Mishel Markovski, Abdallah Amedlous, Eddy Dib, Anna Kaleta, Francesco Dalena, Davide Salusso, Mathias Barreau, Diogenes Honorato Piva, Marco Giuseppe Geloso, Aymeric Magisson, Svetlana Mintova
This study investigates the impact of selenium in different oxidation states, specifically Se6+ and Se4+, on the structural features of MFI-type zeolites. Se4+ is characterized by trigonal pyramidal coordination, forming a [Se4+O3E]2− entity (E being an active lone pair of electrons). The three-coordinated [Se4+O3E]2− entity represents an “empty-corner tetrahedron”, analogous to four-coordinated [Se6+O4]2− and [SiO4]4− tetrahedra. Aiming to understand the impact of lone pair bearing complexes on MFI, Se4+ and Se6+ were introduced through a one-pot synthesis approach giving rise to Se(IV)-MFI and Se(VI)-MFI samples. Both the Se(IV)-MFI and Se(VI)-MFI samples exhibit monoclinic symmetry at room temperature, transitioning into orthorhombic symmetry at temperatures above 100 °C and reverting to monoclinic symmetry upon cooling. A significant difference was observed in terms of the silanol content, i.e. Se(IV)-MFI shows a lower concentration of SiOH compared to Se(VI)-MFI. These observations are coherently supported by 29Si and 77Se NMR, Se K-edge XAS, FT-IR, and Raman spectroscopy, suggesting that Se4+ oxycomplexes with a lone pair of electrons are more favorable for incorporation into the MFI framework compared to Se6+. 77Se NMR analyses revealed similar Se tetrahedral coordination in both Se(VI)-MFI and Se(IV)-MFI, indicating the stabilizing role i.e. oxidation of Se4+ to Se6+ directly during crystallization of MFI. Considering the differences in the silanol content and the similarities in Se coordination states in Se(IV)-MFI and Se(VI)-MFI, the transformation of “empty-corner tetrahedra” into regular tetrahedra i.e. selenite to selenate favors the introduction of Se in the MFI framework. These results provide valuable insights into the tunability of zeolite frameworks using selenium in different oxidation states.
{"title":"The impact of “empty-corner” tetrahedra in the synthesis of MFI type zeolites: unveiling selenium stereoactivity","authors":"Mishel Markovski, Abdallah Amedlous, Eddy Dib, Anna Kaleta, Francesco Dalena, Davide Salusso, Mathias Barreau, Diogenes Honorato Piva, Marco Giuseppe Geloso, Aymeric Magisson, Svetlana Mintova","doi":"10.1039/d5qi00567a","DOIUrl":"https://doi.org/10.1039/d5qi00567a","url":null,"abstract":"This study investigates the impact of selenium in different oxidation states, specifically Se<small><sup>6+</sup></small> and Se<small><sup>4+</sup></small>, on the structural features of MFI-type zeolites. Se<small><sup>4+</sup></small> is characterized by trigonal pyramidal coordination, forming a [Se<small><sup>4+</sup></small>O<small><sub>3</sub></small>E]<small><sup>2−</sup></small> entity (E being an active lone pair of electrons). The three-coordinated [Se<small><sup>4+</sup></small>O<small><sub>3</sub></small>E]<small><sup>2−</sup></small> entity represents an “empty-corner tetrahedron”, analogous to four-coordinated [Se<small><sup>6+</sup></small>O<small><sub>4</sub></small>]<small><sup>2−</sup></small> and [SiO<small><sub>4</sub></small>]<small><sup>4−</sup></small> tetrahedra. Aiming to understand the impact of lone pair bearing complexes on MFI, Se<small><sup>4+</sup></small> and Se<small><sup>6+</sup></small> were introduced through a one-pot synthesis approach giving rise to Se(<small>IV</small>)-MFI and Se(<small>VI</small>)-MFI samples. Both the Se(<small>IV</small>)-MFI and Se(<small>VI</small>)-MFI samples exhibit monoclinic symmetry at room temperature, transitioning into orthorhombic symmetry at temperatures above 100 °C and reverting to monoclinic symmetry upon cooling. A significant difference was observed in terms of the silanol content, <em>i.e.</em> Se(<small>IV</small>)-MFI shows a lower concentration of SiOH compared to Se(<small>VI</small>)-MFI. These observations are coherently supported by <small><sup>29</sup></small>Si and <small><sup>77</sup></small>Se NMR, Se K-edge XAS, FT-IR, and Raman spectroscopy, suggesting that Se<small><sup>4+</sup></small> oxycomplexes with a lone pair of electrons are more favorable for incorporation into the MFI framework compared to Se<small><sup>6+</sup></small>. <small><sup>77</sup></small>Se NMR analyses revealed similar Se tetrahedral coordination in both Se(<small>VI</small>)-MFI and Se(<small>IV</small>)-MFI, indicating the stabilizing role <em>i.e.</em> oxidation of Se<small><sup>4+</sup></small> to Se<small><sup>6+</sup></small> directly during crystallization of MFI. Considering the differences in the silanol content and the similarities in Se coordination states in Se(<small>IV</small>)-MFI and Se(<small>VI</small>)-MFI, the transformation of “empty-corner tetrahedra” into regular tetrahedra <em>i.e.</em> selenite to selenate favors the introduction of Se in the MFI framework. These results provide valuable insights into the tunability of zeolite frameworks using selenium in different oxidation states.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"183 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723246","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Andy Shun-Hoi Cheung, Eugene Yau-Hin Hong, Vivian Wing-Wah Yam
A new class of neutral phosphole oxide-based cyclometalated platinum(II) β-diketonate complexes has been demonstrated to show cooperative self-assembly in THF–water mixtures, modulated by the directional Pt⋯Pt interactions along with π–π stacking and/or hydrophobic interactions. The phosphole oxide-based cyclometalating ligand has been found to play an important role in determining the morphologies of aggregates in THF–water mixtures. Moreover, platinum(II) complexes serving as active materials in resistive memory devices have been found to show promising binary memory performance with a low switching threshold voltage, long retention time and high ON/OFF ratio compared to devices based on reported organometallic complexes. The rich self-assembly and resistive memory properties of the complexes presented in the current work have illustrated the versatility of the robust platinum(II) complexes that could be utilized for the development of functional materials.
{"title":"Phosphole oxide-based cyclometalated platinum(II) β-diketonate complexes for cooperative self-assembly and solution-processable resistive memories with excellent stability","authors":"Andy Shun-Hoi Cheung, Eugene Yau-Hin Hong, Vivian Wing-Wah Yam","doi":"10.1039/d4qi03092c","DOIUrl":"https://doi.org/10.1039/d4qi03092c","url":null,"abstract":"A new class of neutral phosphole oxide-based cyclometalated platinum(<small>II</small>) β-diketonate complexes has been demonstrated to show cooperative self-assembly in THF–water mixtures, modulated by the directional Pt⋯Pt interactions along with π–π stacking and/or hydrophobic interactions. The phosphole oxide-based cyclometalating ligand has been found to play an important role in determining the morphologies of aggregates in THF–water mixtures. Moreover, platinum(<small>II</small>) complexes serving as active materials in resistive memory devices have been found to show promising binary memory performance with a low switching threshold voltage, long retention time and high ON/OFF ratio compared to devices based on reported organometallic complexes. The rich self-assembly and resistive memory properties of the complexes presented in the current work have illustrated the versatility of the robust platinum(<small>II</small>) complexes that could be utilized for the development of functional materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"22 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723247","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Peiqing Long, Chun-Li Hu, Xitao Liu, Jiang-Gao Mao
The growth of bulk nonlinear optical (NLO) crystals that exhibit robust second harmonic generation (SHG) is currently an intriguing and rapidly advancing field for laser and photonic applications. Among the various options available, organic-inorganic hybrid materials offer numerous possibilities due to their distinctive amalgamation of inorganic coordinate frameworks and organic molecules. Herein, we have successfully developed a novel non-centrosymmetric (NCS) organic-inorganic hybrid NLO material, manganese mercury thiocyanate-bis(acetamide), [Mn(CH3CONH2)2][Hg(SCN)4] (MMTA), by synergistically incorporating inorganic polyhedra and organic conjugate molecules. The crystal displays a polar architecture comprising an asymmetric [HgS4] tetrahedron and [MnN4O2] octahedron which are connected by four π-conjugated -S-C≡N- ligands. More intriguingly, inch-size single crystals with dimensions up to 50×50×12 mm3, have been easily grown from aqueous solutions by temperature-lowering method. The optical properties investigation suggests that MMTA is a phase-matching NLO material with a large SHG response approximately 2.5 times that of KH2PO4, demonstrating its potential for NLO applications. Based on a combination of structural analysis and theoretical calculations, it is suggested that the significant SHG response can be attributed to the cooperative interaction between conjugated organic molecules and a highly asymmetric inorganic distorted octahedron. This work introduces an effective approach for the discovery of high-performance quadratic NLO materials, with a particular focus on organic-inorganic hybrid compounds.
{"title":"Bulk Crystal Growth and Optical Properties of Novel Organic-inorganic Hybrid Nonlinear Optical Thiocyanate: [Mn(CH3CONH2)2] [Hg(SCN)4]","authors":"Peiqing Long, Chun-Li Hu, Xitao Liu, Jiang-Gao Mao","doi":"10.1039/d5qi00371g","DOIUrl":"https://doi.org/10.1039/d5qi00371g","url":null,"abstract":"The growth of bulk nonlinear optical (NLO) crystals that exhibit robust second harmonic generation (SHG) is currently an intriguing and rapidly advancing field for laser and photonic applications. Among the various options available, organic-inorganic hybrid materials offer numerous possibilities due to their distinctive amalgamation of inorganic coordinate frameworks and organic molecules. Herein, we have successfully developed a novel non-centrosymmetric (NCS) organic-inorganic hybrid NLO material, manganese mercury thiocyanate-bis(acetamide), [Mn(CH3CONH2)2][Hg(SCN)4] (MMTA), by synergistically incorporating inorganic polyhedra and organic conjugate molecules. The crystal displays a polar architecture comprising an asymmetric [HgS4] tetrahedron and [MnN4O2] octahedron which are connected by four π-conjugated -S-C≡N- ligands. More intriguingly, inch-size single crystals with dimensions up to 50×50×12 mm3, have been easily grown from aqueous solutions by temperature-lowering method. The optical properties investigation suggests that MMTA is a phase-matching NLO material with a large SHG response approximately 2.5 times that of KH2PO4, demonstrating its potential for NLO applications. Based on a combination of structural analysis and theoretical calculations, it is suggested that the significant SHG response can be attributed to the cooperative interaction between conjugated organic molecules and a highly asymmetric inorganic distorted octahedron. This work introduces an effective approach for the discovery of high-performance quadratic NLO materials, with a particular focus on organic-inorganic hybrid compounds.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"13 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723290","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hang Zhang, Zhen Liu, Xiaofei Zhu, Jun-Long Zhang, Liangbing Gan
Fullerene (C70), a promising new photosensitizer, has faced challenges in its biological applications due to its extreme hydrophobicity. In order to enhance the solubility of fullerene (C70) and facilitate its biological applications, we synthesized a novel hydroxyl-modified fullerene compound (C70(OH)8) with excellent photosensitizing properties. The introduction of hydroxyl groups allows it to self-assemble with DSPE-PEG(2000), therefore, we prepared its nanomedicines(C70(OH)8@NP). Under white light irradiation, C70(OH)8@NP stimulates the production of reactive oxygen species (ROS), Furthermore, results has demonstrated that a substantial amount of ROS can also be generated within cells, resulting in cell death. We found that C70(OH)8@NP can induce both apoptosis and pyroptosis in HeLa cells and identified its mechanism of cell death through the activation of Caspase 3/Gasdermin E pathways. Importantly, C70(OH)8@NP demonstrates significant anti-tumor activity in a nude mouse tumor-bearing model. These results highlight the potential of novel fullerene compounds as photodynamic therapy agents.
{"title":"Hydroxyl-Modified Fullerene C70(OH)8 Induces Pyroptosis for Cancer Therapy","authors":"Hang Zhang, Zhen Liu, Xiaofei Zhu, Jun-Long Zhang, Liangbing Gan","doi":"10.1039/d5qi00548e","DOIUrl":"https://doi.org/10.1039/d5qi00548e","url":null,"abstract":"Fullerene (C70), a promising new photosensitizer, has faced challenges in its biological applications due to its extreme hydrophobicity. In order to enhance the solubility of fullerene (C70) and facilitate its biological applications, we synthesized a novel hydroxyl-modified fullerene compound (C70(OH)8) with excellent photosensitizing properties. The introduction of hydroxyl groups allows it to self-assemble with DSPE-PEG(2000), therefore, we prepared its nanomedicines(C70(OH)8@NP). Under white light irradiation, C70(OH)8@NP stimulates the production of reactive oxygen species (ROS), Furthermore, results has demonstrated that a substantial amount of ROS can also be generated within cells, resulting in cell death. We found that C70(OH)8@NP can induce both apoptosis and pyroptosis in HeLa cells and identified its mechanism of cell death through the activation of Caspase 3/Gasdermin E pathways. Importantly, C70(OH)8@NP demonstrates significant anti-tumor activity in a nude mouse tumor-bearing model. These results highlight the potential of novel fullerene compounds as photodynamic therapy agents.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"125 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713418","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xiaoyan Zhang, Hui Li, Na Xu, Xiaodong Liu, Xiu-Li Wang
The synthesis of superclusters is vital for understanding their self-assembly mechanisms, requiring precise control over composition, orientation, and connectivity. The tenets of reticular chemistry afford a systematic approach to the architectural design and regulation of molecular entities, thereby enabling the fulfillment of preconceived structural objectives. Herein, the strategic introduction of transition metal ions, CoII and NiII, has enabled the controlled formation of two novel closely related anionic superclusters based on the {Sr⊂P6M2Mo16O73} clusters: Co12Sr4Mo80P36 (1) and Na4Ni23Sr4Mo88P52 (2). The former manifests a tetrahedral structure, while the latter, derived from topological transformations of cluster 1, exhibits a unique square geometry. Structural elucidation revealed that the integration of MoV ions in a reduced state, in concert with distinct transition metal ions (CoII and NiII), plays a pivotal role in determining the geometric profiles of these superclusters. Furthermore, clusters 1 and 2 demonstrate efficacy as heterogeneous catalysts, significantly promoting the transformation of methyl phenyl sulfide (MPS) to methyl phenyl sulfoxide (MPSO).
{"title":"Engineering geometric metamorphosis in {P6M2Mo16O73}-based high-nuclearity metal superclusters: from tetrahedral to square assemblies via topological transformations","authors":"Xiaoyan Zhang, Hui Li, Na Xu, Xiaodong Liu, Xiu-Li Wang","doi":"10.1039/d5qi00460h","DOIUrl":"https://doi.org/10.1039/d5qi00460h","url":null,"abstract":"The synthesis of superclusters is vital for understanding their self-assembly mechanisms, requiring precise control over composition, orientation, and connectivity. The tenets of reticular chemistry afford a systematic approach to the architectural design and regulation of molecular entities, thereby enabling the fulfillment of preconceived structural objectives. Herein, the strategic introduction of transition metal ions, Co<small><sup>II</sup></small> and Ni<small><sup>II</sup></small>, has enabled the controlled formation of two novel closely related anionic superclusters based on the {Sr⊂P<small><sub>6</sub></small>M<small><sub>2</sub></small>Mo<small><sub>16</sub></small>O<small><sub>73</sub></small>} clusters: <strong>Co<small><sub>12</sub></small>Sr<small><sub>4</sub></small>Mo<small><sub>80</sub></small>P<small><sub>36</sub></small></strong> (<strong>1</strong>) and <strong>Na<small><sub>4</sub></small>Ni<small><sub>23</sub></small>Sr<small><sub>4</sub></small>Mo<small><sub>88</sub></small>P<small><sub>52</sub></small></strong> (<strong>2</strong>). The former manifests a tetrahedral structure, while the latter, derived from topological transformations of cluster <strong>1</strong>, exhibits a unique square geometry. Structural elucidation revealed that the integration of Mo<small><sup>V</sup></small> ions in a reduced state, in concert with distinct transition metal ions (Co<small><sup>II</sup></small> and Ni<small><sup>II</sup></small>), plays a pivotal role in determining the geometric profiles of these superclusters. Furthermore, clusters <strong>1</strong> and <strong>2</strong> demonstrate efficacy as heterogeneous catalysts, significantly promoting the transformation of methyl phenyl sulfide (MPS) to methyl phenyl sulfoxide (MPSO).","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"41 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713341","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Maiyong Zhu, Xinyue Xiang, Xinyao Jiang, Yu Yang, Kai Zhang
Capacitive deionization (CDI) is a highly promising technique for removal ions from water, showing great perspective in desalination of salty water and wastewater remediation. CDI displays an energy efficiency, simple operation, excellent reversibility, long-term stability, and high feasibility for coupling with other techniques. Similar to supercapacitors, the electrode materials play crucial role in determining CDI performance, such as operating voltage, desalination capacity, and the lifecycle of CDI cells. Molybdenum disulfide (MoS2), a typical two-dimensional (2D) metal sulfide, has gained tremendous attention in CDI technique due to its exceptional mechanical, electrical, and optical properties. Herein, we critically reported deliberated the inventory and the recent progress in the rational design of MoS2 based electrodes for CDI cells. We start with a brief introduction to foundation knowledge of CDI system and structure of MoS2. To make the review comprehensive, we then summarized the available common techniques to prepare MoS2 based nanomaterials, spanning from various exfoliation processes, chemical vapor deposition, colloidal synthesis, hydrothermal/solvothermal synthesis, and molten salt synthesis. Significantly, the recent progress of MoS2 based electrodes in CDI application is summarized in detail. These systems are divided into pristine MoS2 and various MoS2 based composite with other species, such as carbon, conducting polymer, metal oxide, MXene, and C3N4. For assisting further development of MoS2 electrodes for efficient and long-term stable CDI, some challenges and possible solutions are outlined.
{"title":"Engineered Molybdenum Disulfide-based Nanomaterials for Capacitive Deionization Application","authors":"Maiyong Zhu, Xinyue Xiang, Xinyao Jiang, Yu Yang, Kai Zhang","doi":"10.1039/d4qi03147d","DOIUrl":"https://doi.org/10.1039/d4qi03147d","url":null,"abstract":"Capacitive deionization (CDI) is a highly promising technique for removal ions from water, showing great perspective in desalination of salty water and wastewater remediation. CDI displays an energy efficiency, simple operation, excellent reversibility, long-term stability, and high feasibility for coupling with other techniques. Similar to supercapacitors, the electrode materials play crucial role in determining CDI performance, such as operating voltage, desalination capacity, and the lifecycle of CDI cells. Molybdenum disulfide (MoS2), a typical two-dimensional (2D) metal sulfide, has gained tremendous attention in CDI technique due to its exceptional mechanical, electrical, and optical properties. Herein, we critically reported deliberated the inventory and the recent progress in the rational design of MoS2 based electrodes for CDI cells. We start with a brief introduction to foundation knowledge of CDI system and structure of MoS2. To make the review comprehensive, we then summarized the available common techniques to prepare MoS2 based nanomaterials, spanning from various exfoliation processes, chemical vapor deposition, colloidal synthesis, hydrothermal/solvothermal synthesis, and molten salt synthesis. Significantly, the recent progress of MoS2 based electrodes in CDI application is summarized in detail. These systems are divided into pristine MoS2 and various MoS2 based composite with other species, such as carbon, conducting polymer, metal oxide, MXene, and C3N4. For assisting further development of MoS2 electrodes for efficient and long-term stable CDI, some challenges and possible solutions are outlined.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"34 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713340","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Weihao Yu, Yijun Qian, Haoqing Ji, Zebin Zhu, Tong Wu, Tao Qian, Chenglin Yan, Jianmei Lu
Membrane separation technologies demonstrate outstanding potential for achieving efficient lithium-ion (Li+) extraction from the battery leachate in a high-value and eco-friendly way, but, up to date, the rare focuses on developing one kind of specific Li+-filter applicable in this context. Herein, we prepared a pyridinic two-dimensional covalent organic framework (2D COF-Py) membrane featuring non-angstrom-sized 1D channels for exclusive Li+ sieving. The 2D COF-Py membrane enabled an excellent Li+ permeance (∼30 mmol m−2 h−1) with impressive Li+/M2+ selectivity of over 47 under any mixed salt conditions (e.g. LiCl-CoCl2, LiCl-NiCl2, and LiCl-MnCl2). The experimental measurements and theoretical calculations revealed the dual roles of pyridine groups in dominating the ion transport behavior across the COF membrane. One role was to ensure fast Li+ transmembrane activity via electrostatic attraction and the other was to suppress M2+ free diffusion by forming strong coordination interactions. When stimulated battery leachate (a quaternary cation solution) was used as the feed solution, the COF-Py membrane not only sustained a striking separation performance under a long-term operation test without losing any trade-off but also maintained structural stability under high-salinity conditions.
{"title":"Intensified ion-to-channel interactions within pyridinic covalent organic framework membranes towards exclusive lithium-ion sieving","authors":"Weihao Yu, Yijun Qian, Haoqing Ji, Zebin Zhu, Tong Wu, Tao Qian, Chenglin Yan, Jianmei Lu","doi":"10.1039/d5qi00062a","DOIUrl":"https://doi.org/10.1039/d5qi00062a","url":null,"abstract":"Membrane separation technologies demonstrate outstanding potential for achieving efficient lithium-ion (Li<small><sup>+</sup></small>) extraction from the battery leachate in a high-value and eco-friendly way, but, up to date, the rare focuses on developing one kind of specific Li<small><sup>+</sup></small>-filter applicable in this context. Herein, we prepared a pyridinic two-dimensional covalent organic framework (2D COF-Py) membrane featuring non-angstrom-sized 1D channels for exclusive Li<small><sup>+</sup></small> sieving. The 2D COF-Py membrane enabled an excellent Li<small><sup>+</sup></small> permeance (∼30 mmol m<small><sup>−2</sup></small> h<small><sup>−1</sup></small>) with impressive Li<small><sup>+</sup></small>/M<small><sup>2+</sup></small> selectivity of over 47 under any mixed salt conditions (<em>e.g.</em> LiCl-CoCl<small><sub>2</sub></small>, LiCl-NiCl<small><sub>2</sub></small>, and LiCl-MnCl<small><sub>2</sub></small>). The experimental measurements and theoretical calculations revealed the dual roles of pyridine groups in dominating the ion transport behavior across the COF membrane. One role was to ensure fast Li<small><sup>+</sup></small> transmembrane activity <em>via</em> electrostatic attraction and the other was to suppress M<small><sup>2+</sup></small> free diffusion by forming strong coordination interactions. When stimulated battery leachate (a quaternary cation solution) was used as the feed solution, the COF-Py membrane not only sustained a striking separation performance under a long-term operation test without losing any trade-off but also maintained structural stability under high-salinity conditions.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"33 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713339","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ziyi Shui, Huiying Tian, Hang Mu, Liuyun Xu, Xiaoming Gao, Xi Chen
Correction for ‘Mn doping for regulating the electronic structure of Co3O4 to construct dual active sites for oxygen electrocatalysis’ by Ziyi Shui et al., Inorg. Chem. Front., 2025, https://doi.org/10.1039/d4qi03005b.
{"title":"Correction: Mn doping for regulating the electronic structure of Co3O4 to construct dual active sites for oxygen electrocatalysis","authors":"Ziyi Shui, Huiying Tian, Hang Mu, Liuyun Xu, Xiaoming Gao, Xi Chen","doi":"10.1039/d5qi90031j","DOIUrl":"https://doi.org/10.1039/d5qi90031j","url":null,"abstract":"Correction for ‘Mn doping for regulating the electronic structure of Co<small><sub>3</sub></small>O<small><sub>4</sub></small> to construct dual active sites for oxygen electrocatalysis’ by Ziyi Shui <em>et al.</em>, <em>Inorg. Chem. Front.</em>, 2025, https://doi.org/10.1039/d4qi03005b.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"27 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713342","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Maximilian J. Klingsiek, Julian Buth, Pia Charlotte Trapp, Andreas Mix, Jan-Hendrik Lamm, Beate Neumann, Georg Stammler, Norbert Werner Mitzel
A synthetic route to flapping poly-Lewis acids (PLAs) based on dibenzocyclooctatetraene was developed. The reactivity of tetradentate boron and aluminium containing PLAs towards various Lewis bases (LB) including drugs was investigated in detail. By using different monodentate LBs, the different effective Lewis acidities (eLA) of the respective pairings was determined and compared with each other. The reaction with multidentate LBs yielded a range of adducts, which were analysed in solution by NMR methods, including DOSY NMR spectroscopy, and in the solid state by X-ray diffraction. The adducts include specific oligomers, and coordination polymers constructed via B–P, Al–P and Al–N interactions. The solid-state structure of these coordination polymers have been determined. The results of complexation of bidentate LB by the tetradentate PLA show that LB is preferentially chelated in the binding pockets, which does not impede the flapping movement during chelating complexation. This phenomenon can be attributed to a reduction in entropy when this flapping motion is lost. The aluminium containing PLAs were observed to form a complex with two caffeine molecules, exhibiting remarkable preference for oxygen functions. In contrast, the reaction with theobromine resulted in the degradation of the PLAs due to the presence of acidic protons in theobromine, leading to the formation of a dimeric aluminium containing theobromine derivative. These findings demonstrate the interaction of PLAs with drugs. They provide a foundation for the advancement of PLAs with a tuneable orientation of Lewis acidic functions.
我们开发了一种基于二苯并环辛四烯的拍打聚路易斯酸（PLA）的合成路线。详细研究了含硼和铝的四价聚乳酸对各种路易斯碱（LB）（包括药物）的反应性。通过使用不同的单齿路易斯碱，确定了各自配对的不同有效路易斯酸度（eLA），并进行了相互比较。通过核磁共振方法（包括 DOSY 核磁共振谱）和 X 射线衍射方法分析了溶液中和固态中的加合物。这些加合物包括特定的低聚物，以及通过 B-P、Al-P 和 Al-N 相互作用形成的配位聚合物。这些配位聚合物的固态结构已经确定。四价聚乳酸与双价枸橼酸的络合结果表明，枸橼酸优先被螯合在结合袋中，这并不妨碍螯合络合过程中的拍打运动。这一现象可归因于失去拍打运动后熵的减少。据观察，含铝聚乳酸能与两个咖啡因分子形成络合物，表现出明显的氧功能偏好。相反，由于可可碱中存在酸性质子，与可可碱反应会导致聚乳酸降解，形成含可可碱衍生物的二聚铝。这些发现证明了聚乳酸与药物的相互作用。它们为开发具有可调路易斯酸性功能取向的聚乳酸奠定了基础。
{"title":"Dibenzocyclooctatetraene Based Poly-Lewis-Acids: Flapping Hosts for Multidentate Guests","authors":"Maximilian J. Klingsiek, Julian Buth, Pia Charlotte Trapp, Andreas Mix, Jan-Hendrik Lamm, Beate Neumann, Georg Stammler, Norbert Werner Mitzel","doi":"10.1039/d5qi00823a","DOIUrl":"https://doi.org/10.1039/d5qi00823a","url":null,"abstract":"A synthetic route to flapping poly-Lewis acids (PLAs) based on dibenzocyclooctatetraene was developed. The reactivity of tetradentate boron and aluminium containing PLAs towards various Lewis bases (LB) including drugs was investigated in detail. By using different monodentate LBs, the different effective Lewis acidities (eLA) of the respective pairings was determined and compared with each other. The reaction with multidentate LBs yielded a range of adducts, which were analysed in solution by NMR methods, including DOSY NMR spectroscopy, and in the solid state by X-ray diffraction. The adducts include specific oligomers, and coordination polymers constructed via B–P, Al–P and Al–N interactions. The solid-state structure of these coordination polymers have been determined. The results of complexation of bidentate LB by the tetradentate PLA show that LB is preferentially chelated in the binding pockets, which does not impede the flapping movement during chelating complexation. This phenomenon can be attributed to a reduction in entropy when this flapping motion is lost. The aluminium containing PLAs were observed to form a complex with two caffeine molecules, exhibiting remarkable preference for oxygen functions. In contrast, the reaction with theobromine resulted in the degradation of the PLAs due to the presence of acidic protons in theobromine, leading to the formation of a dimeric aluminium containing theobromine derivative. These findings demonstrate the interaction of PLAs with drugs. They provide a foundation for the advancement of PLAs with a tuneable orientation of Lewis acidic functions.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"99 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703328","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Catalytic ensembles combining nanoparticles/clusters and atomically dispersed metal sites have demonstrated promising performance for various reactions. However, the optimal combinations between nanoparticles/clusters and metal single atoms remain unexplored. Herein, we integrate machine learning (ML) with density functional theory (DFT) calculations to explore the active ensembles consisting of platinum-based metallic clusters (Pt3M) and nitrogen-coordinated metal single atoms on the N-doped graphene (NC) matrix (Pt3M-M′NC). A total of 1521 candidates were screened using readily available metal properties to estimate the oxygen reduction reaction overpotential (ηORR), resulting in the identification of 24 active Pt3M-M′NC catalysts. Furthermore, the durability based on the ab initio molecular dynamics (AIMD) simulations, dissolution potential (Udiss), and cluster energies (Ecluster) was screened to identify four active and durable Pt3M-M′NC ensembles. The quantitative relationship between ηORR and metal features is deduced, enabling rapid and cost-effective screening of the optimal Pt3M-M′NC ensemble for the ORR. This work provides a comprehensive framework for the rational design of efficient and durable catalysts for oxygen reduction, leveraging the synergistic power of machine learning and DFT calculations to optimize catalytic ensembles with high performance.
{"title":"Unraveling active ensembles consisting of clusters and single atoms for oxygen reduction: a synergy of machine learning and DFT calculations","authors":"Xinyi Li, Dongxu Jiao, Jingxiang Zhao, Xiao Zhao","doi":"10.1039/d5qi00219b","DOIUrl":"https://doi.org/10.1039/d5qi00219b","url":null,"abstract":"Catalytic ensembles combining nanoparticles/clusters and atomically dispersed metal sites have demonstrated promising performance for various reactions. However, the optimal combinations between nanoparticles/clusters and metal single atoms remain unexplored. Herein, we integrate machine learning (ML) with density functional theory (DFT) calculations to explore the active ensembles consisting of platinum-based metallic clusters (Pt<small><sub>3</sub></small>M) and nitrogen-coordinated metal single atoms on the N-doped graphene (NC) matrix (Pt<small><sub>3</sub></small>M-M′NC). A total of 1521 candidates were screened using readily available metal properties to estimate the oxygen reduction reaction overpotential (<em>η</em><small><sup>ORR</sup></small>), resulting in the identification of 24 active Pt<small><sub>3</sub></small>M-M′NC catalysts. Furthermore, the durability based on the <em>ab initio</em> molecular dynamics (AIMD) simulations, dissolution potential (<em>U</em><small><sub>diss</sub></small>), and cluster energies (<em>E</em><small><sub>cluster</sub></small>) was screened to identify four active and durable Pt<small><sub>3</sub></small>M-M′NC ensembles. The quantitative relationship between <em>η</em><small><sup>ORR</sup></small> and metal features is deduced, enabling rapid and cost-effective screening of the optimal Pt<small><sub>3</sub></small>M-M′NC ensemble for the ORR. This work provides a comprehensive framework for the rational design of efficient and durable catalysts for oxygen reduction, leveraging the synergistic power of machine learning and DFT calculations to optimize catalytic ensembles with high performance.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"10 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703327","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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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