In the field of metallo-organic helicates, the controlled synthesis of low-symmetric structures remains a significant challenge on the precise control over the self-assembly process due to their thermodynamically disfavored nature, compared to highly symmetric forms. This study introduces an effective strategy by shifting the design focus from ligands to metal centers. Through precise regulation of the stereoconfiguration, two metal centers are directed to adopt opposite handedness, affording a mesomeric and C1 symmetric helicate structure S, fully characterized by 1H NMR, ESI-MS and SC-XRD. The resulting helicate structure features a well-defined square cavity with a 8.5 Å distance between roof and floor, is capable of accommodating planar polycyclic aromatic hydrocarbons (PAHs) via π–π stacking interaction within optimal range after slight compression. More importantly, the binding constants shows a proportional enhancement with the increasing of number of π-electrons in PAH guests. This work points toward new direction for developing functional low-symmetric metallo-organic supramolecular assemblies. And, the clear structure-function relationship highlights its potential applications in molecular separation and sensing.
{"title":"Controllable self-assembly of mesomeric metallo-organic helicate and its π-electron number dependent encapsulation of polycyclic aromatic hydrocarbons (PAHs)","authors":"huoqing Chen, Haoxuan Xu, Tun Wu, Yuming Guan, Qingwu Long, Qixia Bai, Tian Li, Tian-Yu Liu, Pingshan Wang, Zhe Zhang","doi":"10.1039/d5qi02447a","DOIUrl":"https://doi.org/10.1039/d5qi02447a","url":null,"abstract":"In the field of metallo-organic helicates, the controlled synthesis of low-symmetric structures remains a significant challenge on the precise control over the self-assembly process due to their thermodynamically disfavored nature, compared to highly symmetric forms. This study introduces an effective strategy by shifting the design focus from ligands to metal centers. Through precise regulation of the stereoconfiguration, two metal centers are directed to adopt opposite handedness, affording a <em>mesomeric</em> and <em>C</em><small><sub>1</sub></small> symmetric helicate structure <strong>S</strong>, fully characterized by <small><sup>1</sup></small>H NMR, ESI-MS and SC-XRD. The resulting helicate structure features a well-defined square cavity with a 8.5 Å distance between roof and floor, is capable of accommodating planar polycyclic aromatic hydrocarbons (PAHs) via π–π stacking interaction within optimal range after slight compression. More importantly, the binding constants shows a proportional enhancement with the increasing of number of π-electrons in PAH guests. This work points toward new direction for developing functional low-symmetric metallo-organic supramolecular assemblies. And, the clear structure-function relationship highlights its potential applications in molecular separation and sensing.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"94 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145938121","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}
During the water splitting process for hydrogen production with metal hydroxide electrocatalysts, a self-reconstructing reaction occurring at low potential is the key to efficient operations. In this work, a Ni-Fe(OH)₃ electrocatalyst is designed, in which the built-in electric field formed at the heterojunction results in electron accumulation on Ni and facilitates the reconstruction of Fe(OH)₃ into active FeOOH under a lower applied potential while maintaining structural stable. Triggered by the interfacial electron accumulation and structural reconstruction, the prepared Ni-Fe(OH)₃ anchored on an iron-nickel-foam substrate shows an overpotential of just 453 mV that can drive an ampere level current of 1.0 A cm⁻² in 1.0 M KOH mixed seawater, with remarkable stability for over 360 h. Density functional theory calculations suggest that the in-situ reconstructed Ni-FeOOH enhances the adsorption behavior of intermediates and significantly reduces the energy barrier of the oxygen revolution reaction. These results underscore the great promise of engineering built-in electric field in transition metal hydroxide catalysts for efficient hydrogen production via seawater oxidation。
在金属氢氧化物电催化剂水解制氢过程中，低电位下的自重构反应是高效运行的关键。在这项工作中，设计了一种Ni-Fe（OH）₃电催化剂，其中在异质结处形成的内置电场导致电子在Ni上积聚，并且有利于Fe（OH）₃在较低的施加电位下重构为活性FeOOH，同时保持结构稳定。在界面电子积累和结构重建的触发下，制备的Ni-Fe（OH）₃锚定在铁镍泡沫基板上，其过电位仅为453 mV，在1.0 M KOH混合海水中可以驱动1.0 A cm⁻²的安培电流。密度泛函理论计算表明，原位重构的Ni-FeOOH增强了中间体的吸附行为，显著降低了氧旋转反应的能垒。这些结果强调了工程内置电场在过渡金属氢氧化物催化剂中用于通过海水氧化高效制氢的巨大前景。
{"title":"Built-in electric field triggered interfacial electron accumulation and structural reconstruction for boosting ampere-level-current seawater oxidation","authors":"Xueling Wei, Youjun Huang, Qiguan Wang, Linlin Dang, Xiangyu Zou, Wenhu Li, Taotao Ai, Sumin Wang","doi":"10.1039/d5qi02143j","DOIUrl":"https://doi.org/10.1039/d5qi02143j","url":null,"abstract":"During the water splitting process for hydrogen production with metal hydroxide electrocatalysts, a self-reconstructing reaction occurring at low potential is the key to efficient operations. In this work, a Ni-Fe(OH)₃ electrocatalyst is designed, in which the built-in electric field formed at the heterojunction results in electron accumulation on Ni and facilitates the reconstruction of Fe(OH)₃ into active FeOOH under a lower applied potential while maintaining structural stable. Triggered by the interfacial electron accumulation and structural reconstruction, the prepared Ni-Fe(OH)₃ anchored on an iron-nickel-foam substrate shows an overpotential of just 453 mV that can drive an ampere level current of 1.0 A cm⁻² in 1.0 M KOH mixed seawater, with remarkable stability for over 360 h. Density functional theory calculations suggest that the in-situ reconstructed Ni-FeOOH enhances the adsorption behavior of intermediates and significantly reduces the energy barrier of the oxygen revolution reaction. These results underscore the great promise of engineering built-in electric field in transition metal hydroxide catalysts for efficient hydrogen production via seawater oxidation。","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"39 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145907970","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}
Enhancing the performance of the oxygen evolution reaction (OER) is crucial for improving the overall efficiency of hydrogen production through seawater electrolysis. However, seawater electrolysis imposes stringent requirements on catalyst’s catalytic activity and corrosion resistance. Herein, we present a Ce-NiFeOOH/PO43- electrocatalyst exhibiting exceptional catalytic activity and chloride-corrosion resistance for direct seawater splitting. On one hand, the unique 4f orbitals of the rare earth element Ce cause a reconstruction of the electronic environment at the active sites of the NiFeOOH, enhancing catalytic activity. On the other hand, the phosphate groups provide charge shielding to prevent the electrode from being etched by Cl- in seawater and thereby enhancing the stability of Ce-NiFeOOH/PO43-. Electrochemical tests show that the catalyst can operate stably for 800 h at 0.5 A cm-2 in seawater. When the catalyst is integrated into an anion exchange membrane electrolyzer for seawater electrolysis, Ce-NiFeOOH/PO43- only requires 1.68 V to achieve 0.5 A cm-2. The electrolyzer achieves an efficiency of 74.6% and a hydrogen production cost of $0.897 per GGE H2 at 0.5 A cm-2, superior to the U.S. Department of Energy targets of 65% efficiency and $2 per gallon of gasoline equivalent (GGE) H2 by 2026. This work provides new insights into designing efficient and robust catalysts for green hydrogen production using seawater.
提高析氧反应（OER）性能是提高海水电解制氢整体效率的关键。然而，海水电解对催化剂的催化活性和耐腐蚀性提出了严格的要求。在此，我们提出了一种Ce-NiFeOOH/PO43-电催化剂，它具有优异的催化活性和抗氯化物腐蚀能力，可用于海水直接裂解。一方面，稀土元素Ce独特的4f轨道重建了NiFeOOH活性位点的电子环境，提高了催化活性。另一方面，磷酸基提供电荷屏蔽，防止电极在海水中被Cl-腐蚀，从而提高Ce-NiFeOOH/PO43-的稳定性。电化学试验表明，该催化剂在0.5 A cm-2的海水中可稳定工作800 h。当催化剂集成到阴离子交换膜电解槽中进行海水电解时，Ce-NiFeOOH/PO43-仅需1.68 V即可达到0.5 A cm-2。电解槽的效率为74.6%，在0.5 a cm-2的情况下，每加仑加仑氢气的制氢成本为0.897美元，优于美国能源部到2026年实现65%效率和每加仑汽油当量（GGE）氢气2美元的目标。这项工作为设计高效、稳健的海水绿色制氢催化剂提供了新的见解。
{"title":"Synergistic electronic modulation and Cl- shielding of Fe sites for robust seawater electrolysis","authors":"Hao Wang, Pengwu Jiang, Nannan Jiang, Weili Zhang, Bing Huang, Xuwei Liu, Huihui Jin, Lunhui Guan","doi":"10.1039/d5qi02363g","DOIUrl":"https://doi.org/10.1039/d5qi02363g","url":null,"abstract":"Enhancing the performance of the oxygen evolution reaction (OER) is crucial for improving the overall efficiency of hydrogen production through seawater electrolysis. However, seawater electrolysis imposes stringent requirements on catalyst’s catalytic activity and corrosion resistance. Herein, we present a Ce-NiFeOOH/PO43- electrocatalyst exhibiting exceptional catalytic activity and chloride-corrosion resistance for direct seawater splitting. On one hand, the unique 4f orbitals of the rare earth element Ce cause a reconstruction of the electronic environment at the active sites of the NiFeOOH, enhancing catalytic activity. On the other hand, the phosphate groups provide charge shielding to prevent the electrode from being etched by Cl- in seawater and thereby enhancing the stability of Ce-NiFeOOH/PO43-. Electrochemical tests show that the catalyst can operate stably for 800 h at 0.5 A cm-2 in seawater. When the catalyst is integrated into an anion exchange membrane electrolyzer for seawater electrolysis, Ce-NiFeOOH/PO43- only requires 1.68 V to achieve 0.5 A cm-2. The electrolyzer achieves an efficiency of 74.6% and a hydrogen production cost of $0.897 per GGE H2 at 0.5 A cm-2, superior to the U.S. Department of Energy targets of 65% efficiency and $2 per gallon of gasoline equivalent (GGE) H2 by 2026. This work provides new insights into designing efficient and robust catalysts for green hydrogen production using seawater.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"36 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145907974","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}
Lan Wang, Shuya Zhang, Lingxuan Hu, Xiaoliang Wu, Xiaobin Fan
Porous carbon nanosheets have emerged as promising candidates for electrode materials in energy storage systems. Herein, graphene oxide induced strategy was developed to prepare porous carbon nanosheets derived from starch with potassium hydroxide (KOH) assistance. The surface of graphene oxide contains abundant carboxyl groups that form hydrogen bonds with starch, tightly binding them together. Upon dissolving in water, KOH releases a significant amount of heat, promoting starch gelatinization on the surface of oxidized graphene. The layered structure of oxidized graphene induces the formation of porous carbon nanosheets with KOH assistance during the carbonization process. The obtained samples consist of numerous of carbon nanosheets that create a three-dimensional (3D) interconnected macroporous network. Benefiting from the high specific surface area, interconnected porous carbon nanosheets structure, and rich oxygen functional groups, the GPC-700 electrode demonstrates an impressive specific capacitance of 431.8 F g−1 at 0.5 A g−1, coupled with a good rate characteristic (293.3 F g−1 at 20 A g−1) and excellent electrochemical durability (10,000 cycles, 95.5 % retention). More importantly, the fabricated Zn//ZnSO4//GPC-700 zinc ion hybrid capacitor exhibits a high energy density of 123.1 Wh kg−1 and superior cycle life. This work provides new ideas and feasible methods for preparing biomass-based porous carbon nanosheets as electrode materials for energy storage devices.
多孔碳纳米片已成为储能系统中极具潜力的电极材料。本研究开发了氧化石墨烯诱导策略，在氢氧化钾（KOH）的辅助下制备淀粉衍生的多孔碳纳米片。氧化石墨烯表面含有丰富的羧基，这些羧基与淀粉形成氢键，将它们紧密地结合在一起。当KOH溶解在水中时，会释放出大量的热量，促进氧化石墨烯表面的淀粉糊化。氧化石墨烯的层状结构诱导了碳化过程中在KOH辅助下多孔碳纳米片的形成。所获得的样品由许多碳纳米片组成，这些碳纳米片创建了一个三维（3D）相互连接的大孔网络。得益于高比表面积、互连多孔碳纳米片结构和丰富的氧官能团，GPC-700电极在0.5 A g−1时具有令人印象深刻的431.8 F g−1比电容，以及良好的倍率特性（20a g−1时293.3 F g−1）和优异的电化学耐久性（10,000次循环，95.5%保留率）。更重要的是，制备的Zn//ZnSO4//GPC-700锌离子杂化电容器具有123.1 Wh kg−1的高能量密度和优异的循环寿命。本研究为制备生物质基多孔碳纳米片作为储能器件电极材料提供了新的思路和可行的方法。
{"title":"KOH assistance with graphene oxide induced synthesis of porous carbon nanosheets for supercapacitor and zinc ion hybrid capacitor","authors":"Lan Wang, Shuya Zhang, Lingxuan Hu, Xiaoliang Wu, Xiaobin Fan","doi":"10.1039/d5qi02397a","DOIUrl":"https://doi.org/10.1039/d5qi02397a","url":null,"abstract":"Porous carbon nanosheets have emerged as promising candidates for electrode materials in energy storage systems. Herein, graphene oxide induced strategy was developed to prepare porous carbon nanosheets derived from starch with potassium hydroxide (KOH) assistance. The surface of graphene oxide contains abundant carboxyl groups that form hydrogen bonds with starch, tightly binding them together. Upon dissolving in water, KOH releases a significant amount of heat, promoting starch gelatinization on the surface of oxidized graphene. The layered structure of oxidized graphene induces the formation of porous carbon nanosheets with KOH assistance during the carbonization process. The obtained samples consist of numerous of carbon nanosheets that create a three-dimensional (3D) interconnected macroporous network. Benefiting from the high specific surface area, interconnected porous carbon nanosheets structure, and rich oxygen functional groups, the GPC-700 electrode demonstrates an impressive specific capacitance of 431.8 F g−1 at 0.5 A g−1, coupled with a good rate characteristic (293.3 F g−1 at 20 A g−1) and excellent electrochemical durability (10,000 cycles, 95.5 % retention). More importantly, the fabricated Zn//ZnSO4//GPC-700 zinc ion hybrid capacitor exhibits a high energy density of 123.1 Wh kg−1 and superior cycle life. This work provides new ideas and feasible methods for preparing biomass-based porous carbon nanosheets as electrode materials for energy storage devices.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"94 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145907971","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 fluoride ion (F -) is one of the most important anions because of its usefulness in the maintaining of oral health and bonegrowth, and existence in a variety of clinical, environmental, and food samples. The U.S. Public Health Service recommends a [F -] of 0.7 mg L -1 as the optimal level for the prevention of dental caries in drinking water. Excessive F -exposure for long time causes dental and skeletal fluorosis, joint stiffness, interfere with thyroid hormone production, kidney problem and reproductive issues. Therefore, there is a need for analytical and practical techniques for the selective, sensitive, fast trace detection and quantification of fluoride ion in food, drinks and beverages. The photophysical properties of the metal complexes have been widely exploited in the design of chemosensors for F -ion detection. During the recent past, many metal-complex-based probes have been recognized in the reports, and they are assumed to be promising for the progress of efficient, selective, and sensitive methods for fluoride ion recognition. To the best of our knowledge, several reviews have been written so far, but the majority of them concentrate on organic small molecular chemosensors and some selective metal-based receptors for F -detection but there are hardly any report exists that systematically summarised metal-complex and coordination polymeric frameworks-based receptors for F -ion recognition. This review provides an overview of recent advances in the development of metal-complex-based receptors, including metal-organic frameworks, for selective recognition of fluoride since the last couple of years (2014-2025). This review will particularly address the design concepts, structural features, mechanism of action, recognition efficiency, sensitivity, selectivity, and practical uses of metal-based receptors in fluoride sensing
氟离子（F -）是最重要的阴离子之一，因为它在维持口腔健康和骨骼生长方面有用，并且存在于各种临床，环境和食品样品中。美国公共卫生服务机构建议，饮用水中预防龋齿的最佳水平是0.7 mg L -1。长期过量接触氟会导致牙齿和骨骼氟中毒、关节僵硬、干扰甲状腺激素分泌、肾脏问题和生殖问题。因此，食品、饮料和饮料中氟离子的选择性、灵敏、快速痕量检测和定量需要分析和实用的技术。金属配合物的光物理性质已广泛应用于F离子检测化学传感器的设计中。近年来，许多基于金属配合物的探针在报道中得到了认可，它们被认为是有效、选择性和敏感的氟离子识别方法的有希望的进展。据我们所知，目前已有几篇综述，但大多数都集中在有机小分子化学传感器和一些选择性金属基F离子检测受体上，但几乎没有系统地总结金属配合物和配位聚合物框架基F离子识别受体的报道。本文综述了近年来（2014-2025）用于选择性识别氟化物的金属配合物受体（包括金属有机框架）的最新进展。本文将重点介绍金属基受体在氟传感中的设计概念、结构特点、作用机制、识别效率、灵敏度、选择性和实际应用
{"title":"A broad perspective on metal complex-based optical recognition of fluoride ions: Twelve years (2014-2025) of innovations and applications","authors":"Kingshuk Debsharma, Sunanda Dey, Swapan Dey, Chittaranjan Sinha","doi":"10.1039/d5qi02060c","DOIUrl":"https://doi.org/10.1039/d5qi02060c","url":null,"abstract":"The fluoride ion (F -) is one of the most important anions because of its usefulness in the maintaining of oral health and bonegrowth, and existence in a variety of clinical, environmental, and food samples. The U.S. Public Health Service recommends a [F -] of 0.7 mg L -1 as the optimal level for the prevention of dental caries in drinking water. Excessive F -exposure for long time causes dental and skeletal fluorosis, joint stiffness, interfere with thyroid hormone production, kidney problem and reproductive issues. Therefore, there is a need for analytical and practical techniques for the selective, sensitive, fast trace detection and quantification of fluoride ion in food, drinks and beverages. The photophysical properties of the metal complexes have been widely exploited in the design of chemosensors for F -ion detection. During the recent past, many metal-complex-based probes have been recognized in the reports, and they are assumed to be promising for the progress of efficient, selective, and sensitive methods for fluoride ion recognition. To the best of our knowledge, several reviews have been written so far, but the majority of them concentrate on organic small molecular chemosensors and some selective metal-based receptors for F -detection but there are hardly any report exists that systematically summarised metal-complex and coordination polymeric frameworks-based receptors for F -ion recognition. This review provides an overview of recent advances in the development of metal-complex-based receptors, including metal-organic frameworks, for selective recognition of fluoride since the last couple of years (2014-2025). This review will particularly address the design concepts, structural features, mechanism of action, recognition efficiency, sensitivity, selectivity, and practical uses of metal-based receptors in fluoride sensing","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"1 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145908226","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}
Electrocatalytic polyethylene terephthalate (PET) upcycling has recently emerged as a promising and energy-efficient approach to transform plastic waste into valuable chemicals. By employing renewable electricity, electrochemical systems can activate and cleave the PET-derived small molecule through controllable redox reactions, enabling selective electrochemically oxidation into high-value products.Moreover, coupling anodic PET oxidation with cathodic reactions enables paired electrolysis for simultaneous waste valorization and green fuel production, significantly improving overall energy efficiency. Given the rapid development of advanced catalysts and their outstanding catalytic performance, this review provides a comprehensive and systematic overview of the current progress in electrocatalytic PET upcycling, covering the fundamental reaction mechanisms, the evolution of catalyst design strategies, and the development of integrated paired-electrolysis systems.Particular attention is given to the correlation between electronic structure modulation and catalytic performance, as well as the synergistic coupling between anodic oxidation and cathodic reduction processes. Finally, we identify the key challenges and outline future perspectives toward building efficient electrocatalytic platforms for sustainable plastic waste valorization.
{"title":"Electrocatalytic Upgrading of Polyethylene Terephthalate: Mechanisms, Catalyst Design, and Paired Electrolysis Applications","authors":"Kun Chen, Yun Tong","doi":"10.1039/d5qi02386f","DOIUrl":"https://doi.org/10.1039/d5qi02386f","url":null,"abstract":"Electrocatalytic polyethylene terephthalate (PET) upcycling has recently emerged as a promising and energy-efficient approach to transform plastic waste into valuable chemicals. By employing renewable electricity, electrochemical systems can activate and cleave the PET-derived small molecule through controllable redox reactions, enabling selective electrochemically oxidation into high-value products.Moreover, coupling anodic PET oxidation with cathodic reactions enables paired electrolysis for simultaneous waste valorization and green fuel production, significantly improving overall energy efficiency. Given the rapid development of advanced catalysts and their outstanding catalytic performance, this review provides a comprehensive and systematic overview of the current progress in electrocatalytic PET upcycling, covering the fundamental reaction mechanisms, the evolution of catalyst design strategies, and the development of integrated paired-electrolysis systems.Particular attention is given to the correlation between electronic structure modulation and catalytic performance, as well as the synergistic coupling between anodic oxidation and cathodic reduction processes. Finally, we identify the key challenges and outline future perspectives toward building efficient electrocatalytic platforms for sustainable plastic waste valorization.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"183 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145908227","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}
To enhance the quality of white light (mimicking sunlight-like emission) for solid-state lighting (SSL) applications, a novel imidazolyl-bipyridyl ligand was designed as an ancillary ligand to achieve multi-coloured emission in the Europium (III) complex. The structural engineering in the case of the ligand was crafted by replacing the nitrogen heteroatom with a phenyl moiety to shift the broad green emission (λ = 553 nm) into a narrow blue emission (λ = 460 nm). This blue emission of ligand, when combined with Europium (III) using thenoyltrifluoroacetone (TTA) and dibenzoylmethane (DBM) as anionic ligands, helped to achieve white light emission by exciting with near-UV LED (λex = 390 nm), which had a great advantage to get white emission colour without blue LED (λex = 460 nm). Density Functional Theory (DFT) calculations were performed to theoretically investigate the energy transfer process from the ligand to the emitting level (5D0) of Eu3+ in Eu complexes. These Europium (III) complexes exhibit a unique dual-emissive behaviour (multi-coloured emission), including white emission across various solvents. The Eu(III) complexes have shown excellent properties in a white LED, with a Commission Internationale de l'Éclairage (CIE) coordinate (x = 0.30, y = 0.32), and serve as a functional luminescent thermometer, displaying a colour change with a temperature rise.
{"title":"Hetero Atom (Nitrogen) replaced by Phenyl Insertion in Molecular Eu-complex Facilitated Sun Light-like Emission for Sustainable White LEDs and Non-Contact Thermometer","authors":"Sivakumar Vaidyanathan, Swetha Maredi, Rohit B, Takashi Nakanishi","doi":"10.1039/d5qi02371h","DOIUrl":"https://doi.org/10.1039/d5qi02371h","url":null,"abstract":"To enhance the quality of white light (mimicking sunlight-like emission) for solid-state lighting (SSL) applications, a novel imidazolyl-bipyridyl ligand was designed as an ancillary ligand to achieve multi-coloured emission in the Europium (III) complex. The structural engineering in the case of the ligand was crafted by replacing the nitrogen heteroatom with a phenyl moiety to shift the broad green emission (λ = 553 nm) into a narrow blue emission (λ = 460 nm). This blue emission of ligand, when combined with Europium (III) using thenoyltrifluoroacetone (TTA) and dibenzoylmethane (DBM) as anionic ligands, helped to achieve white light emission by exciting with near-UV LED (λex = 390 nm), which had a great advantage to get white emission colour without blue LED (λex = 460 nm). Density Functional Theory (DFT) calculations were performed to theoretically investigate the energy transfer process from the ligand to the emitting level (5D0) of Eu3+ in Eu complexes. These Europium (III) complexes exhibit a unique dual-emissive behaviour (multi-coloured emission), including white emission across various solvents. The Eu(III) complexes have shown excellent properties in a white LED, with a Commission Internationale de l'Éclairage (CIE) coordinate (x = 0.30, y = 0.32), and serve as a functional luminescent thermometer, displaying a colour change with a temperature rise.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"41 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145903523","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}
In this study, we propose simple template-free synthesis method to obtain high-yield and size-tunable monocrystalline gold nanoplates, and systematically investigate their influence factors and growth mechanism. The synthesis only simply utilizes two chemicals in the whole hydrothermal process-dimethyl sulfoxide (DMSO) and chloroauric acid (HAuCl 4 ). By adjusting the concentration of DMSO and HAuCl 4 , precise control of the size of gold nanoplates (5-20 μm of the side and 50-100 nm of the thickness) has been achieved. Their growth mechanism in a surfactant-free medium has presented and discussed based on the results of time-lapsed high-resolution Transmission electron microscopy (HRTEM) and Scanning Transmission electron microscopy (STEM)/energy-dispersive X-ray spectroscopy (EDX). The hydrolysis products of HAuCl 4 form an unstable complex with DMSO, and the trivalent gold generated from bond cleavage further undergoes disproportionation reactions, leading to the formation of stable gold nanoparticles on the surface of the soft membrane board, which eventually grow into gold nanosheets, with HAuCl 4 acting as the gold precursor and DMSO serving as a reducing agent and shape-directing agent. To present the robust function of these nanoplates, we have applied gold nanoplates to CNT films, and used the rolling process to prepare CNT/AuNPLs composites. Achieves excellent EMI shielding (76 dB in 8-12.4 GHz). This research not only provides new insights into the design of high-performance lightweight shielding materials but also lays a technical foundation for solving the metallization challenges of highly chemically inert substrates, contributing significantly to the advancement of 5G high-frequency communication and aerospace electromagnetic protection technologies.
{"title":"Simple Synthesis of High-yield Monocrystalline Gold Nanoplates as Reinforcement to Enhance the EMI Shielding Performance of Carbon Nanotube Matrix","authors":"Xianwen Ruan, Qian Wang, Wen Li, Xinyang Gu, Yang Cao, Xiaodong Shen, Wenbo Xin","doi":"10.1039/d5qi02055g","DOIUrl":"https://doi.org/10.1039/d5qi02055g","url":null,"abstract":"In this study, we propose simple template-free synthesis method to obtain high-yield and size-tunable monocrystalline gold nanoplates, and systematically investigate their influence factors and growth mechanism. The synthesis only simply utilizes two chemicals in the whole hydrothermal process-dimethyl sulfoxide (DMSO) and chloroauric acid (HAuCl 4 ). By adjusting the concentration of DMSO and HAuCl 4 , precise control of the size of gold nanoplates (5-20 μm of the side and 50-100 nm of the thickness) has been achieved. Their growth mechanism in a surfactant-free medium has presented and discussed based on the results of time-lapsed high-resolution Transmission electron microscopy (HRTEM) and Scanning Transmission electron microscopy (STEM)/energy-dispersive X-ray spectroscopy (EDX). The hydrolysis products of HAuCl 4 form an unstable complex with DMSO, and the trivalent gold generated from bond cleavage further undergoes disproportionation reactions, leading to the formation of stable gold nanoparticles on the surface of the soft membrane board, which eventually grow into gold nanosheets, with HAuCl 4 acting as the gold precursor and DMSO serving as a reducing agent and shape-directing agent. To present the robust function of these nanoplates, we have applied gold nanoplates to CNT films, and used the rolling process to prepare CNT/AuNPLs composites. Achieves excellent EMI shielding (76 dB in 8-12.4 GHz). This research not only provides new insights into the design of high-performance lightweight shielding materials but also lays a technical foundation for solving the metallization challenges of highly chemically inert substrates, contributing significantly to the advancement of 5G high-frequency communication and aerospace electromagnetic protection technologies.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"24 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145895191","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}
Transition metal phosphides (TMPs) are ideal catalyst alternatives to precious metals for water electrolysis. However, their sluggish reaction kinetics hamper practical widespread application. Herein, a S, V-co-doped Ni2P electrocatalyst with a microflower-like spherical structure was successfully constructed via a facile elemental co-doping strategy for overall water splitting. Combined experimental characterizations, in-situ electrochemical measurements, and density functional theory (DFT) calculations demonstrate that S and V co-doping can effectively modulate the local microenvironment of Ni active sites, tune the adsorption energy of reaction intermediates, and reduce the energy barrier of the rate-determining step (RDS), thereby endowing the catalyst with outstanding electrocatalytic activity. Specifically, the catalyst exhibits ultra-low overpotentials of only 208 mV (for OER) and 185 mV (for HER) at a current density of 100 mA cm-2, along with long-term stability of 200 h for both half-reactions. For overall water splitting, a cell voltage of merely 1.42 V is required to achieve 10 mA cm-2. Furthermore, the in-situ formed SOx- and POx- protective layers, derived from the oxidation of surface S and P species, can effectively mitigate Cl- induced corrosion and oxidation. As a result, S,V-Ni2P/NF exhibits excellent OWS performance in saline electrolyte, requiring a cell potential of only 1.48 V to reach 10 mA cm-2. This work provides a facile and efficient approach to enhance the reaction kinetics of transition metal phosphide catalysts via an anion-cation co-doping strategy.
过渡金属磷化物（TMPs）是电解水中贵金属催化剂的理想替代品。然而，它们缓慢的反应动力学阻碍了实际的广泛应用。本文通过简单的元素共掺杂策略，成功构建了一种具有微花状球形结构的S， v共掺杂Ni2P电催化剂，用于整体水分解。结合实验表征、原位电化学测量和密度泛函理论（DFT）计算表明，S和V共掺杂可以有效调节Ni活性位点的局部微环境，调节反应中间体的吸附能，降低速率决定步骤（RDS）的能势，从而使催化剂具有出色的电催化活性。具体来说，该催化剂在电流密度为100 mA cm-2时，表现出仅为208 mV （OER）和185 mV （HER）的超低过电位，并且两种半反应的长期稳定性均为200 h。对于整体水分裂，仅1.42 V的电池电压需要达到10 mA cm-2。此外，原位形成的SOx-和POx-保护层是由表面S和P物质氧化形成的，可以有效地减轻Cl-引起的腐蚀和氧化。因此，S，V- ni2p /NF在盐水电解质中表现出优异的OWS性能，仅需1.48 V的电池电位即可达到10 mA cm-2。本研究为通过阴离子-正离子共掺杂策略提高过渡金属磷化物催化剂的反应动力学提供了一种简便有效的方法。
{"title":"S/V Co-Doped Ni 2 P Microflowers Enable Efficient and Stable Saline Water Electrolysis through Local Microenvironment Engineering","authors":"Jiahui Jiang, Yixuan Li, Guancheng Xu, Bingbing Gong, Weiwei Wang, Hao Jiang, Li Zhang","doi":"10.1039/d5qi01984b","DOIUrl":"https://doi.org/10.1039/d5qi01984b","url":null,"abstract":"Transition metal phosphides (TMPs) are ideal catalyst alternatives to precious metals for water electrolysis. However, their sluggish reaction kinetics hamper practical widespread application. Herein, a S, V-co-doped Ni2P electrocatalyst with a microflower-like spherical structure was successfully constructed via a facile elemental co-doping strategy for overall water splitting. Combined experimental characterizations, in-situ electrochemical measurements, and density functional theory (DFT) calculations demonstrate that S and V co-doping can effectively modulate the local microenvironment of Ni active sites, tune the adsorption energy of reaction intermediates, and reduce the energy barrier of the rate-determining step (RDS), thereby endowing the catalyst with outstanding electrocatalytic activity. Specifically, the catalyst exhibits ultra-low overpotentials of only 208 mV (for OER) and 185 mV (for HER) at a current density of 100 mA cm-2, along with long-term stability of 200 h for both half-reactions. For overall water splitting, a cell voltage of merely 1.42 V is required to achieve 10 mA cm-2. Furthermore, the in-situ formed SOx- and POx- protective layers, derived from the oxidation of surface S and P species, can effectively mitigate Cl- induced corrosion and oxidation. As a result, S,V-Ni2P/NF exhibits excellent OWS performance in saline electrolyte, requiring a cell potential of only 1.48 V to reach 10 mA cm-2. This work provides a facile and efficient approach to enhance the reaction kinetics of transition metal phosphide catalysts via an anion-cation co-doping strategy.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"18 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145907977","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}
Piotr Pander, Dawid Nastula, Paulina H. Marek-Urban, Valery N. Kozhevnikov, J. A. Gareth Williams
In this work we report the second ever example of a fully experimentally confirmed thermally activated delayed fluorescence (TADF) in a dinuclear Ir(III) complex. The said complex displays a singlet–triplet gap ΔEST = 28 ± 5 meV, in agreement with the computational prediction of 31.1 meV – a value smaller than the previous TADF Ir(III) complex. We also demonstrate a proof-of-concept, solution-processed OLED featuring this complex as the luminescent dopant in the emissive layer, achieving external quantum efficiency of up to ∼10% and maximum luminance of 18 000 cd m−2 – values significantly exceeding those reported earlier for Ir(III) TADF. These findings are preceded by a detailed consideration of spectral signs of TADF in the already known Ir(III) complexes. The spectral overlap of photoluminescence (PL) with strong (i.e., spin-allowed) absorption bands is unusual for phosphorescent metal complexes, because the PL originates from the triplet state, which is normally significantly lower in energy than the lowest-lying singlet. In this study, we have scrutinized literature data on iridium(III) complexes that likewise show significant overlap between absorption and PL, and we conclude that a small singlet–triplet energy gap ΔEST in these complexes results in a TADF contribution to their emission. Such a mechanism has hitherto been overlooked in the large body of iridium(III) chemistry. We use computations to clarify the nature of the excited states in these complexes, demonstrating that the distinctive S1 and T1 character of states can be identified as well as confirming that ΔEST is small enough for TADF to occur at room temperature.
在这项工作中，我们报告了在双核Ir（III）配合物中完全实验证实的热激活延迟荧光（TADF）的第二个例子。所述配合物显示出单重态-三重态间隙ΔEST = 28±5 meV，与31.1 meV的计算预测一致，该值小于先前的TADF Ir（III）配合物。我们还展示了一种概念验证、溶液处理的OLED，其特征是该复合物作为发射层中的发光掺杂剂，实现了高达10%的外部量子效率和18000 cd m−2的最大亮度，大大超过了之前报道的Ir(III) TADF。在这些发现之前，详细考虑了已知Ir（III）配合物中TADF的光谱标志。光致发光（PL）与强（即自旋允许的）吸收带的光谱重叠对于磷光金属配合物来说是不寻常的，因为PL起源于三重态，其能量通常明显低于最低的单线态。在这项研究中，我们仔细研究了铱（III）配合物的文献数据，这些配合物在吸收和PL之间同样显示出显著的重叠，我们得出结论，这些配合物中一个小的单重态-三重态能隙ΔEST导致TADF对其发射的贡献。迄今为止，在铱（III）化学的大量研究中，这种机制一直被忽视。我们使用计算来澄清这些复合物中激发态的性质，证明可以识别状态的独特S1和T1特征，并确认ΔEST足够小，可以在室温下发生TADF。
{"title":"Evidence for thermally activated delayed fluorescence in iridium(III) complexes","authors":"Piotr Pander, Dawid Nastula, Paulina H. Marek-Urban, Valery N. Kozhevnikov, J. A. Gareth Williams","doi":"10.1039/d5qi01968k","DOIUrl":"https://doi.org/10.1039/d5qi01968k","url":null,"abstract":"In this work we report the second ever example of a fully experimentally confirmed thermally activated delayed fluorescence (TADF) in a dinuclear Ir(<small>III</small>) complex. The said complex displays a singlet–triplet gap Δ<em>E</em><small><sub>ST</sub></small> = 28 ± 5 meV, in agreement with the computational prediction of 31.1 meV – a value smaller than the previous TADF Ir(<small>III</small>) complex. We also demonstrate a proof-of-concept, solution-processed OLED featuring this complex as the luminescent dopant in the emissive layer, achieving external quantum efficiency of up to ∼10% and maximum luminance of 18 000 cd m<small><sup>−2</sup></small> – values significantly exceeding those reported earlier for Ir(<small>III</small>) TADF. These findings are preceded by a detailed consideration of spectral signs of TADF in the already known Ir(<small>III</small>) complexes. The spectral overlap of photoluminescence (PL) with strong (<em>i.e.</em>, spin-allowed) absorption bands is unusual for phosphorescent metal complexes, because the PL originates from the triplet state, which is normally significantly lower in energy than the lowest-lying singlet. In this study, we have scrutinized literature data on iridium(<small>III</small>) complexes that likewise show significant overlap between absorption and PL, and we conclude that a small singlet–triplet energy gap Δ<em>E</em><small><sub>ST</sub></small> in these complexes results in a TADF contribution to their emission. Such a mechanism has hitherto been overlooked in the large body of iridium(<small>III</small>) chemistry. We use computations to clarify the nature of the excited states in these complexes, demonstrating that the distinctive S<small><sub>1</sub></small> and T<small><sub>1</sub></small> character of states can be identified as well as confirming that Δ<em>E</em><small><sub>ST</sub></small> is small enough for TADF to occur at room temperature.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"23 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145895137","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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