Abstract: The synthesis and complexation of borataalkenes are of burgeoning interests, owing to their isoelectronic structures to alkenes and potential applications in catalysis. Nevertheless, borataalkene lanthanide complexes are significantly underdeveloped to date, which presumably can be attributed to the mismatch between soft π(B=C) donor and hard lanthanide ions. We herein illustrate several tethered borataalkene cerium complexes. Treatment of cerium diylide 1 with excess BEt3 generated complex 2, featuring a 6-membered NBCPCSi ring. Subsequent reactions between 2 and excess KC8 lead to dearylation and ortho-metalation, affording complex [3•K2(Et2O)3]2. Control experiments imply that dearylation likely happened prior to ortho-metalation in the formation of complex [3•K2(Et2O)3]2, as suggested by the isolation of complex 4•K(Et2O)2. In these complexes, the atomic distances between B and C range from 1.461(14)-1.517(16) Å, demonstrating the presence of borataalkene moieties. Quantum chemical calculations elucidate their electronic structures, revealing the η2-B,C-cerium interactions are predominately electrostatic in nature with distinct ligand-to-metal π donations and without significant π backbonding contributions. These findings may open an avenue to other borataalkene f-block complexes and novel catalytic transformations mediated by them.
摘要/ Abstract摘要：硼烷的合成和络合由于其与烯烃的等电子结构以及在催化方面的潜在应用而引起了人们的广泛关注。然而，硼烷系镧系配合物迄今为止还不发达，这可能是由于软π(B=C)给体与硬镧系离子不匹配所致。我们在此举例说明几种系缚的硼烷铈配合物。用过量的BEt3处理二元化铈1生成具有6元NBCPCSi环的配合物2。随后2和过量的KC8之间的反应导致脱酰化和邻金属化，形成络合物[3•K2(Et2O)3]2。对照实验表明，配合物[3•K2(Et2O)3]2的分离表明，在形成配合物[3•K2(Et2O)3]2时，脱酰化可能发生在邻位金属化之前。在这些配合物中，B和C之间的原子距离在1.461(14)-1.517（16）Å之间，表明硼链烯烃部分的存在。量子化学计算阐明了它们的电子结构，揭示了η - 2- b， c -铈相互作用在本质上主要是静电的，具有明显的配体到金属的π捐赠，没有明显的π背键贡献。这些发现可能为其他硼烷f嵌段配合物及其介导的新型催化转化开辟了一条途径。
{"title":"Tethered η 2 -B,C Borataalkene Cerium Complexes","authors":"Wei Su,Laurent Maron,Qing Ye,Ganping Wang,Na Sun","doi":"10.1039/d6qi01313a","DOIUrl":"https://doi.org/10.1039/d6qi01313a","url":null,"abstract":"Abstract: The synthesis and complexation of borataalkenes are of burgeoning interests, owing to their isoelectronic structures to alkenes and potential applications in catalysis. Nevertheless, borataalkene lanthanide complexes are significantly underdeveloped to date, which presumably can be attributed to the mismatch between soft π(B=C) donor and hard lanthanide ions. We herein illustrate several tethered borataalkene cerium complexes. Treatment of cerium diylide 1 with excess BEt3 generated complex 2, featuring a 6-membered NBCPCSi ring. Subsequent reactions between 2 and excess KC8 lead to dearylation and ortho-metalation, affording complex [3•K2(Et2O)3]2. Control experiments imply that dearylation likely happened prior to ortho-metalation in the formation of complex [3•K2(Et2O)3]2, as suggested by the isolation of complex 4•K(Et2O)2. In these complexes, the atomic distances between B and C range from 1.461(14)-1.517(16) Å, demonstrating the presence of borataalkene moieties. Quantum chemical calculations elucidate their electronic structures, revealing the η2-B,C-cerium interactions are predominately electrostatic in nature with distinct ligand-to-metal π donations and without significant π backbonding contributions. These findings may open an avenue to other borataalkene f-block complexes and novel catalytic transformations mediated by them.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"221 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149019754","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}
Symmetry and topological features are crucial for understanding the nonlinear optical (NLO) effects of functional crystals. Here, we apply the topology-symmetry approach of Dornberger-Schiff's order-disorder (OD) theory, combined with topological analysis of underlying nets, to systematically investigate the only practically used deep-ultraviolet (DUV) NLO crystal KBe2BO3F2 (KBBF) and related compounds. The local symmetry of KBBF-type layers and interlayer spaces is characterized, and the maximum degree of order (MDO) polytypes for KBBF, as well as for KBBF-like family Pb2BO3X (X = Cl, Br, I), are described using symmetry groupoids. Topological analysis shows that KBBF and Pb2BO3X structures possess different topological types, despite identical local layer symmetries. Guided by these results, we designed two novel KBBF polytypes with the Pb2BO3X topology of underlying net, and confirmed their thermodynamic stability by first-principles calculations. The designed KBBF-P321 phase exhibits significantly enhanced second harmonic generation (d22 = 0.58 pm/V compared to 0.47 pm/V for KBBF-R32) due to optimal alignment of [BO3] anionic groups in adjacent layers. This work demonstrates that the integration of symmetry-based OD analysis, topological analysis, and first-principles calculations provides a powerful framework for the rational design of advanced nonlinear optical materials with tailored properties.
{"title":"Topology-Symmetry Analysis and Design of Nonlinear Optical Borate-Halide Polytypes","authors":"Olga Reutova,Wenqi Jin,Zhihua Yang,Shilie Pan","doi":"10.1039/d6qi01900e","DOIUrl":"https://doi.org/10.1039/d6qi01900e","url":null,"abstract":"Symmetry and topological features are crucial for understanding the nonlinear optical (NLO) effects of functional crystals. Here, we apply the topology-symmetry approach of Dornberger-Schiff's order-disorder (OD) theory, combined with topological analysis of underlying nets, to systematically investigate the only practically used deep-ultraviolet (DUV) NLO crystal KBe2BO3F2 (KBBF) and related compounds. The local symmetry of KBBF-type layers and interlayer spaces is characterized, and the maximum degree of order (MDO) polytypes for KBBF, as well as for KBBF-like family Pb2BO3X (X = Cl, Br, I), are described using symmetry groupoids. Topological analysis shows that KBBF and Pb2BO3X structures possess different topological types, despite identical local layer symmetries. Guided by these results, we designed two novel KBBF polytypes with the Pb2BO3X topology of underlying net, and confirmed their thermodynamic stability by first-principles calculations. The designed KBBF-P321 phase exhibits significantly enhanced second harmonic generation (d22 = 0.58 pm/V compared to 0.47 pm/V for KBBF-R32) due to optimal alignment of [BO3] anionic groups in adjacent layers. This work demonstrates that the integration of symmetry-based OD analysis, topological analysis, and first-principles calculations provides a powerful framework for the rational design of advanced nonlinear optical materials with tailored properties.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"221 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149019662","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}
Altermagnets exhibit compensated magnetic moments in real space while retaining nonrelativistic spin splitting in momentum space, offering a platform for field-robust, ultrafast spin dynamics. Yet practical routes to reversibly manipulate altermagnetic states remain limited and are dominated by structural or external-field modulation. Here, we introduce a chemical molecular-switch strategy that leverages tautomerism in organic linkers to reversibly control spin states in two-dimensional metal-organic framework (2D MOF). Using a Ni-based 2D frameworks as a representative system, we demonstrate a reversible transition between a nonmagnetic phase (Ni-L1) and an altermagnetic phase (Ni-L2) driven by solvent-assisted lactim-lactam proton transfer, with computed barriers of 0.30 eV (forward) and 0.43 eV (reverse). The altermagnetic state exhibits ligand-centered moments of ~ 0.50 µB and a characteristic spin-split electronic structure with band splitting extending across nearly the entire Brillouin zone. Symmetry analysis attributes this unusually persistent splitting to the reduced local (molecular) symmetry of the lactam linker, which removes mirror-related spin-degeneracy constraints present in higher-symmetry analogues. These results establish tautomerization as a chemically reversible handle for altermagnetic phase control in reticular materials and highlight molecular-scale symmetry as a decisive design parameter for reconfigurable altermagnetic electronics.
{"title":"Reversible On/Off Switching of Altermagnetism in Two-dimensional Metal-Organic-Frameworks via Molecular Tautomerism","authors":"Hongjing Wang,Yixuan Che,Yujin Wang,Xiuling Li,Xiaojun Wu","doi":"10.1039/d6qi00848h","DOIUrl":"https://doi.org/10.1039/d6qi00848h","url":null,"abstract":"Altermagnets exhibit compensated magnetic moments in real space while retaining nonrelativistic spin splitting in momentum space, offering a platform for field-robust, ultrafast spin dynamics. Yet practical routes to reversibly manipulate altermagnetic states remain limited and are dominated by structural or external-field modulation. Here, we introduce a chemical molecular-switch strategy that leverages tautomerism in organic linkers to reversibly control spin states in two-dimensional metal-organic framework (2D MOF). Using a Ni-based 2D frameworks as a representative system, we demonstrate a reversible transition between a nonmagnetic phase (Ni-L1) and an altermagnetic phase (Ni-L2) driven by solvent-assisted lactim-lactam proton transfer, with computed barriers of 0.30 eV (forward) and 0.43 eV (reverse). The altermagnetic state exhibits ligand-centered moments of ~ 0.50 µB and a characteristic spin-split electronic structure with band splitting extending across nearly the entire Brillouin zone. Symmetry analysis attributes this unusually persistent splitting to the reduced local (molecular) symmetry of the lactam linker, which removes mirror-related spin-degeneracy constraints present in higher-symmetry analogues. These results establish tautomerization as a chemically reversible handle for altermagnetic phase control in reticular materials and highlight molecular-scale symmetry as a decisive design parameter for reconfigurable altermagnetic electronics.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"47 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149019679","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}
Ke Chen,Bo Lan,Zhishan Liang,Yucong Zou,Dongdong Qin,Bo Ding,Dongfang Han,Wen-Sheng Zhang,Li Niu,Dongxue Han
Rapid exciton dissociation into free charge carriers is essential for efficient semiconductor photocatalysis, yet high exciton binding energy often constrains photocarrier extraction. While defect creation and morphological tailoring are individually established strategies, their combined effect on exciton dynamics and carrier migration requires clarification. In this work, 3D mesoporous bismuth oxybromide microtubes with abundant oxygen vacancies were synthesized via a mannitolmediated hydrothermal route, effectively overcoming the intrinsic 2D anisotropic growth habit of BiOBr. Transient absorption spectroscopy, photoluminescence decay measurements, and density functional theory calculations demonstrate that the coupling of 3D tubular nanoconfinement and Ov defect states reduces exciton binding energy, accelerates exciton dissociation, and extends carrier lifetimes. Consequently, the optimized Ov-BiOBr microtubes display enhanced O2 adsorption capacity and superior photocatalytic H2O2 production, achieving an apparent quantum yield of 7.2% at 420 nm-a 14.4-fold increase over pristine BiOBr. This study demonstrates a practical defect-morphology co-engineering approach for modulating exciton dynamics in functional semiconductors.
{"title":"Oxygen Vacancy-Rich 3D BiOBr Microtubes Promoting Exciton Dissociation for Efficient Photocatalytic H2O2 Production","authors":"Ke Chen,Bo Lan,Zhishan Liang,Yucong Zou,Dongdong Qin,Bo Ding,Dongfang Han,Wen-Sheng Zhang,Li Niu,Dongxue Han","doi":"10.1039/d6qi01964a","DOIUrl":"https://doi.org/10.1039/d6qi01964a","url":null,"abstract":"Rapid exciton dissociation into free charge carriers is essential for efficient semiconductor photocatalysis, yet high exciton binding energy often constrains photocarrier extraction. While defect creation and morphological tailoring are individually established strategies, their combined effect on exciton dynamics and carrier migration requires clarification. In this work, 3D mesoporous bismuth oxybromide microtubes with abundant oxygen vacancies were synthesized via a mannitolmediated hydrothermal route, effectively overcoming the intrinsic 2D anisotropic growth habit of BiOBr. Transient absorption spectroscopy, photoluminescence decay measurements, and density functional theory calculations demonstrate that the coupling of 3D tubular nanoconfinement and Ov defect states reduces exciton binding energy, accelerates exciton dissociation, and extends carrier lifetimes. Consequently, the optimized Ov-BiOBr microtubes display enhanced O2 adsorption capacity and superior photocatalytic H2O2 production, achieving an apparent quantum yield of 7.2% at 420 nm-a 14.4-fold increase over pristine BiOBr. This study demonstrates a practical defect-morphology co-engineering approach for modulating exciton dynamics in functional semiconductors.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"62 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149019718","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}
Low-dimensional magnetic materials have attracted considerable attention because of the exotic phenomena arising from enhanced quantum fluctuations. Herein, two V3+-based lead vanadium fluorides, Pb6V4F24 and Pb7V4F26, were synthesized by hydrothermal reactions. Single-crystal X-ray diffraction shows that triclinic Pb6V4F24 contains isolated V4 tetramers, whereas monoclinic Pb7V4F26 features screw chains, representing a structural evolution from zero-dimensional clusters to one-dimensional chains. Long-range magnetic order is absent on both compounds down to 2 K. DFT calculations show that Pb6V4F24 behaves magnetically as weakly coupled antiferromagnetic dimers, whereas Pb7V4F26 contains ferromagnetic chains coupled by weak antiferromagnetic interactions.
{"title":"From zero-dimensional square tetramers to one-dimensional screw chains: a structural evolution in V 3+ -based lead vanadium fluorides","authors":"Tianyu Zhu,Wenbin Wei,Du Wang,Zhujing Zhang,Pengfei Zhou,Donger Cheng,Xiaoqin Min,Guang Wang,Junrong Zhang,Zhangzhen He,Xiao Wang,Myung-Hwan Whangbo,Hyun-Joo Koo,Erxi Feng","doi":"10.1039/d6qi01376g","DOIUrl":"https://doi.org/10.1039/d6qi01376g","url":null,"abstract":"Low-dimensional magnetic materials have attracted considerable attention because of the exotic phenomena arising from enhanced quantum fluctuations. Herein, two V3+-based lead vanadium fluorides, Pb6V4F24 and Pb7V4F26, were synthesized by hydrothermal reactions. Single-crystal X-ray diffraction shows that triclinic Pb6V4F24 contains isolated V4 tetramers, whereas monoclinic Pb7V4F26 features screw chains, representing a structural evolution from zero-dimensional clusters to one-dimensional chains. Long-range magnetic order is absent on both compounds down to 2 K. DFT calculations show that Pb6V4F24 behaves magnetically as weakly coupled antiferromagnetic dimers, whereas Pb7V4F26 contains ferromagnetic chains coupled by weak antiferromagnetic interactions.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"62 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149019678","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}
The artificial photosynthesis of alcoholic products in natural seawater faces significant challenges, mainly including ion-interference and catalyst-corrosion, which generally results in reduced catalytic performance in natural seawater for majority of photocatalysts when compared with pure water. Here, we study the artificial photosynthesis of methanol in natural seawater based on a heterojunction photocatalyst (i.e. Cu2O/BMO, BMO = Bi2MoO6) and report a cation-mediated protective mechanism. Notably, it achieves an unprecedented CH3OH generation rate (501.62 μmol g-1 h-1) with high selectivity (95.8%) and long-term stability (>3 days) in natural seawater, affording abnormal performance enhancement when compared with that in pure water and surpassing the majority of reported photocatalysts to date. Theoretical calculations demonstrate that the enhanced performance in natural seawater compared to pure water arises from the strong interaction between Cu2O/BMO and cation ions that uniquely transforms the conventional ionic interference effect into a cation-mediated protective mechanism. Notably, on Cu2O/BMO surface, the cation ions (e.g., Ca2+ and Mg2+) could shield the active sites by mitigating hydroxyl (OH-) interference and stabilize the key reaction intermediates, thus enhancing both activity and stability of the overall artificial photosynthesis system.
{"title":"Navigating Cation Ion Effect for Artificial Photosynthesis of Methanol in Natural Seawater","authors":"Kejing Shen,Yixin Ouyang,Shanshan Zheng,Xinqi Pan,Xiaohui Wu,Xinyi Chen,Zixiong Zeng,Zhifeng Xin,Qiang Li,Yifa Chen","doi":"10.1039/d6qi01522k","DOIUrl":"https://doi.org/10.1039/d6qi01522k","url":null,"abstract":"The artificial photosynthesis of alcoholic products in natural seawater faces significant challenges, mainly including ion-interference and catalyst-corrosion, which generally results in reduced catalytic performance in natural seawater for majority of photocatalysts when compared with pure water. Here, we study the artificial photosynthesis of methanol in natural seawater based on a heterojunction photocatalyst (i.e. Cu2O/BMO, BMO = Bi2MoO6) and report a cation-mediated protective mechanism. Notably, it achieves an unprecedented CH3OH generation rate (501.62 μmol g-1 h-1) with high selectivity (95.8%) and long-term stability (>3 days) in natural seawater, affording abnormal performance enhancement when compared with that in pure water and surpassing the majority of reported photocatalysts to date. Theoretical calculations demonstrate that the enhanced performance in natural seawater compared to pure water arises from the strong interaction between Cu2O/BMO and cation ions that uniquely transforms the conventional ionic interference effect into a cation-mediated protective mechanism. Notably, on Cu2O/BMO surface, the cation ions (e.g., Ca2+ and Mg2+) could shield the active sites by mitigating hydroxyl (OH-) interference and stabilize the key reaction intermediates, thus enhancing both activity and stability of the overall artificial photosynthesis system.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"1 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149013599","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}
This work reports the in-situ synthesis of monolayer hybrid chiral perovskite films R/S-MBAPbBr₃@MBA₂PbBr₄ via temperature modulation, which combining the chiral one-dimensional (1D) R/S-MBAPbBr3 perovskite with two-dimensional (2D) non-luminescent (R/S-MBA)2PbBr4 perovskite. The as-synthesized chiral hybrid films exhibit stronger circularly polarized luminescence (CPL) response than that of the corresponding 1D chiral perovskite films. The circularly polarization-resolved transient absorption (TA) spectra reveal that the enhancement of CPL response stems from the energy transfer between chiral 2D perovskite structure and the defect states of chiral 1D perovskite structure, which can increase the imbalanced spin population in the defect levels. In addition, the CPL response can be further improved by combining the chiral perovskite hybrid films with achiral silver nanowires. TA spectra demonstrate that the localized plasma field enhances the carrier recombination rate without altering their spin polarization lifetime. This work provides guidance for the synthesis of chiral perovskite films with strong CPL response and further provides insight into the relevant mechanism of CPL enhancement.
{"title":"Synergistic Amplification of Circularly Polarized Luminescence in Chiral Perovskite Films via Energy Transfer and Localized Surface Plasmon Resonance","authors":"ting li,Yuan Wang,Laipeng Sun,Yu Wang,Jiaqi Zhao","doi":"10.1039/d6qi02193j","DOIUrl":"https://doi.org/10.1039/d6qi02193j","url":null,"abstract":"This work reports the in-situ synthesis of monolayer hybrid chiral perovskite films R/S-MBAPbBr₃@MBA₂PbBr₄ via temperature modulation, which combining the chiral one-dimensional (1D) R/S-MBAPbBr3 perovskite with two-dimensional (2D) non-luminescent (R/S-MBA)2PbBr4 perovskite. The as-synthesized chiral hybrid films exhibit stronger circularly polarized luminescence (CPL) response than that of the corresponding 1D chiral perovskite films. The circularly polarization-resolved transient absorption (TA) spectra reveal that the enhancement of CPL response stems from the energy transfer between chiral 2D perovskite structure and the defect states of chiral 1D perovskite structure, which can increase the imbalanced spin population in the defect levels. In addition, the CPL response can be further improved by combining the chiral perovskite hybrid films with achiral silver nanowires. TA spectra demonstrate that the localized plasma field enhances the carrier recombination rate without altering their spin polarization lifetime. This work provides guidance for the synthesis of chiral perovskite films with strong CPL response and further provides insight into the relevant mechanism of CPL enhancement.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"24 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149010174","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}
Vasiliki I. Karagianni,Vasiliki Aggeli,Christos Dimitriou,Ioannis Vamvasakis,Yiannis Deligiannakis,Gerasimos S Armatas,Manolis J. Manos
Efficiently remediating divergent classes of water pollutants, specifically soft Lewis acid cations (Pb2+) and highly toxic oxyanions (Cr6+), remains a paramount challenge in environmental chemistry and engineering due to the completely opposing surface chemistries required for their respective immobilization. Herein, we present a new metal sulfide, namely T-AMS-1, (NH4+)1.6(TU)2.3Mn0.8Sn2.2S6•0.3(H2O) (TU=thiourea), an analog of the well-known KMS-1, synthesized via a solventfree, molten thiourea flux route. Unlike KMS-type materials that host alkali metal ions, T-AMS-1 forms a hybrid organicinorganic intercalated structure in which ammonium (NH4+) cations and neutral thiourea (TU) molecules fill the interlayer space. Under optimal batch conditions, T-AMS-1 exhibits rapid kinetics (≤5 min), a high maximum removal capacity (194 mg g -1 ), and selectivity for Pb2+ ions vs. common competitive ionic species. Similarly, for Cr6+ at pH=3, the material displays rapid kinetics (≤4 min), a high removal capacity (157 mg Cr6+ g -1 ), and exceptional selectivity for Cr6+, maintaining outstanding performance even in highly complex real water and seawater matrices. Notably, T-AMS-1, as calcium alginate beads employed as the stationary phase within a column containing sea sand, demonstrates a notable ability to capture both species from real samples under continuous flow and is reusable. This work establishes a solvent-free synthetic strategy for multi-functional, layered metal sulfides that act as versatile platforms for targeted environmental decontamination.
有效修复不同类型的水污染物，特别是软路易斯酸阳离子（Pb2+）和高毒性氧离子（Cr6+），仍然是环境化学和工程中的一个重大挑战，因为它们各自的固定所需的完全相反的表面化学。本文提出了一种新的金属硫化物，即T-AMS-1， （NH4+）1.6(TU)2.3Mn0.8Sn2.2S6•0.3(H2O) （TU=硫脲），它是众所周知的KMS-1的类似物，通过无溶剂的熔融硫脲助熔剂路线合成。与含有碱金属离子的kms型材料不同，T-AMS-1形成了一种杂化的有机无机插层结构，其中铵（NH4+）阳离子和中性硫脲（TU）分子填充了层间空间。在最佳批处理条件下，T-AMS-1表现出快速的动力学（≤5 min），高的最大去除率（194 mg g -1），以及对Pb2+离子的选择性。同样，对于pH=3的Cr6+，该材料表现出快速的动力学（≤4分钟），高去除能力（157 mg Cr6+ g -1），以及对Cr6+的卓越选择性，即使在高度复杂的真实水和海水基质中也保持出色的性能。值得注意的是，T-AMS-1作为海藻酸钙珠珠，在含有海砂的柱中作为固定相，在连续流动下从实际样品中捕获两种物质的能力显著，并且可重复使用。这项工作建立了一种无溶剂合成策略，用于多功能，层状金属硫化物，作为目标环境净化的多功能平台。
{"title":"An ammonium-thiourea-intercalated layered metal sulfide for efficient removal of Pb2+ and Cr6+ from aqueous solutions","authors":"Vasiliki I. Karagianni,Vasiliki Aggeli,Christos Dimitriou,Ioannis Vamvasakis,Yiannis Deligiannakis,Gerasimos S Armatas,Manolis J. Manos","doi":"10.1039/d6qi01326k","DOIUrl":"https://doi.org/10.1039/d6qi01326k","url":null,"abstract":"Efficiently remediating divergent classes of water pollutants, specifically soft Lewis acid cations (Pb2+) and highly toxic oxyanions (Cr6+), remains a paramount challenge in environmental chemistry and engineering due to the completely opposing surface chemistries required for their respective immobilization. Herein, we present a new metal sulfide, namely T-AMS-1, (NH4+)1.6(TU)2.3Mn0.8Sn2.2S6•0.3(H2O) (TU=thiourea), an analog of the well-known KMS-1, synthesized via a solventfree, molten thiourea flux route. Unlike KMS-type materials that host alkali metal ions, T-AMS-1 forms a hybrid organicinorganic intercalated structure in which ammonium (NH4+) cations and neutral thiourea (TU) molecules fill the interlayer space. Under optimal batch conditions, T-AMS-1 exhibits rapid kinetics (≤5 min), a high maximum removal capacity (194 mg g -1 ), and selectivity for Pb2+ ions vs. common competitive ionic species. Similarly, for Cr6+ at pH=3, the material displays rapid kinetics (≤4 min), a high removal capacity (157 mg Cr6+ g -1 ), and exceptional selectivity for Cr6+, maintaining outstanding performance even in highly complex real water and seawater matrices. Notably, T-AMS-1, as calcium alginate beads employed as the stationary phase within a column containing sea sand, demonstrates a notable ability to capture both species from real samples under continuous flow and is reusable. This work establishes a solvent-free synthetic strategy for multi-functional, layered metal sulfides that act as versatile platforms for targeted environmental decontamination.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"192 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149013598","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}
The multivariate approach allows to achieve a controlled degree of structural heterogeneity within metal-organic frameworks (MOFs), offering a powerful means to finely tune the properties of the framework at the molecular level. In this work, we apply this concept to the MIL-140A(Ce) framework to systematically introduce multiple fluorinated terephthalate linkers (Fx-BDC2-), enabling precise modulation of the cooperative CO2 adsorption behaviour through the control of the framework's degree of fluorination. By simultaneously incorporating and varying the nature and content of Fx-BDC2- co-linkers (x = 1, 2, 3) while maintaining F4-BDC2- as a fixed component, we synthesised a large library of mixed-linker F4:Fx_MIL-140A(Ce) materials, whose nature of solid solutions was demonstrated. Across the series, we found that cooperative CO2 adsorption occurs above a threshold degree of fluorination of the framework of 75%, independently of fluorine positional isomerism, as demonstrated by the series of o-, m-, and pF2-BDC2- co-linkers, and is not determined by the content of the perfluorinated linker. The implication of the fluorination threshold on CO2/CH4 selectivity was also assessed, revealing that the onset of CO2-induced cooperative adsorption above this threshold is associated with a dramatic increase in selectivity towards CO2. Since the degree of fluorination of single-linker MOFs is intrinsically fixed, the mixed-linker strategy represents an effective route to continuously tune the framework's composition, thereby enabling the establishment of a structural design principle to control the emergence of cooperative CO₂ adsorption.
{"title":"Switchable cooperative CO adsorption in multivariate fluorinated MIL-140A(Ce) metal-organic frameworks","authors":"Francesca Nerli,Dario Rocchi,Virginia Guiotto,Marco Lessi,Valentina Crocellà,Marco Taddei","doi":"10.1039/d6qi01836j","DOIUrl":"https://doi.org/10.1039/d6qi01836j","url":null,"abstract":"The multivariate approach allows to achieve a controlled degree of structural heterogeneity within metal-organic frameworks (MOFs), offering a powerful means to finely tune the properties of the framework at the molecular level. In this work, we apply this concept to the MIL-140A(Ce) framework to systematically introduce multiple fluorinated terephthalate linkers (Fx-BDC2-), enabling precise modulation of the cooperative CO2 adsorption behaviour through the control of the framework's degree of fluorination. By simultaneously incorporating and varying the nature and content of Fx-BDC2- co-linkers (x = 1, 2, 3) while maintaining F4-BDC2- as a fixed component, we synthesised a large library of mixed-linker F4:Fx_MIL-140A(Ce) materials, whose nature of solid solutions was demonstrated. Across the series, we found that cooperative CO2 adsorption occurs above a threshold degree of fluorination of the framework of 75%, independently of fluorine positional isomerism, as demonstrated by the series of o-, m-, and pF2-BDC2- co-linkers, and is not determined by the content of the perfluorinated linker. The implication of the fluorination threshold on CO2/CH4 selectivity was also assessed, revealing that the onset of CO2-induced cooperative adsorption above this threshold is associated with a dramatic increase in selectivity towards CO2. Since the degree of fluorination of single-linker MOFs is intrinsically fixed, the mixed-linker strategy represents an effective route to continuously tune the framework's composition, thereby enabling the establishment of a structural design principle to control the emergence of cooperative CO₂ adsorption.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"293 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149013602","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}
Ying Chen,Qingyi Feng,Yeqing Yang,Xiaocong Shen,Pingkang Li,Mingyue Yang,Xue Li,Xiang-Long Huang,Yun-Xiao Wang
Despite high theoretical energy density, low cost, and abundant natural resources, the development of emerging room-temperature sodium–sulfur (Na–S) batteries is still confronting many challenges. These key issues include the insulating nature of solid sulfur, the shuttle effect of polysulfides, sluggish reaction kinetics, and sodium dendrite growth. Doped carbon materials hold multiple advantages including tunable electronic structures, abundant polar sites, high specific surface areas, and outstanding electrocatalytic activity, which make them promising for dendrite-free sodium anodes and electrochemically stable sulfur cathodes. This review systematically deciphers the research development of doped carbon materials for Na–S batteries. The electrochemical principles and core challenges of Na–S batteries are discussed first. The key roles of doping sites in Na–S electrochemistry and various typical doping configurations are then elaborated. Next, we place emphasis on the practical applications of doped carbons in Na–S batteries, including cathode hosts, separators/interlayers, and sodium anode skeletons. Finally, the challenges and future directions are summarized, aiming to guide advanced material designs for Na–S batteries.
{"title":"Doped carbons for room-temperature Na–S batteries: a comprehensive review","authors":"Ying Chen,Qingyi Feng,Yeqing Yang,Xiaocong Shen,Pingkang Li,Mingyue Yang,Xue Li,Xiang-Long Huang,Yun-Xiao Wang","doi":"10.1039/d6qi01714b","DOIUrl":"https://doi.org/10.1039/d6qi01714b","url":null,"abstract":"Despite high theoretical energy density, low cost, and abundant natural resources, the development of emerging room-temperature sodium–sulfur (Na–S) batteries is still confronting many challenges. These key issues include the insulating nature of solid sulfur, the shuttle effect of polysulfides, sluggish reaction kinetics, and sodium dendrite growth. Doped carbon materials hold multiple advantages including tunable electronic structures, abundant polar sites, high specific surface areas, and outstanding electrocatalytic activity, which make them promising for dendrite-free sodium anodes and electrochemically stable sulfur cathodes. This review systematically deciphers the research development of doped carbon materials for Na–S batteries. The electrochemical principles and core challenges of Na–S batteries are discussed first. The key roles of doping sites in Na–S electrochemistry and various typical doping configurations are then elaborated. Next, we place emphasis on the practical applications of doped carbons in Na–S batteries, including cathode hosts, separators/interlayers, and sodium anode skeletons. Finally, the challenges and future directions are summarized, aiming to guide advanced material designs for Na–S batteries.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"16 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149010175","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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