The phase (aqueous versus organic) in which FeOOH nanorods are dispersed during interfacial polymerization critically governs the structure and performance of thin film nanocomposite (TFN) reverse osmosis (RO) membranes. Embedding inorganic nanoporous materials into TFN membranes has emerged as a promising route to alleviate the inherent permeability–selectivity trade off and durability constraints of conventional polyamide RO membranes. However, the role of the nanomaterial dispersion phase—a key factor regulating interfacial properties—remains underexplored. Here, cost effective FeOOH nanorods were incorporated into TFN membranes by dispersing them in either the aqueous (TFN A) or organic (TFN O) phase. The FeOOH nanorods modulated interfacial tension and stability, which in turn tailored the physicochemical structure of the polyamide layer, leading to increased crosslinking density, enhanced hydrophilicity, and distinct morphological features. Both TFN A and TFN O membranes exhibited superior desalination performance, mechanical strength, and chemical stability compared to the pristine thin film composite (TFC) membrane. Specifically, TFN A achieved a remarkable 355.7% increase in water flux with minimal flux decline under high pressure, while TFN O maintained NaCl rejection with only a 2.0% reduction after exposure to 10,000 ppm·h chlorine. These results not only demonstrate how FeOOH nanorods regulate interfacial properties to engineer polyamide structure, but also establish a phase-dependent tuning strategy for integrating hydrophilic nanoporous materials into high-performance RO membranes.
{"title":"Embedding of FeOOH Nanorods in the Fabrication of Thin Film Nanocomposite (TFN) Membrane for Enhanced Desalination","authors":"Pengfei Li, Liming Wang, Mingzheng Bao, Yu Yong, Jilong Han, Q. Jason Niu","doi":"10.1039/d5qi02382c","DOIUrl":"https://doi.org/10.1039/d5qi02382c","url":null,"abstract":"The phase (aqueous versus organic) in which FeOOH nanorods are dispersed during interfacial polymerization critically governs the structure and performance of thin film nanocomposite (TFN) reverse osmosis (RO) membranes. Embedding inorganic nanoporous materials into TFN membranes has emerged as a promising route to alleviate the inherent permeability–selectivity trade off and durability constraints of conventional polyamide RO membranes. However, the role of the nanomaterial dispersion phase—a key factor regulating interfacial properties—remains underexplored. Here, cost effective FeOOH nanorods were incorporated into TFN membranes by dispersing them in either the aqueous (TFN A) or organic (TFN O) phase. The FeOOH nanorods modulated interfacial tension and stability, which in turn tailored the physicochemical structure of the polyamide layer, leading to increased crosslinking density, enhanced hydrophilicity, and distinct morphological features. Both TFN A and TFN O membranes exhibited superior desalination performance, mechanical strength, and chemical stability compared to the pristine thin film composite (TFC) membrane. Specifically, TFN A achieved a remarkable 355.7% increase in water flux with minimal flux decline under high pressure, while TFN O maintained NaCl rejection with only a 2.0% reduction after exposure to 10,000 ppm·h chlorine. These results not only demonstrate how FeOOH nanorods regulate interfacial properties to engineer polyamide structure, but also establish a phase-dependent tuning strategy for integrating hydrophilic nanoporous materials into high-performance RO membranes.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"312 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135441","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}
Xue Shen, Zijian Li, Haeseong Jang, Min Gyu Kim, Liqiang Hou, Xien Liu
The development of efficient, stable, and noble-metal-free bifunctional oxygen electrocatalysts is a central challenge for advanced energy devices such as rechargeable zinc-air batteries (ZABs). While single-atom catalysts (SACs) show great promise, their performance is often limited by the scaling relationships of reaction intermediates. This study reports a five-metal (Mn, Fe, Co, Ni, Cu) high-entropy single-atom catalyst (HESAC) synthesized via a precise spatial confinement strategy designed to overcome this limitation. This strategy utilizes a ZIF-8-derived carbon support with a uniform pore size (~1.88 nm) and ultrahigh specific surface area. The microporous confinement effect ensures that each pore accommodates only one acetylacetonate metal salt molecule, effectively preventing the migration and agglomeration of diverse metal atoms during pyrolysis and successfully enabling the construction of high-entropy single-atom sites. The resulting catalyst exceptional bifunctional oxygen electrocatalytic activity in alkaline electrolyte, surpassing the performance of commercial Pt/C for oxygen reduction reaction and IrO2 for oxygen evolution reaction. This superior catalytic performance is readily translated into a high-performance rechargeable zinc-air battery, which demonstrates comprehensively better overall characteristics than its noble-metal-based counterpart. This work not only provides a novel synthetic pathway for designing high-performance HESAC but also demonstrates their significant potential in energy conversion and storage applications.
{"title":"High-Entropy Single-Atom Catalysts via Spatial Confinement Synthesis for Oxygen Electrocatalysis and Zinc-Air Batteries","authors":"Xue Shen, Zijian Li, Haeseong Jang, Min Gyu Kim, Liqiang Hou, Xien Liu","doi":"10.1039/d5qi02434j","DOIUrl":"https://doi.org/10.1039/d5qi02434j","url":null,"abstract":"The development of efficient, stable, and noble-metal-free bifunctional oxygen electrocatalysts is a central challenge for advanced energy devices such as rechargeable zinc-air batteries (ZABs). While single-atom catalysts (SACs) show great promise, their performance is often limited by the scaling relationships of reaction intermediates. This study reports a five-metal (Mn, Fe, Co, Ni, Cu) high-entropy single-atom catalyst (HESAC) synthesized via a precise spatial confinement strategy designed to overcome this limitation. This strategy utilizes a ZIF-8-derived carbon support with a uniform pore size (~1.88 nm) and ultrahigh specific surface area. The microporous confinement effect ensures that each pore accommodates only one acetylacetonate metal salt molecule, effectively preventing the migration and agglomeration of diverse metal atoms during pyrolysis and successfully enabling the construction of high-entropy single-atom sites. The resulting catalyst exceptional bifunctional oxygen electrocatalytic activity in alkaline electrolyte, surpassing the performance of commercial Pt/C for oxygen reduction reaction and IrO2 for oxygen evolution reaction. This superior catalytic performance is readily translated into a high-performance rechargeable zinc-air battery, which demonstrates comprehensively better overall characteristics than its noble-metal-based counterpart. This work not only provides a novel synthetic pathway for designing high-performance HESAC but also demonstrates their significant potential in energy conversion and storage applications.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"29 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122314","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}
Yao Yao, Yanqiang Li, Bin Chen, Yipeng Song, Weiqi Huang, Zhiyong Bai, Junhua Luo, Sangen Zhao
Hybrid perovskites have emerged as promising candidates for birefringent crystals due to their structural diversity.Conventional strategies to enhance birefringence often rely on incorporating highly π-conjugated organic components; however, it remains challenging to reconcile high birefringence (>0.3) and large single crystal growth. Herein, we present the pseudo-halogen engineering that also enables giant birefringence enhancement. By substituting halogen Cl -with polar pseudo-halogen (SCN) -, we designed and synthesized a one-dimensional hybrid perovskite, namely (C6N2H15)Cd(SCN)3, which exhibits high birefringence of Δnexp = 0.37@550 nm, over 12 times that of isostructural (C6N2H16)Cd2Cl6 •2H2O (Δnexp = 0.03@550 nm). This birefringence value not only surpasses all commercial birefringent crystals, but also is even higher than those of many hybrid perovskites composed of π-conjugated cations. Moreover, large single crystals of (C6N2H15)Cd(SCN)3 were readily grown by the facile evaporation method.First-principles calculations reveal that the remarkable birefringence enhancement originates from a tens-of-times increase in polarizability anisotropy of the distorted Cd(SCN)6 octahedra compared to CdCl5 •H2O counterparts. This work provides a novel molecular-level strategy towards designing high-performance birefringent crystals for polarized optics.
{"title":"Molecular Pseudo-Halogen Engineering Enables Remarkable Birefringence Enhancement in Hybrid Perovskites","authors":"Yao Yao, Yanqiang Li, Bin Chen, Yipeng Song, Weiqi Huang, Zhiyong Bai, Junhua Luo, Sangen Zhao","doi":"10.1039/d5qi02592c","DOIUrl":"https://doi.org/10.1039/d5qi02592c","url":null,"abstract":"Hybrid perovskites have emerged as promising candidates for birefringent crystals due to their structural diversity.Conventional strategies to enhance birefringence often rely on incorporating highly <em>π</em>-conjugated organic components; however, it remains challenging to reconcile high birefringence (>0.3) and large single crystal growth. Herein, we present the pseudo-halogen engineering that also enables giant birefringence enhancement. By substituting halogen Cl <small><sup>-</sup></small>with polar pseudo-halogen (SCN) <small><sup>-</sup></small>, we designed and synthesized a one-dimensional hybrid perovskite, namely (C<small><sub>6</sub></small>N<small><sub>2</sub></small>H<small><sub>15</sub></small>)Cd(SCN)<small><sub>3</sub></small>, which exhibits high birefringence of <em>Δn<small><sub>exp</sub></small></em> = 0.37@550 nm, over 12 times that of isostructural (C<small><sub>6</sub></small>N<small><sub>2</sub></small>H<small><sub>16</sub></small>)Cd<small><sub>2</sub></small>Cl<small><sub>6</sub></small> •2H<small><sub>2</sub></small>O (<em>Δn<small><sub>exp</sub></small></em> = 0.03@550 nm). This birefringence value not only surpasses all commercial birefringent crystals, but also is even higher than those of many hybrid perovskites composed of <em>π</em>-conjugated cations. Moreover, large single crystals of (C<small><sub>6</sub></small>N<small><sub>2</sub></small>H<small><sub>15</sub></small>)Cd(SCN)<small><sub>3</sub></small> were readily grown by the facile evaporation method.First-principles calculations reveal that the remarkable birefringence enhancement originates from a tens-of-times increase in polarizability anisotropy of the distorted Cd(SCN)<small><sub>6</sub></small> octahedra compared to CdCl<small><sub>5</sub></small> •H<small><sub>2</sub></small>O counterparts. This work provides a novel molecular-level strategy towards designing high-performance birefringent crystals for polarized optics.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"46 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135440","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}
Lubna Salah, Paulina Marek-Urban, Mieczysław Łapkowski, Fernando B. Dias, Piotr Pander
Metal TADF (thermally activated delayed fluorescence) emitters, here understood as those containing a d-block metal, are an important and ever-growing group of luminophores. Although they often seem to belong more in the transition metal complex world, they are rightful contenders of not only phosphorescent transition metal compounds, but also conventional, metal-free TADF emitters. Their unique properties include extremely short TADF lifetimes, often in the range 0.1–10 µs, fast intersystem crossing (ISC) and reverse ISC (RISC), minimal prompt fluorescence or lack thereof, small Stokes shifts, and temperature-dependent behaviour, including dual TADF/phosphorescence emission – but not every metal TADF emitter displays all of them at once! In this review, we discuss the general photophysical properties of metal TADF emitters and the relevant photophysical approaches applicable to studies of them. We make a brief overview of the most recent examples of computational works on metal TADF luminophores that shed some light on the up-conversion mechanism. Finally, we review some recent examples of Cu(I), Ag(I), Au(I)/Au(III) as well as Zn(II) TADF emitters, and discuss possibly all relevant works on Pd(II), Pt(II), Ir(III), and Zr(IV) TADF complexes. We identify that metal TADF complexes form two principal groups: (I) those analogous to donor–acceptor or charge-transfer TADF emitters and (II) those analogous to multiresonance TADF emitters.
{"title":"Understanding luminescence of metal-containing thermally activated delayed fluorescence (TADF) luminophores","authors":"Lubna Salah, Paulina Marek-Urban, Mieczysław Łapkowski, Fernando B. Dias, Piotr Pander","doi":"10.1039/d5qi02203g","DOIUrl":"https://doi.org/10.1039/d5qi02203g","url":null,"abstract":"Metal TADF (thermally activated delayed fluorescence) emitters, here understood as those containing a d-block metal, are an important and ever-growing group of luminophores. Although they often seem to belong more in the transition metal complex world, they are rightful contenders of not only phosphorescent transition metal compounds, but also conventional, metal-free TADF emitters. Their unique properties include extremely short TADF lifetimes, often in the range 0.1–10 µs, fast intersystem crossing (ISC) and reverse ISC (RISC), minimal prompt fluorescence or lack thereof, small Stokes shifts, and temperature-dependent behaviour, including dual TADF/phosphorescence emission – but not every metal TADF emitter displays all of them at once! In this review, we discuss the general photophysical properties of metal TADF emitters and the relevant photophysical approaches applicable to studies of them. We make a brief overview of the most recent examples of computational works on metal TADF luminophores that shed some light on the up-conversion mechanism. Finally, we review some recent examples of Cu(<small>I</small>), Ag(<small>I</small>), Au(<small>I</small>)/Au(<small>III</small>) as well as Zn(<small>II</small>) TADF emitters, and discuss possibly all relevant works on Pd(<small>II</small>), Pt(<small>II</small>), Ir(<small>III</small>), and Zr(<small>IV</small>) TADF complexes. We identify that metal TADF complexes form two principal groups: (I) those analogous to donor–acceptor or charge-transfer TADF emitters and (II) those analogous to multiresonance TADF emitters.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"8 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122347","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 preparation of high-efficiency, durable and earth-abundant water oxidation electrocatalysts is increasingly appealing and significant challenge for generating the renewable H2 energy source, due to the sluggish kinetics of the key oxygen evolution reaction (OER). Herein, four different morphologies of amorphous FeOOH-modified hetero-structural SnS₂/Ni₃S₂ including rose, cauliflower, spherical and spongy steamed-twisted-roll nano-arrays are direct grown on self-supporting nickel foam (NF) by the hydrothermal and wet chemical immersion methods. Compared with rose, cauliflower and spherical heterostructures, spongy steamed-twisted-roll FeOOH/SnS2/Ni3S2/NF heterostructure indicates the best electrocatalytic OER activity with a ultra-low overpotential of 198 mV at 10 mA·cm-2 and a small Tafel slope of 31.9 mV·dec-1 in alkaline media, and also exhibits the excellent stability with no evident decay of current density after 200 hours of OER. The reason for the exceptional performance of spongy steamed-twisted-roll FeOOH/SnS2/Ni3S2/NF may be ascribed to its improved charge transfer, larger surface area and more electroactive sites. Theoretical study further disclose that the integration of amorphous FeOOH with SnS2/Ni3S2 is beneficial for charge redistribution, adsorption energy regulation of the OER intermediates and the reduction of the reaction energy barrier. Owing to its remarkably improved OER performance, spongy steamed-twisted-roll FeOOH/SnS2/Ni3S2/NF is utilized to fabricate an electrolytic cell Pt–C/NF||FeOOH/SnS2/Ni3S2/NF, whose cell voltage is only 1.42 V at 10 mA·cm-2, significantly exceeding that (1.63 V) of the standard electrolytic cell Pt/C/NF||RuO2/NF.
{"title":"Amorphous FeOOH-modified spongy steamed-twisted-roll SnS2/Ni3S2 hierarchical electrocatalyst for efficient oxygen evolution reaction","authors":"Shi-Jing Wang, Xing Liu, Xiao-Yan Chen, Jian Zhou","doi":"10.1039/d5qi02551f","DOIUrl":"https://doi.org/10.1039/d5qi02551f","url":null,"abstract":"The preparation of high-efficiency, durable and earth-abundant water oxidation electrocatalysts is increasingly appealing and significant challenge for generating the renewable H2 energy source, due to the sluggish kinetics of the key oxygen evolution reaction (OER). Herein, four different morphologies of amorphous FeOOH-modified hetero-structural SnS₂/Ni₃S₂ including rose, cauliflower, spherical and spongy steamed-twisted-roll nano-arrays are direct grown on self-supporting nickel foam (NF) by the hydrothermal and wet chemical immersion methods. Compared with rose, cauliflower and spherical heterostructures, spongy steamed-twisted-roll FeOOH/SnS2/Ni3S2/NF heterostructure indicates the best electrocatalytic OER activity with a ultra-low overpotential of 198 mV at 10 mA·cm-2 and a small Tafel slope of 31.9 mV·dec-1 in alkaline media, and also exhibits the excellent stability with no evident decay of current density after 200 hours of OER. The reason for the exceptional performance of spongy steamed-twisted-roll FeOOH/SnS2/Ni3S2/NF may be ascribed to its improved charge transfer, larger surface area and more electroactive sites. Theoretical study further disclose that the integration of amorphous FeOOH with SnS2/Ni3S2 is beneficial for charge redistribution, adsorption energy regulation of the OER intermediates and the reduction of the reaction energy barrier. Owing to its remarkably improved OER performance, spongy steamed-twisted-roll FeOOH/SnS2/Ni3S2/NF is utilized to fabricate an electrolytic cell Pt–C/NF||FeOOH/SnS2/Ni3S2/NF, whose cell voltage is only 1.42 V at 10 mA·cm-2, significantly exceeding that (1.63 V) of the standard electrolytic cell Pt/C/NF||RuO2/NF.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"1 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135442","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}
Liuxu Wei, Xinjie Xu, Yanan Liu, Zhenyu Yue, Huiqi Jia, Zexing Wu, Zhenyu Xiao, Lei Wang
Metal-organic framework (MOF)-based cathode materials, distinguished by their highly tailorable composition, ordered hierarchical pore systems, and abundant active sites, have emerged as a critical platform for advancing supercapacitor technology beyond the conventional trade-off between energy and power density. This review systematically summarizes recent progress in this field, covering three primary material categories: pristine MOFs, MOF-derived porous carbons, and MOF-derived transition metal compounds (including hydroxides, oxides, sulfides, nitrides, and phosphides). The article analyzes the design strategies, synthesis methodologies, and fundamental structure-performance relationships for each category, highlighting representative breakthroughs in specific capacity, rate capability, and cycling stability. Key challenges, such as intrinsic electrical conductivity, structural durability, and scalable manufacturing, are also critically discussed. Finally, perspectives on future research directions are provided to guide the development of high-performance supercapacitors.
{"title":"Tailoring Metal-Organic Frameworks and Their Derivatives for Advanced Supercapacitor Cathodes: From Design to Electrochemical Performance","authors":"Liuxu Wei, Xinjie Xu, Yanan Liu, Zhenyu Yue, Huiqi Jia, Zexing Wu, Zhenyu Xiao, Lei Wang","doi":"10.1039/d5qi02463c","DOIUrl":"https://doi.org/10.1039/d5qi02463c","url":null,"abstract":"Metal-organic framework (MOF)-based cathode materials, distinguished by their highly tailorable composition, ordered hierarchical pore systems, and abundant active sites, have emerged as a critical platform for advancing supercapacitor technology beyond the conventional trade-off between energy and power density. This review systematically summarizes recent progress in this field, covering three primary material categories: pristine MOFs, MOF-derived porous carbons, and MOF-derived transition metal compounds (including hydroxides, oxides, sulfides, nitrides, and phosphides). The article analyzes the design strategies, synthesis methodologies, and fundamental structure-performance relationships for each category, highlighting representative breakthroughs in specific capacity, rate capability, and cycling stability. Key challenges, such as intrinsic electrical conductivity, structural durability, and scalable manufacturing, are also critically discussed. Finally, perspectives on future research directions are provided to guide the development of high-performance supercapacitors.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"91 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146129672","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}
Luminescent coordination polymers (CPs) often exhibit poor processability and recyclability owing to their insoluble infinite networks. Herein, we report a vapor-driven, reversible crystal-to-crystal transformation between a zero-dimensional (0D) complex and a one-dimensional (1D) luminescent CP, which enables both solution processing and recycling. The 1D CP [Cu2I2(AsPh3)2(meprz)]n (Crys-B) with intense yellow emission was converted to the weakly emissive 0D complex Cu2I2(AsPh3)2(meprz)2 (Crys-A) upon exposure to 2-methylpyrazine (meprz) vapor, and reverted back to Crys-B upon exposure to acetonitrile (CH3CN) vapor. This transformation proceeded smoothly without amorphization, allowing film fabrication via casting or spin-coating in the 0D state, followed by vapor-induced polymerization, while enabling recovery via depolymerization. Comparative studies revealed that the arsine ligand (AsPh3) accelerates vapor-induced switching and enhances the emission contrast relative to its phosphine analog (PPh3). This study established the first copper(I) halide-based luminescent CP to achieve reversible 0D/1D conversion, offering a practical route for processable and recyclable luminescent materials.
{"title":"Latent One-Dimensional Luminescent Coordination Polymer Emerging from Copper(I) Iodide Secondary Building Units","authors":"Kazuma Kikuchi, Shuji Nagata, Takashi Yumura, Takahiro Iwamoto, Kensuke Naka, Hiroaki Imoto","doi":"10.1039/d5qi02376a","DOIUrl":"https://doi.org/10.1039/d5qi02376a","url":null,"abstract":"Luminescent coordination polymers (CPs) often exhibit poor processability and recyclability owing to their insoluble infinite networks. Herein, we report a vapor-driven, reversible crystal-to-crystal transformation between a zero-dimensional (0D) complex and a one-dimensional (1D) luminescent CP, which enables both solution processing and recycling. The 1D CP [Cu2I2(AsPh3)2(meprz)]n (Crys-B) with intense yellow emission was converted to the weakly emissive 0D complex Cu2I2(AsPh3)2(meprz)2 (Crys-A) upon exposure to 2-methylpyrazine (meprz) vapor, and reverted back to Crys-B upon exposure to acetonitrile (CH3CN) vapor. This transformation proceeded smoothly without amorphization, allowing film fabrication via casting or spin-coating in the 0D state, followed by vapor-induced polymerization, while enabling recovery via depolymerization. Comparative studies revealed that the arsine ligand (AsPh3) accelerates vapor-induced switching and enhances the emission contrast relative to its phosphine analog (PPh3). This study established the first copper(I) halide-based luminescent CP to achieve reversible 0D/1D conversion, offering a practical route for processable and recyclable luminescent materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"17 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122349","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 exploration of novel metal-oxo clusters with unique composition and functionality remains an attractive goal in the field of structural chemistry and materials chemistry. By employing a triply synergistic induction strategy that combines ligand induction with structural tailoring effect of halide anions (I-) and lone pair electrons of low-valency p-block metal ions (Pb2+ and Sb3+ ions), two unprecedented organic ligand-decorated lead-antimony oxohalide cluster compounds have been successfully prepared, namely [(HTEOA)SbOPbI]4·2H2O (H3TEOA = triethanolamine) (1) and (HTEOA)3Sb3OPbI3·CH3OH (2). 1 features a sandwich configuration formed by two pairs of Sb-L (L= HTEOA) layers and a central [Pb4O4I4] unit. By contrast, 2 represents a crown configuration consisting of a [Sb3OL3] base and a [PbI3] cap. Compound 1 exhibits excellent irradiation stability and high removal capacity for UO22+ ions, with rapid kinetics response reaching removal rate (RU) of 99.89% within 5 minutes. Even in the presence of high concentrations of competing ions (e.g., Na+, Ca2+ and Mg2+) and in actual water samples, it maintains exceptional selectivity toward UO22+ with high removal efficiency (distribution coefficient (KdU) > 7.42 × 104 mL g-1, RU > 98.64%). This work not only represents a breakthrough in p-block heterometallic oxohalide cluster chemistry, but also expands the potential of antimony oxohalide clusters for radionuclide remendiation.
{"title":"Unprecedented Lead-Antimony Oxohalide Clusters with the Efficient Capture for UO22+ ions","authors":"Jia-Hua Luo, Yu-Wei Ren, Lu Yang, Jing Wang, Hao-Dan Xiao, Feng-Hua Xian, Hai-Yan Sun, Mei-Ling Feng, Bing Hu, Xiao-Ying Huang","doi":"10.1039/d5qi02583d","DOIUrl":"https://doi.org/10.1039/d5qi02583d","url":null,"abstract":"The exploration of novel metal-oxo clusters with unique composition and functionality remains an attractive goal in the field of structural chemistry and materials chemistry. By employing a triply synergistic induction strategy that combines ligand induction with structural tailoring effect of halide anions (I-) and lone pair electrons of low-valency p-block metal ions (Pb2+ and Sb3+ ions), two unprecedented organic ligand-decorated lead-antimony oxohalide cluster compounds have been successfully prepared, namely [(HTEOA)SbOPbI]4·2H2O (H3TEOA = triethanolamine) (1) and (HTEOA)3Sb3OPbI3·CH3OH (2). 1 features a sandwich configuration formed by two pairs of Sb-L (L= HTEOA) layers and a central [Pb4O4I4] unit. By contrast, 2 represents a crown configuration consisting of a [Sb3OL3] base and a [PbI3] cap. Compound 1 exhibits excellent irradiation stability and high removal capacity for UO22+ ions, with rapid kinetics response reaching removal rate (RU) of 99.89% within 5 minutes. Even in the presence of high concentrations of competing ions (e.g., Na+, Ca2+ and Mg2+) and in actual water samples, it maintains exceptional selectivity toward UO22+ with high removal efficiency (distribution coefficient (KdU) > 7.42 × 104 mL g-1, RU > 98.64%). This work not only represents a breakthrough in p-block heterometallic oxohalide cluster chemistry, but also expands the potential of antimony oxohalide clusters for radionuclide remendiation.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"1 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116060","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}
Achieving direct cleavage of CO bonds in biomass under mild conditions to generate high-value-added products via catalytic hydrogenation remains a substantial challenge. We developed a Pd–Fe bimetallic catalyst supported on oxygen vacancy (Ov)-enriched TiO2 for the direct cleavage of CO bonds, and as a result, up to 99% yield of 2-methoxy-4-methylphenol (MMP) was achieved from the conversion of vanillin (VAN) at 140 °C under atmospheric H2 pressure. This study utilizes Ov to enhance hydrogen spillover levels during the reaction process and proposes a novel reaction pathway that avoids the formation of alcohol intermediates. Mechanistic investigations reveal that surface Ov facilitates hydrogen spillover, enabling active hydrogen migration from Pd–Fe sites to TiO2 to form Ti–H species. Through synergistic Pd–Fe bimetallic effects and metal–support interfacial interactions, direct hydrodeoxygenation (HDO) of VAN is achieved, ultimately generating MMP with high selectivity. The catalyst demonstrates excellent stability and broad substrate suitability, maintaining uncompromised activity after five catalytic cycles.
{"title":"Oxygen vacancy-enhanced hydrogen spillover on a bifunctional PdFe/TiO2−x catalyst for highly selective direct hydrodeoxygenation of carbonyl compounds","authors":"Chaofan Deng, Chun Cai","doi":"10.1039/d5qi02432c","DOIUrl":"https://doi.org/10.1039/d5qi02432c","url":null,"abstract":"Achieving direct cleavage of C<img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\"/>O bonds in biomass under mild conditions to generate high-value-added products <em>via</em> catalytic hydrogenation remains a substantial challenge. We developed a Pd–Fe bimetallic catalyst supported on oxygen vacancy (O<small><sub>v</sub></small>)-enriched TiO<small><sub>2</sub></small> for the direct cleavage of C<img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\"/>O bonds, and as a result, up to 99% yield of 2-methoxy-4-methylphenol (MMP) was achieved from the conversion of vanillin (VAN) at 140 °C under atmospheric H<small><sub>2</sub></small> pressure. This study utilizes O<small><sub>v</sub></small> to enhance hydrogen spillover levels during the reaction process and proposes a novel reaction pathway that avoids the formation of alcohol intermediates. Mechanistic investigations reveal that surface O<small><sub>v</sub></small> facilitates hydrogen spillover, enabling active hydrogen migration from Pd–Fe sites to TiO<small><sub>2</sub></small> to form Ti–H species. Through synergistic Pd–Fe bimetallic effects and metal–support interfacial interactions, direct hydrodeoxygenation (HDO) of VAN is achieved, ultimately generating MMP with high selectivity. The catalyst demonstrates excellent stability and broad substrate suitability, maintaining uncompromised activity after five catalytic cycles.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"6 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116145","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 catalytic activation of CO 2 under mild conditions to form value-added heterocyclic products is of paramount interest.Copper sulfides are a large class of materials, many of which are found as minerals in nature. They often show remarkable physical properties, and further studies of their catalytic properties need to be conducted. The simple compound Cu 2 S was designed and its catalytic activities in CO 2 activation are disclosed here. Synthesized Cu 2 S is shown to be an efficient heterogeneous catalyst for the carboxylation of propargylamines under ambient temperature and pressure conditions and the carboxylation of terminal alkynes with one atm CO 2 at 80 °C. CO 2 is transformed into high-value-added chemicals with a wide range of substrates with excellent yields, and the catalyst is easily reused at least 5 times without significant activity reduction. The catalytic and recycling performances are significantly better for synthesized Cu 2 S compared to those of its commercial analogue. In summary, Cu 2 S is a new catalyst that is non-toxic, simple, self-supported, recyclable, and practical. This finding opens the general route to the catalytic properties of Cu 2 S toward, not only mild CO 2 activation applications, but also a variety of other useful reactions.
{"title":"CO 2 Conversion Efficiently Catalyzed under Ambient Conditions by Self-Supported and Recyclable Cu 2 S","authors":"Huili Wang, Tiansheng Wang, Murielle Berlande, Ahmed Subrati, Sergio Enrique Moya, Lionel Salmon, Nathalie Daro, Nathalie Audebrand, Jean-Rene Hamon, Haizhu Yu, Jean-Luc Pozzo, Didier Astruc","doi":"10.1039/d5qi02546j","DOIUrl":"https://doi.org/10.1039/d5qi02546j","url":null,"abstract":"The catalytic activation of CO 2 under mild conditions to form value-added heterocyclic products is of paramount interest.Copper sulfides are a large class of materials, many of which are found as minerals in nature. They often show remarkable physical properties, and further studies of their catalytic properties need to be conducted. The simple compound Cu 2 S was designed and its catalytic activities in CO 2 activation are disclosed here. Synthesized Cu 2 S is shown to be an efficient heterogeneous catalyst for the carboxylation of propargylamines under ambient temperature and pressure conditions and the carboxylation of terminal alkynes with one atm CO 2 at 80 °C. CO 2 is transformed into high-value-added chemicals with a wide range of substrates with excellent yields, and the catalyst is easily reused at least 5 times without significant activity reduction. The catalytic and recycling performances are significantly better for synthesized Cu 2 S compared to those of its commercial analogue. In summary, Cu 2 S is a new catalyst that is non-toxic, simple, self-supported, recyclable, and practical. This finding opens the general route to the catalytic properties of Cu 2 S toward, not only mild CO 2 activation applications, but also a variety of other useful reactions.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"1 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101496","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}
![[double bond, length as m-dash]](https://www.rsc.org/images/entities/char_e001.gif)
O bonds in biomass under mild conditions to generate high-value-added products via catalytic hydrogenation remains a substantial challenge. We developed a Pd–Fe bimetallic catalyst supported on oxygen vacancy (Ov)-enriched TiO2 for the direct cleavage of C
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