Apeksha Singh, Dominic Blätte, Roman Guntermann, Lucie Quincke, Jennifer L. M. Rupp, Thomas Bein
Covalent organic frameworks (COFs) have emerged as promising electrode materials for secondary-ion batteries, where redox-active building blocks and linkages enable tunable redox properties, while ordered pores serve as nanochannels for fast ion transport. We report a novel highly crystalline 2D PyTTF-COF, synthesized by integrating n-type pyrene–benzothiadiazole (PyBT) and p-type tetrathiafulvalene (TTF) subunits via an n-type imine linkage, yielding a bipolar electrode capable of reversible 16 e− dual cation–anion storage. Initially, the dual-ion, redox synergy was tested in a Li-ion half-cell, where PyTTF served as cathode, and 1 м LiPF6 or LiTFSI electrolytes were employed to probe anion-dependent electrochemical behavior. Electrochemical evaluation in Li-ion half cells revealed a wide electrochemical window of 0.1−3.6 V vs. Li/Li+, with markedly enhanced charge-storage kinetics and ion diffusion with LiTFSI relative to LiPF6 electrolytes. The PyTTF electrode delivered specific capacities of 286 mAh g−1 (LiTFSI) and 184 mAh g−1 (LiPF6) at 0.3 A g−1, highlighting the strong influence of anion identity. Systematic variation of LiTFSI salt concentration (1−3 м) revealed strong correlations between electrolyte composition, ion storage dynamics, and interfacial charge-transfer resistance. This study highlights, for the first time, the critical importance of tailoring both charge-carrier identity and electrolyte concentration to unlock the full potential of bipolar COF electrodes for dual-ion batteries.
共价有机框架（COFs）已成为一种很有前途的二次离子电池电极材料，其氧化还原活性构建块和连接可以实现可调的氧化还原性能，而有序孔则可以作为快速离子传输的纳米通道。我们报道了一种新型的高结晶二维PyTTF-COF，通过n型亚胺连接将n型芘-苯并噻唑二唑（PyBT）和p型四噻唑戊烯（TTF）亚基整合合成，产生了能够可逆的16 e -双正负离子存储的双极电极。首先，在锂离子半电池中测试了双离子氧化还原协同作用，其中PyTTF作为阴极，并使用1 μ LiPF6或LiTFSI电解质来探测阴离子依赖的电化学行为。锂离子半电池的电化学评价显示，与Li/Li+相比，LiTFSI的电化学窗口宽为0.1 ~ 3.6 V，相对于LiPF6电解质，LiTFSI的电荷存储动力学和离子扩散明显增强。在0.3 A g−1下，PyTTF电极的比容量为286 mAh g−1 （LiTFSI）和184 mAh g−1 (LiPF6)，突出了阴离子同一性的强烈影响。LiTFSI盐浓度的系统变化（1 ~ 3 μ m）揭示了电解质组成、离子存储动力学和界面电荷转移阻力之间的强相关性。这项研究首次强调了调整电荷载流子身份和电解质浓度对于释放双离子电池双极COF电极的全部潜力的关键重要性。
{"title":"Tuning Redox Behavior of Pyrene–Benzothiadiazole/TTF–Based Covalent Organic Framework Electrodes in Dual-Ion Batteries","authors":"Apeksha Singh, Dominic Blätte, Roman Guntermann, Lucie Quincke, Jennifer L. M. Rupp, Thomas Bein","doi":"10.1002/anie.202522720","DOIUrl":"https://doi.org/10.1002/anie.202522720","url":null,"abstract":"Covalent organic frameworks (COFs) have emerged as promising electrode materials for secondary-ion batteries, where redox-active building blocks and linkages enable tunable redox properties, while ordered pores serve as nanochannels for fast ion transport. We report a novel highly crystalline 2D PyTTF-COF, synthesized by integrating <i>n</i>-type pyrene–benzothiadiazole (PyBT) and <i>p</i>-type tetrathiafulvalene (TTF) subunits via an <i>n</i>-type imine linkage, yielding a bipolar electrode capable of reversible 16 e<sup>−</sup> dual cation–anion storage. Initially, the dual-ion, redox synergy was tested in a Li-ion half-cell, where PyTTF served as cathode, and 1 м LiPF<sub>6</sub> or LiTFSI electrolytes were employed to probe anion-dependent electrochemical behavior. Electrochemical evaluation in Li-ion half cells revealed a wide electrochemical window of 0.1−3.6 V vs. Li/Li<sup>+</sup>, with markedly enhanced charge-storage kinetics and ion diffusion with LiTFSI relative to LiPF<sub>6</sub> electrolytes. The PyTTF electrode delivered specific capacities of 286 mAh g<sup>−1</sup> (LiTFSI) and 184 mAh g<sup>−1</sup> (LiPF<sub>6</sub>) at 0.3 A g<sup>−1</sup>, highlighting the strong influence of anion identity. Systematic variation of LiTFSI salt concentration (1−3 м) revealed strong correlations between electrolyte composition, ion storage dynamics, and interfacial charge-transfer resistance. This study highlights, for the first time, the critical importance of tailoring both charge-carrier identity and electrolyte concentration to unlock the full potential of bipolar COF electrodes for dual-ion batteries.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"42 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146414","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 monomer conversion rate of thioctic acid (TA) and the cross-linking degree of polymer chains significantly influence the performance of materials, making them important research topics. Herein, by selecting a reduced polyoxometalate complex modified with 1-allylpyridinium cations, which exhibits strong near-infrared (NIR) light absorption capability, as both photothermal agent and cross-linking agent, the polymerization of TA is successfully achieved under NIR light irradiation. The incorporation of photothermal agents results in their multiple dispersion throughout the polymerization matrix, facilitating uniform internal heat generation and inside-out thermal diffusion. This mechanism significantly shortens the heat conduction pathway and effectively mitigates the inhomogeneous polymerization typically caused by temperature gradients inherent in conventional heating methods. Moreover, the C─S bonds formed via the reaction between the C═C groups and the disulfide linkages of TA not only suppress depolymerization but also serve as robust anchoring sites within the polymer network. By tuning the monomer composition, TA-based adhesives and elastomers are successfully fabricated, exhibiting excellent re-processability through NIR-triggered remelting or repair. The NIR-light-regulated polymerization approach offers distinct advantages, including operational simplicity, rapid response, and spatiotemporal control, thereby presenting a promising strategy for the synthesis of high-performance TA-based polymers.
{"title":"Near-Infrared Photothermal Polymerization of Thioctic Acid Triggered by Polyoxometalate Crosslinker","authors":"Shuangyu Wu, Hongxue Wang, Bao Li, Lixin Wu","doi":"10.1002/anie.202523605","DOIUrl":"https://doi.org/10.1002/anie.202523605","url":null,"abstract":"The monomer conversion rate of thioctic acid (TA) and the cross-linking degree of polymer chains significantly influence the performance of materials, making them important research topics. Herein, by selecting a reduced polyoxometalate complex modified with 1-allylpyridinium cations, which exhibits strong near-infrared (NIR) light absorption capability, as both photothermal agent and cross-linking agent, the polymerization of TA is successfully achieved under NIR light irradiation. The incorporation of photothermal agents results in their multiple dispersion throughout the polymerization matrix, facilitating uniform internal heat generation and inside-out thermal diffusion. This mechanism significantly shortens the heat conduction pathway and effectively mitigates the inhomogeneous polymerization typically caused by temperature gradients inherent in conventional heating methods. Moreover, the C─S bonds formed via the reaction between the C═C groups and the disulfide linkages of TA not only suppress depolymerization but also serve as robust anchoring sites within the polymer network. By tuning the monomer composition, TA-based adhesives and elastomers are successfully fabricated, exhibiting excellent re-processability through NIR-triggered remelting or repair. The NIR-light-regulated polymerization approach offers distinct advantages, including operational simplicity, rapid response, and spatiotemporal control, thereby presenting a promising strategy for the synthesis of high-performance TA-based polymers.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"176 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139089","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 rapid proliferation of artificial intelligence (AI) and information technologies is driving a sharp increase in global electronic waste, creating an urgent demand for recovering precious metals like gold from secondary resources to achieve environmental and economic benefits. Herein, a polydopamine (PDA)-functionalized β-ketoenamine-linked covalent organic framework composite, denoted as TATP/PDA, is designed in combination with a light-assisted strategy for efficient gold recovery. Benefiting from the synergistic effects of hydrogen bonding and π-π interactions between PDA and the TATP COF, which enhance photoelectric activity and provide abundant adsorption sites, the TATP/PDA exhibits an exceptional adsorption capacity of 5220 mg·g−1, ultrafast adsorption kinetics (>99% removal efficiency within 30 s), and remarkable selectivity in complex matrices. Experimental characterizations disclose that the engineered abundant nitrogen and oxygen active sites, along with the inherent photocatalytic reduction capability, significantly enhance the gold adsorption performance. These key merits position TATP/PDA as one of the best-performing materials in terms of overall performance. In practical application, TATP/PDA exhibits exceptional performance in recovering gold from real e-waste leachate. Moreover, the recovered gold-loaded composite serves as a sustainable photocatalyst for hydrogen evolution. This dual-benefit strategy not only promotes resource recycling but also contributes to the goals of a green and circular economy.
{"title":"Light-Promoted Efficient Gold Recovery Enabled by a Polydopamine-Functionalized Covalent Organic Framework","authors":"Yanyin Wu, Yuyu Guo, Tianwei Xue, Zeyu Shao, Longzhao Xu, Junhua Kuang, Ruiqing Li, Guangkuo Xu, Peng Chen, Wenli Hao, Tongxin Qiao, Xiangcheng Cai, Shuliang Yang, Jun Li, Li Peng","doi":"10.1002/anie.202526042","DOIUrl":"https://doi.org/10.1002/anie.202526042","url":null,"abstract":"The rapid proliferation of artificial intelligence (AI) and information technologies is driving a sharp increase in global electronic waste, creating an urgent demand for recovering precious metals like gold from secondary resources to achieve environmental and economic benefits. Herein, a polydopamine (PDA)-functionalized β-ketoenamine-linked covalent organic framework composite, denoted as TATP/PDA, is designed in combination with a light-assisted strategy for efficient gold recovery. Benefiting from the synergistic effects of hydrogen bonding and π-π interactions between PDA and the TATP COF, which enhance photoelectric activity and provide abundant adsorption sites, the TATP/PDA exhibits an exceptional adsorption capacity of 5220 mg·g<sup>−1</sup>, ultrafast adsorption kinetics (>99% removal efficiency within 30 s), and remarkable selectivity in complex matrices. Experimental characterizations disclose that the engineered abundant nitrogen and oxygen active sites, along with the inherent photocatalytic reduction capability, significantly enhance the gold adsorption performance. These key merits position TATP/PDA as one of the best-performing materials in terms of overall performance. In practical application, TATP/PDA exhibits exceptional performance in recovering gold from real e-waste leachate. Moreover, the recovered gold-loaded composite serves as a sustainable photocatalyst for hydrogen evolution. This dual-benefit strategy not only promotes resource recycling but also contributes to the goals of a green and circular economy.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"3 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139088","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 carbohydrate-based drug discovery, fluorine-containing substituents are widely used to enhance pharmacodynamic and pharmacokinetic profiles. However, the precise incorporation of C(sp3)-perfluoroalkyl moieties at the C2 position of sugar scaffolds remains a significant synthetic challenge. In this study, we report a highly efficient and cost-effective protocol for the synthesis of 2-deoxy-2-perfluoroalkyl glycosides from readily available glycals. This protocol demonstrates exceptional substrate generality, encompassing glucal, galactal, rhamnal, sialic acid, and arabinofuranose derivatives. More importantly, this platform enables the efficient synthesis of diverse C-, N-, and O-glycosides (over 50 examples) under gold(I)-catalyzed conditions, including the synthesis of previously inaccessible 2-deoxy-2-CF3-substituted nucleoside analogues. Additionally, photocatalytically generated 2-deoxy-2-CF3 glycosyl anomeric radicals readily undergo Giese-type additions to alkenes, affording alkylated glycosides, or engage in cross-coupling with aryl bromides to deliver antidiabetic drug candidates. Preliminary biological evaluations indicate that 2-deoxy-2-CF3-modified glycosides exhibit enhanced pharmacological properties, underscoring the translational potential of this synthetic technique for advancing carbohydrate-based therapeutics.
{"title":"Expeditious Synthesis of 2-Deoxy-2-perfluoroalkyl Glycosides","authors":"Shen Cao, Haobo Zhang, Niming Zhu, Peng Xu, Xiaoping Chen, Biao Yu, Xiaheng Zhang","doi":"10.1002/anie.1824435","DOIUrl":"https://doi.org/10.1002/anie.1824435","url":null,"abstract":"In carbohydrate-based drug discovery, fluorine-containing substituents are widely used to enhance pharmacodynamic and pharmacokinetic profiles. However, the precise incorporation of C(sp<sup>3</sup>)-perfluoroalkyl moieties at the C2 position of sugar scaffolds remains a significant synthetic challenge. In this study, we report a highly efficient and cost-effective protocol for the synthesis of 2-deoxy-2-perfluoroalkyl glycosides from readily available glycals. This protocol demonstrates exceptional substrate generality, encompassing glucal, galactal, rhamnal, sialic acid, and arabinofuranose derivatives. More importantly, this platform enables the efficient synthesis of diverse <i>C</i>-, <i>N</i>-, and <i>O</i>-glycosides (over 50 examples) under gold(I)-catalyzed conditions, including the synthesis of previously inaccessible 2-deoxy-2-CF<sub>3</sub>-substituted nucleoside analogues. Additionally, photocatalytically generated 2-deoxy-2-CF<sub>3</sub> glycosyl anomeric radicals readily undergo Giese-type additions to alkenes, affording alkylated glycosides, or engage in cross-coupling with aryl bromides to deliver antidiabetic drug candidates. Preliminary biological evaluations indicate that 2-deoxy-2-CF<sub>3</sub>-modified glycosides exhibit enhanced pharmacological properties, underscoring the translational potential of this synthetic technique for advancing carbohydrate-based therapeutics.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"1 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139087","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}
Yongxin Yang, Kun Zeng, Yan Feng, Qi An, Lu Liu, Futong Ren, Xilin Liang, Genfu Zhao, Songsong Zhi, Hong Guo
The inherent factors influencing the growth of lithium (Li) dendrites and the kinetics of Li+ migration in polymer electrolytes lie in the electron cloud density distribution in the electrolyte. Localized electrons accumulation can trigger the uneven Li+ deposition, ultimately leading to battery failure. To address this critical challenge, the concept of p–π conjugation and B–O sp2 hybridization is innovatively incorporated into covalent organic frameworks (COFs) to mitigate local interfacial Li+ accumulation and improve Li+ migration kinetics in electrolytes by electron delocalization. Furthermore, perfluoroalkyl group with virtues of superior electron regulating capabilities and improved electrochemical-window, is strategically grafted to better match high-voltage cathodes. Under the synergistic role of electron regulation, the electrolyte with pπ–sp2-COF significantly improves overall electrochemical performance of solid-state batteries. Thus, regulating electron density via p-π conjugation and B-O sp2 hybridization promises to open new avenues for the development of COFs-modified polymer electrolytes in solid-state batteries.
{"title":"Modulating Electron Delocalization Structure in Covalent Organic Frameworks Through Conjugation and Hybridization to Boost Li-ion Migration Dynamics","authors":"Yongxin Yang, Kun Zeng, Yan Feng, Qi An, Lu Liu, Futong Ren, Xilin Liang, Genfu Zhao, Songsong Zhi, Hong Guo","doi":"10.1002/anie.202525864","DOIUrl":"https://doi.org/10.1002/anie.202525864","url":null,"abstract":"The inherent factors influencing the growth of lithium (Li) dendrites and the kinetics of Li<sup>+</sup> migration in polymer electrolytes lie in the electron cloud density distribution in the electrolyte. Localized electrons accumulation can trigger the uneven Li<sup>+</sup> deposition, ultimately leading to battery failure. To address this critical challenge, the concept of p–π conjugation and B–O sp<sup>2</sup> hybridization is innovatively incorporated into covalent organic frameworks (COFs) to mitigate local interfacial Li<sup>+</sup> accumulation and improve Li<sup>+</sup> migration kinetics in electrolytes by electron delocalization. Furthermore, perfluoroalkyl group with virtues of superior electron regulating capabilities and improved electrochemical-window, is strategically grafted to better match high-voltage cathodes. Under the synergistic role of electron regulation, the electrolyte with pπ–sp<sup>2</sup>-COF significantly improves overall electrochemical performance of solid-state batteries. Thus, regulating electron density via p-π conjugation and B-O sp<sup>2</sup> hybridization promises to open new avenues for the development of COFs-modified polymer electrolytes in solid-state batteries.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"57 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139070","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}
Ikuya Fujii, Rin Seki, Haruka Kido, Louis Jauffret, Kazuhiko Semba, Yoshiaki Nakao
Here we describe the generation of aryl Grignard reagents from phenol derivatives via C─O bond activation cooperatively catalyzed by Rh─Al heterobimetallic complexes. We discovered that the electron-rich arylmagnesium reagents could be efficiently prepared from the corresponding aryl carbamates, whereas the π-extended arylmagnesium reagents were obtained from the corresponding aryl ethers. This methodology enables the efficient conversion of a broad range of phenol derivatives into the corresponding Grignard reagents, which can subsequently react with various electrophiles to yield a diverse array of organic compounds.
{"title":"Magnesiation of Phenol Derivatives Catalyzed by a Rhodium─Aluminum Complex","authors":"Ikuya Fujii, Rin Seki, Haruka Kido, Louis Jauffret, Kazuhiko Semba, Yoshiaki Nakao","doi":"10.1002/anie.202518631","DOIUrl":"https://doi.org/10.1002/anie.202518631","url":null,"abstract":"Here we describe the generation of aryl Grignard reagents from phenol derivatives <i>via</i> C─O bond activation cooperatively catalyzed by Rh─Al heterobimetallic complexes. We discovered that the electron-rich arylmagnesium reagents could be efficiently prepared from the corresponding aryl carbamates, whereas the π-extended arylmagnesium reagents were obtained from the corresponding aryl ethers. This methodology enables the efficient conversion of a broad range of phenol derivatives into the corresponding Grignard reagents, which can subsequently react with various electrophiles to yield a diverse array of organic compounds.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"59 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139067","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}
Dongxu Zhang, Deli Jiang, Yanhong Liu, Qitao Chen, Lei Xing, Hui Huang, Wei Zhang, Weidong Shi, Zhenhui Kang, Baodong Mao
Modern electrocatalysis typically involves multi-species cascade systems, imposing stringent requirements on catalysts to exhibit multi-component and multifunctional characteristics. Such complexity poses great challenges for identifying and understanding the structural and functional nature of the true active phase. Herein, we report the formation of Cu111 nanolaminates confined within the interface of Cu1.94S/In2S3 heterojunction via in situ electrochemical reconstruction. The synthesized Cu111 nanolaminates act as a single-phase co-activating nanoreactor to preferentially adsorb carbon dioxide (CO2) and cascade N-intermediates, enabling C─N coupling for urea synthesis within an ultra-low and distinct potential window. The optimized Cu1.94S/Cu111/In2S3 catalyst achieves a urea yield rate of 11823.65 µg h−1 mgCu111−1 and an exceptionally high Faradaic efficiency of 69.34% at -0.35 V versus the reversible hydrogen electrode in a flow cell, surpassing all previously reported transition metal electrocatalysts. In situ spectroscopic analyses and theoretical calculations reveal a favorable reaction pathway and nanoconfined synergy on the Cu111 nanolaminates, where CO2 is initially anchored and reduced to *CO and cascaded *NO2 undergoes C─N coupling to form the key *CONO2 intermediate toward urea. This study unveils the true active phase within a complex heterostructure electrocatalyst, which also provides new insights into the rational design of advanced electrocatalysts for other energy and environmental applications.
{"title":"Confined Cu111 Nanolaminates as a Single-Phase Nanoreactor for Efficient Urea Electrosynthesis","authors":"Dongxu Zhang, Deli Jiang, Yanhong Liu, Qitao Chen, Lei Xing, Hui Huang, Wei Zhang, Weidong Shi, Zhenhui Kang, Baodong Mao","doi":"10.1002/anie.2242110","DOIUrl":"https://doi.org/10.1002/anie.2242110","url":null,"abstract":"Modern electrocatalysis typically involves multi-species cascade systems, imposing stringent requirements on catalysts to exhibit multi-component and multifunctional characteristics. Such complexity poses great challenges for identifying and understanding the structural and functional nature of the true active phase. Herein, we report the formation of Cu<sub>111</sub> nanolaminates confined within the interface of Cu<sub>1.94</sub>S/In<sub>2</sub>S<sub>3</sub> heterojunction via in situ electrochemical reconstruction. The synthesized Cu<sub>111</sub> nanolaminates act as a single-phase co-activating nanoreactor to preferentially adsorb carbon dioxide (CO<sub>2</sub>) and cascade N-intermediates, enabling C─N coupling for urea synthesis within an ultra-low and distinct potential window. The optimized Cu<sub>1.94</sub>S/Cu<sub>111</sub>/In<sub>2</sub>S<sub>3</sub> catalyst achieves a urea yield rate of 11823.65 µg h<sup>−1</sup> mg<sub>Cu111</sub><sup>−1</sup> and an exceptionally high Faradaic efficiency of 69.34% at -0.35 V versus the reversible hydrogen electrode in a flow cell, surpassing all previously reported transition metal electrocatalysts. In situ spectroscopic analyses and theoretical calculations reveal a favorable reaction pathway and nanoconfined synergy on the Cu<sub>111</sub> nanolaminates, where CO<sub>2</sub> is initially anchored and reduced to *CO and cascaded *NO<sub>2</sub> undergoes C─N coupling to form the key *CONO<sub>2</sub> intermediate toward urea. This study unveils the true active phase within a complex heterostructure electrocatalyst, which also provides new insights into the rational design of advanced electrocatalysts for other energy and environmental applications.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"7 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139071","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}
Yulan Han, Jiayan Xu, Jiawei Wu, Chenyu Wu, Xiran Cheng, Wenbo Xie, Xiulian Pan, Xinhe Bao, P. Hu
Discovering next-generation heterogeneous catalysts calls for embracing the full complexity of active site formation under realistic conditions. Here, we develop a robust machine learning potential (MLP)-aided computational framework that integrates realistic preparation and reaction conditions to effectively track the formation of active sites and decipher structure-activity relationships. Using syngas conversion over the ZnxCryOz system as a demonstration, we identified that the system preferentially segregates into ZnO and ZnCr2O4 phases, with ZnO forming a monolayer on ZnCr2O4 surfaces under preparation conditions. Under reaction conditions, by deploying CH─O bond dissociation as a descriptor, we found that the ZnO/ZnCr2O4(100) surface is the active surface. Crucially, we pinpoint geometrically linked oxygen vacancy pairs as the true active sites. Full microkinetic analyses conducted on these active sites yield kinetic results that align well with experimental observations. Beyond elucidating the active structure, a model for designing oxide/oxide catalysts to achieve high activity is generalized, opening new pathways for accelerating catalyst discovery across a wide range of reactions.
{"title":"First Principles Identification of Active Sites in Heterogeneous Catalysis: A Case Study on ZnxCryOz for Syngas Conversion","authors":"Yulan Han, Jiayan Xu, Jiawei Wu, Chenyu Wu, Xiran Cheng, Wenbo Xie, Xiulian Pan, Xinhe Bao, P. Hu","doi":"10.1002/anie.202522416","DOIUrl":"https://doi.org/10.1002/anie.202522416","url":null,"abstract":"Discovering next-generation heterogeneous catalysts calls for embracing the full complexity of active site formation under realistic conditions. Here, we develop a robust machine learning potential (MLP)-aided computational framework that integrates realistic preparation and reaction conditions to effectively track the formation of active sites and decipher structure-activity relationships. Using syngas conversion over the Zn<sub>x</sub>Cr<sub>y</sub>O<sub>z</sub> system as a demonstration, we identified that the system preferentially segregates into ZnO and ZnCr<sub>2</sub>O<sub>4</sub> phases, with ZnO forming a monolayer on ZnCr<sub>2</sub>O<sub>4</sub> surfaces under preparation conditions. Under reaction conditions, by deploying CH─O bond dissociation as a descriptor, we found that the ZnO/ZnCr<sub>2</sub>O<sub>4</sub>(100) surface is the active surface. Crucially, we pinpoint geometrically linked oxygen vacancy pairs as the true active sites. Full microkinetic analyses conducted on these active sites yield kinetic results that align well with experimental observations. Beyond elucidating the active structure, a model for designing oxide/oxide catalysts to achieve high activity is generalized, opening new pathways for accelerating catalyst discovery across a wide range of reactions.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"35 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139086","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 heterogeneous photocatalytic systems coupled with oxidant activation hold great promise for environmental remediation but are constrained by radical scavenging and nonselective oxidation. Here, we introduce an overlooked photoswitch-mediated electron transfer (PSMET) mechanism that circumvents reactive oxygen species by enabling direct, ultrafast electron transfer from pollutants to oxidants through a photoactive mediator. Using environmentally benign bismuth oxyiodide as a model catalyst under visible-light irradiation, we achieve unprecedented degradation rates for various electron-rich pollutants such as sulfamethoxazole (t1/2 <2.0 min). This mechanism exhibits pollutant-dependent oxidant utilization mode and selective pollutant degradation characteristics. Mechanistic analyses reveal the formation of a high-potential electron-transfer pathway activated by photoexcitation, directly coupling pollutant oxidation to oxidant reduction within a single electron-transfer cycle. Frontier molecular orbital calculations further demonstrate that the narrow bandgap and p-type semiconductor characteristics selectively facilitate electron extraction from contaminants to oxidants. Remarkably, this PSMET mechanism displays universal applicability with diverse oxidants, maintaining >98% pollutant removals even in complex aqueous matrices and continuous-flow systems. Furthermore, the mechanism allows precise optical control over reaction initiation and termination, offering unparalleled spatiotemporal regulation for sustainable wastewater treatment. Our findings redefine photocatalytic oxidation paradigms and open new pathways toward energy-efficient, optically programmable, and environmentally sustainable remediation technologies.
{"title":"Photoswitch Mediated Electron Highway Driving Direct Pollutant-to-Oxidant Electron Transfer in Ultrafast Fenton-Like Reactions","authors":"Zhi-Quan Zhang, Bin-Bin Zhang, Jing Wang, Chang-Wei Bai, Xin-Jia Chen, Fu-Qiao Yang, Pi-Jun Duan, Fei Chen","doi":"10.1002/anie.202521687","DOIUrl":"https://doi.org/10.1002/anie.202521687","url":null,"abstract":"Traditional heterogeneous photocatalytic systems coupled with oxidant activation hold great promise for environmental remediation but are constrained by radical scavenging and nonselective oxidation. Here, we introduce an overlooked photoswitch-mediated electron transfer (PSMET) mechanism that circumvents reactive oxygen species by enabling direct, ultrafast electron transfer from pollutants to oxidants through a photoactive mediator. Using environmentally benign bismuth oxyiodide as a model catalyst under visible-light irradiation, we achieve unprecedented degradation rates for various electron-rich pollutants such as sulfamethoxazole (t<sub>1/2</sub> <2.0 min). This mechanism exhibits pollutant-dependent oxidant utilization mode and selective pollutant degradation characteristics. Mechanistic analyses reveal the formation of a high-potential electron-transfer pathway activated by photoexcitation, directly coupling pollutant oxidation to oxidant reduction within a single electron-transfer cycle. Frontier molecular orbital calculations further demonstrate that the narrow bandgap and p-type semiconductor characteristics selectively facilitate electron extraction from contaminants to oxidants. Remarkably, this PSMET mechanism displays universal applicability with diverse oxidants, maintaining >98% pollutant removals even in complex aqueous matrices and continuous-flow systems. Furthermore, the mechanism allows precise optical control over reaction initiation and termination, offering unparalleled spatiotemporal regulation for sustainable wastewater treatment. Our findings redefine photocatalytic oxidation paradigms and open new pathways toward energy-efficient, optically programmable, and environmentally sustainable remediation technologies.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"16 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139068","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}
Izabela Kamińska, Justus T. Metternich, Alan M. Szalai, Carolin Smidoda, Sayantani Chakraborty, Lela Vukovic, Sebastian Kruss, Philip Tinnefeld
Single-walled carbon nanotubes (SWCNTs) are promising optical biosensing platforms due to their intrinsic near-infrared fluorescence and environmental sensitivity. While DNA-SWCNT hybrids have been widely studied, the structural arrangement of double-stranded DNA (dsDNA) on SWCNTs and its impact on exciton–fluorophore interactions remain insufficiently characterized. Here, we introduce carbon nanotube energy transfer with vertical nucleic acids (CNETvNA), in which fluorophores are positioned at defined distances from SWCNTs using guanine-defect anchored capture sequences hybridized with complementary oligonucleotides. By systematically varying the duplex length from 12 to 24 base pairs, we probe the distance dependence of dye–SWCNT interactions at the single-molecule level. Fluorescence lifetime imaging microscopy reveals efficient quenching of ATTO542 and ATTO643 dyes, with lifetime distributions reflecting heterogeneous duplex conformations. Molecular dynamics simulations demonstrate that dsDNA duplexes adopt a predominantly perpendicular orientation relative to the SWCNT axis, with increasing tilt and conformational variability at longer lengths. Combining experimental and computational results, we establish a distance dependence of d−5 with 7.4 ± 0.7 nm for 50% quenching efficiency, consistent with theoretical predictions for point dipole donors and 1D acceptors. These findings provide structural insights into DNA-SWCNT conjugates and establish CNETvNA as a rational design principle for SWCNT-based biosensors.
{"title":"Distance-Dependent Energy Transfer Between Organic Fluorophores and Single-Walled Carbon Nanotubes","authors":"Izabela Kamińska, Justus T. Metternich, Alan M. Szalai, Carolin Smidoda, Sayantani Chakraborty, Lela Vukovic, Sebastian Kruss, Philip Tinnefeld","doi":"10.1002/anie.202520411","DOIUrl":"https://doi.org/10.1002/anie.202520411","url":null,"abstract":"Single-walled carbon nanotubes (SWCNTs) are promising optical biosensing platforms due to their intrinsic near-infrared fluorescence and environmental sensitivity. While DNA-SWCNT hybrids have been widely studied, the structural arrangement of double-stranded DNA (dsDNA) on SWCNTs and its impact on exciton–fluorophore interactions remain insufficiently characterized. Here, we introduce carbon nanotube energy transfer with vertical nucleic acids (CNETvNA), in which fluorophores are positioned at defined distances from SWCNTs using guanine-defect anchored capture sequences hybridized with complementary oligonucleotides. By systematically varying the duplex length from 12 to 24 base pairs, we probe the distance dependence of dye–SWCNT interactions at the single-molecule level. Fluorescence lifetime imaging microscopy reveals efficient quenching of ATTO542 and ATTO643 dyes, with lifetime distributions reflecting heterogeneous duplex conformations. Molecular dynamics simulations demonstrate that dsDNA duplexes adopt a predominantly perpendicular orientation relative to the SWCNT axis, with increasing tilt and conformational variability at longer lengths. Combining experimental and computational results, we establish a distance dependence of d<sup>−</sup><sup>5</sup> with 7.4 ± 0.7 nm for 50% quenching efficiency, consistent with theoretical predictions for point dipole donors and 1D acceptors. These findings provide structural insights into DNA-SWCNT conjugates and establish CNETvNA as a rational design principle for SWCNT-based biosensors.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"241 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139069","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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