Photocatalytic uranium extraction from seawater is indispensable for sustainable nuclear energy, yet its efficiency is fundamentally limited by the prevailing indirect superoxide‐mediated reduction pathway, which suffers from sluggish kinetics, oxygen dependency, and poor selectivity. Herein, it is demonstrated that a molecular‐level “sulfone switch”, integrated into a covalent organic framework via edge‐hanging engineering, orchestrates a decisive shift from the indirect to a direct two‐electron transfer pathway for uranium photoreduction. The optimized Py‐DaSO‐COF achieves a remarkable uranium extraction capacity of 21.25 mg g −1 in natural seawater, which is coupled with rapid kinetics and high selectivity against vanadium ions, surpassing most reported photocatalytic systems. Notably, combined experimental and theoretical studies reveal that the electron‐deficient thiophene sulfone group promotes exciton dissociation, stabilizes key *UO 2 intermediates, and suppresses •O 2− generation by diverting electrons directly to adsorbed uranium species. This work establishes a versatile molecular engineering strategy for controlling photocatalytic pathways, highlighting its universal significance for solar‐driven resource recovery and beyond.
光催化从海水中提取铀对于可持续核能是必不可少的，但其效率从根本上受到当前间接超氧化物介导的还原途径的限制，该途径存在动力学缓慢、氧依赖性和选择性差的问题。本文证明了分子水平的“砜开关”，通过挂边工程集成到共价有机框架中，协调了铀光还原从间接到直接双电子转移途径的决定性转变。优化后的Py - DaSO - COF在自然海水中获得了21.25 mg g - 1的铀萃取能力，并且具有快速的动力学和对钒离子的高选择性，超过了大多数报道的光催化体系。值得注意的是，结合实验和理论研究表明，缺乏电子的噻吩砜基团促进激子解离，稳定关键的* o2中间体，并通过将电子直接转移到吸附的铀种来抑制•o2−的产生。这项工作为控制光催化途径建立了一个通用的分子工程策略，突出了其在太阳能驱动的资源回收及其他领域的普遍意义。
{"title":"Sulfone Molecular Switch Enables Direct Two‐Electron Uranium Photoreduction in Programmed Covalent Organic Frameworks","authors":"Guihong Wu, Fengtao Yu, Huiying Lei, Saijin Xiao, Fangru Song, Jianding Qiu","doi":"10.1002/adma.202519608","DOIUrl":"https://doi.org/10.1002/adma.202519608","url":null,"abstract":"Photocatalytic uranium extraction from seawater is indispensable for sustainable nuclear energy, yet its efficiency is fundamentally limited by the prevailing indirect superoxide‐mediated reduction pathway, which suffers from sluggish kinetics, oxygen dependency, and poor selectivity. Herein, it is demonstrated that a molecular‐level “sulfone switch”, integrated into a covalent organic framework via edge‐hanging engineering, orchestrates a decisive shift from the indirect to a direct two‐electron transfer pathway for uranium photoreduction. The optimized Py‐DaSO‐COF achieves a remarkable uranium extraction capacity of 21.25 mg g <jats:sup>−1</jats:sup> in natural seawater, which is coupled with rapid kinetics and high selectivity against vanadium ions, surpassing most reported photocatalytic systems. Notably, combined experimental and theoretical studies reveal that the electron‐deficient thiophene sulfone group promotes exciton dissociation, stabilizes key *UO <jats:sub>2</jats:sub> intermediates, and suppresses •O <jats:sub>2</jats:sub> <jats:sup>−</jats:sup> generation by diverting electrons directly to adsorbed uranium species. This work establishes a versatile molecular engineering strategy for controlling photocatalytic pathways, highlighting its universal significance for solar‐driven resource recovery and beyond.","PeriodicalId":114,"journal":{"name":"Advanced Materials","volume":"147 1","pages":""},"PeriodicalIF":29.4,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145732007","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The high‐entropy strategy offers a viable pathway to activate the inert basal plane of transition metal dichalcogenides (TMDs) for electrocatalysis. This work demonstrates that the “lattice distortion effect”, one of the core effects of high‐entropy materials, plays a crucial role in activating the basal plane of TMDs. A high‐entropy diselenide (ReNbTaMoW)Se 2 (denoted as HESe 2 ) is synthesized via solid‐state reaction. Single‐crystal X‐ray diffraction and atomic resolution scanning transmission electron microscopy reveal a unique fivefold‐modulated structure in HESe 2 , which unexpectedly distorts the rigid trigonal prismatic motif. HESe 2 exhibits exceptional activity for hydrogen evolution reaction (HER), showing a low overpotential of 31 mV at a current density of 10 mA cm −2 , comparable to state‐of‐the‐art precious metal catalysts. In situ X‐ray photoelectron spectroscopy indicates that the distorted structure of HESe 2 remains stable during the HER process. A proton exchange membrane (PEM) electrolyser assembled with HESe 2 cathodic catalyst shows competitive performance and durability with negligible degradation over 400 h. Density functional theory calculations reveal the electron accumulation regions induced by lattice distortion as high‐activity sites, thereby driving the augmented HER performance of HESe 2 . This work presents a universal strategy for boosting the basal plane activity of layered materials through unique lattice distortion effect.
高熵策略为激活过渡金属二硫族化合物惰性基面进行电催化提供了一条可行的途径。这项工作表明，“晶格畸变效应”是高熵材料的核心效应之一，在激活tmd基面中起着至关重要的作用。通过固相反应合成了高熵二硒化物（ReNbTaMoW）Se 2（记为hes2）。单晶X射线衍射和原子分辨率扫描透射电子显微镜揭示了hes2中独特的五重调制结构，这意外地扭曲了刚性的三角棱镜基序。hes2在析氢反应（HER）中表现出优异的活性，在电流密度为10 mA cm - 2时显示出31 mV的低过电位，可与最先进的贵金属催化剂相媲美。原位X射线光电子能谱分析表明，在HER过程中，hes2的畸变结构保持稳定。用HESe 2阴极催化剂组装的质子交换膜（PEM）电解槽在400小时内表现出竞争力和耐久性，降解可以忽略不计。密度泛函数理论计算表明，晶格畸变引起的电子积累区域是高活性位点，从而推动了HESe 2的HER性能增强。本文提出了一种通过独特的晶格畸变效应来提高层状材料基面活性的通用策略。
{"title":"Lattice Distortion in High‐Entropy Transition Metal Diselenide for Augmented Hydrogen Evolution","authors":"Haoyu Yue, Zhongnan Guo, Wenjing Guo, Ruonan Yao, Shuang Zhen, Qiansu Ma, Ming Chen, Jiawei Lin, Wenxia Yuan","doi":"10.1002/adma.202522787","DOIUrl":"https://doi.org/10.1002/adma.202522787","url":null,"abstract":"The high‐entropy strategy offers a viable pathway to activate the inert basal plane of transition metal dichalcogenides (TMDs) for electrocatalysis. This work demonstrates that the “lattice distortion effect”, one of the core effects of high‐entropy materials, plays a crucial role in activating the basal plane of TMDs. A high‐entropy diselenide (ReNbTaMoW)Se <jats:sub>2</jats:sub> (denoted as HESe <jats:sub>2</jats:sub> ) is synthesized via solid‐state reaction. Single‐crystal X‐ray diffraction and atomic resolution scanning transmission electron microscopy reveal a unique fivefold‐modulated structure in HESe <jats:sub>2</jats:sub> , which unexpectedly distorts the rigid trigonal prismatic motif. HESe <jats:sub>2</jats:sub> exhibits exceptional activity for hydrogen evolution reaction (HER), showing a low overpotential of 31 mV at a current density of 10 mA cm <jats:sup>−2</jats:sup> , comparable to state‐of‐the‐art precious metal catalysts. In situ X‐ray photoelectron spectroscopy indicates that the distorted structure of HESe <jats:sub>2</jats:sub> remains stable during the HER process. A proton exchange membrane (PEM) electrolyser assembled with HESe <jats:sub>2</jats:sub> cathodic catalyst shows competitive performance and durability with negligible degradation over 400 h. Density functional theory calculations reveal the electron accumulation regions induced by lattice distortion as high‐activity sites, thereby driving the augmented HER performance of HESe <jats:sub>2</jats:sub> . This work presents a universal strategy for boosting the basal plane activity of layered materials through unique lattice distortion effect.","PeriodicalId":114,"journal":{"name":"Advanced Materials","volume":"15 1","pages":""},"PeriodicalIF":29.4,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145731888","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ruihao Li, Ran Liu, Shima Ghasemi, Pedro Ferreira, Dianting Zou, Feng Sun, Kasper Moth‐Poulsen, Joshua Hihath
Molecular orbital symmetry plays a pivotal role in determining chemical reaction mechanisms. The process of changing chemical reactants into products must transition along a pathway that conserves molecular orbital symmetry to ensure continuity. This principle is so fundamental that reactions that do not conserve symmetry are typically considered “forbidden” due to the high resultant energy barriers. Here, it is demonstrated that it is possible to electrically catalyze these forbidden transitions when a single molecule is bound between two electrodes in a nanoscale junction. A cycloaddition reaction is induced in a norbornadiene (NBD) derivative, converting it to quadricyclane (QC) by utilizing nanoconfinement to place the molecule into a configuration that is far from equilibrium and applying a small voltage to the molecular junction. Traditionally, this reaction can only be induced photochemically due to orbital symmetry selection rules. By directly tracking the reaction dynamics in situ using single‐molecule Raman spectroscopy, it is shown that for this reaction to be electrically catalyzed the molecule must be sterically maneuvered into a configuration near the transition state at the peak of the energy barrier prior to applying the voltage needed to successfully induce the forbidden transition is applied.
{"title":"Electrical Catalysis of Forbidden Transitions in Single‐Molecule Devices","authors":"Ruihao Li, Ran Liu, Shima Ghasemi, Pedro Ferreira, Dianting Zou, Feng Sun, Kasper Moth‐Poulsen, Joshua Hihath","doi":"10.1002/adma.202511822","DOIUrl":"https://doi.org/10.1002/adma.202511822","url":null,"abstract":"Molecular orbital symmetry plays a pivotal role in determining chemical reaction mechanisms. The process of changing chemical reactants into products must transition along a pathway that conserves molecular orbital symmetry to ensure continuity. This principle is so fundamental that reactions that do not conserve symmetry are typically considered “forbidden” due to the high resultant energy barriers. Here, it is demonstrated that it is possible to electrically catalyze these forbidden transitions when a single molecule is bound between two electrodes in a nanoscale junction. A cycloaddition reaction is induced in a norbornadiene (NBD) derivative, converting it to quadricyclane (QC) by utilizing nanoconfinement to place the molecule into a configuration that is far from equilibrium and applying a small voltage to the molecular junction. Traditionally, this reaction can only be induced photochemically due to orbital symmetry selection rules. By directly tracking the reaction dynamics in situ using single‐molecule Raman spectroscopy, it is shown that for this reaction to be electrically catalyzed the molecule must be sterically maneuvered into a configuration near the transition state at the peak of the energy barrier prior to applying the voltage needed to successfully induce the forbidden transition is applied.","PeriodicalId":114,"journal":{"name":"Advanced Materials","volume":"170 1","pages":""},"PeriodicalIF":29.4,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145731891","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Living systems achieve robustness by integrating soft and rigid components into seamless architectures, yet synthetic emulation of this strategy remains limited. Here, we present a strategy to generate multimaterials from a single copolymer by patterning phase separation. Specifically, we design a block copolymer of metastable nanostructure, and then spatially program photocrosslinking to locally arrest phase separation at different levels during annealing, thereby producing patterns that span moduli from regimes of rubbers to plastics. The resulting multimaterial exhibits spatially distinct mechanical properties, but is chemically identical, and is seamlessly integrated through a shared polymer network topology. This approach inherently eliminates interfacial incompatibility of dissimilar materials, enhances structural integrity of the multimaterial, and establishes a versatile platform for programmable, multiscale rigid‐soft integrated devices.
{"title":"Multimaterials by Patterning Microphase Separation of a Single Copolymer","authors":"Congqi Qi, Bohan Liu, Zheqi Chen, Yingwu Luo","doi":"10.1002/adma.202517801","DOIUrl":"https://doi.org/10.1002/adma.202517801","url":null,"abstract":"Living systems achieve robustness by integrating soft and rigid components into seamless architectures, yet synthetic emulation of this strategy remains limited. Here, we present a strategy to generate multimaterials from a single copolymer by patterning phase separation. Specifically, we design a block copolymer of metastable nanostructure, and then spatially program photocrosslinking to locally arrest phase separation at different levels during annealing, thereby producing patterns that span moduli from regimes of rubbers to plastics. The resulting multimaterial exhibits spatially distinct mechanical properties, but is chemically identical, and is seamlessly integrated through a shared polymer network topology. This approach inherently eliminates interfacial incompatibility of dissimilar materials, enhances structural integrity of the multimaterial, and establishes a versatile platform for programmable, multiscale rigid‐soft integrated devices.","PeriodicalId":114,"journal":{"name":"Advanced Materials","volume":"39 1","pages":""},"PeriodicalIF":29.4,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145732002","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yang Wang, Wenfa Chen, Pin Lyu, Huan Lu, Erwen Zhang, Rong Rong, Fanrong Lin, Shuiyan Cao, Yanpeng Liu
In‐sensor computing and logics are the core for advancing machine vision technology, but face challenges in extending such capability into thermal form. Here, a bioinspired thermoreceptor array based on twisted graphene and titanium diselenide (TiSe 2 ) heterostructures is presented. The electron‐phonon interaction between graphene and few‐layer TiSe 2 exhibits strong twist‐angle ( θ ) dependence, as evidenced by varied phonon‐induced gap of graphene (114 ± 13 meV for θ = 1° and 67 ± 6 meV for θ = 7°), enabling sensitive thermal reception at temperature range from 20 to 350 K. Integrating such heterostructure into a (64 × 64) thermoperception array with a convolutional neural network (CNN) framework promotes significant advancements in microscopic thermal imaging, enhancing thermal image detection accuracy by 46% and achieving 99% classification accuracy for pathological cell identification. In addition, the “AND” “OR”, and,“AND/OR” logic operations are demonstrated using these thermoreceptor arrays. This proof‐of‐concept thermoperception arrays also simplify the monolithically integrable architecture of machine vision and offer a potential solution for efficient in‐sensor computing and logics for next‐generation intelligent systems.
{"title":"Twisting van der Waals Heterostructures Enables Thermographic In‐Sensor Computing and Logics","authors":"Yang Wang, Wenfa Chen, Pin Lyu, Huan Lu, Erwen Zhang, Rong Rong, Fanrong Lin, Shuiyan Cao, Yanpeng Liu","doi":"10.1002/adma.202519646","DOIUrl":"https://doi.org/10.1002/adma.202519646","url":null,"abstract":"In‐sensor computing and logics are the core for advancing machine vision technology, but face challenges in extending such capability into thermal form. Here, a bioinspired thermoreceptor array based on twisted graphene and titanium diselenide (TiSe <jats:sub>2</jats:sub> ) heterostructures is presented. The electron‐phonon interaction between graphene and few‐layer TiSe <jats:sub>2</jats:sub> exhibits strong twist‐angle ( <jats:italic>θ</jats:italic> ) dependence, as evidenced by varied phonon‐induced gap of graphene (114 ± 13 meV for <jats:italic>θ =</jats:italic> 1° and 67 ± 6 meV for <jats:italic>θ =</jats:italic> 7°), enabling sensitive thermal reception at temperature range from 20 to 350 K. Integrating such heterostructure into a (64 × 64) thermoperception array with a convolutional neural network (CNN) framework promotes significant advancements in microscopic thermal imaging, enhancing thermal image detection accuracy by 46% and achieving 99% classification accuracy for pathological cell identification. In addition, the “AND” “OR”, and,“AND/OR” logic operations are demonstrated using these thermoreceptor arrays. This proof‐of‐concept thermoperception arrays also simplify the monolithically integrable architecture of machine vision and offer a potential solution for efficient in‐sensor computing and logics for next‐generation intelligent systems.","PeriodicalId":114,"journal":{"name":"Advanced Materials","volume":"43 1","pages":""},"PeriodicalIF":29.4,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145732006","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ming‐Di Gao, Chao‐Yang Guan, Jia‐Yao Wang, Jin‐Ying Qi, Nan‐Nan Deng
Soft materials capable of responding to diverse environmental stimuli are fundamental to advancing soft robotics and intelligent biomedical devices, enabling adaptive, life‐like functions. Here, multimodal photothermal adaptability is reported in azobenzene‐conjugated DNA condensates assembled via liquid‐liquid phase separation (LLPS). These coacervates exhibit a striking temperature‐dependent inversion of their photo‐response: at elevated temperatures, the liquid‐like droplets deform under visible light and dissolve under ultraviolet (UV) light, whereas at lower temperatures, the gel‐like condensates are reshaped by UV light while remaining inert to visible light. This unique bidirectional control is attributed to the synergy of confined azobenzene photochemistry within DNA duplexes and a pronounced isomer‐dependent shift in the system's glass transition and melting temperatures. This platform of multi‐responsive photofluids opens new avenues for applications demanding exquisite spatiotemporal control.
{"title":"Thermally Switchable Photoactivity in Azobenzene‐Functionalized DNA Condensates","authors":"Ming‐Di Gao, Chao‐Yang Guan, Jia‐Yao Wang, Jin‐Ying Qi, Nan‐Nan Deng","doi":"10.1002/adma.202518318","DOIUrl":"https://doi.org/10.1002/adma.202518318","url":null,"abstract":"Soft materials capable of responding to diverse environmental stimuli are fundamental to advancing soft robotics and intelligent biomedical devices, enabling adaptive, life‐like functions. Here, multimodal photothermal adaptability is reported in azobenzene‐conjugated DNA condensates assembled via liquid‐liquid phase separation (LLPS). These coacervates exhibit a striking temperature‐dependent inversion of their photo‐response: at elevated temperatures, the liquid‐like droplets deform under visible light and dissolve under ultraviolet (UV) light, whereas at lower temperatures, the gel‐like condensates are reshaped by UV light while remaining inert to visible light. This unique bidirectional control is attributed to the synergy of confined azobenzene photochemistry within DNA duplexes and a pronounced isomer‐dependent shift in the system's glass transition and melting temperatures. This platform of multi‐responsive photofluids opens new avenues for applications demanding exquisite spatiotemporal control.","PeriodicalId":114,"journal":{"name":"Advanced Materials","volume":"10 1","pages":""},"PeriodicalIF":29.4,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145732036","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The shuttle effect, arising from the dissolution and migration of polyiodide species, severely hinders the practical application of high‐energy‐density zinc‐iodine (Zn─I 2 ) batteries. Conventional carbon‐based cathode materials, relying on weak physical adsorption, fail to effectively confine iodine species. To address this issue, a synergistic strategy is proposed that combines the targeted capture of I − to form BiOI with the potential responsive release of I − from BiOI during the reduction of Bi 3+ to Bi. This approach enables a dynamic and directional capture‐release process at a potential lower than that required for the reduction of I 2 . This methodology is validated through ex situ spectroscopic analysis and Density functional theory (DFT) calculations. This decoupled mechanism suppresses polyiodide formation and ensures efficient cathode reversibility. The incorporation of Bi 2 O 3 also introduces an additional redox couple, contributing extra capacity to the battery. The battery not only efficiently suppresses the inherent side reaction issues of zinc‐iodine batteries, but also achieves a considerably high capacity level in the field of iodine single‐electron conversion. This work provides a universal design principle for manipulating iodine electrochemistry, paving the way for high‐energy, long‐lifespan halogen‐based batteries.
{"title":"Synergistic Strategy of Targeted Capture and Potential Responsive Release for High‐Performance Zinc‐Iodine Batteries","authors":"Hanyu Wen, Bosi Yin, Haokun Wen, Ying Sun, Jiazhuo Li, Hui Li, Zhi Gen Yu, Siwen Zhang, Yong‐Wei Zhang, Tianyi Ma","doi":"10.1002/adma.202516182","DOIUrl":"https://doi.org/10.1002/adma.202516182","url":null,"abstract":"The shuttle effect, arising from the dissolution and migration of polyiodide species, severely hinders the practical application of high‐energy‐density zinc‐iodine (Zn─I <jats:sub>2</jats:sub> ) batteries. Conventional carbon‐based cathode materials, relying on weak physical adsorption, fail to effectively confine iodine species. To address this issue, a synergistic strategy is proposed that combines the targeted capture of I <jats:sup>−</jats:sup> to form BiOI with the potential responsive release of I <jats:sup>−</jats:sup> from BiOI during the reduction of Bi <jats:sup>3+</jats:sup> to Bi. This approach enables a dynamic and directional capture‐release process at a potential lower than that required for the reduction of I <jats:sub>2</jats:sub> . This methodology is validated through ex situ spectroscopic analysis and Density functional theory (DFT) calculations. This decoupled mechanism suppresses polyiodide formation and ensures efficient cathode reversibility. The incorporation of Bi <jats:sub>2</jats:sub> O <jats:sub>3</jats:sub> also introduces an additional redox couple, contributing extra capacity to the battery. The battery not only efficiently suppresses the inherent side reaction issues of zinc‐iodine batteries, but also achieves a considerably high capacity level in the field of iodine single‐electron conversion. This work provides a universal design principle for manipulating iodine electrochemistry, paving the way for high‐energy, long‐lifespan halogen‐based batteries.","PeriodicalId":114,"journal":{"name":"Advanced Materials","volume":"229 1","pages":""},"PeriodicalIF":29.4,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145732000","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yulin Xie, Junrong Wang, Yubin Han, Guoqing Zhu, Lei Li, Qianqian Sun, Chunxia Li
Both tumors and intratumoral bacteria exhibit iron addiction, a shared metabolic dependency that drives their proliferation. Here, inspired by the ancient Chinese fable “The Snipe and the Clam Grapple While the Fisherman Profits” , a nano‐chelator, copper‐deferiprone (Cu‐DFP), is designed and synthesized to deplete iron ions by metal chelation therapy in the tumor microenvironment, thereby “sowing discord” between tumors and intratumoral bacteria and subsequently inducing cuproptosis in both. Specifically, capitalizing on the high iron stores in both tumor cells and intratumoral bacteria, coupled with the superior iron‐chelating capability of DFP, Cu‐DFP effectively hijacks iron ions from these cellular reservoirs while concurrently liberating substantial amounts of copper ions (Cu 2+ ). Iron depletion not only exacerbates the antagonistic rivalry between tumors and bacteria but also disrupts their defense mechanisms against external stressors. Moreover, the released Cu 2+ leads to excessive intracellular copper accumulation, triggering cuproptosis in both. The dying tumor cells and bacteria then release damage‐associated molecular patterns (DAMPs) and pathogen‐associated molecular patterns (PAMPs), respectively, promoting dendritic cells (DCs) maturation and activating antitumor immune responses. By harnessing the iron‐mediated metabolic competition to potentiate cuproptosis, this therapeutic strategy presents an innovative method for addressing intratumoral microbiota in oncology.
{"title":"Antagonistic Iron Competition Induced by Iron Chelators Heightens Cuproptosis in Both Tumors and Intratumoral Bacteria","authors":"Yulin Xie, Junrong Wang, Yubin Han, Guoqing Zhu, Lei Li, Qianqian Sun, Chunxia Li","doi":"10.1002/adma.202515904","DOIUrl":"https://doi.org/10.1002/adma.202515904","url":null,"abstract":"Both tumors and intratumoral bacteria exhibit iron addiction, a shared metabolic dependency that drives their proliferation. Here, inspired by the ancient Chinese fable <jats:italic>“The Snipe and the Clam Grapple While the Fisherman Profits”</jats:italic> , a nano‐chelator, copper‐deferiprone (Cu‐DFP), is designed and synthesized to deplete iron ions by metal chelation therapy in the tumor microenvironment, thereby “sowing discord” between tumors and intratumoral bacteria and subsequently inducing cuproptosis in both. Specifically, capitalizing on the high iron stores in both tumor cells and intratumoral bacteria, coupled with the superior iron‐chelating capability of DFP, Cu‐DFP effectively hijacks iron ions from these cellular reservoirs while concurrently liberating substantial amounts of copper ions (Cu <jats:sup>2+</jats:sup> ). Iron depletion not only exacerbates the antagonistic rivalry between tumors and bacteria but also disrupts their defense mechanisms against external stressors. Moreover, the released Cu <jats:sup>2+</jats:sup> leads to excessive intracellular copper accumulation, triggering cuproptosis in both. The dying tumor cells and bacteria then release damage‐associated molecular patterns (DAMPs) and pathogen‐associated molecular patterns (PAMPs), respectively, promoting dendritic cells (DCs) maturation and activating antitumor immune responses. By harnessing the iron‐mediated metabolic competition to potentiate cuproptosis, this therapeutic strategy presents an innovative method for addressing intratumoral microbiota in oncology.","PeriodicalId":114,"journal":{"name":"Advanced Materials","volume":"75 1","pages":""},"PeriodicalIF":29.4,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145732038","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hong Qiu, Yang Yang, Congcong Liu, Yu Yao, Zhijun Wu, Shengnan He, Hongge Pan, Xianhong Rui, Yan Yu
All‐solid‐state sodium batteries (ASSSBs) are promising due to their exceptional energy density, safety, and abundant sodium resources. Poly(ethylene oxide) (PEO) electrolyte is extensively investigated for ASSSBs, but its practical application is limited by low ionic conductivity and interfacial instability at room/sub‑zero temperatures. Here, a dual‐strategy solid‐state electrolyte design (entirely liquid‐free) is presented in which succinonitrile serves as a plasticizer that synergizes with PEO, creating dual‐ion conduction pathways that achieve an impressive ionic conductivity of 2.75 × 10 −4 S cm −1 at room temperature. Concurrently, sodium difluoro(oxalate)borate undergoes in situ reactions with sodium metal anode, synergizing with the artificially formed NaF interphase layer to facilitate the successful formation of a stable, inorganic salt‐rich solid electrolyte interphase. This mechanism effectively suppresses undesirable side reactions between the polymer and sodium metal anode. Consequently, Na@NaF||Na@NaF symmetric cells exhibit outstanding cycling stability for over 1,500 hours at 0.1 mA cm −2 under room temperature. Full cells based on Na 3 V 2 (PO 4 ) 3 ||Na@NaF retain 91.2% of their initial capacity after 1,000 cycles at 2C. Notably, the ASSSBs deliver a discharge capacity of 88.2 mAh g −1 even at −5 °C, highlighting their suitability for low‐temperature applications. This work establishes an electrolyte‐interface collaborative design paradigm for high‐performance ASSSBs under wide‐temperature operating conditions.
全固态钠电池（ASSSBs）因其卓越的能量密度、安全性和丰富的钠资源而具有广阔的应用前景。聚环氧乙烷（PEO）电解质被广泛研究用于ASSSBs，但其实际应用受到低离子电导率和室温/低温下界面不稳定性的限制。本文提出了一种双策略固态电解质设计（完全无液体），其中丁二腈作为增塑剂与PEO协同作用，形成双离子传导途径，在室温下实现了令人印象深刻的2.75 × 10−4 S cm−1的离子电导率。同时，二氟（草酸）硼酸钠与金属阳极钠发生原位反应，与人工形成的NaF间相层协同作用，促进了稳定的、富含无机盐的固体电解质间相的成功形成。这种机制有效地抑制了聚合物与金属钠阳极之间的不良副反应。因此，Na@NaF||Na@NaF对称电池在室温下0.1 mA cm−2下表现出超过1500小时的出色循环稳定性。基于na3v2 (po4) 3| |Na@NaF的全电池在2C下循环1000次后仍保持其初始容量的91.2%。值得注意的是，asssb即使在- 5°C下也能提供88.2 mAh g - 1的放电容量，突出了它们在低温应用中的适用性。这项工作为宽温度工作条件下的高性能asssb建立了电解质界面协同设计范例。
{"title":"Dual‐Conduction Polymer Electrolyte and Stable Interphase Engineering for Room‐/Subzero‐Temperature, Long‐Cycling All‐Solid‐State Sodium Batteries","authors":"Hong Qiu, Yang Yang, Congcong Liu, Yu Yao, Zhijun Wu, Shengnan He, Hongge Pan, Xianhong Rui, Yan Yu","doi":"10.1002/adma.202519121","DOIUrl":"https://doi.org/10.1002/adma.202519121","url":null,"abstract":"All‐solid‐state sodium batteries (ASSSBs) are promising due to their exceptional energy density, safety, and abundant sodium resources. Poly(ethylene oxide) (PEO) electrolyte is extensively investigated for ASSSBs, but its practical application is limited by low ionic conductivity and interfacial instability at room/sub‑zero temperatures. Here, a dual‐strategy solid‐state electrolyte design (entirely liquid‐free) is presented in which succinonitrile serves as a plasticizer that synergizes with PEO, creating dual‐ion conduction pathways that achieve an impressive ionic conductivity of 2.75 × 10 <jats:sup>−4</jats:sup> S cm <jats:sup>−1</jats:sup> at room temperature. Concurrently, sodium difluoro(oxalate)borate undergoes in situ reactions with sodium metal anode, synergizing with the artificially formed NaF interphase layer to facilitate the successful formation of a stable, inorganic salt‐rich solid electrolyte interphase. This mechanism effectively suppresses undesirable side reactions between the polymer and sodium metal anode. Consequently, Na@NaF||Na@NaF symmetric cells exhibit outstanding cycling stability for over 1,500 hours at 0.1 mA cm <jats:sup>−2</jats:sup> under room temperature. Full cells based on Na <jats:sub>3</jats:sub> V <jats:sub>2</jats:sub> (PO <jats:sub>4</jats:sub> ) <jats:sub>3</jats:sub> ||Na@NaF retain 91.2% of their initial capacity after 1,000 cycles at 2C. Notably, the ASSSBs deliver a discharge capacity of 88.2 mAh g <jats:sup>−1</jats:sup> even at −5 °C, highlighting their suitability for low‐temperature applications. This work establishes an electrolyte‐interface collaborative design paradigm for high‐performance ASSSBs under wide‐temperature operating conditions.","PeriodicalId":114,"journal":{"name":"Advanced Materials","volume":"10 1","pages":""},"PeriodicalIF":29.4,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145731883","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Wenye Zhang, Wenjie Huang, Jiangqiong Wang, Baoquan Wan, George Chen, Jun‐Wei Zha
Cross‐linked polyethylene (XLPE) with favorable electrical and mechanical properties is a key component of high voltage power transmission. However, damages caused by strong electrical and high mechanical stresses tend to initiate structural degradation of insulating materials, which in severe cases can lead to catastrophic failure of equipment. The irreversible curing property of XLPE presents significant challenges in self‐healing after damage and recycling after decommissioning. Herein, an innovative strategy is developed that utilizes Cu‐catalyzed amination to synthesize functionalized polyethylene, combined with dynamic covalent chemistry to prepare tailorable covalent adaptable networks (CANs). Due to the exchange of dual dynamic covalent bonds, the prepared CANs exhibit excellent self‐healing and recycling properties, with performance recovery efficiency close to 100% after mechanical and electrical damage. Furthermore, the ingeniously designed structure of CANs, which combines “strong” permanent cross‐linking with “weak” dynamic cross‐linking, achieves a higher toughness of 102.0 MJ m −3 and excellent electrical insulation properties (electric field distortion rate of only 7% at 70 °C) than XLPE. This work promotes the environmental friendliness and long life of XLPE, paving the way for a new generation of sustainable cable insulation.
{"title":"Covalent Adaptable Network Enables Sustainable Polyethylene for Next‐Generation Cable Insulation","authors":"Wenye Zhang, Wenjie Huang, Jiangqiong Wang, Baoquan Wan, George Chen, Jun‐Wei Zha","doi":"10.1002/adma.202516696","DOIUrl":"https://doi.org/10.1002/adma.202516696","url":null,"abstract":"Cross‐linked polyethylene (XLPE) with favorable electrical and mechanical properties is a key component of high voltage power transmission. However, damages caused by strong electrical and high mechanical stresses tend to initiate structural degradation of insulating materials, which in severe cases can lead to catastrophic failure of equipment. The irreversible curing property of XLPE presents significant challenges in self‐healing after damage and recycling after decommissioning. Herein, an innovative strategy is developed that utilizes Cu‐catalyzed amination to synthesize functionalized polyethylene, combined with dynamic covalent chemistry to prepare tailorable covalent adaptable networks (CANs). Due to the exchange of dual dynamic covalent bonds, the prepared CANs exhibit excellent self‐healing and recycling properties, with performance recovery efficiency close to 100% after mechanical and electrical damage. Furthermore, the ingeniously designed structure of CANs, which combines “strong” permanent cross‐linking with “weak” dynamic cross‐linking, achieves a higher toughness of 102.0 MJ m <jats:sup>−3</jats:sup> and excellent electrical insulation properties (electric field distortion rate of only 7% at 70 °C) than XLPE. This work promotes the environmental friendliness and long life of XLPE, paving the way for a new generation of sustainable cable insulation.","PeriodicalId":114,"journal":{"name":"Advanced Materials","volume":"7 1","pages":""},"PeriodicalIF":29.4,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145731998","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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