyst, demonstrating performance significantly superior to previously reported catalysts at room temperature. 0.0001 mol % catalyst loading is sufficient to obtain the product, and the highest turnover number (680000) and turnover frequency (34000 min–1) were achieved.
{"title":"A Study on the [3+2] Cycloaddition Reaction of Square Planar Ni(II) Azido Complexes: Structure, Properties, and Catalytic Applications of the Products","authors":"Akash Shrivastav, Raj Kumar Sahani, Subrato Bhattacharya","doi":"10.1021/acs.inorgchem.5c01111","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01111","url":null,"abstract":"Two square planar Ni(II) azido complexes [Ni(N<sub>3</sub>)(L1)] and [Ni(N<sub>3</sub>)(L2)] (where L1 = <i>N</i>-phenyl-2-(pyridin-2-ylmethylene)hydrazine-1-carbothioamide; L2 = (<i>E</i>)-1-(((2-(diethylamino)ethyl)imino)methyl)naphthalen-2-olato) were used to study the effect of auxiliary ligands on the [3+2] cycloaddition reactions with different dipolarophiles. The reactivity of the complex [Ni(N<sub>3</sub>)(L1)] was greater than that of the complex [Ni(N<sub>3</sub>)(L2)]. [Ni(N<sub>3</sub>)(L1)] gives an N2-triazolato product with an electron-deficient alkyne R<sub>1</sub>─C≡C─R<sub>2</sub> with R<sub>1</sub> = R<sub>2</sub> = COOCH<sub>3</sub>, COOEt, or R<sub>1</sub> = CF<sub>3</sub>, R<sub>2</sub> = COOEt while [Ni(N<sub>3</sub>)(L2)] gives a homobimetallic bis(μ-NN’-triazolato) bridged product only with F<sub>3</sub>C─C≡C─COOEt. The complex [Ni(N<sub>3</sub>)(L2)] reacts with dialkyl acetylene-dicarboxylate alkyne, yielding N1-triazolato products under strictly anhydrous conditions, whereas the same reaction under ambient conditions yielded a new unexpected octahedral complex in which the alkyne is converted into a novel O, O donor bidentate ligand. The nature of the predominant triazolato isomer (N1/N2) was experimentally confirmed by single-crystal X-ray diffraction analysis and also verified by DFT calculations. [Ni(N<sub>3</sub>)(L1)] gives a homobimetallic bis(μ-tetrazolato) bridged product by the [3+2] cycloaddition reaction of 2-cyanopyridine and 2-cyanopyrimidine. [Ni(N<sub>3</sub>)(L1)] also underwent a 1,3-dipolar cycloaddition with phenyl isothiocyanate at room temperature, giving the corresponding tetrazolato-thione complex, while the same reaction with [Ni(N<sub>3</sub>)(L2)] does not proceed. Both complexes give Ni(II) isothiocyanate complexes by the reaction of carbon disulfide. The catalytic activities of all the Ni(II) complexes were evaluated for the synthesis of 2-amino-3-cyano-4H-pyran derivatives. [Ni(triazolate<sup>COOMe,COOMe</sup>–N<sup>2</sup>)(L1)] (<b>complex 3</b>) emerged as a highly efficient catalyst, demonstrating performance significantly superior to previously reported catalysts at room temperature. 0.0001 mol % catalyst loading is sufficient to obtain the product, and the highest turnover number (680000) and turnover frequency (34000 min<sup>–1</sup>) were achieved.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"16 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858165","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-22DOI: 10.1021/acs.inorgchem.4c05579
Juan Andrés Nieto-Simón, Marta María González-Barrios, Adrián Gómez-Herrero, María Teresa Fernández-Díaz, Jesús Prado-Gonjal, Elizabeth Castillo-Martínez
Hollandite-type oxides, KyVxTi8–xO16, x = 0.25, 0.5, 0.75, 1, 1.25, 1.5, and 2, are synthesized via the citrate method and evaluated as potential electrode materials for potassium-ion batteries (KIBs). Neutron powder diffraction (NPD) confirms an undistorted I4/m structure, uniform K content (1.4 ≤ y ≤ 1.6), and high potassium isotropic displacement parameter (Biso). This decreases significantly for x ≥ 1, correlating with tunnel narrowing and vanadium’s stronger polarization. Transmission electron microscopy (TEM) techniques, including selected area electron diffraction (SAED), annular bright field (ABF), and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) identify superstructure reflections assigned to potassium/vacancy short-range order along the c axis with disorder between tunnels. Magnetic studies reveal paramagnetic behavior down to 2 K, with antiferromagnetic interactions at low temperature except for x = 0.25 composition, which exhibits ferromagnetic interactions. The experimental magnetic moment suggests a low Ti3+ content, with notable deviations at x = 1.25. The electrochemical performance is assessed via galvanostatic cycling using 2.5 M potassium bis(fluorosulfonyl)imide (KFSI) in triethyl phosphate (TEP) as electrolyte. At a rate of C/10, 2 K+ are reversibly de/inserted per formula unit, comparable to K0.17TiO2. At C/5, K1.5V0.75Ti7.25O16 demonstrates a reversible de/insertion of 1 K+/f.u., highlighting its potential for rechargeable KIBs.
{"title":"Exploring Hollandite-Type KyVxTi8–xO16 (0.25 ≤ x ≤ 2) as Electrode Materials in Potassium-Ion Batteries (KIBs)","authors":"Juan Andrés Nieto-Simón, Marta María González-Barrios, Adrián Gómez-Herrero, María Teresa Fernández-Díaz, Jesús Prado-Gonjal, Elizabeth Castillo-Martínez","doi":"10.1021/acs.inorgchem.4c05579","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05579","url":null,"abstract":"Hollandite-type oxides, K<i><sub>y</sub></i>V<i><sub>x</sub></i>Ti<sub>8–<i>x</i></sub>O<sub>16</sub>, <i>x</i> = 0.25, 0.5, 0.75, 1, 1.25, 1.5, and 2, are synthesized via the citrate method and evaluated as potential electrode materials for potassium-ion batteries (KIBs). Neutron powder diffraction (NPD) confirms an undistorted <i>I</i>4/<i>m</i> structure, uniform K content (1.4 ≤ <i>y</i> ≤ 1.6), and high potassium isotropic displacement parameter (B<sub>iso</sub>). This decreases significantly for <i>x</i> ≥ 1, correlating with tunnel narrowing and vanadium’s stronger polarization. Transmission electron microscopy (TEM) techniques, including selected area electron diffraction (SAED), annular bright field (ABF), and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) identify superstructure reflections assigned to potassium/vacancy short-range order along the <i>c</i> axis with disorder between tunnels. Magnetic studies reveal paramagnetic behavior down to 2 K, with antiferromagnetic interactions at low temperature except for <i>x</i> = 0.25 composition, which exhibits ferromagnetic interactions. The experimental magnetic moment suggests a low Ti<sup>3+</sup> content, with notable deviations at <i>x</i> = 1.25. The electrochemical performance is assessed via galvanostatic cycling using 2.5 M potassium bis(fluorosulfonyl)imide (KFSI) in triethyl phosphate (TEP) as electrolyte. At a rate of C/10, 2 K<sup>+</sup> are reversibly de/inserted per formula unit, comparable to K<sub>0.17</sub>TiO<sub>2</sub>. At C/5, K<sub>1.5</sub>V<sub>0.75</sub>Ti<sub>7.25</sub>O<sub>16</sub> demonstrates a reversible de/insertion of 1 K<sup>+</sup>/f.u., highlighting its potential for rechargeable KIBs.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"17 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858185","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-22DOI: 10.1021/acs.inorgchem.4c04620
Adam Musa, Monica Katiyar
Chalcogenide perovskites, such as BaZrS3, have emerged as promising alternatives to lead-based halide perovskites, addressing toxicity and instability concerns while maintaining strong near-band-edge absorption and high carrier mobility. In this study, titanium-doped BaZrS3 (BaZr1–xTixS3, x = 0–0.08) was synthesized via citric acid–based sol–gel method, followed by sulfurization at 1050 °C. Structural characterization confirmed the a single-phase distorted orthorhombic perovskite without phase separation, even at 8% Ti doping. Raman spectroscopy revealed no significant structural disorder induced by Ti substitution, while SEM/TEM analyses demonstrated a uniform morphology and pseudocubicnanoparticles (∼200 nm) in size. XPS validated the presence of Ba2+, Zr4+and S2– in their expected oxidation states. UV–Vis spectroscopy showed a tunable bandgap reduction from 1.8 eV (pristine) to 1.2 eV (x = 0.08), aligning with the Shockley–Queisser limit. Hall effect measurements revealed enhanced carrier mobility (27.4 cm2/V·s at x = 0.08) and consistent n-type carrier concentrations (∼1016 cm–3), indicating improved conductivity. The thermogravimetric analysis further confirmed exceptional thermal stability (<2% Mass loss up to 800 °C). These results underscore the efficacy of Ti doping in optimizing optoelectronic properties while preserving structural integrity and stability. Collectively, this work positions Ti-doped BaZrS3 as a scalable, lead-free perovskite candidate for high-efficiency photovoltaic applications.
{"title":"Titanium-Doped BaZrS3 Chalcogenide Perovskite for Photovoltaic Applications: Structural, Optical, and Electrical Properties","authors":"Adam Musa, Monica Katiyar","doi":"10.1021/acs.inorgchem.4c04620","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04620","url":null,"abstract":"Chalcogenide perovskites, such as BaZrS<sub>3</sub>, have emerged as promising alternatives to lead-based halide perovskites, addressing toxicity and instability concerns while maintaining strong near-band-edge absorption and high carrier mobility. In this study, titanium-doped BaZrS<sub>3</sub> (BaZr<sub>1</sub><sub>–</sub><sub><i>x</i></sub>Ti<sub><i>x</i></sub>S<sub>3</sub>, <i>x</i> = 0–0.08) was synthesized via citric acid–based sol–gel method, followed by sulfurization at 1050 °C. Structural characterization confirmed the a single-phase distorted orthorhombic perovskite without phase separation, even at 8% Ti doping. Raman spectroscopy revealed no significant structural disorder induced by Ti substitution, while SEM/TEM analyses demonstrated a uniform morphology and pseudocubicnanoparticles (∼200 nm) in size. XPS validated the presence of Ba<sup>2+</sup>, Zr<sup>4+</sup>and S<sup>2–</sup> in their expected oxidation states. UV–Vis spectroscopy showed a tunable bandgap reduction from 1.8 eV (pristine) to 1.2 eV (<i>x</i> = 0.08), aligning with the Shockley–Queisser limit. Hall effect measurements revealed enhanced carrier mobility (27.4 cm<sup>2</sup>/V·s at <i>x</i> = 0.08) and consistent n-type carrier concentrations (∼10<sup>16</sup> cm<sup>–3</sup>), indicating improved conductivity. The thermogravimetric analysis further confirmed exceptional thermal stability (<2% Mass loss up to 800 °C). These results underscore the efficacy of Ti doping in optimizing optoelectronic properties while preserving structural integrity and stability. Collectively, this work positions Ti-doped BaZrS<sub>3</sub> as a scalable, lead-free perovskite candidate for high-efficiency photovoltaic applications.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"6 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862249","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-22DOI: 10.1021/acs.inorgchem.5c00564
Yi Liu, Xinyuan Liu, Wenhui Chang, Hanzhi Zhang, Qiqi Zhang, Yi Liu, Xinyuan Jiang, Li Tao, Cheng Ma, Lu-Nan Zhang, Yongge Wei, Lubin Ni
In this study, a polyoxometalate-based inorganic–organic hybrid material, Na4[Cu4(Gly)2(HGly)2(H4W12O42)]Cl2·20H2O (1) (Gly = glycine), was synthesized via a self-assembly approach by incorporating copper ions and glycine into the paradodecatungstate anion [H4W12O42]8–. The structure and properties of compound 1 were systematically characterized using single crystal X-ray diffraction, elemental analysis, powder X-ray diffraction, FTIR, Raman spectroscopy, cyclic voltammetry (CV), and UV–vis spectroscopy. Additionally, its anticancer activity was evaluated in vitro against human liver cancer cells (HepG2) and human renal epithelial cells (HEK293T) using the MTT assay, yielding an IC50 value of 36.232 ± 0.41 μM. The findings demonstrate that compound 1 effectively inhibits the proliferation of liver cancer cells, highlighting its potential as a candidate for polyoxotungstate (POT)-based anticancer drug development.
{"title":"A Copper Paradodecatungstate-B Compound Decorated by Glycine Ligand: Synthesis, Structure, and Anticancer Activities","authors":"Yi Liu, Xinyuan Liu, Wenhui Chang, Hanzhi Zhang, Qiqi Zhang, Yi Liu, Xinyuan Jiang, Li Tao, Cheng Ma, Lu-Nan Zhang, Yongge Wei, Lubin Ni","doi":"10.1021/acs.inorgchem.5c00564","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00564","url":null,"abstract":"In this study, a polyoxometalate-based inorganic–organic hybrid material, Na<sub>4</sub>[Cu<sub>4</sub>(Gly)<sub>2</sub>(HGly)<sub>2</sub>(H<sub>4</sub>W<sub>12</sub>O<sub>42</sub>)]Cl<sub>2</sub>·20H<sub>2</sub>O (<b>1</b>) (Gly = glycine), was synthesized via a self-assembly approach by incorporating copper ions and glycine into the paradodecatungstate anion [H<sub>4</sub>W<sub>12</sub>O<sub>42</sub>]<sup>8–</sup>. The structure and properties of compound <b>1</b> were systematically characterized using single crystal X-ray diffraction, elemental analysis, powder X-ray diffraction, FTIR, Raman spectroscopy, cyclic voltammetry (CV), and UV–vis spectroscopy. Additionally, its anticancer activity was evaluated in vitro against human liver cancer cells (HepG2) and human renal epithelial cells (HEK293T) using the MTT assay, yielding an IC<sub>50</sub> value of 36.232 ± 0.41 μM. The findings demonstrate that compound <b>1</b> effectively inhibits the proliferation of liver cancer cells, highlighting its potential as a candidate for polyoxotungstate (POT)-based anticancer drug development.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"43 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858245","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Near-infrared (NIR) light-emitting diodes (LEDs) are potential devices that could become the core components in biological imaging, security monitoring, etc., which are currently constrained by suboptimal luminous efficiency due to the absence of excellent luminescent materials. Here, we report a double perovskite Cs2NaInCl6 that is suitable for Cr3+ doping and exhibits broad NIR emission. Through direct absorption and energy transfer (ET) from the self-trapped excitons (STEs) induced in the Cs2NaInCl6 matrix, Cr3+ can be excited to 4T1(P), 4T1(F), and 4T2(F) levels. Then, the broad emission with a full width at half-maximum (FWHM) of ∼150 nm, spanning 800 to 1300 nm, and a high photoluminescence quantum yield (PLQY) of up to 70% can be realized, resulting from the 4T2→4A2 transition of Cr3+. Subsequently, the introduction of Yb3+ endows Cs2NaInCl6:Cr3+,Yb3+ with a higher PLQY of 76% at the optimal doping ratio than Cs2NaInCl6:Cr3+. Ultimately, a miniaturized NIR LED device packaged based on Cs2NaInCl6:15%Cr3+,15%Yb3+ has been fabricated, which demonstrates superior performance for night vision, traceless perspective detection, and biological imaging. This work not only screens out a suitable Cs2NaInCl6 matrix for Cr3+ doping with high PLQY but also promotes its luminescence performance through Yb3+ doping for NIR LED applications.
{"title":"Cr3+/Yb3+ Codoped Cs2NaInCl6 Double Perovskites for Near-Infrared Light-Emitting Diodes","authors":"Xinyu Fu, Huwei Li, Hongxia Yue, Zheyu Li, Jing Feng, Hongjie Zhang","doi":"10.1021/acs.inorgchem.5c00924","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00924","url":null,"abstract":"Near-infrared (NIR) light-emitting diodes (LEDs) are potential devices that could become the core components in biological imaging, security monitoring, etc., which are currently constrained by suboptimal luminous efficiency due to the absence of excellent luminescent materials. Here, we report a double perovskite Cs<sub>2</sub>NaInCl<sub>6</sub> that is suitable for Cr<sup>3+</sup> doping and exhibits broad NIR emission. Through direct absorption and energy transfer (ET) from the self-trapped excitons (STEs) induced in the Cs<sub>2</sub>NaInCl<sub>6</sub> matrix, Cr<sup>3+</sup> can be excited to <sup>4</sup>T<sub>1</sub>(P), <sup>4</sup>T<sub>1</sub>(F), and <sup>4</sup>T<sub>2</sub>(F) levels. Then, the broad emission with a full width at half-maximum (<i>FWHM</i>) of ∼150 nm, spanning 800 to 1300 nm, and a high photoluminescence quantum yield (PLQY) of up to 70% can be realized, resulting from the <sup>4</sup>T<sub>2</sub>→<sup>4</sup>A<sub>2</sub> transition of Cr<sup>3+</sup>. Subsequently, the introduction of Yb<sup>3+</sup> endows Cs<sub>2</sub>NaInCl<sub>6</sub>:Cr<sup>3+</sup>,Yb<sup>3+</sup> with a higher PLQY of 76% at the optimal doping ratio than Cs<sub>2</sub>NaInCl<sub>6</sub>:Cr<sup>3+</sup>. Ultimately, a miniaturized NIR LED device packaged based on Cs<sub>2</sub>NaInCl<sub>6</sub>:15%Cr<sup>3+</sup>,15%Yb<sup>3+</sup> has been fabricated, which demonstrates superior performance for night vision, traceless perspective detection, and biological imaging. This work not only screens out a suitable Cs<sub>2</sub>NaInCl<sub>6</sub> matrix for Cr<sup>3+</sup> doping with high PLQY but also promotes its luminescence performance through Yb<sup>3+</sup> doping for NIR LED applications.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"91 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858246","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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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