Zhuo Han, Haofeng Wu, Ge Niu, Baichuan Tang, Zhongyi Zhao, Minmeng Tang, Linhua Zhu, Yanhong Chao, Wenshuai Zhu, Yuanbin She
Adsorption has emerged as a green and promising solution for antibiotic removal in wastewater treatment system, driving an urgent demand for designing high-performance and eco-friendly adsorbents that enable rapid, efficient elimination of antibiotic contaminants. Herein, a high-activity Fe-based metal-organic framework (Fe-MOF) was in-situ integrated with a copper-cobalt-iron layered double hydroxide (CuCoFe-LDH) via a two-step hydrothermal synthesis process, successfully fabricating an engineered Fe-MOF@CuCoFe-LDH composite adsorbent that exhibits significantly enhanced adsorption capacity and broad applicability. The Fe-MOF nanospheres were uniformly hybridized into the two-dimensional nanocluster flakes of the ternary hydrotalcite CuCoFe-LDH, forming a hierarchical heterostructure. This synergistic configuration substantially boosted the density of active surface sites on the LDH-based adsorbent, resulting in significantly improved adsorption kinetics along with enhanced absorbate-binding capacity. The removal efficiency of tetracycline antibiotic (TC) by the as-prepared Fe-MOF@CuCoFe-LDH composite reaches 94.8%, even at a high initial TC concentration of 300 mg/L, which represents a 36.7% and 9.4% increase compared to that of pristine Fe-MOF and CuCoFe-LDH, respectively. A high Langmuir maximum adsorption capacity of 2500 mg/g was achieved. The adsorption mechanism was speculated to be the metal complexation, metal-π, H-bond and electrostatic interaction as well as hydrophobic interaction. In addition, Fe-MOF@CuCoFe-LDH composite demonstrated exceptional cycling stability, retaining 97.8% TC removal efficiency through five adsorption-desorption cycles, highlighting its outstanding adaptability and promising potential for practical wastewater remediation applications.
{"title":"Iron-based organic framework modified Cu-Co-Fe ternary layered double hydroxide enhanced adsorptive removal of antibiotics","authors":"Zhuo Han, Haofeng Wu, Ge Niu, Baichuan Tang, Zhongyi Zhao, Minmeng Tang, Linhua Zhu, Yanhong Chao, Wenshuai Zhu, Yuanbin She","doi":"10.1039/d5dt02540k","DOIUrl":"https://doi.org/10.1039/d5dt02540k","url":null,"abstract":"Adsorption has emerged as a green and promising solution for antibiotic removal in wastewater treatment system, driving an urgent demand for designing high-performance and eco-friendly adsorbents that enable rapid, efficient elimination of antibiotic contaminants. Herein, a high-activity Fe-based metal-organic framework (Fe-MOF) was in-situ integrated with a copper-cobalt-iron layered double hydroxide (CuCoFe-LDH) via a two-step hydrothermal synthesis process, successfully fabricating an engineered Fe-MOF@CuCoFe-LDH composite adsorbent that exhibits significantly enhanced adsorption capacity and broad applicability. The Fe-MOF nanospheres were uniformly hybridized into the two-dimensional nanocluster flakes of the ternary hydrotalcite CuCoFe-LDH, forming a hierarchical heterostructure. This synergistic configuration substantially boosted the density of active surface sites on the LDH-based adsorbent, resulting in significantly improved adsorption kinetics along with enhanced absorbate-binding capacity. The removal efficiency of tetracycline antibiotic (TC) by the as-prepared Fe-MOF@CuCoFe-LDH composite reaches 94.8%, even at a high initial TC concentration of 300 mg/L, which represents a 36.7% and 9.4% increase compared to that of pristine Fe-MOF and CuCoFe-LDH, respectively. A high Langmuir maximum adsorption capacity of 2500 mg/g was achieved. The adsorption mechanism was speculated to be the metal complexation, metal-π, H-bond and electrostatic interaction as well as hydrophobic interaction. In addition, Fe-MOF@CuCoFe-LDH composite demonstrated exceptional cycling stability, retaining 97.8% TC removal efficiency through five adsorption-desorption cycles, highlighting its outstanding adaptability and promising potential for practical wastewater remediation applications.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"55 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145995938","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Bin Liu, Wen-Hui Huang, Qian-Qian Liang, Zi-Chen Shi, Jianhui Yang
The structural transformation of metal-metal bonding dimer induced by external stimuli is of scientific significance in terms of both M-M compounds synthesis and reactivity. This paper reported the transformation stimulated by Et3N from paddle-wheel Ru2(CH3CO2)4+ with a typical open-shell electronic configuration σ2π4δ2π*2δ* to Ru2(CH3CO2)2(CH3O)2(hfac)2 (2) (hfac = hexafluoroacetylacetonate) undergoing a stable asymmetric intermediate Ru2(CH3CO2)2(CH3O)3(hfac)(CH3OH) (1), and both compounds 1 and 2 exhibit a edge-sharing bi-octahedra (ESBO) characteristic close-shell electronic configuration σ2π2δ2δ*2π*2. The evolution of solution species revealed by temperature- and time-dependent electrospray ionization mass spectrometry (ESI-MS) suggests a step by step transformation mechanism, convincing that the Ru2 dimer can adapt to changes in metal-metal bonding type and oxidation state without undergoing dissociation to monomeric Ru fragments. This is the first mechanism exploration of the M-M dimer structural transformation study using ESI-MS. The results not only reveal the important reactivity of dimetal carboxylates with ligands exchanging, but also deep understand the conversion mechanism of M-M multiple bonds type affected by the coordination environment
{"title":"A step by step structural transformation of Ru-Ru bonding unit from paddle-wheel to edge-sharing bi-octahedra configuration","authors":"Bin Liu, Wen-Hui Huang, Qian-Qian Liang, Zi-Chen Shi, Jianhui Yang","doi":"10.1039/d5dt02334c","DOIUrl":"https://doi.org/10.1039/d5dt02334c","url":null,"abstract":"The structural transformation of metal-metal bonding dimer induced by external stimuli is of scientific significance in terms of both M-M compounds synthesis and reactivity. This paper reported the transformation stimulated by Et3N from paddle-wheel Ru2(CH3CO2)4+ with a typical open-shell electronic configuration σ2π4δ2π*2δ* to Ru2(CH3CO2)2(CH3O)2(hfac)2 (2) (hfac = hexafluoroacetylacetonate) undergoing a stable asymmetric intermediate Ru2(CH3CO2)2(CH3O)3(hfac)(CH3OH) (1), and both compounds 1 and 2 exhibit a edge-sharing bi-octahedra (ESBO) characteristic close-shell electronic configuration σ2π2δ2δ*2π*2. The evolution of solution species revealed by temperature- and time-dependent electrospray ionization mass spectrometry (ESI-MS) suggests a step by step transformation mechanism, convincing that the Ru2 dimer can adapt to changes in metal-metal bonding type and oxidation state without undergoing dissociation to monomeric Ru fragments. This is the first mechanism exploration of the M-M dimer structural transformation study using ESI-MS. The results not only reveal the important reactivity of dimetal carboxylates with ligands exchanging, but also deep understand the conversion mechanism of M-M multiple bonds type affected by the coordination environment","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"38 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145993170","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pavel V Burlak, Anastasia M. Cheplakova, Denis G. Samsonenko, Andrey S. Vinogradov, Konstantin A Kovalenko, Vladimir P Fedin
Cadmium(II) can form complexes with coordination numbers 6 and 7, which makes them labile, especially with relatively weak ligands like perfluorinated carboxylates. Confining the coordination environment with chelating ligands such as 2,2'-bipyridyl (2,2'-bpy) is a promising approach to obtain complexes with more predictable geometry and stability. Using this strategy, MOFs with anions of octafluorobiphenyldicarboxylic acid (H₂oFbpdc) were successfully synthesized in different alcohols. Compound [Cd(2,2'-bpy)(oFbpdc)] · CH₃OH (1 * MeOH) exhibits a 3D framework, whereas the other phases [Cd(2,2'-bpy)(oFbpdc)] · G} (2 · G), G = EtOH, iPrOH, tBuOH) adopt a layered structure. Thermal activation of all phases results in guest removal, yielding the non-porous phase [Cd(2,2'-bpy)(oFbpdc)] (2). Despite its non-porous nature, 2 undergoes a structural transformation upon CO₂ adsorption into an open form with a specific surface area of 237 m²·g⁻¹. This transformed phase shows good adsorption selectivity for binary C₂H₂/CH₄ and CO₂/CH₄ mixtures.
镉（II）可以形成配位数为6和7的配合物，这使得它们不稳定，特别是与全氟羧酸盐等相对弱的配体。用螯合配体（如2,2'-联吡啶（2,2'-bpy））限制配位环境是获得具有更可预测几何形状和稳定性的配合物的一种很有前途的方法。利用这一策略，在不同的醇中成功地合成了含辛氟联苯二羧酸（H₂oFbpdc）阴离子的mof。化合物[Cd(2,2′-bpy)(oFbpdc)]·CH₃OH （1 * MeOH）呈三维结构，而其他相[Cd(2,2′-bpy)（oFbpdc)]·G}(2·G), G = EtOH, iPrOH, tBuOH）呈层状结构。所有相的热活化导致客体去除，产生无孔相[Cd(2,2'-bpy)(oFbpdc)](2)。尽管它是无孔的，但在CO₂吸附后，2的结构会发生转变，形成一个开放的结构，其比表面积为237 m²·g⁻¹。转化相对C₂H₂/CH₄和CO₂/CH₄二元混合物具有良好的吸附选择性。
{"title":"Confinement of Cd(II) by 2,2′ -Bipyridyl: Control of Structural Transformations and Porosity in Perfluorinated Biphenyldicarboxylate MOFs","authors":"Pavel V Burlak, Anastasia M. Cheplakova, Denis G. Samsonenko, Andrey S. Vinogradov, Konstantin A Kovalenko, Vladimir P Fedin","doi":"10.1039/d5dt02607e","DOIUrl":"https://doi.org/10.1039/d5dt02607e","url":null,"abstract":"Cadmium(II) can form complexes with coordination numbers 6 and 7, which makes them labile, especially with relatively weak ligands like perfluorinated carboxylates. Confining the coordination environment with chelating ligands such as 2,2'-bipyridyl (2,2'-bpy) is a promising approach to obtain complexes with more predictable geometry and stability. Using this strategy, MOFs with anions of octafluorobiphenyldicarboxylic acid (H₂oFbpdc) were successfully synthesized in different alcohols. Compound [Cd(2,2'-bpy)(oFbpdc)] · CH₃OH (<strong>1 * MeOH</strong>) exhibits a 3D framework, whereas the other phases [Cd(2,2'-bpy)(oFbpdc)] · G} (<strong>2 · G</strong>), G = EtOH, <em>i</em>PrOH, <em>t</em>BuOH) adopt a layered structure. Thermal activation of all phases results in guest removal, yielding the non-porous phase [Cd(2,2'-bpy)(oFbpdc)] (<strong>2</strong>). Despite its non-porous nature, <strong>2</strong> undergoes a structural transformation upon CO₂ adsorption into an open form with a specific surface area of 237 m²·g⁻¹. This transformed phase shows good adsorption selectivity for binary C₂H₂/CH₄ and CO₂/CH₄ mixtures.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"83 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145972264","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Beryllium, despite belonging to the s-block of the periodic table, has long remained a chemical enigma. Its notorious toxicity, stringent handling requirements, and limited availability have collectively stunted the pace of exploratory research compared to its heavier congeners. Yet, in the last decade, pioneering efforts by many research groups have challenged this narrative by uncovering a surprising spectrum of unusual and unprecedented molecular architectures of beryllium compounds. Recent advances have demonstrated that beryllium can engage in bonding- and reactivity patterns previously considered inaccessible to s-block elements. These include the realization of multiple-bond character, the stabilization of low-coordinate and open-shell species, and the isolation of compounds featuring unusual electronic structures. Notable achievements encompass the synthesis of beryllium complexes supported by strong donor ligands such as CAACs, the isolation of diberyllocene featuring a Be–Be bond, and the first structurally isolated beryllium radical cations and tricoordinate radical species. In parallel, the emergence of heterobimetallic systems featuring polarized Be–M interactions across the s-, p-, and d-blocks has underscore the ability of beryllium to engage in cooperative bonding and reactivity with diverse metal partners. This review aims to comprehensively document the recent breakthroughs in molecular organometallic chemistry of beryllium in the last decade, emphasizing the unusual bonding paradigms and reactivity that redefine the long-standing perception of s-block inertness.
{"title":"Beryllium gets going, finally. Recent highlights in the organometallic chemistry of beryllium","authors":"Vadapalli Chandrasekhar, Bhagyashree Das","doi":"10.1039/d5dt02876k","DOIUrl":"https://doi.org/10.1039/d5dt02876k","url":null,"abstract":"Beryllium, despite belonging to the s-block of the periodic table, has long remained a chemical enigma. Its notorious toxicity, stringent handling requirements, and limited availability have collectively stunted the pace of exploratory research compared to its heavier congeners. Yet, in the last decade, pioneering efforts by many research groups have challenged this narrative by uncovering a surprising spectrum of unusual and unprecedented molecular architectures of beryllium compounds. Recent advances have demonstrated that beryllium can engage in bonding- and reactivity patterns previously considered inaccessible to s-block elements. These include the realization of multiple-bond character, the stabilization of low-coordinate and open-shell species, and the isolation of compounds featuring unusual electronic structures. Notable achievements encompass the synthesis of beryllium complexes supported by strong donor ligands such as CAACs, the isolation of diberyllocene featuring a Be–Be bond, and the first structurally isolated beryllium radical cations and tricoordinate radical species. In parallel, the emergence of heterobimetallic systems featuring polarized Be–M interactions across the s-, p-, and d-blocks has underscore the ability of beryllium to engage in cooperative bonding and reactivity with diverse metal partners. This review aims to comprehensively document the recent breakthroughs in molecular organometallic chemistry of beryllium in the last decade, emphasizing the unusual bonding paradigms and reactivity that redefine the long-standing perception of s-block inertness.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"49 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145993172","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The luminescent phase of the blue-emitting phosphor BaMgSi4O10:Eu2+, the structure of which was previously reported to be a gillespite (BaFeSi4O10)-type structure, has been identified by detailed investigations through single-crystal X-ray diffraction (XRD) analysis, powder Rietveld analysis and luminescence measurements. The actual blue-emitting phase was newly found to be BaMgSi3O8:Eu2+, whose host lattice has a triclinic alkali feldspar-type structure.
{"title":"Crystal structure elucidation and luminescence properties of a blue-emitting BaMgSi3O8:Eu2+ phosphor with an alkali feldspar structure","authors":"Wataru Hikita, Mineo Sato and Kenji Toda","doi":"10.1039/D5DT02821C","DOIUrl":"10.1039/D5DT02821C","url":null,"abstract":"<p >The luminescent phase of the blue-emitting phosphor BaMgSi<small><sub>4</sub></small>O<small><sub>10</sub></small>:Eu<small><sup>2+</sup></small>, the structure of which was previously reported to be a gillespite (BaFeSi<small><sub>4</sub></small>O<small><sub>10</sub></small>)-type structure, has been identified by detailed investigations through single-crystal X-ray diffraction (XRD) analysis, powder Rietveld analysis and luminescence measurements. The actual blue-emitting phase was newly found to be BaMgSi<small><sub>3</sub></small>O<small><sub>8</sub></small>:Eu<small><sup>2+</sup></small>, whose host lattice has a triclinic alkali feldspar-type structure.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" 5","pages":" 2148-2155"},"PeriodicalIF":3.3,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145986301","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Supercapacitors have emerged as a crucial class of energy storage devices due to their high power density and long cycle life. However, the development of electrode materials that combine high specific capacitance and robust stability remains a challenge. In this work, two-dimensional (2D) Ni-based metal-organic frameworks (Ni-MOFs) were employed as precursors to synthesize Ni₃S₂ nanoparticles embedded within porous carbon nanosheets via a straightforward pyrolysis-vulcanization process. By systematically adjusting the auxiliary ligand in the MOF precursor and the subsequent calcination temperature (600, 800, and 1000 °C), the composition and morphology of the final materials were effectively tuned. The sample derived from Ni-MOF-a at 1000 °C (Ni-MOF-a@S10) exhibited optimal electrochemical performance, delivering a high specific capacitance of 497 F/g at 0.5 A/g and an outstanding cycling stability with 76.9% capacitance retention after 3000 cycles at 10 A/g. Kinetic analysis revealed that the charge storage was primarily governed by a surface-capacitive mechanism, which facilitated excellent rate capability. Furthermore, an asymmetric supercapacitor assembled with Ni-MOF-a@S10 as the positive electrode demonstrated a high power density of 1128.56 W/kg. This study not only presents a high-performance electrode material but also validates a versatile strategy for designing MOF-derived nanostructures for advanced energy storage applications.
超级电容器因其高功率密度和长循环寿命而成为一种重要的储能设备。然而，结合高比电容和稳健稳定性的电极材料的开发仍然是一个挑战。在这项工作中，二维（2D） Ni基金属有机框架（Ni- mofs）被用作前驱体，通过直接的热解-硫化工艺合成了嵌入在多孔碳纳米片中的Ni₃S₂纳米颗粒。通过系统地调整MOF前驱体中的辅助配体以及随后的煅烧温度（600、800和1000℃），可以有效地调整最终材料的组成和形貌。Ni-MOF-a样品在1000°C （Ni-MOF-a@S10）下表现出最佳的电化学性能，在0.5 a /g下具有497 F/g的高比电容，在10 a /g下循环3000次后具有76.9%的电容保持率。动力学分析表明，电荷存储主要由表面电容机制控制，这有利于优异的倍率性能。此外，以Ni-MOF-a@S10为正极组装的非对称超级电容器的功率密度高达1128.56 W/kg。这项研究不仅提出了一种高性能的电极材料，而且验证了一种用于先进储能应用的mof衍生纳米结构设计的通用策略。
{"title":"Temperature-controlled synthesis of MOF-derived Ni3S2/C nanocomposites for high-performance supercapacitors","authors":"Xin Wang, Jian Luan, Ying Yang, Wen-Long Duan, Tian-Fang Cui, Wenze Li","doi":"10.1039/d5dt02866c","DOIUrl":"https://doi.org/10.1039/d5dt02866c","url":null,"abstract":"Supercapacitors have emerged as a crucial class of energy storage devices due to their high power density and long cycle life. However, the development of electrode materials that combine high specific capacitance and robust stability remains a challenge. In this work, two-dimensional (2D) Ni-based metal-organic frameworks (Ni-MOFs) were employed as precursors to synthesize Ni₃S₂ nanoparticles embedded within porous carbon nanosheets via a straightforward pyrolysis-vulcanization process. By systematically adjusting the auxiliary ligand in the MOF precursor and the subsequent calcination temperature (600, 800, and 1000 °C), the composition and morphology of the final materials were effectively tuned. The sample derived from Ni-MOF-a at 1000 °C (Ni-MOF-a@S10) exhibited optimal electrochemical performance, delivering a high specific capacitance of 497 F/g at 0.5 A/g and an outstanding cycling stability with 76.9% capacitance retention after 3000 cycles at 10 A/g. Kinetic analysis revealed that the charge storage was primarily governed by a surface-capacitive mechanism, which facilitated excellent rate capability. Furthermore, an asymmetric supercapacitor assembled with Ni-MOF-a@S10 as the positive electrode demonstrated a high power density of 1128.56 W/kg. This study not only presents a high-performance electrode material but also validates a versatile strategy for designing MOF-derived nanostructures for advanced energy storage applications.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"58 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145972259","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Highly emissive Cu(I) halide complexes with short decay lifetimes (several μs scale) have attracted attention. Here, three dinuclear four-coordinate Cu(I) halide complexes containing unsymmetric diphosphine [Cu 2 X 2 (L1) 2 ] (L1 = 9-(4,5-bis(diphenylphosphino)-2-(1H-pyrrol-1-yl)phenyl)-9H-carbazole, X = I (1), Br(2), Cl (3)) were synthesized, and their structures, photophysical and photocatalytic hydrogen production properties were characterized. In these complexes, two copper(I) centers are bridged by two halogen ligands to form a dinuclear structure with a four membered Cu 2 X 2 ring. Complex 3 has a mirror symmetric form, whereas complexes 1 and 2 have a centrosymmetric form. At ambient temperature, complexes 1-3 in the powder state emit intense greenish yellow to yellow delayed fluorescence (λ em = 573-590 nm, τ = 1.2-1.5 μs, Φ = 9.62%-19.58%). The introduction of 1-pyrrolyl and 9-carbazolyl substituents into the diphosphine resulted in the red-shifted emission and shorter decay lifetime of the complexes. The very short decay lifetime (1.2 ~ 1.5 μs) will prevent a roll-off of efficiency with increasing current density in OLED devices. The emissions of the complexes 1-3 are originated from (metal+ halide)-to-ligand and intra-ligand charge transfer. Under visible-light irradiation, complexes 1-3 displayed photocatalytic H 2 evolution activity. Complex 3 showed the highest hydrogen production rate of 156.3 μmol g-1 h-1 .
{"title":"Dinuclear Copper(I) Halide Complexes Containing Unsymmetric Diphosphine: Structure, Photophysical and Photocatalytic Hydrogen Production Properties","authors":"Shi-Ji Li, Li Liu, Xinxin Zhong, Fa-Bao Li, Fengyan Li, Hai-Mei Qin","doi":"10.1039/d5dt02914g","DOIUrl":"https://doi.org/10.1039/d5dt02914g","url":null,"abstract":"Highly emissive Cu(I) halide complexes with short decay lifetimes (several μs scale) have attracted attention. Here, three dinuclear four-coordinate Cu(I) halide complexes containing unsymmetric diphosphine [Cu 2 X 2 (L1) 2 ] (L1 = 9-(4,5-bis(diphenylphosphino)-2-(1H-pyrrol-1-yl)phenyl)-9H-carbazole, X = I (1), Br(2), Cl (3)) were synthesized, and their structures, photophysical and photocatalytic hydrogen production properties were characterized. In these complexes, two copper(I) centers are bridged by two halogen ligands to form a dinuclear structure with a four membered Cu 2 X 2 ring. Complex 3 has a mirror symmetric form, whereas complexes 1 and 2 have a centrosymmetric form. At ambient temperature, complexes 1-3 in the powder state emit intense greenish yellow to yellow delayed fluorescence (λ em = 573-590 nm, τ = 1.2-1.5 μs, Φ = 9.62%-19.58%). The introduction of 1-pyrrolyl and 9-carbazolyl substituents into the diphosphine resulted in the red-shifted emission and shorter decay lifetime of the complexes. The very short decay lifetime (1.2 ~ 1.5 μs) will prevent a roll-off of efficiency with increasing current density in OLED devices. The emissions of the complexes 1-3 are originated from (metal+ halide)-to-ligand and intra-ligand charge transfer. Under visible-light irradiation, complexes 1-3 displayed photocatalytic H 2 evolution activity. Complex 3 showed the highest hydrogen production rate of 156.3 μmol g-1 h-1 .","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"8 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145972262","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pieter Geysens, Roy Heyns, Robert Markowski, Johannes Ingenmey, Luc Van Meervelt, Alexandru Vlad, Barbara Kirchner, Jan Fransaer, Koen Binnemans
The physicochemical properties of highly concentrated electrolytes consisting of potassium bis(trifluoromethylsulfonyl)imide in oligo(ethyleneglycol) dimethyl ethers (glymes) are reported. The solvation structures were analyzed by Raman spectroscopy, single crystal X-ray diffraction, and theoretical calculations revealing significant ion-pairing at high concentrations for the shorter glymes. To assess the viability of these electrolytes in next-generation potassium-ion batteries, they were subjected to galvanostatic cycling on the new organic cathode material K2-Co-PTtSA, wherein PTtSA = benzene-1,2,4,5-tetra-methylsulfonamide. The results point to a better capacity retention with these electrolytes compared to a benchmark electrolyte consisting of 1 mol L 1 KPF6 in a mixture of ethylene carbonate and propylene carbonate, but a worse performance at high C-rates due to the high viscosities.
报道了由二（三氟甲基磺酰基）亚胺钾在低聚（乙二醇）二甲基醚（glymes）中组成的高浓度电解质的物理化学性质。通过拉曼光谱、单晶x射线衍射和理论计算分析了溶剂化结构，揭示了较短的glymes在高浓度下存在显著的离子配对。为了评估这些电解质在下一代钾离子电池中的可行性，他们在新的有机正极材料K2-Co-PTtSA上进行恒流循环，其中PTtSA =苯-1,2,4,5-四甲基磺酰胺。结果表明，与由1 mol L 1 KPF6在碳酸乙烯和碳酸丙烯混合物中组成的基准电解质相比，这些电解质具有更好的容量保持性，但由于高粘度，在高c速率下性能较差。
{"title":"Solvation structure of potassium bis(trifluoromethylsulfonyl)imide-glyme highly concentrated electrolytes and cycling on organic cathodes","authors":"Pieter Geysens, Roy Heyns, Robert Markowski, Johannes Ingenmey, Luc Van Meervelt, Alexandru Vlad, Barbara Kirchner, Jan Fransaer, Koen Binnemans","doi":"10.1039/d5dt02781k","DOIUrl":"https://doi.org/10.1039/d5dt02781k","url":null,"abstract":"The physicochemical properties of highly concentrated electrolytes consisting of potassium bis(trifluoromethylsulfonyl)imide in oligo(ethyleneglycol) dimethyl ethers (glymes) are reported. The solvation structures were analyzed by Raman spectroscopy, single crystal X-ray diffraction, and theoretical calculations revealing significant ion-pairing at high concentrations for the shorter glymes. To assess the viability of these electrolytes in next-generation potassium-ion batteries, they were subjected to galvanostatic cycling on the new organic cathode material K2-Co-PTtSA, wherein PTtSA = benzene-1,2,4,5-tetra-methylsulfonamide. The results point to a better capacity retention with these electrolytes compared to a benchmark electrolyte consisting of 1 mol L 1 KPF6 in a mixture of ethylene carbonate and propylene carbonate, but a worse performance at high C-rates due to the high viscosities.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"57 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145993169","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Sooan Bae, Jihyeon Park, Laurin Rademacher, Songhyun Lee, Chaehyeong Lee, Vivek Bharatbhai Kathiriyam, Maryam Nojabaee, Andreas Friedrich, Jaeyoung Lee and Jin Won Kim
Despite their high theoretical energy density, the commercial viability of lithium–sulfur batteries (LSBs) is impeded by issues of poor sustainability, primarily stemming from the shuttle effect of lithium polysulfides. To address this challenge, we have developed a novel copper phosphide (CuP2) electrocatalyst. Through ball-milling, CuP2 is synthesized with copper- and oxide-based catalytic surface active sites that demonstrate strong adsorption of lithium polysulfides. This enhanced adsorption effectively suppresses the shuttle effect, leading to significant improvements in battery lifespan and initial capacity. By optimizing the CuP2 content in the interlayer to 10 wt%, enhanced cell reversibility is achieved. A coin cell fabricated with the optimized interlayer delivers an initial capacity of 964 mAh g−1 and maintains a robust capacity of 600 mAh g−1 after 500 cycles at a 0.5 C rate. Critically, the practical applicability of this approach is confirmed in a pouch cell, where the areal capacity is doubled to 2.2 mAh cm−2 with the inclusion of the CuP2 catalyst. This work, therefore, presents a new avenue for the rational design of highly efficient electrocatalysts for next-generation LSBs.
尽管理论能量密度很高，但锂硫电池（LSBs）的商业可行性受到可持续性差的问题的阻碍，主要源于锂多硫化物的穿梭效应。为了解决这一挑战，我们开发了一种新型的磷化铜（CuP 2）电催化剂。通过球磨法制备了铜基和氧化物基催化表面活性位点的CuP - 2，它们对锂多硫化物具有较强的吸附能力。这种增强的吸附有效地抑制了穿梭效应，导致电池寿命和初始容量的显着改善。通过优化中间层中CuP - 2的含量至10 wt%，增强了细胞的可逆性。采用优化中间层制造的硬币电池可提供964 mAh g -1的初始容量，并在0.5 C的速率下在500次循环后保持600 mAh g -1的稳健容量。至关重要的是，这种方法的实际适用性在袋状电池中得到了证实，在包含CuP 2催化剂的情况下，面积容量翻了一番，达到2.2 mAh cm -2。因此，本研究为下一代LSB高效电催化剂的合理设计提供了一条新的途径。
{"title":"A copper phosphide electrocatalyst enables high-areal-capacity and long-term stability in lithium–sulfur pouch cells","authors":"Sooan Bae, Jihyeon Park, Laurin Rademacher, Songhyun Lee, Chaehyeong Lee, Vivek Bharatbhai Kathiriyam, Maryam Nojabaee, Andreas Friedrich, Jaeyoung Lee and Jin Won Kim","doi":"10.1039/D5DT02825F","DOIUrl":"10.1039/D5DT02825F","url":null,"abstract":"<p >Despite their high theoretical energy density, the commercial viability of lithium–sulfur batteries (LSBs) is impeded by issues of poor sustainability, primarily stemming from the shuttle effect of lithium polysulfides. To address this challenge, we have developed a novel copper phosphide (CuP<small><sub>2</sub></small>) electrocatalyst. Through ball-milling, CuP<small><sub>2</sub></small> is synthesized with copper- and oxide-based catalytic surface active sites that demonstrate strong adsorption of lithium polysulfides. This enhanced adsorption effectively suppresses the shuttle effect, leading to significant improvements in battery lifespan and initial capacity. By optimizing the CuP<small><sub>2</sub></small> content in the interlayer to 10 wt%, enhanced cell reversibility is achieved. A coin cell fabricated with the optimized interlayer delivers an initial capacity of 964 mAh g<small><sup>−1</sup></small> and maintains a robust capacity of 600 mAh g<small><sup>−1</sup></small> after 500 cycles at a 0.5 C rate. Critically, the practical applicability of this approach is confirmed in a pouch cell, where the areal capacity is doubled to 2.2 mAh cm<small><sup>−2</sup></small> with the inclusion of the CuP<small><sub>2</sub></small> catalyst. This work, therefore, presents a new avenue for the rational design of highly efficient electrocatalysts for next-generation LSBs.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" 5","pages":" 2288-2296"},"PeriodicalIF":3.3,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2026/dt/d5dt02825f?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145968978","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hyunyong Kim, Yunha Hwang, Hyunwoo Jung, Jin Sung Cheong, Jiyeon Han, Seung Jae Lee
Zinc finger (ZF) proteins require zinc ion (Zn2+) to maintain structural integrity, which facilitates nucleic acid recognition. ZBTB20 is a Broad-complex, Tramtrack, and Bric-à-brac (BTB)–ZF transcription factor that regulates neuronal differentiation in the developing cortex, although the biochemical properties of the ZF domains in ZBTB20 remain to be further investigated. In this study, we demonstrate structural and functional aspects of five CX2CX12HX3H-type ZF domains based on the metal dependence of ZBTB20. Circular dichroism (CD) studies indicate that Zn2+ preserves the ββα secondary structure of ZBTB20(ZFs), whereas Zn2+ removal disrupts this structural motif, indicating the requirement for intact metal–coordination in maintaining the native fold. The d–d transition spectra establish tetrahedral (Td) metal–coordination and reveal the high oxidative susceptibility of these domains compared with other classical CX2CX12HX3H-type ZF proteins. Interaction studies of ZBTB20(ZFs) identify brn2-F3 (Kd = 1.2 ± 0.1 nM) to represent the specific binding region within the human brn2 promoter, which provides a mechanistic explanation for ZBTB20-mediated Brain-2 (Brn2) repression in neuronal development. Reconstruction of apo-ZBTB20(ZFs) with metal ions result in diminished binding to brn2-F3, highlighting that strict preservation of native Zn2+–coordination is essential for recognition of nucleic acids. Overall, our work advances new insights into the Zn2+ dependent behavior of the ZBTB family and establishes a biochemical basis for selective promoter recognition.
{"title":"Coordination and oxidation properties of ZBTB20: CX2CX12HX3H-type zinc fingers","authors":"Hyunyong Kim, Yunha Hwang, Hyunwoo Jung, Jin Sung Cheong, Jiyeon Han, Seung Jae Lee","doi":"10.1039/d5dt02032h","DOIUrl":"https://doi.org/10.1039/d5dt02032h","url":null,"abstract":"Zinc finger (ZF) proteins require zinc ion (Zn<small><sup>2+</sup></small>) to maintain structural integrity, which facilitates nucleic acid recognition. ZBTB20 is a Broad-complex, Tramtrack, and Bric-à-brac (BTB)–ZF transcription factor that regulates neuronal differentiation in the developing cortex, although the biochemical properties of the ZF domains in ZBTB20 remain to be further investigated. In this study, we demonstrate structural and functional aspects of five CX<small><sub>2</sub></small>CX<small><sub>12</sub></small>HX<small><sub>3</sub></small>H-type ZF domains based on the metal dependence of ZBTB20. Circular dichroism (CD) studies indicate that Zn<small><sup>2+</sup></small> preserves the ββα secondary structure of ZBTB20(ZFs), whereas Zn<small><sup>2+</sup></small> removal disrupts this structural motif, indicating the requirement for intact metal–coordination in maintaining the native fold. The d–d transition spectra establish tetrahedral (<em>T</em><small><sub>d</sub></small>) metal–coordination and reveal the high oxidative susceptibility of these domains compared with other classical CX<small><sub>2</sub></small>CX<small><sub>12</sub></small>HX<small><sub>3</sub></small>H-type ZF proteins. Interaction studies of ZBTB20(ZFs) identify <em>brn2</em>-F3 (<em>K</em><small><sub>d</sub></small> = 1.2 ± 0.1 nM) to represent the specific binding region within the human <em>brn2</em> promoter, which provides a mechanistic explanation for ZBTB20-mediated Brain-2 (Brn2) repression in neuronal development. Reconstruction of apo-ZBTB20(ZFs) with metal ions result in diminished binding to <em>brn2</em>-F3, highlighting that strict preservation of native Zn<small><sup>2+</sup></small>–coordination is essential for recognition of nucleic acids. Overall, our work advances new insights into the Zn<small><sup>2+</sup></small> dependent behavior of the ZBTB family and establishes a biochemical basis for selective promoter recognition.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"266 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145968922","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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