Deok-Ho Roh, Dayun Jung, James B. Gerken, Jesse J. Martinez, Eric Kazyak, Shannon S. Stahl
Direct recycling of lithium-ion battery cathodes offers considerable appeal over metallurgical approaches. Here, we demonstrate a mediated electrochemical method for direct regeneration of degraded LiFePO4 (LFP). The approach uses a redox mediator, iron propylenediamine tetraacetate, that undergoes electrochemical reduction and is circulated through an external reservoir, where it supplies the electrons needed to regenerate LFP in the presence of Li+ ions derived from LiOH oxidation. Rapid outer-sphere electron transfer is observed from the mediator to the degraded LFP material. This feature, together with good aqueous solubility of the mediator (0.3 M), supports current densities up to 100 mA/cm2, and this electrochemical recycling process is demonstrated on 100 g scale. 57Fe Mössbauer spectroscopy is used to monitor the correction of structural defects in the degraded LFP, providing the basis for regeneration of LFP that matches the electrochemical performance of pristine LFP.
{"title":"Redox-Mediated Electrochemical Regeneration of Spent LiFePO4 Battery Cathodes","authors":"Deok-Ho Roh, Dayun Jung, James B. Gerken, Jesse J. Martinez, Eric Kazyak, Shannon S. Stahl","doi":"10.1002/anie.202520213","DOIUrl":"https://doi.org/10.1002/anie.202520213","url":null,"abstract":"Direct recycling of lithium-ion battery cathodes offers considerable appeal over metallurgical approaches. Here, we demonstrate a mediated electrochemical method for direct regeneration of degraded LiFePO<sub>4</sub> (LFP). The approach uses a redox mediator, iron propylenediamine tetraacetate, that undergoes electrochemical reduction and is circulated through an external reservoir, where it supplies the electrons needed to regenerate LFP in the presence of Li<sup>+</sup> ions derived from LiOH oxidation. Rapid outer-sphere electron transfer is observed from the mediator to the degraded LFP material. This feature, together with good aqueous solubility of the mediator (0.3 M), supports current densities up to 100 mA/cm<sup>2</sup>, and this electrochemical recycling process is demonstrated on 100 g scale. <sup>57</sup>Fe Mössbauer spectroscopy is used to monitor the correction of structural defects in the degraded LFP, providing the basis for regeneration of LFP that matches the electrochemical performance of pristine LFP.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"1 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146341","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}
Bin Wang, Beining Guo, Muhammad Mamoor, Yueyue Kong, Lu Wang, Fengbo Wang, Zhongxin Jing, Guangmeng Qu, Xiyu He, Lingtong Kong, Pengtu Zhang, Liqiang Xu
Lithium–sulfur batteries, despite their high specific capacity, high theoretical energy density, environmental benignity, and low cost-related unique advantages, face critical challenges including polysulfide shuttling, sluggish redox kinetics, and uncontrolled lithium dendrite growth. Here, we propose a magnetic field cooperative regulation strategy that concurrently optimizes both sulfur cathode and lithium via spin engineering and magnetohydrodynamic (MHD) effects. Bilayer-hollow FeNi boride bipyramids (FeNi─B) with nanoreactor architectures were designed, in which an external magnetic field triggers 3d-orbital electron spin rearrangement. Simultaneously, the uniform distribution of ions and dendrite-free deposition were achieved by driving lithium-ion spiral convection through MHD effects. It is worth noting that the optimized cells exhibit exceptional cycling stability under extreme conditions (−40°C). Density functional theory and multiphysics simulations jointly reveal two mechanisms: Spin-polarization-enhanced adsorption energy for sulfur species and lithium protection via Lorentz-force-mediated ion transport. This work establishes a novel paradigm for designing magnetic field-responsive electrocatalysts and manipulating spin-orbit coupling, offering broad implications for multiphysical-field strategies in next-generation batteries.
{"title":"Constructing Wide-Temperature-Range Li–S Batteries Through Synergistic Boride Spin-Polarization Coupling Regulation and Magnetohydrodynamic Effects","authors":"Bin Wang, Beining Guo, Muhammad Mamoor, Yueyue Kong, Lu Wang, Fengbo Wang, Zhongxin Jing, Guangmeng Qu, Xiyu He, Lingtong Kong, Pengtu Zhang, Liqiang Xu","doi":"10.1002/anie.202519187","DOIUrl":"https://doi.org/10.1002/anie.202519187","url":null,"abstract":"Lithium–sulfur batteries, despite their high specific capacity, high theoretical energy density, environmental benignity, and low cost-related unique advantages, face critical challenges including polysulfide shuttling, sluggish redox kinetics, and uncontrolled lithium dendrite growth. Here, we propose a magnetic field cooperative regulation strategy that concurrently optimizes both sulfur cathode and lithium via spin engineering and magnetohydrodynamic (MHD) effects. Bilayer-hollow FeNi boride bipyramids (FeNi─B) with nanoreactor architectures were designed, in which an external magnetic field triggers 3d-orbital electron spin rearrangement. Simultaneously, the uniform distribution of ions and dendrite-free deposition were achieved by driving lithium-ion spiral convection through MHD effects. It is worth noting that the optimized cells exhibit exceptional cycling stability under extreme conditions (−40°C). Density functional theory and multiphysics simulations jointly reveal two mechanisms: Spin-polarization-enhanced adsorption energy for sulfur species and lithium protection via Lorentz-force-mediated ion transport. This work establishes a novel paradigm for designing magnetic field-responsive electrocatalysts and manipulating spin-orbit coupling, offering broad implications for multiphysical-field strategies in next-generation batteries.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"315 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146381","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}
Arushi Garg, Jordan Vigier, Hélène Lebel, Tatiana Besset
The quest for synthetic tools to achieve molecular complexity is of paramount importance. In recent years, strategies have been developed for the late-stage functionalization of molecules. Anomeric amides have emerged as valuable reagents in this active research area due to their broad range of synthetic applications, and they continue to draw growing interest from the scientific community. This minireview aims to discuss and highlight recent progress in using anomeric amides across a variety of synthetic transformations.
{"title":"Anomeric Amides: Valuable Reagents in Synthetic Organic Chemistry","authors":"Arushi Garg, Jordan Vigier, Hélène Lebel, Tatiana Besset","doi":"10.1002/anie.202525799","DOIUrl":"https://doi.org/10.1002/anie.202525799","url":null,"abstract":"The quest for synthetic tools to achieve molecular complexity is of paramount importance. In recent years, strategies have been developed for the late-stage functionalization of molecules. Anomeric amides have emerged as valuable reagents in this active research area due to their broad range of synthetic applications, and they continue to draw growing interest from the scientific community. This minireview aims to discuss and highlight recent progress in using anomeric amides across a variety of synthetic transformations.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"79 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146380","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}
Jia Wang, Dongxian Li, Zedong Zhang, Zechao Zhuang, Jiarui Yang, Shule Wang, Tao Gan, Dingsheng Wang, Jianchun Jiang
Cyclohexanol is a key intermediate for nylon manufacture, yet its industrial synthesis relies on partial oxidation of cyclohexane at ∼2 MPa with <5% single-pass conversion, an energetically wasteful and atom-inefficient process that demands extensive recycle and generates substantial emissions. Here, we introduce an oxygen-atom-efficient synthetic strategy that transforms polycarbonate (PC) waste directly into cyclohexanol through a non-oxidative catalytic route. The method leverages the intrinsic oxygen functionality of the polymer as a built-in source of hydroxyl groups, thereby eliminating the conventional oxidation step. A RuLa dual-atom (RuLa-DA) catalyst anchored on CoAl oxide enables cooperative hydrogen activation and spillover through moderated Ru–H binding, driving selective aromatic-ring hydrogenation under mild gas-phase conditions. Operating at 0.25 MPa and a 4.2 s residence time, the tandem hydropyrolysis–hydrogenation process affords a 69.9% yield and 95.4% selectivity for cyclohexanol, maintaining >95% selectivity for post-consumer PC over 100 feed cycles. Life-cycle and techno-economic analyses indicate the potential environmental and economic advantages, showing a 35% cost reduction and a threefold lower carbon footprint relative to the fossil route. This oxygen-retentive hydrogenation paradigm establishes a general approach for valorizing oxygen-rich substrates and suggests a conceptually viable pathway toward atom-economical synthesis and circular chemical manufacturing.
{"title":"Selective Upcycling of Polycarbonate Waste to Cyclohexanol via RuLa Dual-Atom Catalysis","authors":"Jia Wang, Dongxian Li, Zedong Zhang, Zechao Zhuang, Jiarui Yang, Shule Wang, Tao Gan, Dingsheng Wang, Jianchun Jiang","doi":"10.1002/anie.202524681","DOIUrl":"https://doi.org/10.1002/anie.202524681","url":null,"abstract":"Cyclohexanol is a key intermediate for nylon manufacture, yet its industrial synthesis relies on partial oxidation of cyclohexane at ∼2 MPa with <5% single-pass conversion, an energetically wasteful and atom-inefficient process that demands extensive recycle and generates substantial emissions. Here, we introduce an oxygen-atom-efficient synthetic strategy that transforms polycarbonate (PC) waste directly into cyclohexanol through a non-oxidative catalytic route. The method leverages the intrinsic oxygen functionality of the polymer as a built-in source of hydroxyl groups, thereby eliminating the conventional oxidation step. A RuLa dual-atom (RuLa-DA) catalyst anchored on CoAl oxide enables cooperative hydrogen activation and spillover through moderated Ru–H binding, driving selective aromatic-ring hydrogenation under mild gas-phase conditions. Operating at 0.25 MPa and a 4.2 s residence time, the tandem hydropyrolysis–hydrogenation process affords a 69.9% yield and 95.4% selectivity for cyclohexanol, maintaining >95% selectivity for post-consumer PC over 100 feed cycles. Life-cycle and techno-economic analyses indicate the potential environmental and economic advantages, showing a 35% cost reduction and a threefold lower carbon footprint relative to the fossil route. This oxygen-retentive hydrogenation paradigm establishes a general approach for valorizing oxygen-rich substrates and suggests a conceptually viable pathway toward atom-economical synthesis and circular chemical manufacturing.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"247 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146379","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}
Yinlong Chang, Weiqiang Gao, Sen Wang, Bangban Zhu, Kexuan Zhao, Jijiang Hu, Khak Ho Lim, Pingwei Liu, Wen-Jun Wang, Bo-Geng Li, Qingyue Wang
Noncatalytic polyolefin upcycling offers distinct advantages in eliminating catalyst costs and enhancing operational stability, yet it remains highly challenging under mild conditions. Herein, we develop an aqua-oxidation strategy that converts polyethylene into carboxylic acids at 160°C without using any catalysts or organic solvents. The mass yield of carboxylic acid is up to 97.8 wt%, of which 72.1% is comprised by C4–C10 dicarboxylic acids. The roles of H2O and O2 play in aqua-oxidation were further investigated in an in situ liquid-phase spectroscopic reactor filled with isotope-labeled D2O. It reveals that O2 governs the effective initiation and oxidation of polyethylene. Whereas H2O serves as a key medium to intensify oxygen–polyethylene interaction uniformly and inhibit localized oxidation, promoting selective upcycling to narrow-distributed acids. Moreover, this strategy allows for upcycling diverse commercial polyolefins with additives. This study presents a breakthrough in the noncatalytic upcycling of polyolefins under mild conditions and demonstrates the potential of this eco-friendly and streamlined strategy for advancing plastic circularity.
{"title":"Aqua-Oxidation of Polyethylene Into Carboxylic Acids Under Mild Conditions: A Catalyst-Free Upcycling Strategy for Nonpolar Plastics","authors":"Yinlong Chang, Weiqiang Gao, Sen Wang, Bangban Zhu, Kexuan Zhao, Jijiang Hu, Khak Ho Lim, Pingwei Liu, Wen-Jun Wang, Bo-Geng Li, Qingyue Wang","doi":"10.1002/anie.202523067","DOIUrl":"https://doi.org/10.1002/anie.202523067","url":null,"abstract":"Noncatalytic polyolefin upcycling offers distinct advantages in eliminating catalyst costs and enhancing operational stability, yet it remains highly challenging under mild conditions. Herein, we develop an aqua-oxidation strategy that converts polyethylene into carboxylic acids at 160°C without using any catalysts or organic solvents. The mass yield of carboxylic acid is up to 97.8 wt%, of which 72.1% is comprised by C<sub>4</sub>–C<sub>10</sub> dicarboxylic acids. The roles of H<sub>2</sub>O and O<sub>2</sub> play in aqua-oxidation were further investigated in an in situ liquid-phase spectroscopic reactor filled with isotope-labeled D<sub>2</sub>O. It reveals that O<sub>2</sub> governs the effective initiation and oxidation of polyethylene. Whereas H<sub>2</sub>O serves as a key medium to intensify oxygen–polyethylene interaction uniformly and inhibit localized oxidation, promoting selective upcycling to narrow-distributed acids. Moreover, this strategy allows for upcycling diverse commercial polyolefins with additives. This study presents a breakthrough in the noncatalytic upcycling of polyolefins under mild conditions and demonstrates the potential of this eco-friendly and streamlined strategy for advancing plastic circularity.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"51 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146544","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}
Lijun Wang, Jiabiao Yan, Kai Shi, Bingji Huang, Lisong Chen, Jianlin Shi
The development of active electrocatalysts for converting biomass-derived aromatic alcohols into value-added acids is of great significance. Ni(OH)2 has been employed as a cost-effective catalyst, unfortunately, suffering from rather low catalytic activity due to the considerable energy barrier to transform into active NiOOH and the weak interaction with reactants. To address these limitations, a novel “product ligand-modification” (PLM) strategy has been proposed here simply by adopting the target molecule ligands as modification units, which simultaneously facilitates the Ni(II)/Ni(III) redox kinetics and significantly enriches reactants at the catalytic surface via profound π-π stacking interaction. The PLM strategy has been demonstrated to exhibit exceptionally high performance in electro-oxidizing aromatic alcohols into corresponding acids across various product ligand-Ni(OH)2 (PL-Ni(OH)2) catalysts. As a typical paradigm, the aromatic ligand FDCA-modified Ni(OH)2 catalyst (termed FDCA-Ni(OH)2) demonstrates significantly enhanced BHMF electrocatalytic oxidation activity, featuring a BHMF conversion rate of >99.4%, FDCA selectivity and yield of 99.2% and 98.6%, and Faradaic efficiency of 99.0%. Furthermore, FDCA-Ni(OH)2 features an excellent stability for over 250 h in a flow electrolyzer to produce FDCA with a >99.0% purity. This PLM strategy offers valuable insights into the performance enhancement of Ni(OH)2 catalyst for the targeted conversion of aromatic reactants.
开发活性电催化剂将生物质衍生的芳香醇转化为增值酸具有重要意义。Ni(OH)2是一种经济高效的催化剂，但由于转化为活性NiOOH的能量障碍较大，与反应物的相互作用较弱，因此其催化活性较低。为了解决这些限制，本文提出了一种新的“产物配体修饰”（PLM）策略，该策略简单地采用目标分子配体作为修饰单元，同时促进Ni(II)/Ni（III）氧化还原动力学，并通过深刻的π-π堆叠相互作用显著富集催化表面的反应物。PLM策略已被证明在不同的产物配体ni (OH)2 （PL-Ni(OH)2）催化剂上电氧化芳香族醇成相应的酸时表现出异常高的性能。作为典型范例，芳香族配体FDCA修饰的Ni(OH)2催化剂（称为FDCA-Ni(OH)2）具有显著增强的BHMF电催化氧化活性，BHMF转化率为99.4%，FDCA选择性和产率分别为99.2%和98.6%，法拉第效率为99.0%。此外，FDCA- ni (OH)2在流动电解槽中具有250小时以上的优异稳定性，可生产纯度为99.0%的FDCA。该PLM策略为提高Ni(OH)2催化剂的性能提供了有价值的见解，用于芳香反应物的靶向转化。
{"title":"Product Ligand-Modification on Ni(OH)2 for Boosted Electrocatalytic Oxidation of Aromatic Alcohols","authors":"Lijun Wang, Jiabiao Yan, Kai Shi, Bingji Huang, Lisong Chen, Jianlin Shi","doi":"10.1002/anie.202525813","DOIUrl":"https://doi.org/10.1002/anie.202525813","url":null,"abstract":"The development of active electrocatalysts for converting biomass-derived aromatic alcohols into value-added acids is of great significance. Ni(OH)<sub>2</sub> has been employed as a cost-effective catalyst, unfortunately, suffering from rather low catalytic activity due to the considerable energy barrier to transform into active NiOOH and the weak interaction with reactants. To address these limitations, a novel “product ligand-modification” (PLM) strategy has been proposed here simply by adopting the target molecule ligands as modification units, which simultaneously facilitates the Ni(II)/Ni(III) redox kinetics and significantly enriches reactants at the catalytic surface via profound π-π stacking interaction. The PLM strategy has been demonstrated to exhibit exceptionally high performance in electro-oxidizing aromatic alcohols into corresponding acids across various product ligand-Ni(OH)<sub>2</sub> (PL-Ni(OH)<sub>2</sub>) catalysts. As a typical paradigm, the aromatic ligand FDCA-modified Ni(OH)<sub>2</sub> catalyst (termed FDCA-Ni(OH)<sub>2</sub>) demonstrates significantly enhanced BHMF electrocatalytic oxidation activity, featuring a BHMF conversion rate of >99.4%, FDCA selectivity and yield of 99.2% and 98.6%, and Faradaic efficiency of 99.0%. Furthermore, FDCA-Ni(OH)<sub>2</sub> features an excellent stability for over 250 h in a flow electrolyzer to produce FDCA with a >99.0% purity. This PLM strategy offers valuable insights into the performance enhancement of Ni(OH)<sub>2</sub> catalyst for the targeted conversion of aromatic reactants.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"34 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146417","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}
Unraveling the mechanism of O─O bond formation on metal-oxo is critical yet remains a central challenge in electrocatalytic water oxidation. Herein, we show the pH-independent O─O bond formation pathway in edge-shared dual [MnO6] motifs. By manipulating the atomic-scale connectivity of [MnO6] units, two structurally well-defined sodium manganese pyrophosphate compounds with edge-sharing (Mn-edge) and corner-sharing (Mn-corner) [MnO6] octahedral configurations were synthesized with similar chemical composition and morphology, except that the Mn ∼ Mn distance in Mn-edge is significantly shorter than that in Mn-corner. Electrochemical and spectroscopic analyses reveal that Mn-edge exhibits an unprecedented pH-independent evolution of O2. Isotope-labeling experiments and in situ Raman spectroscopy identify a direct coupling mechanism between Mn−O species in Mn-edge, bypassing the conventional nucleophilic water attack. Density functional theory calculations further support that Mn-oxo coupling between asymmetric MnVI ∼ MnV centers drastically reduces the energy barrier for O─O bond formation. These findings establish the connectivity of [MnO6] as a critical descriptor for water oxidation mechanism and offer a new design strategy for efficient catalysts inspired by natural oxygen-evolving complexes.
{"title":"Discovering the pH-independent Oxygen–Oxygen Formation via Direct Mn-oxo Coupling","authors":"Shujiao Yang, Hongyu Liang, Kaihang Yue, Xiaohan Liu, Zhiyuan Yin, Haonan Qin, Sisi Li, Yujia Fan, Haoquan Zheng, Xue-Peng Zhang, Rui Cao, Ya Yan, Shuangyin Wang, Wei Zhang","doi":"10.1002/anie.202524172","DOIUrl":"https://doi.org/10.1002/anie.202524172","url":null,"abstract":"Unraveling the mechanism of O─O bond formation on metal-oxo is critical yet remains a central challenge in electrocatalytic water oxidation. Herein, we show the pH-independent O─O bond formation pathway in edge-shared dual [MnO<sub>6</sub>] motifs. By manipulating the atomic-scale connectivity of [MnO<sub>6</sub>] units, two structurally well-defined sodium manganese pyrophosphate compounds with edge-sharing (Mn-edge) and corner-sharing (Mn-corner) [MnO<sub>6</sub>] octahedral configurations were synthesized with similar chemical composition and morphology, except that the Mn ∼ Mn distance in Mn-edge is significantly shorter than that in Mn-corner. Electrochemical and spectroscopic analyses reveal that Mn-edge exhibits an unprecedented pH-independent evolution of O<sub>2</sub>. Isotope-labeling experiments and in situ Raman spectroscopy identify a direct coupling mechanism between Mn−O species in Mn-edge, bypassing the conventional nucleophilic water attack. Density functional theory calculations further support that Mn-oxo coupling between asymmetric Mn<sup>VI</sup> ∼ Mn<sup>V</sup> centers drastically reduces the energy barrier for O─O bond formation. These findings establish the connectivity of [MnO<sub>6</sub>] as a critical descriptor for water oxidation mechanism and offer a new design strategy for efficient catalysts inspired by natural oxygen-evolving complexes.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"59 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146413","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}
Understanding the basis of product selectivity is a central issue in catalyst design. Catalytic nitrogen reduction (N2R) provides a salient example; whereas ammonia (NH3) is the common product of N2R, hydrazine (N2H4) is produced under certain conditions. Using mechanism-guided design, we report a strategy for tuning redox potential that enables selective reduction of dinitrogen to hydrazine by iron complexes in polar protic media. Incorporation of cationic trimethylammonium (NMe3+) or proton-responsive dimethylamino (NMe2) groups into a tris(phosphino)borane (P3B) ligand framework affords redox-tunable iron precatalysts that operate efficiently in methanol. Computational analyses reveal that these ligand modifications anodically shift the reduction potential of an iron hydrazido (Fe═NNH2) intermediate by >400 mV, thereby influencing the key branch point for hydrazine versus ammonia. Critical to success is positioning the cationic charges remote from the Fe–N2 binding site to preserve the high degree of N2 activation required for functionalization. Newly prepared tricationic iron complexes, soluble and stable in polar protic media, catalyze N2R with N-fixed yields of up to 73% per reducing equivalent consumed, and with hydrazine selectivity exceeding 20:1 over ammonia. This work highlights the use of remote electrostatic effects to tune multi-electron catalytic product profiles from a 6e– to a 4e– product.
{"title":"Remote Positioning of Cations Tunes Catalytic Fe-Mediated Nitrogen Fixation Selectivity for Hydrazine Instead of Ammonia in Protic Media","authors":"Lucie Nurdin, Hoimin Jung, Jonas C. Peters","doi":"10.1002/anie.202524836","DOIUrl":"https://doi.org/10.1002/anie.202524836","url":null,"abstract":"Understanding the basis of product selectivity is a central issue in catalyst design. Catalytic nitrogen reduction (N<sub>2</sub>R) provides a salient example; whereas ammonia (NH<sub>3</sub>) is the common product of N<sub>2</sub>R, hydrazine (N<sub>2</sub>H<sub>4</sub>) is produced under certain conditions. Using mechanism-guided design, we report a strategy for tuning redox potential that enables selective reduction of dinitrogen to hydrazine by iron complexes in polar protic media. Incorporation of cationic trimethylammonium (NMe<sub>3</sub><sup>+</sup>) or proton-responsive dimethylamino (NMe<sub>2</sub>) groups into a tris(phosphino)borane (P<sub>3</sub><sup>B</sup>) ligand framework affords redox-tunable iron precatalysts that operate efficiently in methanol. Computational analyses reveal that these ligand modifications anodically shift the reduction potential of an iron hydrazido (Fe═NNH<sub>2</sub>) intermediate by >400 mV, thereby influencing the key branch point for hydrazine versus ammonia. Critical to success is positioning the cationic charges remote from the Fe–N<sub>2</sub> binding site to preserve the high degree of N<sub>2</sub> activation required for functionalization. Newly prepared tricationic iron complexes, soluble and stable in polar protic media, catalyze N<sub>2</sub>R with N-fixed yields of up to 73% per reducing equivalent consumed, and with hydrazine selectivity exceeding 20:1 over ammonia. This work highlights the use of remote electrostatic effects to tune multi-electron catalytic product profiles from a 6e<sup>–</sup> to a 4e<sup>–</sup> product.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"11 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146541","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}
Narrowband emissive polycyclic aromatic heterocycles (PAHs) featuring multiple resonance thermally-activated delayed fluorescence (MR-TADF) are capable of achieving high color purity with high exciton utilization efficiency via reverse intersystem crossing (RISC). However, thermally-activated RISC remains the rate-limiting step in MR-TADF molecules due to the typically large singlet and triplet energy gap (ΔEST) and weak spin-orbital coupling. To overcome this challenge, we introduce three carbonyl-containing organoboron PAHs doped with selenium atoms (pSeXBNO, 1pSeXBN, and pSeXBN) for the first time. Introducing single or dual selenium-embedded carbonyl heterocycles into the MR core enables significant orbital delocalization of carbonyls, resulting in small ΔEST and ultrafast RISC rates of 7.5 × 106 s−1 for pSeXBNO, 1.5 × 107 s−1 for 1pSeXBN, and 4.8 × 107 s−1 for pSeXBN. The non-sensitized OLED employing pSeXBN achieves an emission peak at 478 nm with a narrow bandwidth of 28 nm, along with a maximum external quantum efficiency (EQE) of 32.6% and retaining 28.4% at 1000 cd m−2, representing state-of-the-art performance for blue MR-TADF materials. Moreover, bi-color white OLED employing pSeXBN exhibits excellent performance with a maximum EQE of 30.9% and 23.2% retained at 1000 cd m−2. These advances demonstrate the role of carbonyl here is of significant guidance in forwarding narrowband blue materials.
具有多共振热激活延迟荧光（MR-TADF）特性的窄带发射多环芳香族杂环（PAHs）能够通过反向系统间交叉（RISC）获得高颜色纯度和高激子利用率。然而，热激活的RISC仍然是MR-TADF分子的速率限制步骤，这是由于典型的大单线态和三重态能隙（ΔEST）和弱自旋轨道耦合。为了克服这一挑战，我们首次引入了三种掺杂硒原子的含羰基有机硼多环芳烃（pSeXBNO， 1pSeXBN和pSeXBN）。在MR核中引入单或双嵌入硒的羰基杂环使得羰基的轨道离域显著，导致pSeXBNO的ΔEST和超快的RISC速率为7.5 × 106 s−1,1pSeXBN为1.5 × 107 s−1，pSeXBN为4.8 × 107 s−1。采用pSeXBN的非敏化OLED在478 nm处达到发射峰，窄带宽为28 nm，最大外量子效率（EQE）为32.6%，在1000 cd m−2时保持28.4%，代表了蓝色MR-TADF材料的最先进性能。此外，采用pSeXBN的双色白光OLED表现出优异的性能，最大EQE为30.9%，在1000 cd m−2时保持23.2%。这些进展表明羰基在这里的作用对窄带蓝色材料的制备具有重要的指导意义。
{"title":"The Important Role of Carbonyl in Accelerating Reverse Intersystem Crossing for Selenium-Based Organoboron Narrowband Blue Emitters","authors":"Zhihai Yang, Yuling Chen, Zijian Chen, Suyu Liao, Xinge Li, Sheng Liao, Denghui Liu, Guanwei Sun, Zhizhi Li, Simin Jiang, Juntao Hu, Yu Fu, Xuewei Nie, Guo-Xi Yang, Xiangyi Cheng, Tong Wang, Mengke Li, Ming-De Li, Junji Kido, Shi-Jian Su","doi":"10.1002/anie.5497802","DOIUrl":"https://doi.org/10.1002/anie.5497802","url":null,"abstract":"Narrowband emissive polycyclic aromatic heterocycles (PAHs) featuring multiple resonance thermally-activated delayed fluorescence (MR-TADF) are capable of achieving high color purity with high exciton utilization efficiency via reverse intersystem crossing (RISC). However, thermally-activated RISC remains the rate-limiting step in MR-TADF molecules due to the typically large singlet and triplet energy gap (Δ<i>E</i><sub>ST</sub>) and weak spin-orbital coupling. To overcome this challenge, we introduce three carbonyl-containing organoboron PAHs doped with selenium atoms (pSeXBNO, 1pSeXBN, and pSeXBN) for the first time. Introducing single or dual selenium-embedded carbonyl heterocycles into the MR core enables significant orbital delocalization of carbonyls, resulting in small Δ<i>E</i><sub>ST</sub> and ultrafast RISC rates of 7.5 × 10<sup>6</sup> s<sup>−1</sup> for pSeXBNO, 1.5 × 10<sup>7</sup> s<sup>−1</sup> for 1pSeXBN, and 4.8 × 10<sup>7</sup> s<sup>−1</sup> for pSeXBN. The non-sensitized OLED employing pSeXBN achieves an emission peak at 478 nm with a narrow bandwidth of 28 nm, along with a maximum external quantum efficiency (EQE) of 32.6% and retaining 28.4% at 1000 cd m<sup>−2</sup>, representing state-of-the-art performance for blue MR-TADF materials. Moreover, bi-color white OLED employing pSeXBN exhibits excellent performance with a maximum EQE of 30.9% and 23.2% retained at 1000 cd m<sup>−2</sup>. These advances demonstrate the role of carbonyl here is of significant guidance in forwarding narrowband blue materials.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"34 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146409","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}
p-Benzoyl-l-phenylalanine (pBzF) is a widely used noncanonical amino acid (ncAA) that expands the chemical repertoire of proteins. Its benzophenone (BP) chromophore undergoes near-quantitative intersystem crossing (ISC) to a triplet state, furnishing a highly efficient, site-addressable photoreactive handle. Beyond photochemistry, the bulky, hydrophobic side chain introduces distinct steric and electronic effects that enable new reactivity in protein active sites. Genetic incorporation of pBzF in vivo, including directed evolution, has unlocked applications ranging from site-specific photo-crosslinking for interaction mapping to engineering antibody fragments, sharpening monoclonal antibody (mAb) epitope recognition, and creating protein-based photocatalysts. pBzF has also proved powerful for mechanistic studies by stabilizing short-lived intermediates. More recently, pBzF-containing proteins have been leveraged in light-driven transformations, including [2+2] photocycloadditions, deracemizations, and dehalogenations, and in the construction of artificial photosynthetic systems. This review critically discusses these advances and establishes pBzF as a versatile photochemical and structural motif for building proteins with non-natural, light-responsive, and catalytically competent functions.
{"title":"p-Benzoyl-l-phenylalanine as a Multifunctional Noncanonical Amino Acid in Synthetic Biology: Photoprobing, Photocatalysis, and Structural Programming for Biocontainment","authors":"Surendar R. Jakka, Govindasamy Mugesh","doi":"10.1002/anie.202525502","DOIUrl":"https://doi.org/10.1002/anie.202525502","url":null,"abstract":"<i>p</i>-Benzoyl-<span>l</span>-phenylalanine (pBzF) is a widely used noncanonical amino acid (ncAA) that expands the chemical repertoire of proteins. Its benzophenone (BP) chromophore undergoes near-quantitative intersystem crossing (ISC) to a triplet state, furnishing a highly efficient, site-addressable photoreactive handle. Beyond photochemistry, the bulky, hydrophobic side chain introduces distinct steric and electronic effects that enable new reactivity in protein active sites. Genetic incorporation of pBzF in vivo, including directed evolution, has unlocked applications ranging from site-specific photo-crosslinking for interaction mapping to engineering antibody fragments, sharpening monoclonal antibody (mAb) epitope recognition, and creating protein-based photocatalysts. pBzF has also proved powerful for mechanistic studies by stabilizing short-lived intermediates. More recently, pBzF-containing proteins have been leveraged in light-driven transformations, including [2+2] photocycloadditions, deracemizations, and dehalogenations, and in the construction of artificial photosynthetic systems. This review critically discusses these advances and establishes pBzF as a versatile photochemical and structural motif for building proteins with non-natural, light-responsive, and catalytically competent functions.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"69 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146408","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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