Xikun Zhang, Weibin Yan, Jing Li, Yuchi Zhang, Hongtao Qu, Yuanguo Wu, Liuxi Yang, Amanda Kale, Nikolay Tumanov, Alexandru Vlad, Yu Li, Bao-Lian Su
Sodium dual-ion batteries (SDIBs) are emerging as promising energy storage systems due to their low cost, environmental friendliness, and high operating voltage. However, the structural instability of the commonly used graphite cathode limits its long-term performance, posing a significant obstacle to large-scale applications. Here, for the first time, we report the use of the anion pillar strategy in the interlayer of the graphite cathode to expand and maintain permanently the layer spacing, preventing structural collapse and facilitating (de)intercalation, leading to an exceptional electrochemical performance of SDIBs. A high specific capacity of 162 mAh g−1 at a current density of 200 mA g−1, corresponding to a high energy density of 560 Wh kg−1 is achieved. More impressively, the specific capacity can be maintained at 101 mAh g−1 at a high current density of 2000 mA g−1, with a high capacity retention of 74.0% after 15 500 cycles is obtained, corresponding to a capacity decay rate as low as 0.0017% per cycle and anion pillars remain stable in the interlayer of graphite. This study presents a novel and effective strategy for improving the performance and stability of graphite cathodes in SDIBs, offering valuable insights for the development of next-generation energy storage systems.
钠双离子电池（sdib）具有成本低、环境友好、工作电压高等优点，正在成为一种有前景的储能系统。然而，常用的石墨阴极结构的不稳定性限制了其长期性能，对大规模应用构成了重大障碍。在这里，我们首次报道了在石墨阴极的中间层中使用阴离子柱策略来扩大和永久保持层间距，防止结构崩溃并促进（去）插层，从而导致sdib具有优异的电化学性能。在200 mA g−1的电流密度下，实现了162 mAh g−1的高比容量，相当于560 Wh kg−1的高能量密度。更令人印象深刻的是，在2000 mA g−1的高电流密度下，比容量可以保持在101 mAh g−1，在15 500次循环后，容量保持率高达74.0%，相当于每个循环的容量衰减率低至0.0017%，并且阴离子柱在石墨层间保持稳定。该研究为提高sdib中石墨阴极的性能和稳定性提供了一种新颖有效的策略，为下一代储能系统的开发提供了有价值的见解。
{"title":"Anion Pillars Enable High Energy Density Sodium Dual-Ion Battery With Ultra-Long Cycle Life","authors":"Xikun Zhang, Weibin Yan, Jing Li, Yuchi Zhang, Hongtao Qu, Yuanguo Wu, Liuxi Yang, Amanda Kale, Nikolay Tumanov, Alexandru Vlad, Yu Li, Bao-Lian Su","doi":"10.1002/anie.202521536","DOIUrl":"https://doi.org/10.1002/anie.202521536","url":null,"abstract":"Sodium dual-ion batteries (SDIBs) are emerging as promising energy storage systems due to their low cost, environmental friendliness, and high operating voltage. However, the structural instability of the commonly used graphite cathode limits its long-term performance, posing a significant obstacle to large-scale applications. Here, for the first time, we report the use of the anion pillar strategy in the interlayer of the graphite cathode to expand and maintain permanently the layer spacing, preventing structural collapse and facilitating (de)intercalation, leading to an exceptional electrochemical performance of SDIBs. A high specific capacity of 162 mAh g<sup>−1</sup> at a current density of 200 mA g<sup>−1</sup>, corresponding to a high energy density of 560 Wh kg<sup>−1</sup> is achieved. More impressively, the specific capacity can be maintained at 101 mAh g<sup>−1</sup> at a high current density of 2000 mA g<sup>−1</sup>, with a high capacity retention of 74.0% after 15 500 cycles is obtained, corresponding to a capacity decay rate as low as 0.0017% per cycle and anion pillars remain stable in the interlayer of graphite. This study presents a novel and effective strategy for improving the performance and stability of graphite cathodes in SDIBs, offering valuable insights for the development of next-generation energy storage systems.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"7 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101922","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 rational modulation of band structures in organic semiconductors is central to advancing photocatalytic performance but remains challenging for hydrogen-bonded organic frameworks (HOFs) due to their structural sensitivity to the modification of organic building units (OBUs). Here, based on the stable mesoporous framework HOF-102, π-conjugation-extended and donor-acceptor-tuned OBUs were predesigned by substituting the steric naphthalene units with benzene-vinyl derivatives bearing ─H, ─CH3, or ─CN groups. Through a shape-fitted π─π stacking strategy, three mesoporous HOFs isoreticular with HOF-102 were synthesized from the tailored OBUs, namely HOF-1022, HOF-1022(CH3), and HOF-1022(CN). These as-synthesized HOFs exhibit pronounced variations in visible-light absorption, with band gaps adjustable from 2.46 to 1.86 eV. Among these HOFs, the D-A-optimized HOF-1022(CN) possesses the narrowest band gap and exhibits significantly enhanced intraframework electron transfer and suppressed charge recombination, yielding an impressive hydrogen evolution activity of 168.2 mmol g−1 h−1, which is 8.5 times higher than that of HOF-1022(CH3), and an apparent quantum yield (AQY) of 7.3% at 420 nm. This study represents the first demonstration of band-gap engineering in HOFs materials and establishes a generalizable molecular-design principle for developing high-performance HOFs-based photocatalysts.
{"title":"Band-Gap Engineering of Isoreticular Hydrogen-Bonded Organic Frameworks for Boosting Photocatalytic Hydrogen Evolution","authors":"Guanglai Mo, Yunke Jin, Yingjia Deng, Chenghao Zhang, Jiabao Liu, Qingyu Niu, Xiangyu Gao, Yunbo Bi, Hongyu Chen, Peng Li","doi":"10.1002/anie.202525987","DOIUrl":"https://doi.org/10.1002/anie.202525987","url":null,"abstract":"The rational modulation of band structures in organic semiconductors is central to advancing photocatalytic performance but remains challenging for hydrogen-bonded organic frameworks (HOFs) due to their structural sensitivity to the modification of organic building units (OBUs). Here, based on the stable mesoporous framework HOF-102, π-conjugation-extended and donor-acceptor-tuned OBUs were predesigned by substituting the steric naphthalene units with benzene-vinyl derivatives bearing ─H, ─CH<sub>3</sub>, or ─CN groups. Through a shape-fitted π─π stacking strategy, three mesoporous HOFs isoreticular with HOF-102 were synthesized from the tailored OBUs, namely HOF-1022, HOF-1022(CH<sub>3</sub>), and HOF-1022(CN). These as-synthesized HOFs exhibit pronounced variations in visible-light absorption, with band gaps adjustable from 2.46 to 1.86 eV. Among these HOFs, the D-A-optimized HOF-1022(CN) possesses the narrowest band gap and exhibits significantly enhanced intraframework electron transfer and suppressed charge recombination, yielding an impressive hydrogen evolution activity of 168.2 mmol g<sup>−1</sup> h<sup>−1</sup>, which is 8.5 times higher than that of HOF-1022(CH<sub>3</sub>), and an apparent quantum yield (AQY) of 7.3% at 420 nm. This study represents the first demonstration of band-gap engineering in HOFs materials and establishes a generalizable molecular-design principle for developing high-performance HOFs-based photocatalysts.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"29 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146102056","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}
Ziheng Zhang, Machuan Hou, Jiangtao Yu, Peixin Jiao, Jing Liu, Yanxia Deng, Meihong Che, Jiahua Zhao, Zixin Liang, Lunhua He, Limin Zhou, Zhenhua Yan, Jun Chen, Kai Zhang
Layered oxide cathodes are primary candidates for high-performance sodium-ion batteries, which often suffer from structural degradation during deep Na+ (de)intercalation processes. Incorporating electrochemically inactive cations into the transition metal (TM) layers has emerged as a mainstream strategy to enhance structural stability through the so-called pinning effect. However, the microstructural heterogeneity of inactive cations within the TM layers and the spatial extent of their influence remain poorly understood. In this work, we regulate the pinning domain by modulating configurational entropy of inactive ions (Sconfig-I), thereby promoting their dispersion and maximizing the spatial extent of the pinning effect. Additionally, we establish a correlation between Sconfig-I and local structural fluctuations using quantitative experimental analyses. Compared with samples lacking sufficient pinning domains, the sample with 21% Sconfig-I (denoted as S-I-21%) exhibits markedly improved structural homogeneity and optimally dispersed pinning dopants. Accordingly, S-I-21% delivers a high reversible capacity of 145 mAh g−1 and maintains ∼80% capacity retention after 500 cycles within a wide voltage window (2.0−4.3 V). These findings highlight the effect domain of dopants and their role in regulating structural chemistry, providing design principles for robust layered cathodes.
层状氧化物阴极是高性能钠离子电池的主要候选材料，但在深度Na+ (de)插入过程中往往会出现结构退化。在过渡金属（TM）层中加入电化学非活性阳离子已经成为通过所谓的钉住效应来增强结构稳定性的主流策略。然而，TM层内非活性阳离子的微观结构异质性及其影响的空间范围仍然知之甚少。在这项工作中，我们通过调制非活性离子（Sconfig-I）的构型熵来调节钉住域，从而促进它们的色散并最大化钉住效应的空间范围。此外，我们通过定量实验分析建立了sconfig - 1与局部结构波动之间的相关性。与缺乏足够钉钉域的样品相比，含有21% Sconfig-I（记为S-I-21%）的样品具有明显改善的结构均匀性和最佳分散的钉钉掺杂剂。因此，S-I-21%提供145 mAh g - 1的高可逆容量，并在宽电压窗（2.0 - 4.3 V）内500次循环后保持约80%的容量保留。这些发现突出了掺杂剂的影响域及其在调节结构化学中的作用，为坚固的层状阴极提供了设计原则。
{"title":"Manipulating the Dispersed Domain of Pinning Dopants in Layered Oxide Cathodes for Sodium-Ion Batteries","authors":"Ziheng Zhang, Machuan Hou, Jiangtao Yu, Peixin Jiao, Jing Liu, Yanxia Deng, Meihong Che, Jiahua Zhao, Zixin Liang, Lunhua He, Limin Zhou, Zhenhua Yan, Jun Chen, Kai Zhang","doi":"10.1002/anie.202520105","DOIUrl":"https://doi.org/10.1002/anie.202520105","url":null,"abstract":"Layered oxide cathodes are primary candidates for high-performance sodium-ion batteries, which often suffer from structural degradation during deep Na<sup>+</sup> (de)intercalation processes. Incorporating electrochemically inactive cations into the transition metal (TM) layers has emerged as a mainstream strategy to enhance structural stability through the so-called pinning effect. However, the microstructural heterogeneity of inactive cations within the TM layers and the spatial extent of their influence remain poorly understood. In this work, we regulate the pinning domain by modulating configurational entropy of inactive ions (S<sub>config</sub>-I), thereby promoting their dispersion and maximizing the spatial extent of the pinning effect. Additionally, we establish a correlation between S<sub>config</sub>-I and local structural fluctuations using quantitative experimental analyses. Compared with samples lacking sufficient pinning domains, the sample with 21% S<sub>config</sub>-I (denoted as S-I-21%) exhibits markedly improved structural homogeneity and optimally dispersed pinning dopants. Accordingly, S-I-21% delivers a high reversible capacity of 145 mAh g<sup>−1</sup> and maintains ∼80% capacity retention after 500 cycles within a wide voltage window (2.0−4.3 V). These findings highlight the effect domain of dopants and their role in regulating structural chemistry, providing design principles for robust layered cathodes.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"23 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146102059","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}
Jian Wei, Ni Zhen, Zuohu Zhou, Fengbo Yan, Yang Xu, Fangfang Liu, Aibing Yang, Siming Qi, Zeqi Yu, Jun Zhao, Lei Zhang
Tin oxo clusters (TOCs) have been recognized as the most promising photoresist candidates for high numerical aperture extreme ultraviolet (High-NA EUV) lithography. To enhance the adhesion between the exposed cluster species and the silicon dioxide substrate, herein, we incorporate silane moieties to functionalize the surface of TOCs for the first time. By synergistically integrating the high radiation sensitivity of Sn and substrate affinity of Si, ultrahigh resolution patterning at the sub-8 nm scale has been successfully achieved, which represents the best performance in TOC photoresists. Multiple spectroscopic analyses and theoretical calculations on reaction mechanisms indicate that the incorporated Si moieties function dually by capturing scattered secondary electrons (SEs) to produce silyl radicals that guide the formation of dense Si-O-Si structure, while simultaneously enhancing interfacial adhesion to the SiO2 substrate. Such a synergistic process yields diverse and abundant Sn-O-Sn/Sn-O-Si/Si-O-Si networks, collectively realizing higher resolution and lower line-edge roughness (LER). This work not only introduces a new family of Sn-Si oxo cluster resists but also demonstrates the potential of atomic-level interfacial engineering for next-generation ultrahigh-resolution semiconductor manufacturing technologies.
锡氧簇（TOCs）被认为是高数值孔径极紫外光刻（高na EUV）光刻中最有前途的光刻胶候选材料。为了增强暴露团簇与二氧化硅衬底之间的粘附性，本文首次在toc表面加入硅烷基团进行功能化。通过协同整合Sn的高辐射敏感性和Si的衬底亲和力，成功实现了亚8 nm尺度的超高分辨率图像化，这是TOC光阻剂的最佳性能。多种光谱分析和反应机理的理论计算表明，加入的Si基团通过捕获散射二次电子（SEs）产生硅基自由基来引导致密Si- o -Si结构的形成，同时增强与SiO2衬底的界面附着力。这种协同过程产生多样化和丰富的Sn-O-Sn/Sn-O-Si/Si-O-Si网络，共同实现更高的分辨率和更低的线边缘粗糙度（LER）。这项工作不仅介绍了一个新的Sn-Si氧化氧簇抗蚀剂家族，而且还展示了下一代超高分辨率半导体制造技术的原子级界面工程潜力。
{"title":"Atomically Precise Interfacial Engineering on Tin-Silicon Oxo Clusters for Sub-8 nm Lithography","authors":"Jian Wei, Ni Zhen, Zuohu Zhou, Fengbo Yan, Yang Xu, Fangfang Liu, Aibing Yang, Siming Qi, Zeqi Yu, Jun Zhao, Lei Zhang","doi":"10.1002/anie.202524320","DOIUrl":"https://doi.org/10.1002/anie.202524320","url":null,"abstract":"Tin oxo clusters (TOCs) have been recognized as the most promising photoresist candidates for high numerical aperture extreme ultraviolet (High-NA EUV) lithography. To enhance the adhesion between the exposed cluster species and the silicon dioxide substrate, herein, we incorporate silane moieties to functionalize the surface of TOCs for the first time. By synergistically integrating the high radiation sensitivity of Sn and substrate affinity of Si, ultrahigh resolution patterning at the sub-8 nm scale has been successfully achieved, which represents the best performance in TOC photoresists. Multiple spectroscopic analyses and theoretical calculations on reaction mechanisms indicate that the incorporated Si moieties function dually by capturing scattered secondary electrons (SEs) to produce silyl radicals that guide the formation of dense Si-O-Si structure, while simultaneously enhancing interfacial adhesion to the SiO<sub>2</sub> substrate. Such a synergistic process yields diverse and abundant Sn-O-Sn/Sn-O-Si/Si-O-Si networks, collectively realizing higher resolution and lower line-edge roughness (LER). This work not only introduces a new family of Sn-Si oxo cluster resists but also demonstrates the potential of atomic-level interfacial engineering for next-generation ultrahigh-resolution semiconductor manufacturing technologies.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"67 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146102053","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 [Bi2]m[Bi2Te3]n family features a natural heterostructure of metallic [Bi2] bilayers (BL) and topological insulator [Bi2Te3] quintuple layers (QL). We demonstrate that increasing the BL ratio ((m/(m + n))) enhances key thermoelectric properties. Bi4Te3 (m = 3; n = 3) exhibits a sharpened Dirac cone and a high carrier mobility (117 cm2 V−1 s−1) twice that of Bi1Te1 (m = 1; n = 2). This stems from strengthened σ-bonding interlayer coupling, which reduces the carrier effective mass. Concurrently, the abundant [Bi2]-BL lower Te vacancy formation energy, suppressing electron carrier concentration and synergistically boosting the Seebeck coefficient. This work provides the first direct experimental and theoretical evidence for the sharpening of the Dirac cone via a metallic [Bi2] bilayer engineering strategy. It addresses the key limitations of Bi1Te1, and the established structure-property relationship, together with the metallic [Bi2]-BL engineering strategy for sharpening the Dirac cone, further offers valuable insights for the rational design of thermoelectric materials and performance optimization across the entire Bi/Te material family.
[Bi2]m[Bi2Te3]n家族具有金属[Bi2]双层（BL）和拓扑绝缘体[Bi2Te3]五层（QL）的天然异质结构。我们证明了增加BL比（(m/(m + n))）可以提高关键的热电性能。Bi4Te3 （m = 3, n = 3）表现出锐化的狄拉克锥和高载流子迁移率（117 cm2 V−1 s−1），是Bi1Te1 （m = 1, n = 2）的两倍。这是由于层间σ键耦合增强导致载流子有效质量降低所致。同时，丰富的[Bi2]-BL降低了Te空位形成能，抑制了载流子浓度，协同提高了Seebeck系数。这项工作为通过金属[Bi2]双层工程策略锐化狄拉克锥提供了第一个直接的实验和理论证据。它解决了Bi1Te1的主要局限性，建立了结构-性能关系，以及金属[Bi2]-BL用于锐化狄拉克锥的工程策略，进一步为热电材料的合理设计和整个Bi/Te材料家族的性能优化提供了有价值的见解。
{"title":"Sharpened Dirac Cone and Elevated Carrier Mobility in Bi4Te3 Engineered by a High [Bi2] Bilayer Content for Thermoelectrics","authors":"Chao Guo, Fei Jia, Yu-Qian Wu, Xin-Yi Liu, Yi-Meng Liu, Ling Chen, Li-Ming Wu","doi":"10.1002/anie.202524705","DOIUrl":"https://doi.org/10.1002/anie.202524705","url":null,"abstract":"The [Bi<sub>2</sub>]<i><sub>m</sub></i>[Bi<sub>2</sub>Te<sub>3</sub>]<i><sub>n</sub></i> family features a natural heterostructure of metallic [Bi<sub>2</sub>] bilayers (BL) and topological insulator [Bi<sub>2</sub>Te<sub>3</sub>] quintuple layers (QL). We demonstrate that increasing the BL ratio ((<i>m</i>/(<i>m</i> + <i>n</i>))) enhances key thermoelectric properties. Bi<sub>4</sub>Te<sub>3</sub> (<i>m</i> = 3; <i>n</i> = 3) exhibits a sharpened Dirac cone and a high carrier mobility (117 cm<sup>2</sup> V<sup>−1</sup> s<sup>−1</sup>) twice that of Bi<sub>1</sub>Te<sub>1</sub> (<i>m</i> = 1; <i>n</i> = 2). This stems from strengthened <i>σ</i>-bonding interlayer coupling, which reduces the carrier effective mass. Concurrently, the abundant [Bi<sub>2</sub>]-BL lower Te vacancy formation energy, suppressing electron carrier concentration and synergistically boosting the Seebeck coefficient. This work provides the first direct experimental and theoretical evidence for the sharpening of the Dirac cone via a metallic [Bi<sub>2</sub>] bilayer engineering strategy. It addresses the key limitations of Bi<sub>1</sub>Te<sub>1</sub>, and the established structure-property relationship, together with the metallic [Bi<sub>2</sub>]-BL engineering strategy for sharpening the Dirac cone, further offers valuable insights for the rational design of thermoelectric materials and performance optimization across the entire Bi/Te material family.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"30 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146102054","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}
Conventional hard carbons offering high sodium-ion (Na+) storage capacity through closed pores formed by disordered short carbon sheets stacking, but suffer from tortuous diffusion paths that hinder rate capability in sodium-ion batteries (SIBs). Herein, an amorphous carbon (AC) anode capable of 10C fast-charging was successfully developed via constructing Na+ highways through embedding interconnected carbon sheets with large interlayer spacing into a disordered carbon matrix by a molecular cross-linking strategy. Na+ Highways provide direct routes that bypass the inherent tortuosity, mitigate diffusion resistance, and facilitate rapid Na+ access to closed pores that serve as efficient reservoirs, thereby fully unlocking the Na+ storage potential of AC. As evaluated in practical 1000 mAh pouch full cells, the optimized AC anode delivers a high specific capacity of 298 mAh g−1 at a 10C rate, which directly enables the pouch cells to achieve a 92% state of charge within 6 min. Furthermore, the full cells exhibit excellent cycling stability, retaining 94% of their initial capacity over 1000 cycles due to the structural robustness of the AC anode. This work provides a practical design strategy for high-performance AC anodes, paving the way for the use of ultra-fast-charging SIBs in frequency control within new type power systems.
{"title":"Highways Construction in Amorphous Carbon Anode Enables 10C Fast-Charging Sodium-Ion Batteries","authors":"Haizhou Liu, Ying Xu, Shuhao Xiao, Manyi Xie, Shufan Jia, Lin-Bo Huang, Yu-Jie Guo, Wen-Peng Wang, Yu-Guo Guo","doi":"10.1002/anie.202525941","DOIUrl":"https://doi.org/10.1002/anie.202525941","url":null,"abstract":"Conventional hard carbons offering high sodium-ion (Na<sup>+</sup>) storage capacity through closed pores formed by disordered short carbon sheets stacking, but suffer from tortuous diffusion paths that hinder rate capability in sodium-ion batteries (SIBs). Herein, an amorphous carbon (AC) anode capable of 10C fast-charging was successfully developed via constructing Na<sup>+</sup> highways through embedding interconnected carbon sheets with large interlayer spacing into a disordered carbon matrix by a molecular cross-linking strategy. Na<sup>+</sup> Highways provide direct routes that bypass the inherent tortuosity, mitigate diffusion resistance, and facilitate rapid Na<sup>+</sup> access to closed pores that serve as efficient reservoirs, thereby fully unlocking the Na<sup>+</sup> storage potential of AC. As evaluated in practical 1000 mAh pouch full cells, the optimized AC anode delivers a high specific capacity of 298 mAh g<sup>−</sup><sup>1</sup> at a 10C rate, which directly enables the pouch cells to achieve a 92% state of charge within 6 min. Furthermore, the full cells exhibit excellent cycling stability, retaining 94% of their initial capacity over 1000 cycles due to the structural robustness of the AC anode. This work provides a practical design strategy for high-performance AC anodes, paving the way for the use of ultra-fast-charging SIBs in frequency control within new type power systems.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"1 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146102055","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}
Wet-chemical processing of metals, for example, galvanic deposition, etching, and nanoparticle synthesis, usually requires complexing agents. In particular, for noble metal processing, anionic complexing species, such as halides or sulfide are indispensable. While it is known that these species strongly adsorb on metal surfaces and affect metal nucleation and growth, the detailed role of these anions in the underlying atomistic processes is less clear. Often, it is assumed that surface complexes are involved, but experimental evidence for the latter is still lacking. Here, we present direct in situ video-rate scanning tunneling microscopy observations of gold–bromide and gold–sulfur surface complexes on Au(100) electrodes. Based on the intramolecular resolution images obtained in these studies, these species can be assigned to a dimeric planar and a linear complex. Once formed, the surfaces complexes are stable even at rather negative potentials and diffuse as molecular species on the Au surface.
{"title":"Observations of Isolated Mobile Au–Br and Au–S Surface Complexes on Au(100) Electrodes","authors":"Chaolong Yang, Olaf M. Magnussen","doi":"10.1002/anie.202520653","DOIUrl":"https://doi.org/10.1002/anie.202520653","url":null,"abstract":"Wet-chemical processing of metals, for example, galvanic deposition, etching, and nanoparticle synthesis, usually requires complexing agents. In particular, for noble metal processing, anionic complexing species, such as halides or sulfide are indispensable. While it is known that these species strongly adsorb on metal surfaces and affect metal nucleation and growth, the detailed role of these anions in the underlying atomistic processes is less clear. Often, it is assumed that surface complexes are involved, but experimental evidence for the latter is still lacking. Here, we present direct in situ video-rate scanning tunneling microscopy observations of gold–bromide and gold–sulfur surface complexes on Au(100) electrodes. Based on the intramolecular resolution images obtained in these studies, these species can be assigned to a dimeric planar <span data-altimg=\"/cms/asset/19714429-f235-4ef6-aa6e-a17865a6a8a2/anie71281-math-0001.png\"></span><img alt=\"mathematical equation\" src=\"/cms/asset/19714429-f235-4ef6-aa6e-a17865a6a8a2/anie71281-math-0001.png\"/> and a linear <span data-altimg=\"/cms/asset/c0fcf4d7-9a87-483d-baf4-e5390ba0d026/anie71281-math-0002.png\"></span><img alt=\"mathematical equation\" src=\"/cms/asset/c0fcf4d7-9a87-483d-baf4-e5390ba0d026/anie71281-math-0002.png\"/> complex. Once formed, the surfaces complexes are stable even at rather negative potentials and diffuse as molecular species on the Au surface.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"87 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146102057","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}
Jiaming Yi, Zhiwei Xing, Zhuozhi Lai, Qing Guo, Huixia Lv, Sai Wang, Qi Sun
Precise modulation of ion permselectivity in synthetic membranes is crucial for advancing separation and energy conversion technologies. Here, we demonstrate that neutral substituents can reprogram the intrinsic ion selectivity of cationic covalent organic framework (COF) membranes by introducing secondary local interactions that compete with long‐range Coulombic forces. Using triaminoguanidinium‐based COFs as a model system, we systematically varied both the number and type of substituents on 1,3,5‐trialdehyde linkers. The introduced substituents generated secondary interactions that modulated the primary Coulombic interactions between guanidinium cations and Cl – counterions. When two or more hydroxyl groups were present on the aldehyde linkers, these interactions immobilized anions and inverted the effective surface potential from positive to negative, thereby switching the transport polarity from anion‐ to cation‐selective behavior. In contrast, methoxy substitution weakened Coulombic interactions, enhancing anion selectivity. This tunable control over the local chemical microenvironment enabled programmable and reversible ion permselectivity without altering the permanent framework charge. Leveraging this mechanism, we achieved record‐high ionic thermoelectric performance, 25.9 W m −2 for a single membrane and 39.1 W m −2 for a stacked configuration under a 50 K temperature gradient. This work establishes substituent‐mediated secondary interactions as a general and powerful strategy for programming ion transport, bridging biological selectivity principles with the design of adaptive COF‐based membranes for energy harvesting and separation.
合成膜中离子选择性的精确调节对于推进分离和能量转换技术至关重要。在这里，我们证明了中性取代基可以通过引入与远程库仑力竞争的二次局部相互作用，重新编程阳离子共价有机框架（COF）膜的固有离子选择性。使用基于三胺胍的COFs作为模型系统，我们系统地改变了1,3,5 -三醛连接体上取代基的数量和类型。引入的取代基产生了二级相互作用，调节了胍离子和Cl -反离子之间的初级库仑相互作用。当两个或两个以上的羟基存在于醛连接体上时，这些相互作用固定了阴离子，并将有效表面电位从正极反转为负极，从而将传输极性从阴离子选择行为转变为阳离子选择行为。相反，甲氧基取代削弱了库仑相互作用，增强了阴离子的选择性。这种对局部化学微环境的可调控制在不改变永久框架电荷的情况下实现了可编程和可逆的离子选择性。利用这一机制，我们实现了创纪录的高离子热电性能，在50 K温度梯度下，单膜为25.9 W m−2，堆叠配置为39.1 W m−2。这项工作建立了取代基介导的二级相互作用作为一种通用的、强大的离子传输编程策略，将生物选择性原理与自适应COF基膜的设计连接起来，用于能量收集和分离。
{"title":"Substituent‐Induced Secondary Interactions Reprogram Ion Permselectivity in Cationic Covalent Organic Framework Membranes","authors":"Jiaming Yi, Zhiwei Xing, Zhuozhi Lai, Qing Guo, Huixia Lv, Sai Wang, Qi Sun","doi":"10.1002/anie.202523731","DOIUrl":"https://doi.org/10.1002/anie.202523731","url":null,"abstract":"Precise modulation of ion permselectivity in synthetic membranes is crucial for advancing separation and energy conversion technologies. Here, we demonstrate that neutral substituents can reprogram the intrinsic ion selectivity of cationic covalent organic framework (COF) membranes by introducing secondary local interactions that compete with long‐range Coulombic forces. Using triaminoguanidinium‐based COFs as a model system, we systematically varied both the number and type of substituents on 1,3,5‐trialdehyde linkers. The introduced substituents generated secondary interactions that modulated the primary Coulombic interactions between guanidinium cations and Cl <jats:sup>–</jats:sup> counterions. When two or more hydroxyl groups were present on the aldehyde linkers, these interactions immobilized anions and inverted the effective surface potential from positive to negative, thereby switching the transport polarity from anion‐ to cation‐selective behavior. In contrast, methoxy substitution weakened Coulombic interactions, enhancing anion selectivity. This tunable control over the local chemical microenvironment enabled programmable and reversible ion permselectivity without altering the permanent framework charge. Leveraging this mechanism, we achieved record‐high ionic thermoelectric performance, 25.9 W m <jats:sup>−2</jats:sup> for a single membrane and 39.1 W m <jats:sup>−</jats:sup> <jats:sup>2</jats:sup> for a stacked configuration under a 50 K temperature gradient. This work establishes substituent‐mediated secondary interactions as a general and powerful strategy for programming ion transport, bridging biological selectivity principles with the design of adaptive COF‐based membranes for energy harvesting and separation.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"90 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098158","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}
Lu Gao, Chaofan Yuan, Wenying Yu, Sheng Guo, Na Tian, Xiaolei Zhang, Yihe Zhang, Hongwei Huang
The simultaneous production of hydrogen (H 2 ) and hydrogen peroxide (H 2 O 2 ) from pure water represents an ideal solar‐to‐chemical pathway for sustainable fuel and oxidant generation. However, conventional photocatalysts face intrinsic limitations, including sluggish carrier dynamics and insufficient power for water oxidation. Herein, we unveil an intramolecular electron transfer pathway from cyano groups to hydroxyl groups in C 3 N 5 that creates a high‐performance piezo‐photocatalyst for water splitting. The hydroxyl/cyano groups direct electron‐hole flow, optimizing the surface potential and dipole moment (DM) for a stronger piezoelectric response. Interestingly, the piezoelectric polarization induced by mechanical strain in MCN‐8 enhances its H + desorption ability to facilitate a rapid adsorption‐reaction‐desorption process. In situ infrared spectroscopy results indicate that MCN‐8 generates key substances such as ·O 2− and ·OOH, clarifying the water oxidation process. Thus, the rates of H 2 and H 2 O 2 release by its piezo‐photocatalysis were 4.14 mmol g −1 h −1 and 1.39 mmol g −1 h −1 , respectively. Under simulated outdoor sunlight and ultrasonic conditions, the as‐fabricated MCN‐8/PVDF‐HFP composite film retains its ability to produce H 2 and H 2 O 2 . This strategy of enhancing the piezo‐photocatalytic performance through surface group modulation provides a new idea for the development of highly efficient and multifunctional water decomposition catalysts.
{"title":"Piezoelectric Polarization Optimized Photocharge Separation and Surface Proton Cycling for Efficient Pure Water Splitting","authors":"Lu Gao, Chaofan Yuan, Wenying Yu, Sheng Guo, Na Tian, Xiaolei Zhang, Yihe Zhang, Hongwei Huang","doi":"10.1002/anie.202525592","DOIUrl":"https://doi.org/10.1002/anie.202525592","url":null,"abstract":"The simultaneous production of hydrogen (H <jats:sub>2</jats:sub> ) and hydrogen peroxide (H <jats:sub>2</jats:sub> O <jats:sub>2</jats:sub> ) from pure water represents an ideal solar‐to‐chemical pathway for sustainable fuel and oxidant generation. However, conventional photocatalysts face intrinsic limitations, including sluggish carrier dynamics and insufficient power for water oxidation. Herein, we unveil an intramolecular electron transfer pathway from cyano groups to hydroxyl groups in C <jats:sub>3</jats:sub> N <jats:sub>5</jats:sub> that creates a high‐performance piezo‐photocatalyst for water splitting. The hydroxyl/cyano groups direct electron‐hole flow, optimizing the surface potential and dipole moment (DM) for a stronger piezoelectric response. Interestingly, the piezoelectric polarization induced by mechanical strain in MCN‐8 enhances its H <jats:sup>+</jats:sup> desorption ability to facilitate a rapid adsorption‐reaction‐desorption process. In situ infrared spectroscopy results indicate that MCN‐8 generates key substances such as ·O <jats:sub>2</jats:sub> <jats:sup>−</jats:sup> and ·OOH, clarifying the water oxidation process. Thus, the rates of H <jats:sub>2</jats:sub> and H <jats:sub>2</jats:sub> O <jats:sub>2</jats:sub> release by its piezo‐photocatalysis were 4.14 mmol g <jats:sup>−1</jats:sup> h <jats:sup>−1</jats:sup> and 1.39 mmol g <jats:sup>−1</jats:sup> h <jats:sup>−1</jats:sup> , respectively. Under simulated outdoor sunlight and ultrasonic conditions, the as‐fabricated MCN‐8/PVDF‐HFP composite film retains its ability to produce H <jats:sub>2</jats:sub> and H <jats:sub>2</jats:sub> O <jats:sub>2</jats:sub> . This strategy of enhancing the piezo‐photocatalytic performance through surface group modulation provides a new idea for the development of highly efficient and multifunctional water decomposition catalysts.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"1 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098159","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}
Christiane Huhn, Clémence Mille, Sheng-Yang Ho, Felix Lützenkirchen, Vladimir Khayenko, Melanie Hein, Christian Werner, Matthias Kneussel, Johannes W. Hell, Christian G. Specht, Hans M. Maric
Direct visualization of postsynaptic scaffolds in living neurons is essential for dissecting synaptic dynamics and plasticity. Existing methods for live synapse visualization have major constraints, relying on genetic engineering or multistep application of live-cell incompatible antibodies or nanobodies. Available affinity probes and delivery strategies lack the required contrast due to incomplete or excess delivery. Here, we introduce Sylives, a set of compact, synthetic fluorescent peptides that enable high-contrast live imaging of inhibitory (gephyrin) and excitatory (PSD-95) postsynaptic scaffolds in native neurons. Critically, by pre-purification of the redox-cleavable CPP-probe conjugate we overcome side-product formation of in-situ coupling strategies, achieving reliable cytosolic delivery and restored scaffold binding after intracellular reduction. The Sylive design addresses the need for nanomolar probe levels versus micromolar CPP for clean labelling and efficient delivery by decoupling targeting and uptake. Through quantitative evaluation of uptake and off-target binding, we defined a transferrable parameter space for effective intracellular delivery. Near traceless Sylive uptake and target specificity are validated by direct comparison to transiently expressed proteins and immunolabeling in fixed neurons. The reduction-sensitive Sylive conjugates enable high-contrast, specificity-restored labelling of endogenous postsynaptic sites without genetic modification and offer a modular platform for targeting alternative intracellular proteins in living primary neurons.
{"title":"Redox-Activated Probes Enable High-Contrast Live Imaging of Native Postsynaptic Scaffolds","authors":"Christiane Huhn, Clémence Mille, Sheng-Yang Ho, Felix Lützenkirchen, Vladimir Khayenko, Melanie Hein, Christian Werner, Matthias Kneussel, Johannes W. Hell, Christian G. Specht, Hans M. Maric","doi":"10.1002/anie.202519933","DOIUrl":"https://doi.org/10.1002/anie.202519933","url":null,"abstract":"Direct visualization of postsynaptic scaffolds in living neurons is essential for dissecting synaptic dynamics and plasticity. Existing methods for live synapse visualization have major constraints, relying on genetic engineering or multistep application of live-cell incompatible antibodies or nanobodies. Available affinity probes and delivery strategies lack the required contrast due to incomplete or excess delivery. Here, we introduce Sylives, a set of compact, synthetic fluorescent peptides that enable high-contrast live imaging of inhibitory (gephyrin) and excitatory (PSD-95) postsynaptic scaffolds in native neurons. Critically, by pre-purification of the redox-cleavable CPP-probe conjugate we overcome side-product formation of in-situ coupling strategies, achieving reliable cytosolic delivery and restored scaffold binding after intracellular reduction. The Sylive design addresses the need for nanomolar probe levels versus micromolar CPP for clean labelling and efficient delivery by decoupling targeting and uptake. Through quantitative evaluation of uptake and off-target binding, we defined a transferrable parameter space for effective intracellular delivery. Near traceless Sylive uptake and target specificity are validated by direct comparison to transiently expressed proteins and immunolabeling in fixed neurons. The reduction-sensitive Sylive conjugates enable high-contrast, specificity-restored labelling of endogenous postsynaptic sites without genetic modification and offer a modular platform for targeting alternative intracellular proteins in living primary neurons.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"41 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098246","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}
and a linear 
complex. Once formed, the surfaces complexes are stable even at rather negative potentials and diffuse as molecular species on the Au surface.
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：