Jun Shu,Xianbo Wu,Zixin Tang,Tao Feng,Johannes Karges,Weidong Jiang,Gilles Gasser,Hui Chao
Most clinically used chemotherapeutic agents act by inducing apoptosis. However, their clinical effectiveness is often limited by poor therapeutic efficacy and the rapid development of drug resistance. In contrast, oncosis, as an inflammatory form of cell death independent of adenosine triphosphate (ATP) and apoptotic pathways, exhibits unique advantages in overcoming tumor drug resistance and regulating anti-tumor immune responses. Herein, we present the first iridium(III)-based immunogenic oncosis inducers designed to concurrently induce oncosis and activate the cGAS-STING pathway, thereby bridging chemotherapy with immunotherapy. Through a bioisosteric design strategy, we identified benzoselenazole and benzothiazole derivatives as key pharmacophores for triggering oncosis. These iridium(III)-based oncosis-inducers rapidly disrupt mitochondrial architecture, induce oxidative stress, and promote Ca(II) release, which subsequently activate calpain and porimin to initiate oncosis in multidrug-resistant cancer cells. Transcriptomic profiling further revealed their ability to regulate actin cytoskeleton organization, modulate ABC transporter activity, and affect glycolysis/gluconeogenesis. Notably, the metal complexes induce mitochondrial swelling and mt-DNA damage, leading to robust activation of the cGAS-STING innate immune pathway and eliciting a strong anticancer immune response. Based on these multimodal mechanisms, the Ir(III)-based immunogenic oncosis inducers were able to effectively kill drug-resistant cancer cells and enhance the anticancer immune response in tumor mouse models.
{"title":"Boosting Cancer Chemoimmunotherapy with Mitochondria-Targeting Iridium(III)-Based Immunogenic Oncosis Inducers.","authors":"Jun Shu,Xianbo Wu,Zixin Tang,Tao Feng,Johannes Karges,Weidong Jiang,Gilles Gasser,Hui Chao","doi":"10.1002/anie.202521242","DOIUrl":"https://doi.org/10.1002/anie.202521242","url":null,"abstract":"Most clinically used chemotherapeutic agents act by inducing apoptosis. However, their clinical effectiveness is often limited by poor therapeutic efficacy and the rapid development of drug resistance. In contrast, oncosis, as an inflammatory form of cell death independent of adenosine triphosphate (ATP) and apoptotic pathways, exhibits unique advantages in overcoming tumor drug resistance and regulating anti-tumor immune responses. Herein, we present the first iridium(III)-based immunogenic oncosis inducers designed to concurrently induce oncosis and activate the cGAS-STING pathway, thereby bridging chemotherapy with immunotherapy. Through a bioisosteric design strategy, we identified benzoselenazole and benzothiazole derivatives as key pharmacophores for triggering oncosis. These iridium(III)-based oncosis-inducers rapidly disrupt mitochondrial architecture, induce oxidative stress, and promote Ca(II) release, which subsequently activate calpain and porimin to initiate oncosis in multidrug-resistant cancer cells. Transcriptomic profiling further revealed their ability to regulate actin cytoskeleton organization, modulate ABC transporter activity, and affect glycolysis/gluconeogenesis. Notably, the metal complexes induce mitochondrial swelling and mt-DNA damage, leading to robust activation of the cGAS-STING innate immune pathway and eliciting a strong anticancer immune response. Based on these multimodal mechanisms, the Ir(III)-based immunogenic oncosis inducers were able to effectively kill drug-resistant cancer cells and enhance the anticancer immune response in tumor mouse models.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"209 1","pages":"e21242"},"PeriodicalIF":16.6,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145696699","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}
X-ray time-lapse flexible imaging and information retrieval significantly broaden the application scope of X-ray technologies, while posing new challenges for the design of advanced scintillators. Herein, we report a phase transition-guided strategy for the rational design of Mn-doped ternary cadmium chlorides long afterglow emitters, wherein crystal growth dynamics are precisely modulated via solubility-controlled synthesis. By sequentially preparing powders and single crystals of Cs2CdCl4:Mn, Cs3Cd2Cl7:Mn, and CsCdCl3:Mn, we achieve phase-selective synthesis through fine-tuning of mixed solvent ratios, establishing a robust framework for phase engineering in the Mn-doped Cs-Cd-Cl system. Among them, CsCdCl3:Mn exhibits the highest trap density, resulting in a pronounced scintillation afterglow. Benefiting from this unique property, a flexible scintillating film fabricated by embedding phosphor powders into a polymer matrix enables high-resolution time-lapse X-ray imaging (13.6 lp mm-1), along with thermally stimulated image retrieval after X-ray exposure. This work not only presents a generalizable approach for phase-controlled afterglow modulation in Mn-doped chlorides, but also offers new avenues toward flexible, high-performance X-ray scintillators with delayed visualization capabilities.
{"title":"Sequential Phase-Engineered Afterglow Modulation in Mn-Doped Cs-Cd-Cl Perovskites for X-ray Time-Lapse Flexible Imaging.","authors":"Chao Wang,Zhengguang Yan,Zixi Yin,Qingsong Hu,Dongpeng Yan,Jiawen Xiao","doi":"10.1002/anie.202523858","DOIUrl":"https://doi.org/10.1002/anie.202523858","url":null,"abstract":"X-ray time-lapse flexible imaging and information retrieval significantly broaden the application scope of X-ray technologies, while posing new challenges for the design of advanced scintillators. Herein, we report a phase transition-guided strategy for the rational design of Mn-doped ternary cadmium chlorides long afterglow emitters, wherein crystal growth dynamics are precisely modulated via solubility-controlled synthesis. By sequentially preparing powders and single crystals of Cs2CdCl4:Mn, Cs3Cd2Cl7:Mn, and CsCdCl3:Mn, we achieve phase-selective synthesis through fine-tuning of mixed solvent ratios, establishing a robust framework for phase engineering in the Mn-doped Cs-Cd-Cl system. Among them, CsCdCl3:Mn exhibits the highest trap density, resulting in a pronounced scintillation afterglow. Benefiting from this unique property, a flexible scintillating film fabricated by embedding phosphor powders into a polymer matrix enables high-resolution time-lapse X-ray imaging (13.6 lp mm-1), along with thermally stimulated image retrieval after X-ray exposure. This work not only presents a generalizable approach for phase-controlled afterglow modulation in Mn-doped chlorides, but also offers new avenues toward flexible, high-performance X-ray scintillators with delayed visualization capabilities.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"130 1","pages":"e23858"},"PeriodicalIF":16.6,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145696724","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}
Achieving high fluorescence efficiency in organic fluorophores within the second near-infrared window (NIR-II, 1000∼1700 nm) remains challenging, as extended π-conjugation and active intramolecular motions typically funnel excitation energy into non-radiative decay. Here, we present peripheral cyanation as a molecular design strategy that directly modulates excited-state dynamics and suppresses non-radiative relaxation. Incorporation of cyano groups (A') into the D-A-D scaffold of BBTCz afforded BBTCzCN with an A'-D-A-D-A' architecture, which significantly reduced vibronic coupling compared to the parent dye. Upon encapsulation with DSPE-mPEG5000, BBTCzCN nanoparticles (NPs) retained a high FLQY of 2.8% with a record-high brightness of 565 M-1 cm-1, representing a 10.4-fold enhancement over BBTCz NPs and placing it among the brightest organic NIR-II emitters reported to date. Mechanistic studies combining density functional theory and ultrafast spectroscopy revealed that cyanation synergistically suppressed vibrational relaxation and internal conversion, thereby prolonging radiative decay pathways. As a result, BBTCzCN NPs enabled high-resolution vascular imaging, real-time lymphatic tracking, and precise intraoperative delineation of tumors and peritoneal metastases. This work establishes peripheral cyanation as a broadly applicable molecular design strategy for tailoring excited-state decay pathways, advancing the development of next-generation NIR-II fluorophores for deep-tissue imaging and image-guided surgery.
{"title":"Suppressing Non-Radiative Decay via Cyanation: A Promising Design Strategy for Bright Organic NIR-II Fluorophores.","authors":"Weili Wang,Jinjun Shao,Diya Xie,Leichen Wang,Kang Xu,Anqing Mei,Huili Ma,Wei Han,Peng Chen,Xiaochen Dong","doi":"10.1002/anie.202522260","DOIUrl":"https://doi.org/10.1002/anie.202522260","url":null,"abstract":"Achieving high fluorescence efficiency in organic fluorophores within the second near-infrared window (NIR-II, 1000∼1700 nm) remains challenging, as extended π-conjugation and active intramolecular motions typically funnel excitation energy into non-radiative decay. Here, we present peripheral cyanation as a molecular design strategy that directly modulates excited-state dynamics and suppresses non-radiative relaxation. Incorporation of cyano groups (A') into the D-A-D scaffold of BBTCz afforded BBTCzCN with an A'-D-A-D-A' architecture, which significantly reduced vibronic coupling compared to the parent dye. Upon encapsulation with DSPE-mPEG5000, BBTCzCN nanoparticles (NPs) retained a high FLQY of 2.8% with a record-high brightness of 565 M-1 cm-1, representing a 10.4-fold enhancement over BBTCz NPs and placing it among the brightest organic NIR-II emitters reported to date. Mechanistic studies combining density functional theory and ultrafast spectroscopy revealed that cyanation synergistically suppressed vibrational relaxation and internal conversion, thereby prolonging radiative decay pathways. As a result, BBTCzCN NPs enabled high-resolution vascular imaging, real-time lymphatic tracking, and precise intraoperative delineation of tumors and peritoneal metastases. This work establishes peripheral cyanation as a broadly applicable molecular design strategy for tailoring excited-state decay pathways, advancing the development of next-generation NIR-II fluorophores for deep-tissue imaging and image-guided surgery.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"133 1","pages":"e22260"},"PeriodicalIF":16.6,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145696727","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}
Zinc-iodine (Zn-I2) batteries attract increasing attention for inherent safety and cost-effectiveness. However, challenges like sluggish iodine kinetics and polyiodide shuttle effect seriously impede their practical viability. Herein, we develop a diffusion-retarded strategy, where carbon cage-encapsulated Cu-doped ZnO nanoparticles are tailored on scalable carbon paper substrates as iodine cathodes to simultaneously retard polyiodide shuttle effect and accelerate iodine species reaction kinetics. Specifically, the physical barrier formed by carbon cage and porous fiber effectively retards the diffusion of polyiodides, while the intermodulated single-atom Cu sites and adjacent Zn sites in Cu-ZnO nanoparticles show remarkable catalytic activity and chemisorption for iodine species, respectively. Hence, the obtained Zn-I2 batteries exhibit an ultra-low polarization voltage of 26.7 mV (1 A g-1) and endure an ultra-long cycle life over 40 000 cycles at 5 A g-1. Notably, the batteries maintain over 5000 cycles with a capacity degradation rate of barely 0.007% per cycle at 60 °C, while the capacity decline is 20.8 mAh g-1 under -20 °C (vs. 25 °C), as well as over 1150 cycles at a negative/positive (N/P) ratio of 2.5. Overall, high-performance Zn-I2 batteries under harsh conditions through the diffusion-retarded strategy provide valuable guidance for rational cathode designs toward practical Zn-I2 battery systems.
锌碘（Zn-I2）电池因其固有的安全性和成本效益越来越受到人们的关注。然而，碘动力学迟缓和多碘离子穿梭效应等挑战严重阻碍了它们的实际可行性。在此，我们开发了一种扩散延迟策略，将碳笼封装的cu掺杂ZnO纳米颗粒定制在可扩展的碳纸衬底上作为碘阴极，同时延迟多碘化物穿梭效应并加速碘物质反应动力学。具体来说，碳笼和多孔纤维形成的物理屏障有效地阻碍了多碘化物的扩散，而Cu- zno纳米颗粒中互调的单原子Cu位点和相邻的Zn位点分别对碘种表现出显著的催化活性和化学吸附作用。因此，获得的锌- i2电池具有26.7 mV （1 A g-1）的超低极化电压，并且在5 A g-1下具有超过40000次的超长循环寿命。值得注意的是，电池在60°C下保持超过5000次循环，每次循环的容量退化率仅为0.007%，而在-20°C（相对于25°C）下容量下降20.8 mAh g-1，以及在负/正（N/P）比为2.5时超过1150次循环。综上所述，通过扩散阻滞策略制备出恶劣条件下的高性能Zn-I2电池，为实际Zn-I2电池系统的合理阴极设计提供了有价值的指导。
{"title":"A Diffusion-Retarded Strategy for Practical Zn-I2 Batteries Under Harsh Conditions.","authors":"Zheng Lian,Wu Yang,Zhenzhen Wu,Linxin Zhong,Zhexuan Liu,Zhongxin Chen,Guanwu Lian,Emmanuel Iwuoha,Kasim Ocakoglu,Jun Lu,Shanqing Zhang,Guangmin Zhou,Xinwen Peng","doi":"10.1002/anie.202515756","DOIUrl":"https://doi.org/10.1002/anie.202515756","url":null,"abstract":"Zinc-iodine (Zn-I2) batteries attract increasing attention for inherent safety and cost-effectiveness. However, challenges like sluggish iodine kinetics and polyiodide shuttle effect seriously impede their practical viability. Herein, we develop a diffusion-retarded strategy, where carbon cage-encapsulated Cu-doped ZnO nanoparticles are tailored on scalable carbon paper substrates as iodine cathodes to simultaneously retard polyiodide shuttle effect and accelerate iodine species reaction kinetics. Specifically, the physical barrier formed by carbon cage and porous fiber effectively retards the diffusion of polyiodides, while the intermodulated single-atom Cu sites and adjacent Zn sites in Cu-ZnO nanoparticles show remarkable catalytic activity and chemisorption for iodine species, respectively. Hence, the obtained Zn-I2 batteries exhibit an ultra-low polarization voltage of 26.7 mV (1 A g-1) and endure an ultra-long cycle life over 40 000 cycles at 5 A g-1. Notably, the batteries maintain over 5000 cycles with a capacity degradation rate of barely 0.007% per cycle at 60 °C, while the capacity decline is 20.8 mAh g-1 under -20 °C (vs. 25 °C), as well as over 1150 cycles at a negative/positive (N/P) ratio of 2.5. Overall, high-performance Zn-I2 batteries under harsh conditions through the diffusion-retarded strategy provide valuable guidance for rational cathode designs toward practical Zn-I2 battery systems.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"17 1","pages":"e15756"},"PeriodicalIF":16.6,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145696763","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}
Zhijian Liu, Yan Liu, Yuqi Zhang, Yeyu Deng, Zhong Zheng, Ruth Knibbe, Tianxiang Gao, Mingzhe Li, Ziye Wang, Bingqian Zhang, Xue Jia, Di Zhang, Heng Liu, Xuqiang Shao, Zhengyang Gao, Li Wei, Hao Li, Weijie Yang
A universal design framework for high-performance catalysts remains challenging due to diverse structures and active sites. We developed a framework integrating weighted atom-centered symmetry function (wACSF) descriptors with machine learning, microkinetic modeling, and high-throughput screening. The wACSF descriptors unify geometric and chemical characteristics of active sites across different catalyst families. ML models trained on wACSF accurately predicted adsorption free energies of hydroxyl (ΔGOH*, R2 = 0.84) and oxygen (ΔGO*, R2 = 0.91) for intermetallic alloys, metal oxides, perovskites, and single-atom catalysts in the two-electron water oxidation reaction (2e− WOR). Density functional theory and microkinetic modeling yielded a universal 2e− WOR volcano model that agreed well with experiments. High-throughput screening with ML-predicted ΔGOH* identified LiScO2, which achieved 90% H2O2 Faradaic efficiency at 2.2 V vs. reversible hydrogen electrode (RHE) with 168-hour stability (82%–86% retention). Experimental activity (log(j) = 1.56) matched theoretical predictions (log(j) = 1.28) within 5% deviation at 2.4 V_RHE. This universal framework provides a general paradigm for rational catalyst design and is implemented in the Digital Catalysis Platform (DigCat), enabling efficient discovery across diverse material classes and electrochemical reactions.
{"title":"Universal Catalyst Design Framework for Electrochemical Hydrogen Peroxide Synthesis Facilitated by Local Atomic Environment Descriptors","authors":"Zhijian Liu, Yan Liu, Yuqi Zhang, Yeyu Deng, Zhong Zheng, Ruth Knibbe, Tianxiang Gao, Mingzhe Li, Ziye Wang, Bingqian Zhang, Xue Jia, Di Zhang, Heng Liu, Xuqiang Shao, Zhengyang Gao, Li Wei, Hao Li, Weijie Yang","doi":"10.1002/anie.202518027","DOIUrl":"https://doi.org/10.1002/anie.202518027","url":null,"abstract":"A universal design framework for high-performance catalysts remains challenging due to diverse structures and active sites. We developed a framework integrating weighted atom-centered symmetry function (wACSF) descriptors with machine learning, microkinetic modeling, and high-throughput screening. The wACSF descriptors unify geometric and chemical characteristics of active sites across different catalyst families. ML models trained on wACSF accurately predicted adsorption free energies of hydroxyl (ΔG<sub>OH</sub><sub>*</sub>, R<sup>2</sup> = 0.84) and oxygen (ΔG<sub>O*</sub>, R<sup>2</sup> = 0.91) for intermetallic alloys, metal oxides, perovskites, and single-atom catalysts in the two-electron water oxidation reaction (2e<sup>−</sup> WOR). Density functional theory and microkinetic modeling yielded a universal 2e<sup>−</sup> WOR volcano model that agreed well with experiments. High-throughput screening with ML-predicted ΔG<sub>OH*</sub> identified LiScO<sub>2</sub>, which achieved 90% H<sub>2</sub>O<sub>2</sub> Faradaic efficiency at 2.2 V vs. reversible hydrogen electrode (RHE) with 168-hour stability (82%–86% retention). Experimental activity (log(<i>j</i>) = 1.56) matched theoretical predictions (log(<i>j</i>) = 1.28) within 5% deviation at 2.4 V_RHE. This universal framework provides a general paradigm for rational catalyst design and is implemented in the Digital Catalysis Platform (<i>DigCat</i>), enabling efficient discovery across diverse material classes and electrochemical reactions.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"3 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145697090","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}
Pub Date : 2025-12-08DOI: 10.1002/anie.2025-m1711050300
Achieving specific interactions of metal-oxo clusters with biological substrates becomes possible through organic functionalization. The illustration depicts a dartboard that symbolizes the enzyme's active site as the molecular target. The darts represent clusters bearing distinct organic functionalities, designed to enable selective interactions with the protein surface. This concept highlights the potential of molecular design strategies to achieve precise bioinorganic recognition. More in the Communication (e202518349) by Mhamad Aly Moussawi, Tatjana N. Parac-Vogt, and co-workers.
通过有机功能化实现金属氧簇与生物底物的特定相互作用成为可能。该图描绘了一个飞镖靶，象征着酶的活性位点作为分子靶标。这些飞镖代表了具有不同有机功能的簇，旨在与蛋白质表面进行选择性相互作用。这一概念强调了分子设计策略实现精确生物无机识别的潜力。通讯中的更多内容（e202518349），作者：mohammad Aly Moussawi， Tatjana N. Parac-Vogt及其同事。
{"title":"Frontispiece: Finding the Key: Binding of Metal-Oxo Clusters to the Enzyme Active Site Enabled by “Click” (Bio)Conjugation","authors":"","doi":"10.1002/anie.2025-m1711050300","DOIUrl":"10.1002/anie.2025-m1711050300","url":null,"abstract":"<p>Achieving specific interactions of metal-oxo clusters with biological substrates becomes possible through organic functionalization. The illustration depicts a dartboard that symbolizes the enzyme's active site as the molecular target. The darts represent clusters bearing distinct organic functionalities, designed to enable selective interactions with the protein surface. This concept highlights the potential of molecular design strategies to achieve precise bioinorganic recognition. More in the Communication (e202518349) by Mhamad Aly Moussawi, Tatjana N. Parac-Vogt, and co-workers.\u0000\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure></p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"64 50","pages":""},"PeriodicalIF":16.9,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/anie.2025-m1711050300","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145697264","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yongqi Sun,Gui Chu,Xiaobo Zhu,Tobias U Schulli,Tongen Lin,Desheng Feng,Xiaodong Ma,Lianzhou Wang
Oxygen vacancies (OVs) play a critical role in tuning the properties of oxides, yet their rational control remains challenging. We present a meticulous engineering approach to modulate OVs in lithium-rich layered oxides (LRLOs), a promising cathode material for next-generation lithium-ion batteries. Guided by a Mn-O2 binary phase diagram, our method achieves accurate and broad tuning of the oxygen partial pressure (PO2) during calcination using a pyrometallurgical CO/CO2 gas pair. Using an ultra-high-Mn LRLO model, we quantify a thermodynamic equilibrium between OV concentration and a wide PO2 range (10-0.7-10-10.0 atm). Structural characterizations reveal progressive lattice expansion and an unprecedented enhancement of Li@Mn6 superstructures. An optimized LRLO with 3.8 mol % OVs shows a sixfold improvement in initial discharge capacity (175.9 mAh g-1) over a reference sample (28.5 mAh g-1) at 0.1C, achieving a maximum capacity of 287.9 mAh g-1. Theoretical calculations clarify the role of OVs in modifying the electronic structure of LRLOs, which enables ideal conditioning for facile and reversible anion redox. This study provides a generalizable and facile strategy for OV engineering, which accelerates the commercial viability of LRLOs and offers a new framework for the rational design of other modern materials.
氧空位（OVs）在调整氧化物的性质方面起着至关重要的作用，但其合理控制仍然具有挑战性。我们提出了一种精细的工程方法来调制富锂层状氧化物（LRLOs）中的OVs， LRLOs是下一代锂离子电池的一种有前途的正极材料。在Mn-O2二元相图的指导下，我们的方法在使用火法CO/CO2气体对煅烧过程中实现了精确和广泛的氧分压（PO2）调节。使用超高mn LRLO模型，我们量化了OV浓度与PO2范围（10-0.7-10-10.0 atm）之间的热力学平衡。结构表征揭示了渐进式晶格膨胀和Li@Mn6上部结构的前所未有的增强。优化后的电压比为3.8 mol %的LRLO在0.1C时的初始放电容量（175.9 mAh g-1）比参考样品（28.5 mAh g-1）提高了6倍，达到了287.9 mAh g-1的最大容量。理论计算阐明了OVs在改变LRLOs电子结构中的作用，从而为容易和可逆的阴离子氧化还原提供了理想的条件。该研究为OV工程提供了一种可推广和便捷的策略，加速了LRLOs的商业可行性，并为其他现代材料的合理设计提供了新的框架。
{"title":"Thermodynamic Control of Oxygen Vacancies for Li-Rich Cathode Materials.","authors":"Yongqi Sun,Gui Chu,Xiaobo Zhu,Tobias U Schulli,Tongen Lin,Desheng Feng,Xiaodong Ma,Lianzhou Wang","doi":"10.1002/anie.202518127","DOIUrl":"https://doi.org/10.1002/anie.202518127","url":null,"abstract":"Oxygen vacancies (OVs) play a critical role in tuning the properties of oxides, yet their rational control remains challenging. We present a meticulous engineering approach to modulate OVs in lithium-rich layered oxides (LRLOs), a promising cathode material for next-generation lithium-ion batteries. Guided by a Mn-O2 binary phase diagram, our method achieves accurate and broad tuning of the oxygen partial pressure (PO2) during calcination using a pyrometallurgical CO/CO2 gas pair. Using an ultra-high-Mn LRLO model, we quantify a thermodynamic equilibrium between OV concentration and a wide PO2 range (10-0.7-10-10.0 atm). Structural characterizations reveal progressive lattice expansion and an unprecedented enhancement of Li@Mn6 superstructures. An optimized LRLO with 3.8 mol % OVs shows a sixfold improvement in initial discharge capacity (175.9 mAh g-1) over a reference sample (28.5 mAh g-1) at 0.1C, achieving a maximum capacity of 287.9 mAh g-1. Theoretical calculations clarify the role of OVs in modifying the electronic structure of LRLOs, which enables ideal conditioning for facile and reversible anion redox. This study provides a generalizable and facile strategy for OV engineering, which accelerates the commercial viability of LRLOs and offers a new framework for the rational design of other modern materials.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"3 1","pages":"e18127"},"PeriodicalIF":16.6,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145696726","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}
Qian Zheng,Zehua Liu,Yuandong Yan,Shicheng Yan,Zhigang Zou
Although cobalt-based materials are promising catalysts for electrochemical nitrate-to-ammonia reduction, achieving stable operation at high current densities remains challenging due to significant overpotential issues. To address this, we engineered a CoOOH/(CoxSn1- x)3O4 assembly to stabilize low-spin Co3+ (t2 g 6eg 0) active centers, enabling highly durable performance under high current density operation. Sn doping in the underlying (CoxSn1- x)3O4 strengthens the stability of Co3+ within the CoOOH catalytic layer by inducing an interfacial electric field at the CoOOH/(CoxSn1- x)3O4 junction. This field promotes electron transfer from Co3+ species in CoOOH to (CoxSn1- x)3O4, thereby stabilizing the critical Co3+ active centers during high-current operation. The enhanced interfacial electric field arises from the higher electronegativity of Sn4+ (1.706) compared to Co3+ (1.693). Consequently, the CoOOH/(CoxSn1- x)3O4 catalyst achieves a remarkable Faradaic efficiency of 96.7% for NH4 + generation at -0.3 V versus RHE (110 mA cm-2) and demonstrates exceptional long-term stability for 1000 h at 100 mA cm-2. This work demonstrates that creating an interface electric field is an efficient strategy to stabilize electroreduction active centers at high currents.
虽然钴基材料是很有前途的电化学硝酸还原制氨催化剂，但由于严重的过电位问题，在高电流密度下实现稳定运行仍然具有挑战性。为了解决这个问题，我们设计了CoOOH/(CoxSn1- x)3O4组件来稳定低自旋Co3+ (t2 g 6eg 0)活性中心，从而在高电流密度操作下实现高度耐用的性能。在CoOOH/(CoxSn1- x)3O4中掺杂Sn，通过在CoOOH/(CoxSn1- x)3O4结处产生界面电场，增强了CoOOH催化层内Co3+的稳定性。该电场促进CoOOH中的Co3+电子向（CoxSn1- x）3O4转移，从而在大电流运行时稳定临界Co3+活性中心。Sn4+的电负性（1.706）高于Co3+(1.693)，导致界面电场增强。因此，与RHE （110 mA cm-2）相比，CoOOH/(CoxSn1- x)3O4催化剂在-0.3 V下产生NH4 +的法拉第效率达到了96.7%，并且在100 mA cm-2下表现出了1000小时的长期稳定性。这项工作表明，在大电流下，创建界面电场是稳定电还原活性中心的有效策略。
{"title":"Unlocking Durable and Efficient Nitrate-to-Ammonia Electrocatalysis via Interface-Stabilized Trivalent Cobalt.","authors":"Qian Zheng,Zehua Liu,Yuandong Yan,Shicheng Yan,Zhigang Zou","doi":"10.1002/anie.202522042","DOIUrl":"https://doi.org/10.1002/anie.202522042","url":null,"abstract":"Although cobalt-based materials are promising catalysts for electrochemical nitrate-to-ammonia reduction, achieving stable operation at high current densities remains challenging due to significant overpotential issues. To address this, we engineered a CoOOH/(CoxSn1- x)3O4 assembly to stabilize low-spin Co3+ (t2 g 6eg 0) active centers, enabling highly durable performance under high current density operation. Sn doping in the underlying (CoxSn1- x)3O4 strengthens the stability of Co3+ within the CoOOH catalytic layer by inducing an interfacial electric field at the CoOOH/(CoxSn1- x)3O4 junction. This field promotes electron transfer from Co3+ species in CoOOH to (CoxSn1- x)3O4, thereby stabilizing the critical Co3+ active centers during high-current operation. The enhanced interfacial electric field arises from the higher electronegativity of Sn4+ (1.706) compared to Co3+ (1.693). Consequently, the CoOOH/(CoxSn1- x)3O4 catalyst achieves a remarkable Faradaic efficiency of 96.7% for NH4 + generation at -0.3 V versus RHE (110 mA cm-2) and demonstrates exceptional long-term stability for 1000 h at 100 mA cm-2. This work demonstrates that creating an interface electric field is an efficient strategy to stabilize electroreduction active centers at high currents.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"22 1","pages":"e22042"},"PeriodicalIF":16.6,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145696761","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}
Yangze Xu,Futong Liu,Yixuan Jiang,Zihan Su,Xiaobo Ma,Yin Hu,Ping Lu
Highly efficient circularly polarized luminescence (CPL) emitters with narrowband emission are promising for ultra-high-definition (UHD) and three-dimensional (3D) displays. Herein, we put forward an "asymmetric spiro-carbon-locking architecture" strategy to construct chiral multiple resonance thermally activated delayed fluorescence (MR-TADF) emitters. Two pairs of enantiomers, (R/S)-BN-FLCz and (R/S)-BN-FLTPA, are successfully achieved, which show high photoluminescence quantum yields exceeding 95%, narrow full-width at half-maximums (FWHMs) of 24-26 nm (0.11-0.12 eV) and 26-27 nm (0.12 eV) in films over a wide range of dopant concentrations (1-30 wt%), and obvious mirror-image CPL properties in both solution and film states. As a result, the sensitizer-free organic light-emitting diodes (OLEDs) based on BN-FLCz and BN-FLTPA exhibit pure green emission with the FWHMs of 26 nm (0.12 eV) and 27 nm (0.13 eV), Commission International de l'Eclairage (CIE) coordinates of (0.16, 0.72) and (0.18, 0.73), and the record-breaking maximum external quantum efficiencies (EQEmaxs) of 37.9% and 39.8%, respectively. Even at the high doping concentration of 30 wt%, the EQEmaxs for BN-FLCz and BN-FLTPA remain at 35.5% and 36.6% without sacrificing the color fidelity. Furthermore, the circularly polarized organic light-emitting diodes (CP-OLEDs) with (R/S)-BN-FLCz and (R/S)-BN-FLTPA displayed clear circularly polarized electroluminescence (CPEL) signals with electroluminescence dissymmetry factors (gEL) of +0.85/-1.19 × 10-3 and +0.84/-1.22 × 10-3, respectively.
{"title":"Circularly Polarized MR-TADF Emitters with an Asymmetric Spiro-Carbon-Locking Architecture for Concentration-Quenching-Resistant Narrowband Circularly Polarized Electroluminescence.","authors":"Yangze Xu,Futong Liu,Yixuan Jiang,Zihan Su,Xiaobo Ma,Yin Hu,Ping Lu","doi":"10.1002/anie.202522906","DOIUrl":"https://doi.org/10.1002/anie.202522906","url":null,"abstract":"Highly efficient circularly polarized luminescence (CPL) emitters with narrowband emission are promising for ultra-high-definition (UHD) and three-dimensional (3D) displays. Herein, we put forward an \"asymmetric spiro-carbon-locking architecture\" strategy to construct chiral multiple resonance thermally activated delayed fluorescence (MR-TADF) emitters. Two pairs of enantiomers, (R/S)-BN-FLCz and (R/S)-BN-FLTPA, are successfully achieved, which show high photoluminescence quantum yields exceeding 95%, narrow full-width at half-maximums (FWHMs) of 24-26 nm (0.11-0.12 eV) and 26-27 nm (0.12 eV) in films over a wide range of dopant concentrations (1-30 wt%), and obvious mirror-image CPL properties in both solution and film states. As a result, the sensitizer-free organic light-emitting diodes (OLEDs) based on BN-FLCz and BN-FLTPA exhibit pure green emission with the FWHMs of 26 nm (0.12 eV) and 27 nm (0.13 eV), Commission International de l'Eclairage (CIE) coordinates of (0.16, 0.72) and (0.18, 0.73), and the record-breaking maximum external quantum efficiencies (EQEmaxs) of 37.9% and 39.8%, respectively. Even at the high doping concentration of 30 wt%, the EQEmaxs for BN-FLCz and BN-FLTPA remain at 35.5% and 36.6% without sacrificing the color fidelity. Furthermore, the circularly polarized organic light-emitting diodes (CP-OLEDs) with (R/S)-BN-FLCz and (R/S)-BN-FLTPA displayed clear circularly polarized electroluminescence (CPEL) signals with electroluminescence dissymmetry factors (gEL) of +0.85/-1.19 × 10-3 and +0.84/-1.22 × 10-3, respectively.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"209 1","pages":"e22906"},"PeriodicalIF":16.6,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145696762","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}
Conductive metal-organic frameworks (c-MOFs), composed of metal nodes and redox-active ligands, have attracted growing interest due to the coexistence of porosity and charge transport. Notably, their electrical performance is closely related to the packing and ligand oxidation state within the framework, which has rarely been explored. Typical divalent metal nodes favor saturated intralayer square-planar coordination to ligands in a single oxidation state, thereby predetermining the framework topology. Here, we report a packing and topology control strategy, achieved by tuning the ligand oxidation state and grounded in lanthanides (e.g., Gd) versatile coordination chemistry. Diffuse reflectance spectroscopy and single-crystal transport measurements reveal that, at low temperature, coordination of Gd3+ with 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) in a lower mixed oxidation state (-4 and -5) yields a more ordered porous packing (Gd1.5HHTP) with superior electronic transport performance. In contrast, at elevated temperature, the ligand adopts a higher oxidation state (-3), and coordination with Gd3+ yields a densely packed structure with local coordination disorder (GdHHTP), resulting in a markedly reduced electrical conductivity. This study demonstrates ligand-oxidation-state tuning provides an effective strategy for the precise control of structural order and charge transport in c-MOFs, laying a theoretical foundation for the rational design of materials with tunable electronic properties.
{"title":"Packing Order Control in Conductive Metal-Organic Frameworks by Tuning Ligand Oxidation State.","authors":"Yunlong Fan,Bin Jiang,Zhenghan Zhang,Haoyang Zhang,Luming Yang,Tianyang Chen,Liu He,Yanjun Liu,Jinkun Guo,Tongyang Zhao,Ran Du,Cen Tang,Jian Li,Maojun Zheng,Jin-Hu Dou","doi":"10.1002/anie.202522424","DOIUrl":"https://doi.org/10.1002/anie.202522424","url":null,"abstract":"Conductive metal-organic frameworks (c-MOFs), composed of metal nodes and redox-active ligands, have attracted growing interest due to the coexistence of porosity and charge transport. Notably, their electrical performance is closely related to the packing and ligand oxidation state within the framework, which has rarely been explored. Typical divalent metal nodes favor saturated intralayer square-planar coordination to ligands in a single oxidation state, thereby predetermining the framework topology. Here, we report a packing and topology control strategy, achieved by tuning the ligand oxidation state and grounded in lanthanides (e.g., Gd) versatile coordination chemistry. Diffuse reflectance spectroscopy and single-crystal transport measurements reveal that, at low temperature, coordination of Gd3+ with 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) in a lower mixed oxidation state (-4 and -5) yields a more ordered porous packing (Gd1.5HHTP) with superior electronic transport performance. In contrast, at elevated temperature, the ligand adopts a higher oxidation state (-3), and coordination with Gd3+ yields a densely packed structure with local coordination disorder (GdHHTP), resulting in a markedly reduced electrical conductivity. This study demonstrates ligand-oxidation-state tuning provides an effective strategy for the precise control of structural order and charge transport in c-MOFs, laying a theoretical foundation for the rational design of materials with tunable electronic properties.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"44 1","pages":"e22424"},"PeriodicalIF":16.6,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145696698","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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