Traditional recycling methods for retired lithium-ion battery cathode materials typically involve destructive metallurgical processes to extract transition metals, overlooking their intrinsic structural value. This review focuses on LiCoO2 (LCO) and emphasizes an emerging “waste-to-value” strategy: directly modifying and restructuring spent LCO into high-performance oxygen evolution reaction (OER) electrocatalysts. The formation of lithium vacancies, lattice distortions, phase transitions, and surface residues generated in spent LCO during battery long-term cycling affects the electronic structure and coordination environment of the cobalt atoms, leading to enhanced OER performance. Various modification techniques such as heteroatom doping, interface engineering, and phase reconstruction are systematically discussed. Additionally, the mechanisms of the OER process are elucidated, highlighting how different defects modulate the d-band centers, optimize the adsorption energy of oxygen intermediates, and trigger distinct reaction mechanisms. Finally, we discuss the current challenges in using spent LCO as an electrocatalyst and proposes future perspectives on its advantages, which span from half-cells to the overall water splitting process. This comprehensive review summarizes the valuable applications of converting spent LCO into electrocatalysts and provides novel insights for maximizing its residual worth.
{"title":"Structural Reconstruction of Spent LiCoO2 and Regulation Mechanism of Electrocatalytic Oxygen Evolution","authors":"Keyi Zhong,Shize Zhang,Yinghao Wang,Qingcui Liu,Wenhua Cheng","doi":"10.1039/d6qi01957a","DOIUrl":"https://doi.org/10.1039/d6qi01957a","url":null,"abstract":"Traditional recycling methods for retired lithium-ion battery cathode materials typically involve destructive metallurgical processes to extract transition metals, overlooking their intrinsic structural value. This review focuses on LiCoO2 (LCO) and emphasizes an emerging “waste-to-value” strategy: directly modifying and restructuring spent LCO into high-performance oxygen evolution reaction (OER) electrocatalysts. The formation of lithium vacancies, lattice distortions, phase transitions, and surface residues generated in spent LCO during battery long-term cycling affects the electronic structure and coordination environment of the cobalt atoms, leading to enhanced OER performance. Various modification techniques such as heteroatom doping, interface engineering, and phase reconstruction are systematically discussed. Additionally, the mechanisms of the OER process are elucidated, highlighting how different defects modulate the d-band centers, optimize the adsorption energy of oxygen intermediates, and trigger distinct reaction mechanisms. Finally, we discuss the current challenges in using spent LCO as an electrocatalyst and proposes future perspectives on its advantages, which span from half-cells to the overall water splitting process. This comprehensive review summarizes the valuable applications of converting spent LCO into electrocatalysts and provides novel insights for maximizing its residual worth.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"30 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173170","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}
Catalysts with stable structures and exposed active sites are highly desirable for optimizing catalytic performance, yet their rational design remains a critical challenge in the field. Herein, we demonstrate that the diphosphine ligand 1,4bis(diphenylphosphino)butane (Dppb) can effectively trigger the exposure of active sites on the reported Pt/PdAg14(PR3)8(SR)6 nanoclusters, thereby inducing their structural transformation into Pt/PdAg14(Dppb)3(SR)6 nanoclusters.Benefiting from their unsaturated coordination environment and favorable electronic properties, the non-phosphinecoordinated Ag(SR)3 metal motifs serve as the dominant active centers for the electrocatalytic nitrate reduction reaction (NO3RR), which significantly facilitates the adsorption and activation of NO3 -. Notably, the core Pd and Pt atoms regulate the electronic configuration of the nanoclusters to promote the adsorption and activation of reaction intermediates, among which Pd doping exhibits superior modulation performance compared to Pt doping. This work not only clarifies the structureactivity relationship of ligand-engineered nanocatalysts but also highlights the synergistic strategy of ligand-regulated active site exposure and heteroatom doping as an effective approach for developing high-performance nanocatalysts toward sustainable environmental applications.2
{"title":"Multidentate-Phosphine Unlocks Active Ag Sites in Pt/PdAg14 Nanoclusters for Efficient Electrocatalytic Nitrate Reduction","authors":"Manman Zhou,Xuhui Ding,Qian Cheng,Yuanxin Du,Shan Jin,lin xiong,Yahui Li,Xu-Cheng Fu,Manzhou Zhu","doi":"10.1039/d6qi02081j","DOIUrl":"https://doi.org/10.1039/d6qi02081j","url":null,"abstract":"Catalysts with stable structures and exposed active sites are highly desirable for optimizing catalytic performance, yet their rational design remains a critical challenge in the field. Herein, we demonstrate that the diphosphine ligand 1,4bis(diphenylphosphino)butane (Dppb) can effectively trigger the exposure of active sites on the reported Pt/PdAg14(PR3)8(SR)6 nanoclusters, thereby inducing their structural transformation into Pt/PdAg14(Dppb)3(SR)6 nanoclusters.Benefiting from their unsaturated coordination environment and favorable electronic properties, the non-phosphinecoordinated Ag(SR)3 metal motifs serve as the dominant active centers for the electrocatalytic nitrate reduction reaction (NO3RR), which significantly facilitates the adsorption and activation of NO3 -. Notably, the core Pd and Pt atoms regulate the electronic configuration of the nanoclusters to promote the adsorption and activation of reaction intermediates, among which Pd doping exhibits superior modulation performance compared to Pt doping. This work not only clarifies the structureactivity relationship of ligand-engineered nanocatalysts but also highlights the synergistic strategy of ligand-regulated active site exposure and heteroatom doping as an effective approach for developing high-performance nanocatalysts toward sustainable environmental applications.2","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"19 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173172","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}
Uranium is a strategic resource for the nuclear industry, but its mining and utilization can cause environmental contamination. In aquatic environments, the highly stable and soluble uranyl ion (UO22+) exhibits both chemical toxicity and radioactivity, posing serious threats to ecosystems and human health. Accordingly, rapid, highly sensitive, and anti-interference detection of UO22+ has become a major focus in nano-biochemical sensing. This review systematically summarizes recent advances in specific recognition strategies and signal transduction mechanisms for UO22+. From the perspective of molecular recognition, we outline the design of diverse recognition elements, including traditional coordination-based small-molecule ligands (N-donor, O-donor, S/O-mixed, and multidentate amidoxime ligands), lanthanide metal nodes, and synergistic coordination-hydrogen-bonding motifs, together with biomacromolecular and biomimetic strategies such as aptamers and molecular/ion imprinting. We further discuss how chemical recognition events are converted into readable optical or electrical outputs in UO22+ sensing systems. Representative mechanisms include nanozyme activity modulation, target-induced complex formation, and fluorescence, photoelectrochemical, or electrochemical signaling based on fluorescence resonance energy transfer, aggregation-induced emission, inner filter effect, charge transfer, and ion exchange. Finally, we highlight key challenges in applying current UO22+ biochemical sensors to complex water matrices and discuss future directions, including highly selective anti-interference materials, multimodal sensing platforms, and portable intelligent devices. This review aims to provide a theoretical basis and design guidance for next-generation high-performance platforms for trace uranium pollution monitoring.
{"title":"Nano-biochemical sensors for trace uranyl detection: Advances in Recognition elements and signal output strategies","authors":"Zhen Zhen,Jiaqi Cui,Xiao Tan,Lima Ge,Yunlong Bai,Ruibing Feng,Weiqiang Tan,Jie Niu,Guo-Dong Li,Huining Chai,Guangyao Zhang","doi":"10.1039/d6qi02017h","DOIUrl":"https://doi.org/10.1039/d6qi02017h","url":null,"abstract":"Uranium is a strategic resource for the nuclear industry, but its mining and utilization can cause environmental contamination. In aquatic environments, the highly stable and soluble uranyl ion (UO22+) exhibits both chemical toxicity and radioactivity, posing serious threats to ecosystems and human health. Accordingly, rapid, highly sensitive, and anti-interference detection of UO22+ has become a major focus in nano-biochemical sensing. This review systematically summarizes recent advances in specific recognition strategies and signal transduction mechanisms for UO22+. From the perspective of molecular recognition, we outline the design of diverse recognition elements, including traditional coordination-based small-molecule ligands (N-donor, O-donor, S/O-mixed, and multidentate amidoxime ligands), lanthanide metal nodes, and synergistic coordination-hydrogen-bonding motifs, together with biomacromolecular and biomimetic strategies such as aptamers and molecular/ion imprinting. We further discuss how chemical recognition events are converted into readable optical or electrical outputs in UO22+ sensing systems. Representative mechanisms include nanozyme activity modulation, target-induced complex formation, and fluorescence, photoelectrochemical, or electrochemical signaling based on fluorescence resonance energy transfer, aggregation-induced emission, inner filter effect, charge transfer, and ion exchange. Finally, we highlight key challenges in applying current UO22+ biochemical sensors to complex water matrices and discuss future directions, including highly selective anti-interference materials, multimodal sensing platforms, and portable intelligent devices. This review aims to provide a theoretical basis and design guidance for next-generation high-performance platforms for trace uranium pollution monitoring.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"31 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173169","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}
Marie Poisson,Michail Papadakis,Foteini Chatzipetri,Anna Katsari,Emmanouil Nikoloudakis,Athanassios G. Coutsolelos,Maylis Orio,Renaud Hardré
We report the synthesis and characterization of a series of mononuclear nickel thiosemicarbazone complexes bearing phosphorus-functionalized phenyl groups designed to improve their solubility and tune their catalytic properties for hydrogen evolution. NiTSC-PO(OEt)₂ and NiTSC-PO(OH)₂, which carry diethyl phosphonate and phosphonic acid groups, respectively, at the para position of the ligand phenyl rings, were investigated in dimethylformamide using trifluoroacetic acid as the proton source. NiTSC-PO(OH)₂ exhibited notable catalytic activity in aqueous acetate buffer and its photocatalytic performance was further evaluated in combination with nitrogen-doped carbon dots as photosensitizers and a mixture of tris(2-carboxyethyl)phosphine/ascorbic acid as sacrificial electron donor. The two complexes display complementary performances: NiTSC-PO(OEt)2 is the more active electrocatalyst in organic medium, whereas NiTSC-PO(OH)2 operates in water and under photocatalytic conditions. Ligand functionalization thus influences catalytic activity through both solubility and electronic effects, showing that a single substitution strategy can provide, within the same catalyst family, members suited to different reaction media.
{"title":"An \"All-Terrain\" Ligand Design Strategy: Phosphorus-Functionalized Nickel Thiosemicarbazones for Hydrogen Evolution in Organic and Aqueous Media","authors":"Marie Poisson,Michail Papadakis,Foteini Chatzipetri,Anna Katsari,Emmanouil Nikoloudakis,Athanassios G. Coutsolelos,Maylis Orio,Renaud Hardré","doi":"10.1039/d6qi01982j","DOIUrl":"https://doi.org/10.1039/d6qi01982j","url":null,"abstract":"We report the synthesis and characterization of a series of mononuclear nickel thiosemicarbazone complexes bearing phosphorus-functionalized phenyl groups designed to improve their solubility and tune their catalytic properties for hydrogen evolution. NiTSC-PO(OEt)₂ and NiTSC-PO(OH)₂, which carry diethyl phosphonate and phosphonic acid groups, respectively, at the para position of the ligand phenyl rings, were investigated in dimethylformamide using trifluoroacetic acid as the proton source. NiTSC-PO(OH)₂ exhibited notable catalytic activity in aqueous acetate buffer and its photocatalytic performance was further evaluated in combination with nitrogen-doped carbon dots as photosensitizers and a mixture of tris(2-carboxyethyl)phosphine/ascorbic acid as sacrificial electron donor. The two complexes display complementary performances: NiTSC-PO(OEt)2 is the more active electrocatalyst in organic medium, whereas NiTSC-PO(OH)2 operates in water and under photocatalytic conditions. Ligand functionalization thus influences catalytic activity through both solubility and electronic effects, showing that a single substitution strategy can provide, within the same catalyst family, members suited to different reaction media.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"12 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173171","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}
Dithiolene ligands have long fascinated chemists for their non-innocent redox properties. The transition metal complexes with delocalized unpaired electrons on the ligand find applications in catalysis, magnetism, and molecular electronics. Despite extensive studies on Fe, Co, Ni, Pd, Pt, Mo, and W congeners featuring monoanionic dithiolene radicals, first-row analogues, particularly manganese with its versatile Mnᴵᴵ redox chemistry, remain elusive due to synthetic challenges in accessing the radical centre in the dithiolene ligand, which favours over-reduction to dianions during metallation. Here, we present two elusive manganese(II)-bis(dithiolene) diradical complexes, synthesised via a protocol that selectively generates and stabilises the monoanionic radical state, five-coordinate [Mn(II)(LS•)2(THF)] (1), alongside a four-coordinate tetrahedral [Mn(II)(LSe•)2] (2). They are unprecedented to date. Single-crystal X-ray diffraction reveals that the coordination geometries of Mn(II) ions are distorted square-pyramidal and tetrahedral in 1 and 2, respectively. These complexes were characterized by UV-VIS, IR, Raman, XPS, and EPR spectroscopy. The local spin state of Mn(II) ions, the spin ground states of the complexes and the nature of Mn(II)-radical interactions were studied by temperature-dependent magnetic susceptibility measurements. Combined magnetic and EPR measurements suggest that the central Mn(II) ion of this series of Mn(II)-bis(dithiolene)diradical complexes (1-2) most likely possesses SMn2+ = 5/2 (high spin). The central Mn(II) ions of 1-2 are antiferromagnetically coupled with two unpaired electrons on the dithiolene ligands, leading to spin ground states ST = 3/2. Broken-symmetry DFT and ab initio CASSCF calculations reproduce this spin ground state and quantify the three exchange interactions within the Radical–Mn(II)–Radical core. For 2, the CASSCF Mn–radical coupling (−44.8 cm−1) agrees with the value fitted to the magnetic data (−44.01 cm−1), and the direct radical–radical interaction is found to be negligible in tetrahedral 2 but substantial in square-pyramidal 1.
{"title":"Isolation of Four-/Five-Coordinate Manganese(II)-Bis(dithiolene-radical): Exchange Coupling","authors":"Sujit Das,Christel L Mascarenhas,Saurav Ghosh,Sonam Suthar,Arpan Mondal,Harichandhana Elamplakkattu,Björn Schwarz,Liviu Ungur,Kartik Chandra Mondal","doi":"10.1039/d6qi01048b","DOIUrl":"https://doi.org/10.1039/d6qi01048b","url":null,"abstract":"Dithiolene ligands have long fascinated chemists for their non-innocent redox properties. The transition metal complexes with delocalized unpaired electrons on the ligand find applications in catalysis, magnetism, and molecular electronics. Despite extensive studies on Fe, Co, Ni, Pd, Pt, Mo, and W congeners featuring monoanionic dithiolene radicals, first-row analogues, particularly manganese with its versatile Mnᴵᴵ redox chemistry, remain elusive due to synthetic challenges in accessing the radical centre in the dithiolene ligand, which favours over-reduction to dianions during metallation. Here, we present two elusive manganese(II)-bis(dithiolene) diradical complexes, synthesised via a protocol that selectively generates and stabilises the monoanionic radical state, five-coordinate [Mn(II)(LS•)2(THF)] (1), alongside a four-coordinate tetrahedral [Mn(II)(LSe•)2] (2). They are unprecedented to date. Single-crystal X-ray diffraction reveals that the coordination geometries of Mn(II) ions are distorted square-pyramidal and tetrahedral in 1 and 2, respectively. These complexes were characterized by UV-VIS, IR, Raman, XPS, and EPR spectroscopy. The local spin state of Mn(II) ions, the spin ground states of the complexes and the nature of Mn(II)-radical interactions were studied by temperature-dependent magnetic susceptibility measurements. Combined magnetic and EPR measurements suggest that the central Mn(II) ion of this series of Mn(II)-bis(dithiolene)diradical complexes (1-2) most likely possesses SMn2+ = 5/2 (high spin). The central Mn(II) ions of 1-2 are antiferromagnetically coupled with two unpaired electrons on the dithiolene ligands, leading to spin ground states ST = 3/2. Broken-symmetry DFT and ab initio CASSCF calculations reproduce this spin ground state and quantify the three exchange interactions within the Radical–Mn(II)–Radical core. For 2, the CASSCF Mn–radical coupling (−44.8 cm−1) agrees with the value fitted to the magnetic data (−44.01 cm−1), and the direct radical–radical interaction is found to be negligible in tetrahedral 2 but substantial in square-pyramidal 1.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"18 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152776","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}
Anode-free aqueous zinc-ion batteries (AF-AZIBs) eliminate excess metallic Zn but impose stringent requirements on Zn plating/stripping reversibility. Herein, inspired by traditional gilding, we develop an ultrathin metal-foil lamination strategy to construct Ag@Cu and Au@Cu current collectors. Comparative experiments, finite-element simulations, and density functional theory calculations show that Ag@Cu provides a more homogeneous surface and interfacial electric field, while its moderate Zn–Ag interaction and favorable interfacial kinetics promote uniform nucleation, compact growth, and reversible stripping. Consequently, Zn//Ag@Cu cells sustain 3000 cycles at 5 mA cm−2 and 1 mAh cm−2 with an average coulombic efficiency of 99.96%. The anode-free full cell pairing Ag@Cu with an electrochemically pre-zincified NH4V4O10 cathode (ZnNV) retains 96.4% of its capacity after 200 cycles at 1 A g−1, and a pouch-type cell further demonstrates larger-format feasibility. This work establishes ultrathin metal-foil lamination as an effective interface-engineering route toward highly reversible AF-AZIBs.
无阳极水锌离子电池（af - azib）消除了过量的金属锌，但对锌的电镀/剥离可逆性有严格的要求。在此，受传统镀金的启发，我们开发了一种超薄金属箔层压策略来构建Ag@Cu和Au@Cu集热器。对比实验、有限元模拟和密度泛函理论计算表明，Ag@Cu提供了更均匀的表面和界面电场，而适度的Zn-Ag相互作用和良好的界面动力学促进了均匀的成核、致密生长和可逆剥离。因此，Zn//Ag@Cu电池在5 mA cm - 2和1 mAh cm - 2下可维持3000次循环，平均库仑效率为99.96%。无阳极的全电池配对Ag@Cu与电化学预镀锌的nh4v4010阴极（ZnNV）在1 Ag−1下循环200次后仍保持96.4%的容量，并且袋型电池进一步证明了更大尺寸的可行性。这项工作建立了超薄金属箔层压作为一个有效的界面工程路线，以获得高度可逆的af - azib。
{"title":"Gilding-inspired ultrathin metal-foil lamination for reversible zinc deposition in anode-free aqueous zinc-ion batteries","authors":"Qi-qun Lei,Zhuo Li,Wei-jia Song,Li-li Du,Peng-fei Wang,Zhe Gong,Fa-nian Shi,Kai Zhu","doi":"10.1039/d6qi02026g","DOIUrl":"https://doi.org/10.1039/d6qi02026g","url":null,"abstract":"Anode-free aqueous zinc-ion batteries (AF-AZIBs) eliminate excess metallic Zn but impose stringent requirements on Zn plating/stripping reversibility. Herein, inspired by traditional gilding, we develop an ultrathin metal-foil lamination strategy to construct Ag@Cu and Au@Cu current collectors. Comparative experiments, finite-element simulations, and density functional theory calculations show that Ag@Cu provides a more homogeneous surface and interfacial electric field, while its moderate Zn–Ag interaction and favorable interfacial kinetics promote uniform nucleation, compact growth, and reversible stripping. Consequently, Zn//Ag@Cu cells sustain 3000 cycles at 5 mA cm−2 and 1 mAh cm−2 with an average coulombic efficiency of 99.96%. The anode-free full cell pairing Ag@Cu with an electrochemically pre-zincified NH4V4O10 cathode (ZnNV) retains 96.4% of its capacity after 200 cycles at 1 A g−1, and a pouch-type cell further demonstrates larger-format feasibility. This work establishes ultrathin metal-foil lamination as an effective interface-engineering route toward highly reversible AF-AZIBs.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"1 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152777","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}
A series of first-row transition-metal complexes bearing pyridinophane macrocycles, (RN4)MIICl2(1-6; M = Mn, Fe, Co; R = tBu, Me), were synthesized to enable a systematic comparison of metal-dependent structural, redox, and catalytic properties within a unified N4 coordination environment. Single-crystal X-ray structures showed consistent octahedral geometries of the series, with axial M-N elongation modulated by ligand sterics and metal identity. Cyclic voltammetry and DFT calculations revealed metal-centered oxidations and ligand-centered reductions, the latter exhibiting pronounced dependence on both the ligand and the metal, with increasingly accessible reduction potentials from Mn to Co. One-electron oxidation yielded MIII derivatives 1+-3+, whose structural and magnetic parameters confirmed high-spin MnIII and FeIII, but a low-spin CoIII state for 3⁺. The catalytic reactivity of 1-6 and 1⁺-3⁺ was evaluated in C(sp2)-C(sp2) Kumada cross-coupling of aryl bromides with PhMgCl. Co complexes displayed the highest activity, whereas Mn and Fe complexes were inactive or poorly selective. Cross-coupling yields correlated strongly with E1/2,red, indicating that access to low-valent MI intermediates is essential for productive catalysis. These results establish pyridinophane ligands as a powerful framework for isolating metal-dependent reactivity trends and provide insight into the distinct catalytic behavior of Mn, Fe, and Co complexes under identical ligand environments.
为了在统一的N4配位环境下系统地比较金属依赖的结构、氧化还原和催化性能，合成了一系列含有吡啶烷大环的第一行过渡金属配合物（RN4）MIICl2（1-6; M = Mn, Fe, Co; R = tBu, Me）。单晶x射线结构显示该系列的八面体几何形状一致，轴向M-N延伸率受配体位和金属同一性调节。循环伏安法和DFT计算揭示了以金属为中心的氧化和以配体为中心的还原，后者对配体和金属都表现出明显的依赖性，从Mn到Co的还原电位越来越高。单电子氧化产生了MIII衍生物1+-3+，其结构和磁性参数证实了高自旋的MnIII和FeIII，但3+的自旋状态为低自旋的CoIII。在芳基溴与PhMgCl的C(sp2)-C(sp2) Kumada交叉偶联中，对1-6和1 + 3 +的催化活性进行了评价。Co配合物的活性最高，而Mn和Fe配合物则无活性或选择性差。交叉偶联产率与E1/2（红色）密切相关，表明获得低价MI中间体对于生产催化至关重要。这些结果建立了吡啶配体作为分离金属依赖反应性趋势的强大框架，并提供了在相同配体环境下Mn， Fe和Co配合物的独特催化行为的见解。
{"title":"Exploring C(sp)-C(sp) Kumada Cross-Coupling with Pyridinophane-supported Mn, Fe, and Co Complexes","authors":"Donghyun Jeong,Liviu M. Mirica","doi":"10.1039/d6qi01865c","DOIUrl":"https://doi.org/10.1039/d6qi01865c","url":null,"abstract":"A series of first-row transition-metal complexes bearing pyridinophane macrocycles, (RN4)MIICl2(1-6; M = Mn, Fe, Co; R = tBu, Me), were synthesized to enable a systematic comparison of metal-dependent structural, redox, and catalytic properties within a unified N4 coordination environment. Single-crystal X-ray structures showed consistent octahedral geometries of the series, with axial M-N elongation modulated by ligand sterics and metal identity. Cyclic voltammetry and DFT calculations revealed metal-centered oxidations and ligand-centered reductions, the latter exhibiting pronounced dependence on both the ligand and the metal, with increasingly accessible reduction potentials from Mn to Co. One-electron oxidation yielded MIII derivatives 1+-3+, whose structural and magnetic parameters confirmed high-spin MnIII and FeIII, but a low-spin CoIII state for 3⁺. The catalytic reactivity of 1-6 and 1⁺-3⁺ was evaluated in C(sp2)-C(sp2) Kumada cross-coupling of aryl bromides with PhMgCl. Co complexes displayed the highest activity, whereas Mn and Fe complexes were inactive or poorly selective. Cross-coupling yields correlated strongly with E1/2,red, indicating that access to low-valent MI intermediates is essential for productive catalysis. These results establish pyridinophane ligands as a powerful framework for isolating metal-dependent reactivity trends and provide insight into the distinct catalytic behavior of Mn, Fe, and Co complexes under identical ligand environments.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"13 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152775","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
This review addresses these limitations and proposes forward-looking strategies based on rational material design, interpretable machine learning frameworks, comprehensive regulatory guidelines, and circular manufacturing practices to chart a path toward sustainable, intelligent, and multifunctional supercapacitors that can smoothly integrate into future technologies while supporting an environmentally responsible energy landscape.The rapid evolution in energy storage technologies has placed supercapacitors (SCs) at the heart of next-generation applications. SCs bridge the gap between traditional capacitors and batteries due to their fast-charging capability, high power output, and long cycle life. New developments have inspired novel directions in material design, electrode architecture, and hybrid configurations. These involve new trends such as flexible, stretchable, biodegradable, and edible supercapacitors, as well as electrochromic and even self-healing systems with previously unattainable energy and power densities. New materials, including conductive hydrogels, MXenes, biopolymers, and hybrid nanocomposites, drove the development of novel functionalities. These have resolved some of the existing challenges in wearable electronics, sustainable energy storage, and, especially, biomedical implants. These materials exhibit excellent electrochemical performance combined with high mechanical flexibility. Meanwhile, the integration of machine learning (ML) into supercapacitor-related research is revolutionizing materials science through rapid material discovery, optimized fabrication procedures, and the prediction of device performance with unprecedented accuracy. ML-based frameworks also enable real-time health monitoring, lifetime prediction, and automated device design, with significantly fewer experimental cycles. The convergence of these innovative material trends, together with multifunctional capabilities and ML-driven methodologies, propels next-generation supercapacitors toward intelligent, adaptive, and application-specific energy systems. Even so, several major challenges remain and need to be addressed, including achieving long-term stability, improving biocompatibility, developing enhanced characterization techniques, and implementing scalable manufacturing processes. This review addresses these limitations and proposes forward-looking strategies based on rational material design, interpretable machine learning frameworks, comprehensive regulatory guidelines, and circular manufacturing practices to chart a path toward sustainable, intelligent, and multifunctional supercapacitors that can smoothly integrate into future technologies while supporting an environmentally responsible energy landscape
{"title":"Next-Generation Supercapacitors: Integrating Advanced Materials, Emerging Functionalities, and Machine Learning","authors":"Kaustubh Kumbhar,Tajala Magray,Mahboobeh Shahbazi,Pradip Bhikaji Sarawade,Brahim Aissa,Dattatray Sadashiv Dhawale","doi":"10.1039/d6qi01806h","DOIUrl":"https://doi.org/10.1039/d6qi01806h","url":null,"abstract":"This review addresses these limitations and proposes forward-looking strategies based on rational material design, interpretable machine learning frameworks, comprehensive regulatory guidelines, and circular manufacturing practices to chart a path toward sustainable, intelligent, and multifunctional supercapacitors that can smoothly integrate into future technologies while supporting an environmentally responsible energy landscape.The rapid evolution in energy storage technologies has placed supercapacitors (SCs) at the heart of next-generation applications. SCs bridge the gap between traditional capacitors and batteries due to their fast-charging capability, high power output, and long cycle life. New developments have inspired novel directions in material design, electrode architecture, and hybrid configurations. These involve new trends such as flexible, stretchable, biodegradable, and edible supercapacitors, as well as electrochromic and even self-healing systems with previously unattainable energy and power densities. New materials, including conductive hydrogels, MXenes, biopolymers, and hybrid nanocomposites, drove the development of novel functionalities. These have resolved some of the existing challenges in wearable electronics, sustainable energy storage, and, especially, biomedical implants. These materials exhibit excellent electrochemical performance combined with high mechanical flexibility. Meanwhile, the integration of machine learning (ML) into supercapacitor-related research is revolutionizing materials science through rapid material discovery, optimized fabrication procedures, and the prediction of device performance with unprecedented accuracy. ML-based frameworks also enable real-time health monitoring, lifetime prediction, and automated device design, with significantly fewer experimental cycles. The convergence of these innovative material trends, together with multifunctional capabilities and ML-driven methodologies, propels next-generation supercapacitors toward intelligent, adaptive, and application-specific energy systems. Even so, several major challenges remain and need to be addressed, including achieving long-term stability, improving biocompatibility, developing enhanced characterization techniques, and implementing scalable manufacturing processes. This review addresses these limitations and proposes forward-looking strategies based on rational material design, interpretable machine learning frameworks, comprehensive regulatory guidelines, and circular manufacturing practices to chart a path toward sustainable, intelligent, and multifunctional supercapacitors that can smoothly integrate into future technologies while supporting an environmentally responsible energy landscape","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"238 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151991","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}
Manganese-based layered oxides are promising cathode materials for low-cost sodium-ion batteries, but their electrochemical performance is often limited by complex multiphase evolution, Mn3+-driven Jahn–Teller distortion, and sluggish Na+ transport. Herein, Na0.9MnO2 is selected as a model system to develop a Cu/Ti co-substitution strategy for phase-competition engineering. Cu preferentially promotes β-phase formation, whereas Cu/Ti suppresses Jahn–Teller distortion and stabilizes the local MnO6 coordination environment, cooperatively directing the phase assemblage toward a coherent β/P2 intergrowth structure. Structural and spectroscopic analyses reveal reduced lattice distortion, alleviated depth-dependent Mn valence heterogeneity, improved local coordination reversibility, and the formation of a compositionally graded cathode–electrolyte interphase, collectively mitigating bulk and interfacial degradation. Benefiting from this coupled bulk–interface regulation, Na0.9Mn0.90Cu0.05Ti0.05O2 delivers discharge capacities of 163.55 mAh g−1 at 0.1 C and 97.79 mAh g−1 at 2 C over 1.8–4.3 V, demonstrating enhanced Na+ storage kinetics. A non-presodiated full cell further achieves an initial discharge capacity of 96.47 mAh g−1 at 0.1 C over 1.5–4.2 V, providing preliminary validation of its practical feasibility. This work establishes hetero-cation-induced phase-competition engineering as an effective approach for simultaneously regulating phase evolution, lattice distortion, Na+ transport, and interfacial chemistry in low-cost manganese-based layered oxide cathodes.
锰基层状氧化物是一种很有前途的低成本钠离子电池正极材料，但其电化学性能往往受到复杂的多相演化、Mn3+驱动的Jahn-Teller畸变和Na+传输缓慢的限制。本文选择Na0.9MnO2作为模型体系，开发Cu/Ti共取代策略，用于阶段竞争工程。Cu优先促进β相的形成，而Cu/Ti抑制jhn - teller畸变并稳定局部MnO6配位环境，共同引导相组合向相干β/P2互生结构方向发展。结构和光谱分析表明，减少了晶格畸变，减轻了深度依赖的Mn价非均质性，改善了局部配位可逆性，并形成了成分梯度的阴极-电解质界面相，共同减轻了体积和界面降解。得益于这种耦合体界面调节，Na0.9Mn0.90Cu0.05Ti0.05O2在0.1 C和1.8-4.3 V下的放电容量分别为163.55 mAh g - 1和97.79 mAh g - 1，表现出增强的Na+存储动力学。在0.1 C、1.5-4.2 V条件下，无沉淀的全电池进一步实现了96.47 mAh g−1的初始放电容量，初步验证了其实际可行性。这项工作建立了异质阳离子诱导的相竞争工程作为同时调节低成本锰基层状氧化物阴极的相演化、晶格畸变、Na+输运和界面化学的有效方法。
{"title":"Formulating low-cost β-type intergrowth sodium manganese-based layered oxide cathodes: competitive phase regulation, stabilized bulk/interfacial chemistry, and suppressed Jahn–Teller distortion","authors":"Haiyan Li,Yifeng Liu,Yameng Fan,Haiyan Hu,Yaping Yan,Xinyu Liu,Hanshen Xin,Wentao Wu,Yanfang Zhu,Shun Wang,Yao Xiao","doi":"10.1039/d6qi01709f","DOIUrl":"https://doi.org/10.1039/d6qi01709f","url":null,"abstract":"Manganese-based layered oxides are promising cathode materials for low-cost sodium-ion batteries, but their electrochemical performance is often limited by complex multiphase evolution, Mn3+-driven Jahn–Teller distortion, and sluggish Na+ transport. Herein, Na0.9MnO2 is selected as a model system to develop a Cu/Ti co-substitution strategy for phase-competition engineering. Cu preferentially promotes β-phase formation, whereas Cu/Ti suppresses Jahn–Teller distortion and stabilizes the local MnO6 coordination environment, cooperatively directing the phase assemblage toward a coherent β/P2 intergrowth structure. Structural and spectroscopic analyses reveal reduced lattice distortion, alleviated depth-dependent Mn valence heterogeneity, improved local coordination reversibility, and the formation of a compositionally graded cathode–electrolyte interphase, collectively mitigating bulk and interfacial degradation. Benefiting from this coupled bulk–interface regulation, Na0.9Mn0.90Cu0.05Ti0.05O2 delivers discharge capacities of 163.55 mAh g−1 at 0.1 C and 97.79 mAh g−1 at 2 C over 1.8–4.3 V, demonstrating enhanced Na+ storage kinetics. A non-presodiated full cell further achieves an initial discharge capacity of 96.47 mAh g−1 at 0.1 C over 1.5–4.2 V, providing preliminary validation of its practical feasibility. This work establishes hetero-cation-induced phase-competition engineering as an effective approach for simultaneously regulating phase evolution, lattice distortion, Na+ transport, and interfacial chemistry in low-cost manganese-based layered oxide cathodes.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"29 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151992","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}
Polar metal halide perovskites that exhibit the bulk photovoltaic effect (BPVE) are promising candidates for self-powered X-ray detection because they can generate photoresponses at zero bias. However, typical interlayer noncovalent interactions often suffer from limited directionality and weak anchoring capability, which hinders the simultaneous construction of polar structures and enhancement of lattice stability. Herein, we develop a carboxyl-substitution strategy to construct a polar two-dimensional (8-AOC) 2 PbBr 4 (8-AOC = 8-aminocaprylic acid) perovskite, thereby achieving efficient and durable self-powered X-ray detection. Carboxyl substitution is accompanied by inorganic-framework distortion within the polar P2 1 space group and by a cross-linked interlayer hydrogen-bonding network that inhibits ion migration. Consequently, the detector achieves a high sensitivity of 128.08 μC Gy -1 cm -2 and a LoD of 98.8 nGy s -1 at zero bias, approximately 1/56 of the conventional medical diagnostic dose rate threshold (5.5 μGy s -1 ). Notably, the device retains 95.9% of its initial sensitivity after 30 days of ambient storage and delivers stable responses during repeated X-ray irradiation, demonstrating strong storage and irradiation-cycling stability. This work presents carboxyl-group functionalization as a strategy for combining polar-structure design with interlayer hydrogen-bond stabilization in self-powered X-ray detectors.
表现出体光伏效应（BPVE）的极性金属卤化物钙钛矿是自供电x射线探测的有希望的候选者，因为它们可以在零偏置下产生光响应。然而，典型的层间非共价相互作用往往具有有限的方向性和较弱的锚定能力，阻碍了极性结构的同时构建和晶格稳定性的增强。在此，我们开发了一种羧基取代策略来构建极性二维（8-AOC） 2 PbBr 4 （8-AOC = 8-氨基丙烯酸）钙钛矿，从而实现了高效耐用的自供电x射线检测。羧基取代伴随着极性P2 1空间基内的无机骨架扭曲和抑制离子迁移的交联层间氢键网络。因此，该检测器在零偏置下的灵敏度为128.08 μC Gy -1 cm -2， LoD为98.8 nGy s -1，约为传统医学诊断剂量率阈值（5.5 μGy s -1）的1/56。值得注意的是，该装置在环境储存30天后仍保持其初始灵敏度的95.9%，并在重复x射线照射时提供稳定的响应，显示出强大的储存和照射循环稳定性。这项工作提出了羧基功能化作为结合极性结构设计和层间氢键稳定的自供电x射线探测器的策略。
{"title":"Carboxyl-Group-Anchored Structural Polarity in a Layered Metal Halide for High-Performance Self-Powered X-ray Detection","authors":"Chengke Fu,Huang Ye,Junhua Luo,Hang Li,Lijun Xu,Chengshu Zhang,Yao Li,Mutong Geng,Qianwen Guan,Ji Qi","doi":"10.1039/d6qi02100j","DOIUrl":"https://doi.org/10.1039/d6qi02100j","url":null,"abstract":"Polar metal halide perovskites that exhibit the bulk photovoltaic effect (BPVE) are promising candidates for self-powered X-ray detection because they can generate photoresponses at zero bias. However, typical interlayer noncovalent interactions often suffer from limited directionality and weak anchoring capability, which hinders the simultaneous construction of polar structures and enhancement of lattice stability. Herein, we develop a carboxyl-substitution strategy to construct a polar two-dimensional (8-AOC) 2 PbBr 4 (8-AOC = 8-aminocaprylic acid) perovskite, thereby achieving efficient and durable self-powered X-ray detection. Carboxyl substitution is accompanied by inorganic-framework distortion within the polar P2 1 space group and by a cross-linked interlayer hydrogen-bonding network that inhibits ion migration. Consequently, the detector achieves a high sensitivity of 128.08 μC Gy -1 cm -2 and a LoD of 98.8 nGy s -1 at zero bias, approximately 1/56 of the conventional medical diagnostic dose rate threshold (5.5 μGy s -1 ). Notably, the device retains 95.9% of its initial sensitivity after 30 days of ambient storage and delivers stable responses during repeated X-ray irradiation, demonstrating strong storage and irradiation-cycling stability. This work presents carboxyl-group functionalization as a strategy for combining polar-structure design with interlayer hydrogen-bond stabilization in self-powered X-ray detectors.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"12 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151990","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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