Fa Wang,Qianqian Gu,Yawei Xiao,Hongru Jiang,Xiufen Ma,Jihui Li
Aqueous zinc-ion batteries are considered ideal candidates for large-scale energy storage, yet the sluggish kinetics of vanadium-based cathodes severely limit their electrochemical performance. Here, we propose a room-temperature spontaneous chemical reconstruction strategy grounded in the hard–soft acid–base theory, achieving a phase transition from V2O5 to oxygen-deficient KV3O8via a facile coprecipitation method. We reveal that the strong interaction between K+, acting as a mild Lewis acid, and lattice oxygen not only enables K+ intercalation to construct structural pillars but also thermodynamically induces spontaneous lattice oxygen loss, thereby introducing oxygen vacancies and establishing a V4+/V5+ mixed-valence system. This dual effect simultaneously enhances intrinsic electronic conductivity, widens interlayer ion-transport channels, and lowers diffusion barriers, yielding ultrafast Zn2+ diffusion kinetics with a diffusion coefficient of 1.3 × 10−10 cm2 s−1. Consequently, the KV3O8 cathode delivers a high specific capacity of 342.4 mAh g−1 at 0.3 A g−1 and retains 81.1% capacity after 5830 cycles at 5 A g−1. Moreover, a flexible pouch cell assembled with this cathode exhibits exceptional voltage stability and capacity retention under severe mechanical bending. This work reinterprets ion pre-intercalation from the perspective of lattice oxygen chemistry, offering new design principles for next-generation layered electrode materials in aqueous batteries.
水溶液锌离子电池被认为是大规模储能的理想选择，但钒基阴极的缓慢动力学严重限制了其电化学性能。在此，我们提出了一种基于硬-软酸碱理论的室温自发化学重构策略，通过易共沉淀法实现了从V2O5到缺氧kv3o8的相变。研究发现，K+作为温和的Lewis酸与晶格氧之间的强相互作用，不仅使K+插入形成结构柱，而且在热力学上引起自发的晶格氧损失，从而引入氧空位，建立V4+/V5+混合价体系。这种双重效应同时提高了本征电子电导率，拓宽了层间离子传输通道，降低了扩散势垒，产生了超快的Zn2+扩散动力学，扩散系数为1.3 × 10−10 cm2 s−1。因此，KV3O8阴极在0.3 a g−1下提供了342.4 mAh g−1的高比容量，在5a g−1下循环5830次后保持81.1%的容量。此外，用这种阴极组装的柔性袋状电池在严重的机械弯曲下表现出优异的电压稳定性和容量保持。本研究从晶格氧化学的角度重新解释了离子预插层，为下一代水电池层状电极材料的设计提供了新的原理。
{"title":"Room-temperature chemical reconfiguration enables oxygen-deficient KVO for ultrafast and durable zinc-ion storage","authors":"Fa Wang,Qianqian Gu,Yawei Xiao,Hongru Jiang,Xiufen Ma,Jihui Li","doi":"10.1039/d6qi01926a","DOIUrl":"https://doi.org/10.1039/d6qi01926a","url":null,"abstract":"Aqueous zinc-ion batteries are considered ideal candidates for large-scale energy storage, yet the sluggish kinetics of vanadium-based cathodes severely limit their electrochemical performance. Here, we propose a room-temperature spontaneous chemical reconstruction strategy grounded in the hard–soft acid–base theory, achieving a phase transition from V2O5 to oxygen-deficient KV3O8via a facile coprecipitation method. We reveal that the strong interaction between K+, acting as a mild Lewis acid, and lattice oxygen not only enables K+ intercalation to construct structural pillars but also thermodynamically induces spontaneous lattice oxygen loss, thereby introducing oxygen vacancies and establishing a V4+/V5+ mixed-valence system. This dual effect simultaneously enhances intrinsic electronic conductivity, widens interlayer ion-transport channels, and lowers diffusion barriers, yielding ultrafast Zn2+ diffusion kinetics with a diffusion coefficient of 1.3 × 10−10 cm2 s−1. Consequently, the KV3O8 cathode delivers a high specific capacity of 342.4 mAh g−1 at 0.3 A g−1 and retains 81.1% capacity after 5830 cycles at 5 A g−1. Moreover, a flexible pouch cell assembled with this cathode exhibits exceptional voltage stability and capacity retention under severe mechanical bending. This work reinterprets ion pre-intercalation from the perspective of lattice oxygen chemistry, offering new design principles for next-generation layered electrode materials in aqueous batteries.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"42 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218203","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}
Stanislav Petrovskii,Marco Moors,Jonas Lorenz,Andrea Prager,Jan Griebel,Alina Petrovskaia,Kirill Monakhov
To establish a systematic strategy for the controlled immobilization of functional organic-inorganic hybrids involving a hexavanadate core, a series of thiophene-functionalized V6 conjugates (V6-SX) are synthesized and fully characterized. Their adsorption behavior on Au(111) is investigated by combining scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). All compounds exhibit a general tendency to adsorb on Au(111). However, the resulting surface organization is found to depend strongly on the molecular structure of the organic-inorganic hybrids, adsorption conditions, and solvent. As a consequence, a wide range of nanoscale architectures is obtained, including single molecules, sparse aggregates, compact monolayers, multilayers, and larger molecular agglomerates. Scanning tunneling spectroscopy (STS) measurements reveals the characteristic four-step resistive switching behavior of V6-based molecules immobilized on the surface. Notably, the optimized V6/Au(111) interface exhibits exceptional stability of the immobilized molecules, enabling both forward and backward potential sweeps to be recorded within a single roomtemperature STS experiment. These measurements provide the first direct experimental evidence of fully reversible, four-step switching of a V6-oxo core strongly coupled to a conductive metal surface.
{"title":"Hexavanadate-Thiophene Hybrids on Au(111): Adsorption and Reversible Single-Molecule Switching","authors":"Stanislav Petrovskii,Marco Moors,Jonas Lorenz,Andrea Prager,Jan Griebel,Alina Petrovskaia,Kirill Monakhov","doi":"10.1039/d6qi01859a","DOIUrl":"https://doi.org/10.1039/d6qi01859a","url":null,"abstract":"To establish a systematic strategy for the controlled immobilization of functional organic-inorganic hybrids involving a hexavanadate core, a series of thiophene-functionalized V6 conjugates (V6-SX) are synthesized and fully characterized. Their adsorption behavior on Au(111) is investigated by combining scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). All compounds exhibit a general tendency to adsorb on Au(111). However, the resulting surface organization is found to depend strongly on the molecular structure of the organic-inorganic hybrids, adsorption conditions, and solvent. As a consequence, a wide range of nanoscale architectures is obtained, including single molecules, sparse aggregates, compact monolayers, multilayers, and larger molecular agglomerates. Scanning tunneling spectroscopy (STS) measurements reveals the characteristic four-step resistive switching behavior of V6-based molecules immobilized on the surface. Notably, the optimized V6/Au(111) interface exhibits exceptional stability of the immobilized molecules, enabling both forward and backward potential sweeps to be recorded within a single roomtemperature STS experiment. These measurements provide the first direct experimental evidence of fully reversible, four-step switching of a V6-oxo core strongly coupled to a conductive metal surface.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"12 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218197","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, defect-rich porous ZnS-Vs samples were prepared using ZIF-8 as a precursor. Through electrostatic self-assembly with CuCo-PBA, a novel S-scheme het-erojunction photocatalyst (ZnS-Vs/CuCo-PBA) was constructed for photocatalytic hy-drogen production and peroxymonosulfate (PMS) activation to degrade polystyrene (PS) microplastics. Morphological and structural characterization indicates that ZnS inherits the regular morphology of ZIF-8, exhibits tight interfacial bonding with CuCo-PBA, and uniform elemental distribution. Band structure and photoelectrochemical measurements confirm that the S-scheme built-in electric field synergizes with ZnS vacancies to signif-icantly enhance photo-generated carrier separation and broaden the visible light response. Performance tests showed a hydrogen evolution rate of 1.75ZnS 3/CuCo PBA reaching 15.62 mmol·g-1·h-1; under 5 mM PMS, PS microplastics degradation reached 76% after 8 h with 54.8% TOC mineralization. Degradation pathway and toxicity analyses indicate SO₄·⁻ and ·OH as primary active species, facilitating ring-opening, chain scission, and deep mineralization, with significantly reduced intermediate toxicity. Theoretical analysis shows the hydrogen adsorption energy barrier approaches zero (ΔGH* = -0.13 eV), en-hancing hydrogen evolution kinetics. Mechanistic analysis reveals the ternary synergistic effects among S-vacancy, S-type heterojunction, and PMS, enabling the efficient utiliza-tion of photogenerated charges, generating a wealth of active species, thereby facilitating high-efficiency photocatalytic hydrogen production and accelerating the degradation of microplastics. This work provides new insights for designing MOF-derived defective S-scheme heterojunction photocatalysts.
{"title":"S-scheme heterojunction based on ZnS-Vs and CuCo-PBA inte-grate peroxymonosulfate synergistic effect for photocatalytic hy-drogen production and microplastic degradation","authors":"Rongfeng Guan,Chengkai Li,Kaiwen Sun,Changlei Huang,Liushuai Zhou,Changjian Zhou","doi":"10.1039/d6qi01820c","DOIUrl":"https://doi.org/10.1039/d6qi01820c","url":null,"abstract":"In this study, defect-rich porous ZnS-Vs samples were prepared using ZIF-8 as a precursor. Through electrostatic self-assembly with CuCo-PBA, a novel S-scheme het-erojunction photocatalyst (ZnS-Vs/CuCo-PBA) was constructed for photocatalytic hy-drogen production and peroxymonosulfate (PMS) activation to degrade polystyrene (PS) microplastics. Morphological and structural characterization indicates that ZnS inherits the regular morphology of ZIF-8, exhibits tight interfacial bonding with CuCo-PBA, and uniform elemental distribution. Band structure and photoelectrochemical measurements confirm that the S-scheme built-in electric field synergizes with ZnS vacancies to signif-icantly enhance photo-generated carrier separation and broaden the visible light response. Performance tests showed a hydrogen evolution rate of 1.75ZnS 3/CuCo PBA reaching 15.62 mmol·g-1·h-1; under 5 mM PMS, PS microplastics degradation reached 76% after 8 h with 54.8% TOC mineralization. Degradation pathway and toxicity analyses indicate SO₄·⁻ and ·OH as primary active species, facilitating ring-opening, chain scission, and deep mineralization, with significantly reduced intermediate toxicity. Theoretical analysis shows the hydrogen adsorption energy barrier approaches zero (ΔGH* = -0.13 eV), en-hancing hydrogen evolution kinetics. Mechanistic analysis reveals the ternary synergistic effects among S-vacancy, S-type heterojunction, and PMS, enabling the efficient utiliza-tion of photogenerated charges, generating a wealth of active species, thereby facilitating high-efficiency photocatalytic hydrogen production and accelerating the degradation of microplastics. This work provides new insights for designing MOF-derived defective S-scheme heterojunction photocatalysts.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"163 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218200","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}
Song Pan,Lufei Xiang,Xiaonan Xu,Jiaming Li,Lina Zhou,Yisi Liu,Dongbin Xiong,Yuehua Kong,Yue Du
The development of efficient and durable non-precious-metal bifunctional oxygen electrocatalysts remains a central challenge for advancing metal–air battery technology, largely due to the intrinsic activity–stability trade-off originating from the unfavorable adsorption energetics of oxygen intermediates. Herein, we report a targeted electronic structure reconfiguration strategy for Fe2P via precise Mo doping, producing a high-performance catalyst for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). The incorporated Mo atoms act as atomic-scale electron donors that transfer electron density into the Fe–P framework, forming Fe–P–Mo bonding networks that induce charge redistribution and an upshift of the Fe d-band center toward the Fermi level, thereby rebalancing the adsorption energetics of the oxygen intermediates (*O, *OH, and *OOH) toward the Sabatier optimum and lowering the energy barriers of the rate-determining steps of both the ORR and the OER. The optimized catalyst exhibits remarkable bifunctional performance, delivering a half-wave potential of 0.87 V for the ORR and an OER potential (Ej=10) of 1.56 V versus RHE at 10 mA cm−2. This yields a small potential gap (ΔE) of 0.69 V, comparable to that of the noble-metal benchmark (Pt/C + RuO2, 0.68 V). In a zinc–air battery, the catalyst achieves a peak power density of 170.2 mW cm−2 and stable cycling for more than 700 h, outperforming its Pt/C + RuO2-based counterpart (142.9 mW cm−2 and ∼140 h). This work clarifies the mechanistic link between doping-induced electronic modulation and electrocatalytic performance, offering design principles for next-generation energy conversion materials.
开发高效、耐用的非贵金属双功能氧电催化剂仍然是推进金属-空气电池技术的核心挑战，这主要是由于氧中间体的不利吸附能量所导致的内在活性与稳定性之间的权衡。在此，我们报告了一种通过精确Mo掺杂对Fe2P进行定向电子结构重构的策略，为氧还原反应（ORR）和氧析反应（OER）制备了高性能催化剂。结合的Mo原子充当原子尺度的电子供体，将电子密度转移到Fe - p框架中，形成Fe - p - Mo键网络，诱导电荷重新分配和Fe -d带中心向费米能级上移，从而重新平衡氧中间体（*O， *OH和*OOH）的吸附能量，使其向萨巴蒂尔最优方向移动，并降低ORR和OER的速率决定步骤的能量垒。优化后的催化剂表现出显著的双功能性能，在10 mA cm−2时，ORR的半波电位为0.87 V， OER电位（Ej=10）为1.56 V。这产生了0.69 V的小电势间隙（ΔE），与贵金属基准（Pt/C + RuO2, 0.68 V）相当。在锌空气电池中，催化剂的峰值功率密度为170.2 mW cm - 2，稳定循环时间超过700小时，优于Pt/C + ruo2基催化剂（142.9 mW cm - 2和~ 140小时）。这项工作阐明了掺杂诱导的电子调制和电催化性能之间的机制联系，为下一代能量转换材料的设计提供了原则。
{"title":"Tailoring the electronic architecture of FeP by Mo doping for advanced bifunctional oxygen electrocatalysis in Zn–air batteries","authors":"Song Pan,Lufei Xiang,Xiaonan Xu,Jiaming Li,Lina Zhou,Yisi Liu,Dongbin Xiong,Yuehua Kong,Yue Du","doi":"10.1039/d6qi01880g","DOIUrl":"https://doi.org/10.1039/d6qi01880g","url":null,"abstract":"The development of efficient and durable non-precious-metal bifunctional oxygen electrocatalysts remains a central challenge for advancing metal–air battery technology, largely due to the intrinsic activity–stability trade-off originating from the unfavorable adsorption energetics of oxygen intermediates. Herein, we report a targeted electronic structure reconfiguration strategy for Fe2P via precise Mo doping, producing a high-performance catalyst for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). The incorporated Mo atoms act as atomic-scale electron donors that transfer electron density into the Fe–P framework, forming Fe–P–Mo bonding networks that induce charge redistribution and an upshift of the Fe d-band center toward the Fermi level, thereby rebalancing the adsorption energetics of the oxygen intermediates (*O, *OH, and *OOH) toward the Sabatier optimum and lowering the energy barriers of the rate-determining steps of both the ORR and the OER. The optimized catalyst exhibits remarkable bifunctional performance, delivering a half-wave potential of 0.87 V for the ORR and an OER potential (Ej=10) of 1.56 V versus RHE at 10 mA cm−2. This yields a small potential gap (ΔE) of 0.69 V, comparable to that of the noble-metal benchmark (Pt/C + RuO2, 0.68 V). In a zinc–air battery, the catalyst achieves a peak power density of 170.2 mW cm−2 and stable cycling for more than 700 h, outperforming its Pt/C + RuO2-based counterpart (142.9 mW cm−2 and ∼140 h). This work clarifies the mechanistic link between doping-induced electronic modulation and electrocatalytic performance, offering design principles for next-generation energy conversion materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"53 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173173","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}
Di- and poly-metalation of organic molecules provides a powerful platform for constructing structurally diverse organometallic compounds and enabling multi-site functionalization. However, the mechanistic details of sequential metalation, especially the interplay between consecutive metalation steps, remain poorly understood. Here, we report a synergistic dimetalation strategy for the efficient synthesis of 1,2-digold(I) alkenes from alkenyl 1,2-bis(boronate) esters. In this process, the alkenyl monogold(I) intermediate readily captures a coordinatively unsaturated gold(I) species by aurophilic interactions to form a gem-digold(I) structure, which then undergoes a base-promoted 1,2-gold migration with elimination of the boronate group to afford the 1,2-digold(I) alkene in nearly quantitative yield. We proved the general applicability of this synergistic dimetalation approach by synthesizing a diverse set of 1,2-digold(I) alkenes. Upon photoexcitation, it efficiently activates the C–Cl bond of dichloromethane, generating chloromethyl radicals and causing the catalytically inactive mixed-valence gold(I)/gold(0) nanoclusters. By elucidating the aurophilic interaction-based synergistic dimetalation mechanism, this work not only provides a rational route to polymetalated organic molecules but also unveils a photoinduced pathway for C–Cl bond activation of solvent molecules, offering a new insight into the deactivation of gold(I) catalysts.
{"title":"1,2-Digold(I) alkenes: synergistic dimetalation synthesis and photoinduced C–Cl activation","authors":"Mingzhe Qin,Xiao-Yi Zhai,Wei Wan,Mengyu Yang,Yu Xia,Liang Zhao","doi":"10.1039/d6qi02123a","DOIUrl":"https://doi.org/10.1039/d6qi02123a","url":null,"abstract":"Di- and poly-metalation of organic molecules provides a powerful platform for constructing structurally diverse organometallic compounds and enabling multi-site functionalization. However, the mechanistic details of sequential metalation, especially the interplay between consecutive metalation steps, remain poorly understood. Here, we report a synergistic dimetalation strategy for the efficient synthesis of 1,2-digold(I) alkenes from alkenyl 1,2-bis(boronate) esters. In this process, the alkenyl monogold(I) intermediate readily captures a coordinatively unsaturated gold(I) species by aurophilic interactions to form a gem-digold(I) structure, which then undergoes a base-promoted 1,2-gold migration with elimination of the boronate group to afford the 1,2-digold(I) alkene in nearly quantitative yield. We proved the general applicability of this synergistic dimetalation approach by synthesizing a diverse set of 1,2-digold(I) alkenes. Upon photoexcitation, it efficiently activates the C–Cl bond of dichloromethane, generating chloromethyl radicals and causing the catalytically inactive mixed-valence gold(I)/gold(0) nanoclusters. By elucidating the aurophilic interaction-based synergistic dimetalation mechanism, this work not only provides a rational route to polymetalated organic molecules but also unveils a photoinduced pathway for C–Cl bond activation of solvent molecules, offering a new insight into the deactivation of gold(I) catalysts.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"11 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173168","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}
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}
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