Unlocking the potential of ammonium perchlorate (AP) by achieving a highly synergistic, rapid, and concentrated energy release process is essential for realizing a revolutionary improvement in the thrust of composite solid propellants. In this study, we employ a strategy that integrates a simple solution synthesis method with highly active Co2+ ions, tetrazole-based high-energy ligands, and high-energy ClO4- anions to prepare energetic coordination compounds (ECCs): [Co(1-MAT)6](ClO4)21 and [Co(2-MAT)4(H2O)2](ClO4)22. This approach achieves a dual enhancement by improving the catalytic performance of AP and significantly increasing the total heat release (ΔH) of the system. Single-crystal X-ray diffraction revealed that both compounds possess isolated structures, which was further supported by elemental analysis and FT-IR spectroscopy results. The high-temperature decomposition (HTD) of 1a (5 wt% of 1 in AP) exhibits excellent energy-release performance, as evidenced by a decrease in the exothermic peak temperature from 457 °C (pure AP) to 315 °C. Moreover, compared to pure AP (230 kJ mol-1, 559 J g-1), the mixture 1a showed a lowered activation energy of 144 kJ mol-1 along with a concomitant rise in ΔH to 1166 J g-1. In contrast to the baseline without additives, the addition of Al/AP to combustion pellet-based 1 and 2 resulted in a significant increase in the burning rate. This distinctive structure represents a good strategy designed to simultaneously enhance both the energy output and catalytic efficiency of propellants.
{"title":"Tetrazole-based energetic coordination compounds as enhanced catalysts for the thermal decomposition of ammonium perchlorate.","authors":"Bo-Wen Fan,Meng Cui,Jing Qin,Jun Hu,Mei-Qing Lai,Jian-Gang Xu,Fa-Kun Zheng,Guo-Cong Guo","doi":"10.1039/d5dt03123k","DOIUrl":"https://doi.org/10.1039/d5dt03123k","url":null,"abstract":"Unlocking the potential of ammonium perchlorate (AP) by achieving a highly synergistic, rapid, and concentrated energy release process is essential for realizing a revolutionary improvement in the thrust of composite solid propellants. In this study, we employ a strategy that integrates a simple solution synthesis method with highly active Co2+ ions, tetrazole-based high-energy ligands, and high-energy ClO4- anions to prepare energetic coordination compounds (ECCs): [Co(1-MAT)6](ClO4)21 and [Co(2-MAT)4(H2O)2](ClO4)22. This approach achieves a dual enhancement by improving the catalytic performance of AP and significantly increasing the total heat release (ΔH) of the system. Single-crystal X-ray diffraction revealed that both compounds possess isolated structures, which was further supported by elemental analysis and FT-IR spectroscopy results. The high-temperature decomposition (HTD) of 1a (5 wt% of 1 in AP) exhibits excellent energy-release performance, as evidenced by a decrease in the exothermic peak temperature from 457 °C (pure AP) to 315 °C. Moreover, compared to pure AP (230 kJ mol-1, 559 J g-1), the mixture 1a showed a lowered activation energy of 144 kJ mol-1 along with a concomitant rise in ΔH to 1166 J g-1. In contrast to the baseline without additives, the addition of Al/AP to combustion pellet-based 1 and 2 resulted in a significant increase in the burning rate. This distinctive structure represents a good strategy designed to simultaneously enhance both the energy output and catalytic efficiency of propellants.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"19 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147495112","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}
Naorem Jemes Jemes Meitei, Yu Ting Chu, Chien-Hung Li, Rahimeh Eshaghi Malekshah, Wei-Min Ching, Tsung-Ting Shih, Sodio C. N. Hsu
Nitrite reduction is a critical process in biological systems, with implications for disease pathology and therapeutic development. This study investigates the copper-mediated reduction of nitrite to nitric oxide (NO) using unsymmetrical β-diketiminato copper(II) nitrito complexes with thiol derivatives as reducing agents. The reaction of LCu(NO2) with 4-tert-butyl benzyl thiol (tBuBzSH), benzyl thiol (BzSH), and biologically active thiols like L-cysteine (Cys), yield quantitative NO, free ligand, disulfide, and an insoluble copper(I)-thiolate polymer (YPR), characterized by FT-IR, NMR, and X-ray photoelectron spectroscopy (XPS). Mechanistic analysis reveals a transient Cu(II)-thiolate intermediate (λmax = 590 nm) formed via acid-base exchange, generating nitrous acid (HNO2) that reacts with excess thiol to form S-nitrosothiol (RSNO). NO releases through RSNO and forming the stable Cu(I)-thiolate polymer. XPS confirms the presence of Cu(I) in YPtBuBz and YPBz as well as mixed-valent Cu(I/II) in YPCys with a clear satellite peak, which is supported by Auger parameter calculations. This work highlights the potential of copper complexes for NO generation and provides a deeper understanding of the underlying mechanisms.
{"title":"Copper Nitrite Reduction by Thiols: Mechanistic Insights into NO Release en route to Copper Thiolate Formation","authors":"Naorem Jemes Jemes Meitei, Yu Ting Chu, Chien-Hung Li, Rahimeh Eshaghi Malekshah, Wei-Min Ching, Tsung-Ting Shih, Sodio C. N. Hsu","doi":"10.1039/d5dt02535d","DOIUrl":"https://doi.org/10.1039/d5dt02535d","url":null,"abstract":"Nitrite reduction is a critical process in biological systems, with implications for disease pathology and therapeutic development. This study investigates the copper-mediated reduction of nitrite to nitric oxide (NO) using unsymmetrical β-diketiminato copper(II) nitrito complexes with thiol derivatives as reducing agents. The reaction of LCu(NO<small><sub>2</sub></small>) with 4-<em>tert</em>-butyl benzyl thiol (<em><small><sup>t</sup></small></em>BuBzSH), benzyl thiol (BzSH), and biologically active thiols like L-cysteine (Cys), yield quantitative NO, free ligand, disulfide, and an insoluble copper(I)-thiolate polymer (<strong>YP</strong><small><sub>R</sub></small>), characterized by FT-IR, NMR, and X-ray photoelectron spectroscopy (XPS). Mechanistic analysis reveals a transient Cu(II)-thiolate intermediate (λ<small><sub>max</sub></small> = 590 nm) formed via acid-base exchange, generating nitrous acid (HNO<small><sub>2</sub></small>) that reacts with excess thiol to form S-nitrosothiol (RSNO). NO releases through RSNO and forming the stable Cu(I)-thiolate polymer. XPS confirms the presence of Cu(I) in <strong>YP</strong><small><sub>tBuBz</sub></small> and <strong>YP</strong><small><sub>Bz</sub></small> as well as mixed-valent Cu(I/II) in<strong> YP</strong><small><sub>Cys</sub></small> with a clear satellite peak, which is supported by Auger parameter calculations. This work highlights the potential of copper complexes for NO generation and provides a deeper understanding of the underlying mechanisms.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"17 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147496506","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}
Chang-Yuan He, Kun Hu, Jing-Yang Zhou, Long Wu, Jian-Han Zhang
Two new Mo-Te-O compounds, (NH₄)₂MgMo₄Te₂O₁₈ and β-MoTe₂O₇, have been synthesized and structurally characterized as frameworks constructed from distorted MoO₆ octahedra and TeO₃ trigonal pyramids with stereochemically active lone pairs.The two phases feature distinct Mo-O-Te connectivities and dimensionalities, leading to different degrees of optical anisotropy. Polarized optical microscopy measurements reveal that both compounds exhibit moderate birefringence, which is further rationalized by density functional theory calculations.The incorporation of Mg²⁺ in (NH₄)₂MgMo₄Te₂O₁₈ results in a more structurally elaborate framework, and this compound shows a black crystal surface with a white interior, indicative of surface-related electronic effects. Combined experimental and theoretical results highlight the role of cooperative MoO₆-TeO₃distortions and framework connectivity in governing optical anisotropy in Mo-Te-O oxides.
{"title":"Optical Anisotropy in Mo-Te-O Frameworks Constructed from Distorted MoO₆ and TeO₃ Units","authors":"Chang-Yuan He, Kun Hu, Jing-Yang Zhou, Long Wu, Jian-Han Zhang","doi":"10.1039/d6dt00289g","DOIUrl":"https://doi.org/10.1039/d6dt00289g","url":null,"abstract":"Two new Mo-Te-O compounds, (NH₄)₂MgMo₄Te₂O₁₈ and β-MoTe₂O₇, have been synthesized and structurally characterized as frameworks constructed from distorted MoO₆ octahedra and TeO₃ trigonal pyramids with stereochemically active lone pairs.The two phases feature distinct Mo-O-Te connectivities and dimensionalities, leading to different degrees of optical anisotropy. Polarized optical microscopy measurements reveal that both compounds exhibit moderate birefringence, which is further rationalized by density functional theory calculations.The incorporation of Mg²⁺ in (NH₄)₂MgMo₄Te₂O₁₈ results in a more structurally elaborate framework, and this compound shows a black crystal surface with a white interior, indicative of surface-related electronic effects. Combined experimental and theoretical results highlight the role of cooperative MoO₆-TeO₃distortions and framework connectivity in governing optical anisotropy in Mo-Te-O oxides.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"42 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147489416","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}
Citrate plays a multifaceted and crucial role as a key intermediate in the Krebs cycle (citric acid cycle or TCA cycle), the central metabolic pathway for energy production or a source of ATP in aerobic organisms. Besides a metabolic regulator, dysregulation of citrate levels is intricately linked to the pathology of multiple diseases, including metabolism in cancer cells. Abnormal citrate concentrations have been associated with kidney stones, inflammation, metabolic disorders, cancers, non-alcoholic fatty liver diseases, neurological disorders, etc., highlighting its diagnostic and prognostic value. Therefore, the selective recognition and monitoring of changes in the citrate levels is useful for advancing our understanding of these diseases, enabling early diagnosis, and guiding effective therapeutic strategies. Developing a selective receptor for citrate is challenging due to its close structural resemblance to competing biological anions (PO43-, NO3-, tartrate, HCO3-, etc.) and its lower levels than other common anions in biological media. The uniquely attractive optical properties of luminescent Ln(III) probes, narrow emission bands, photobleaching resistance, photostability, especially long luminescence lifetime, and hard oxophillic nature of tripositive Ln(III) ions, make them ideal for time-gated luminescence measurements for trinegative hard [citrate]3- ions with enhanced S/N ratio and minimized scattering and autofluorescence from the media. We report here the rationale and fundamental design principles for an emissive Eu(III)-probe: [Eu(EDTA3AQ)(H2O)3]Cl (Eu.1), containing EDTA-bisamide-linked to two 3-aminoquinolines as antennae for the selective sensing of citrate3- as an important regulatory metabolite at physiological pH using highly sensitive and selective time-resolved luminescence (TRL) from Eu.1. The facile displacement of three labile inner-sphere H2O molecules and coordinative unsaturation at Eu(III) centre in Eu.1 satisfying the steric demand for preferential 1:1 binding of [citrate]3- at Eu(III) are found to be important design criteria, which were comprehensively studied using various solution-based spectroscopic studies and DFT. The [EuL-citrate] complexation, solution speciation, effects of variation of coordination number of Eu(III), and change in hydration numbers (q) were studied and validated to gain an insightful correlation of the rationale of Eu.1 probe design based on luminescence sensing mechanism of Eu.1 for citrate. The strong electrostatic binding of [citrate]3- via displacing H2Os in the 1st-sphere in Eu.1 suppresses the nonradiative vibrational energy transfer (VET), resulting in enhanced TRL from the f-f transitions, and thus acts as a reversible, selective and sensitive turn-ON sensor at the ppb level of citrate using both the TRL intensity and lifetime-based modalities.
{"title":"Rational design and evaluation of the sensing mechanism of a europium(III)-based luminescent turn-ON chemosensor for citrate","authors":"Ashwini Kumari Shaw, Nitin Shukla, Ashis Kumar Patra","doi":"10.1039/d5dt02901e","DOIUrl":"https://doi.org/10.1039/d5dt02901e","url":null,"abstract":"Citrate plays a multifaceted and crucial role as a key intermediate in the Krebs cycle (citric acid cycle or TCA cycle), the central metabolic pathway for energy production or a source of ATP in aerobic organisms. Besides a metabolic regulator, dysregulation of citrate levels is intricately linked to the pathology of multiple diseases, including metabolism in cancer cells. Abnormal citrate concentrations have been associated with kidney stones, inflammation, metabolic disorders, cancers, non-alcoholic fatty liver diseases, neurological disorders, etc., highlighting its diagnostic and prognostic value. Therefore, the selective recognition and monitoring of changes in the citrate levels is useful for advancing our understanding of these diseases, enabling early diagnosis, and guiding effective therapeutic strategies. Developing a selective receptor for citrate is challenging due to its close structural resemblance to competing biological anions (PO43-, NO3-, tartrate, HCO3-, etc.) and its lower levels than other common anions in biological media. The uniquely attractive optical properties of luminescent Ln(III) probes, narrow emission bands, photobleaching resistance, photostability, especially long luminescence lifetime, and hard oxophillic nature of tripositive Ln(III) ions, make them ideal for time-gated luminescence measurements for trinegative hard [citrate]3- ions with enhanced S/N ratio and minimized scattering and autofluorescence from the media. We report here the rationale and fundamental design principles for an emissive Eu(III)-probe: [Eu(EDTA3AQ)(H2O)3]Cl (Eu.1), containing EDTA-bisamide-linked to two 3-aminoquinolines as antennae for the selective sensing of citrate3- as an important regulatory metabolite at physiological pH using highly sensitive and selective time-resolved luminescence (TRL) from Eu.1. The facile displacement of three labile inner-sphere H2O molecules and coordinative unsaturation at Eu(III) centre in Eu.1 satisfying the steric demand for preferential 1:1 binding of [citrate]3- at Eu(III) are found to be important design criteria, which were comprehensively studied using various solution-based spectroscopic studies and DFT. The [EuL-citrate] complexation, solution speciation, effects of variation of coordination number of Eu(III), and change in hydration numbers (q) were studied and validated to gain an insightful correlation of the rationale of Eu.1 probe design based on luminescence sensing mechanism of Eu.1 for citrate. The strong electrostatic binding of [citrate]3- via displacing H2Os in the 1st-sphere in Eu.1 suppresses the nonradiative vibrational energy transfer (VET), resulting in enhanced TRL from the f-f transitions, and thus acts as a reversible, selective and sensitive turn-ON sensor at the ppb level of citrate using both the TRL intensity and lifetime-based modalities.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"20 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147489359","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}
We have conducted studies on the pathways of the heterogeneously catalytic decarbonylation of lactic acid (LA) to acetaldehyde (AD) with unsupported NaNO3 and amorphous silica-alumina (SiO2-Al2O3)-based materials by catalytic testing, IR spectroscopic monitoring, ammonia temperature-programmed desorption and IR spectroscopy of pyridine adsorption. A combination of IR monitoring and catalytic studies illustrates that the catalytic performance is dependent on the content of in situ generated lactate salts and that the interaction of lactate with SiO2-Al2O3 enables stabilization of the lactates against easy lactate dehydration to acrylates and subsequent acrylate polymerization. A combination of IR monitoring, surface acid property and catalytic studies indicates that the AD yield and selectivity to AD increase with decreasing surface acidity considering lactate hydrolysis causing loss of the lactates and competing formation of PolyLA and coke. The finding that the ratio of selectivity to AD to selectivity to acrylic acid almost does not change with varying intrinsic surface acidity suggests that both the LA decarbonylation and dehydration are lactate dependent and that the catalytic process of the LA decarbonylation is irrespective of the intrinsic surface acid sites. A probable mechanism of the heterogeneously catalytic LA decarbonylation is proposed, in which the lactates act as the catalytic active species while physisorbed LA acts both as the Brønsted acid sites assisting in the catalysis and a product intermediate. Besides, the reactivity of LA with SiO2-Al2O3 with regards to the catalytic active species and reaction pathways is discussed.
{"title":"On pathways of heterogeneous catalytic decarbonylation of lactic acid to acetaldehyde","authors":"Lin Huang, Chuan Wang, De Sheng Theng, Lili Zhang","doi":"10.1039/d5dt03122b","DOIUrl":"https://doi.org/10.1039/d5dt03122b","url":null,"abstract":"We have conducted studies on the pathways of the heterogeneously catalytic decarbonylation of lactic acid (LA) to acetaldehyde (AD) with unsupported NaNO3 and amorphous silica-alumina (SiO2-Al2O3)-based materials by catalytic testing, IR spectroscopic monitoring, ammonia temperature-programmed desorption and IR spectroscopy of pyridine adsorption. A combination of IR monitoring and catalytic studies illustrates that the catalytic performance is dependent on the content of in situ generated lactate salts and that the interaction of lactate with SiO2-Al2O3 enables stabilization of the lactates against easy lactate dehydration to acrylates and subsequent acrylate polymerization. A combination of IR monitoring, surface acid property and catalytic studies indicates that the AD yield and selectivity to AD increase with decreasing surface acidity considering lactate hydrolysis causing loss of the lactates and competing formation of PolyLA and coke. The finding that the ratio of selectivity to AD to selectivity to acrylic acid almost does not change with varying intrinsic surface acidity suggests that both the LA decarbonylation and dehydration are lactate dependent and that the catalytic process of the LA decarbonylation is irrespective of the intrinsic surface acid sites. A probable mechanism of the heterogeneously catalytic LA decarbonylation is proposed, in which the lactates act as the catalytic active species while physisorbed LA acts both as the Brønsted acid sites assisting in the catalysis and a product intermediate. Besides, the reactivity of LA with SiO2-Al2O3 with regards to the catalytic active species and reaction pathways is discussed.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"12 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147489415","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}
Sajjad Hussain, Zulfqar Ali Sheikh, K. Karuppasamy, Ghazanfar Nazir, Abdullah Al-Kahtani, Hyun-Seok Kim, Deok-kee Kim, Jongwan Jung, Akram Alfantazi, Dhanasekaran Vikraman
Perovskite-type oxides are considered promising electrode materials for supercapacitors due to their excellent ion intercalation and exchange capabilities. However, their practical application is hindered by intrinsically poor electrical conductivity, limited electroactive sites, and rapid surface redox reactions, which collectively result in low power density and inadequate cycling stability. To overcome these limitations, we integrated carbon nanotubes (CNTs) with perovskite-based composites to enhance electrical conductivity, create additional active edges, improve mass transfer characteristics, and achieve exceptional electrochemical stability within an environmentally benign material architecture. Herein, we report a rational design and hydrothermal synthesis of ternary WS₂/MgFeO₃-CNT (WMC) hybrid composites, wherein MgFeO₃ nanoparticles are uniformly anchored on WS₂ nanoflakes and integrated within a conductive CNT scaffold. By systematically varying the CNT content, we identified the optimized WMC-2 composition, which exhibited remarkable electrochemical performance with a high specific capacity of 420 C/g at 1 A/g and excellent cycling stability, retaining 93% of its initial capacity after 5000 consecutive charge-discharge cycles. Furthermore, an asymmetric supercapacitor device assembled with WMC-2 and activated carbon (WMC-2//AC) delivered a high energy density of 47 Wh/kg at a power density of 2250 W/kg in 6 M KOH electrolyte, along with outstanding long-term durability (89% capacity retention after 5000 cycles). These findings demonstrate the significant potential of WMC hybrid electrodes for advanced energy storage applications, offering a promising pathway for developing high-performance supercapacitors through rational multicomponent design.
钙钛矿型氧化物具有优异的离子嵌入和交换能力，被认为是超级电容器极具发展前景的电极材料。然而，它们的实际应用受到本质上较差的导电性、有限的电活性位点和快速的表面氧化还原反应的阻碍，这些共同导致低功率密度和不充分的循环稳定性。为了克服这些限制，我们将碳纳米管（CNTs）与钙钛矿基复合材料集成在一起，以提高导电性，创造额外的活性边，改善传质特性，并在环境友好的材料结构中实现卓越的电化学稳定性。在这里，我们报告了一种合理的设计和水热合成三元WS₂/MgFeO₃-CNT （WMC）杂化复合材料，其中MgFeO₃纳米颗粒均匀地固定在WS₂纳米片上，并集成在导电碳纳米管支架中。通过系统地改变碳纳米管的含量，我们确定了优化的WMC-2成分，该成分具有显著的电化学性能，在1 a /g下具有420 C/g的高比容量，并且具有良好的循环稳定性，在连续5000次充放电循环后仍保持93%的初始容量。此外，由WMC-2和活性炭（WMC-2//AC）组装的非对称超级电容器装置在6 M KOH电解质中，以2250 W/kg的功率密度提供了47 Wh/kg的高能量密度，并具有出色的长期耐用性（循环5000次后容量保持89%）。这些发现证明了WMC混合电极在先进储能应用中的巨大潜力，为通过合理的多组分设计开发高性能超级电容器提供了一条有希望的途径。
{"title":"Designing the tungsten sulfide blended perovskite anchored carbon nanotube composites for the high-performance supercapacitor","authors":"Sajjad Hussain, Zulfqar Ali Sheikh, K. Karuppasamy, Ghazanfar Nazir, Abdullah Al-Kahtani, Hyun-Seok Kim, Deok-kee Kim, Jongwan Jung, Akram Alfantazi, Dhanasekaran Vikraman","doi":"10.1039/d6dt00613b","DOIUrl":"https://doi.org/10.1039/d6dt00613b","url":null,"abstract":"Perovskite-type oxides are considered promising electrode materials for supercapacitors due to their excellent ion intercalation and exchange capabilities. However, their practical application is hindered by intrinsically poor electrical conductivity, limited electroactive sites, and rapid surface redox reactions, which collectively result in low power density and inadequate cycling stability. To overcome these limitations, we integrated carbon nanotubes (CNTs) with perovskite-based composites to enhance electrical conductivity, create additional active edges, improve mass transfer characteristics, and achieve exceptional electrochemical stability within an environmentally benign material architecture. Herein, we report a rational design and hydrothermal synthesis of ternary WS₂/MgFeO₃-CNT (WMC) hybrid composites, wherein MgFeO₃ nanoparticles are uniformly anchored on WS₂ nanoflakes and integrated within a conductive CNT scaffold. By systematically varying the CNT content, we identified the optimized WMC-2 composition, which exhibited remarkable electrochemical performance with a high specific capacity of 420 C/g at 1 A/g and excellent cycling stability, retaining 93% of its initial capacity after 5000 consecutive charge-discharge cycles. Furthermore, an asymmetric supercapacitor device assembled with WMC-2 and activated carbon (WMC-2//AC) delivered a high energy density of 47 Wh/kg at a power density of 2250 W/kg in 6 M KOH electrolyte, along with outstanding long-term durability (89% capacity retention after 5000 cycles). These findings demonstrate the significant potential of WMC hybrid electrodes for advanced energy storage applications, offering a promising pathway for developing high-performance supercapacitors through rational multicomponent design.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"89 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478629","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}
Maqsood Iqbal, Jiazheng Zhou, Aqsa Munawar, Juanjuan Lu, Junjie Li
Heavy metal oxyhalides have emerged as promising candidates for advanced photoelectric functional materials due to their distinguished structural characteristics and properties. This study reports the synthesis and characterization of two isostructural compounds, Cd5Se4O12X2 (X = Cl, Br), designed through rare Te-Se substitution from the new emerging Cd5Te4O12X2 (X = Cl, Br, I) compound. The Te-Se substitution induces the reorganization of Cd coordination environments, resulting a structural transition from P21/c (Cd5Te4O12X2, X = Cl, Br, I) to C2/c (Cd5Se4O12X2, X = Cl, Br) space group. The title compounds feature a three-dimensional structure composed of [CdO8], [CdO5], [CdO4X2], and [SeO3] polyhedral units. Cd5Se4O12Cl2 and Cd5Se4O12Br2 exhibit wide optical band gaps (in oxyhalides) of 4.96 eV and 4.68 eV, respectively. The birefringence value of Cd5Se4O12Cl2/Cd5Se4O12Br2 was determined to be 0.089/0.093@1064 nm. The results illustrate the feasibility of Te-Se substitution in the oxyhalide family and offer valuable insights for developing new oxyhalide-based functional materials with adjustable properties.
{"title":"Se-Te Replacement Induced Structural Transition and Enhanced Band Gaps in Cd5Se4O12Cl2 and Cd5Se4O12Br2","authors":"Maqsood Iqbal, Jiazheng Zhou, Aqsa Munawar, Juanjuan Lu, Junjie Li","doi":"10.1039/d5dt03047a","DOIUrl":"https://doi.org/10.1039/d5dt03047a","url":null,"abstract":"Heavy metal oxyhalides have emerged as promising candidates for advanced photoelectric functional materials due to their distinguished structural characteristics and properties. This study reports the synthesis and characterization of two isostructural compounds, Cd<small><sub>5</sub></small>Se<small><sub>4</sub></small>O<small><sub>12</sub></small>X<small><sub>2</sub></small> (X = Cl, Br), designed through rare Te-Se substitution from the new emerging Cd<small><sub>5</sub></small>Te<small><sub>4</sub></small>O<small><sub>12</sub></small>X<small><sub>2</sub></small> (X = Cl, Br, I) compound. The Te-Se substitution induces the reorganization of Cd coordination environments, resulting a structural transition from <em>P</em>2<small><sub>1</sub></small>/<em>c</em> (Cd<small><sub>5</sub></small>Te<small><sub>4</sub></small>O<small><sub>12</sub></small>X<small><sub>2</sub></small>, X = Cl, Br, I) to <em>C</em>2/<em>c</em> (Cd<small><sub>5</sub></small>Se<small><sub>4</sub></small>O<small><sub>12</sub></small>X<small><sub>2</sub></small>, X = Cl, Br) space group. The title compounds feature a three-dimensional structure composed of [CdO<small><sub>8</sub></small>], [CdO<small><sub>5</sub></small>], [CdO<small><sub>4</sub></small>X<small><sub>2</sub></small>], and [SeO<small><sub>3</sub></small>] polyhedral units. Cd<small><sub>5</sub></small>Se<small><sub>4</sub></small>O<small><sub>12</sub></small>Cl<small><sub>2</sub></small> and Cd<small><sub>5</sub></small>Se<small><sub>4</sub></small>O<small><sub>12</sub></small>Br<small><sub>2</sub></small> exhibit wide optical band gaps (in oxyhalides) of 4.96 eV and 4.68 eV, respectively. The birefringence value of Cd<small><sub>5</sub></small>Se<small><sub>4</sub></small>O<small><sub>12</sub></small>Cl<small><sub>2</sub></small>/Cd<small><sub>5</sub></small>Se<small><sub>4</sub></small>O<small><sub>12</sub></small>Br<small><sub>2</sub></small> was determined to be 0.089/0.093@1064 nm. The results illustrate the feasibility of Te-Se substitution in the oxyhalide family and offer valuable insights for developing new oxyhalide-based functional materials with adjustable properties.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"15 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147492597","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}
Solid oxide fuel cells (SOFCs) have attracted much attention due to their high efficiency and environmental friendliness. However, high operating temperatures lead to material degradation, which limits their application. When the temperature is reduced to an intermediate range (600–800 °C), the kinetics of the cathode oxygen reduction reaction (ORR) becomes the performance bottleneck. Iron-based perovskite cathodes, with advantages including low cost and structural stability, are strong alternatives to cobalt-based materials. However, their ORR activity is insufficient due to the limited generation and migration of oxygen vacancies. This review comprehensively summarizes recent advances in performances enhancement strategies for iron-based perovskite cathodes, including A-site and B-site doping, high-entropy design, and non-metal anion doping. We particularly highlight the underlying mechanisms through which these strategies synergistically optimize the electronic structure, enhance oxygen ion transport, and accelerate surface reaction kinetics. Finally, we provide perspectives on future research directions, emphasizing the critical role of in situ characterization combined with theoretical modeling for mechanistic insights, and the potential of novel structural engineering paradigms to guide the rational design of high performance, durable cathodes for intermediate-temperature SOFCs.
{"title":"Enhancing the ORR activity of Fe-based perovskite cathodes for intermediate-temperature solid oxide fuel cells: alternative strategies and performance optimization","authors":"Long Li, Qi Qian, Zihan Ma, Zhenhua Wang, Rongli Gao, Wei Cai, Xiong Zhou","doi":"10.1039/d5dt02767e","DOIUrl":"https://doi.org/10.1039/d5dt02767e","url":null,"abstract":"Solid oxide fuel cells (SOFCs) have attracted much attention due to their high efficiency and environmental friendliness. However, high operating temperatures lead to material degradation, which limits their application. When the temperature is reduced to an intermediate range (600–800 °C), the kinetics of the cathode oxygen reduction reaction (ORR) becomes the performance bottleneck. Iron-based perovskite cathodes, with advantages including low cost and structural stability, are strong alternatives to cobalt-based materials. However, their ORR activity is insufficient due to the limited generation and migration of oxygen vacancies. This review comprehensively summarizes recent advances in performances enhancement strategies for iron-based perovskite cathodes, including A-site and B-site doping, high-entropy design, and non-metal anion doping. We particularly highlight the underlying mechanisms through which these strategies synergistically optimize the electronic structure, enhance oxygen ion transport, and accelerate surface reaction kinetics. Finally, we provide perspectives on future research directions, emphasizing the critical role of <em>in situ</em> characterization combined with theoretical modeling for mechanistic insights, and the potential of novel structural engineering paradigms to guide the rational design of high performance, durable cathodes for intermediate-temperature SOFCs.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"120 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478627","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}
Nagihan Kocaağa, Aysegul Turkkol, Ceren CAN KARANLIK, Mehmet Dincer Bilgin, Ali Erdogmus
Schiff base decorated non-ionic phthalocyanine compounds with different metals and metal free version were synthesized and characterized through different spectroscopic techniques.The influence of central metal on the photophysicochemical properties was systematically investigated in DMSO. Obtained results reveal that the singlet oxygen quantum yield followed the order In3b>Zn3b>3bH 2 Pc in DMSO. All synthesized non-ionic phthalocyanine compounds except metal-free phthalocyanine (0.12 for 3bH 2 Pc) have good Φ ∆ values (0.71 for Zn3b, 0.85 for In3b) compared to the unsubstituted ZnPc in DMSO (Φ ∆ = 0.67). In addition to photophysicochemical studies, in vitro PDT studies were also performed on PC3 prostate cancer cells to evaluate the biological activity of Pcs. All compounds exhibited low dark cytotoxicity at the selected concentration. Upon light irradiation, phthalocyanine-mediated PDT significantly reduced cell viability and induced apoptotic cell death. These effects were accompanied by a pronounced increase in intracellular ROS generation, particularly in cells treated with metallophthalocyanine-mediated PDT. In particular, In3b-and Zn3b-mediated PDT exhibited markedly enhanced cytotoxic and apoptotic effects compared to metal-free 3bH₂Pc. These findings demonstrate a strong correlation between improved photophysical properties, increased ROS generation, and enhanced in vitro PDT efficacy.
{"title":"IN VITRO EVALUATION OF SCHIFF BASE DECORATED PHTHALOCYANINES FOR PHOTODYNAMIC THERAPY IN PC3 PROSTATE CANCER CELLS","authors":"Nagihan Kocaağa, Aysegul Turkkol, Ceren CAN KARANLIK, Mehmet Dincer Bilgin, Ali Erdogmus","doi":"10.1039/d6dt00397d","DOIUrl":"https://doi.org/10.1039/d6dt00397d","url":null,"abstract":"Schiff base decorated non-ionic phthalocyanine compounds with different metals and metal free version were synthesized and characterized through different spectroscopic techniques.The influence of central metal on the photophysicochemical properties was systematically investigated in DMSO. Obtained results reveal that the singlet oxygen quantum yield followed the order In3b>Zn3b>3bH 2 Pc in DMSO. All synthesized non-ionic phthalocyanine compounds except metal-free phthalocyanine (0.12 for 3bH 2 Pc) have good Φ ∆ values (0.71 for Zn3b, 0.85 for In3b) compared to the unsubstituted ZnPc in DMSO (Φ ∆ = 0.67). In addition to photophysicochemical studies, in vitro PDT studies were also performed on PC3 prostate cancer cells to evaluate the biological activity of Pcs. All compounds exhibited low dark cytotoxicity at the selected concentration. Upon light irradiation, phthalocyanine-mediated PDT significantly reduced cell viability and induced apoptotic cell death. These effects were accompanied by a pronounced increase in intracellular ROS generation, particularly in cells treated with metallophthalocyanine-mediated PDT. In particular, In3b-and Zn3b-mediated PDT exhibited markedly enhanced cytotoxic and apoptotic effects compared to metal-free 3bH₂Pc. These findings demonstrate a strong correlation between improved photophysical properties, increased ROS generation, and enhanced in vitro PDT efficacy.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"45 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147489419","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 swift rise of digital communications, particularly in the realm of big data and the Internet of Things (IoT), has accelerated the development of next-generation data storage technologies. Resistive switching (RS) memory devices and artificial synapses remain appealing alternatives, offering low power consumption, ability to accommodate various capacities, and rapid speed. Neuromorphic computing aims to simulate the neuronal structure and functioning of the human brain, enabling advancements in human perception, interpretation, and autonomous adaptation. Halide perovskites are a group of materials that possess several benefits, such as a significant distance over which charge carriers can move, strong ability to absorb light, ability to carry both positive and negative charges, ability to conduct ions, and the ability to be processed in solution. Photovoltaic, light-emitting diode, laser, and photodetector are merely some of the numerous areas in which they have proven useful. This article provides an extensive review of the most contemporary advancements in halide perovskite-based artificial synapses and RS memory devices. To begin with, this paper introduces the overall structure and distinctive features of RS memory devices. Next, we delve into the exceptional memory performance supported by comprehensive operational processes. This review also aims at laying the groundwork for the rational development of halide perovskite memory devices and artificial synapses, which will lead to notable performance improvements. Lastly, the present obstacles and the possibilities for future progress are discussed.
{"title":"Halide Perovskite Based Memory Devices and Neuromorphic Computing","authors":"Tufan Paul, Aditi Sahoo, Soumen Maiti, Pulak Pal, Kalyan Kumar Chattopadhyay","doi":"10.1039/d5dt02579f","DOIUrl":"https://doi.org/10.1039/d5dt02579f","url":null,"abstract":"The swift rise of digital communications, particularly in the realm of big data and the Internet of Things (IoT), has accelerated the development of next-generation data storage technologies. Resistive switching (RS) memory devices and artificial synapses remain appealing alternatives, offering low power consumption, ability to accommodate various capacities, and rapid speed. Neuromorphic computing aims to simulate the neuronal structure and functioning of the human brain, enabling advancements in human perception, interpretation, and autonomous adaptation. Halide perovskites are a group of materials that possess several benefits, such as a significant distance over which charge carriers can move, strong ability to absorb light, ability to carry both positive and negative charges, ability to conduct ions, and the ability to be processed in solution. Photovoltaic, light-emitting diode, laser, and photodetector are merely some of the numerous areas in which they have proven useful. This article provides an extensive review of the most contemporary advancements in halide perovskite-based artificial synapses and RS memory devices. To begin with, this paper introduces the overall structure and distinctive features of RS memory devices. Next, we delve into the exceptional memory performance supported by comprehensive operational processes. This review also aims at laying the groundwork for the rational development of halide perovskite memory devices and artificial synapses, which will lead to notable performance improvements. Lastly, the present obstacles and the possibilities for future progress are discussed.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"7 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147479009","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：