This paper presents multipyridine-containing covalent organic frameworks (COFs) with precisely defined position and number of pyridinium cationic groups. Specifically, three terpyridine- and quarterpyridine-based trialdehydes were synthesized, and utilized as the starting monomers to polymerize with trimethylpyridinium bromide to yield vinylene-linked iTPy-COF, iTPPy-COF and iQPPy-COF, respectively. Thus constructed donor-acceptor cationic COFs exhibit considerably high light-visible catalytic efficiency for hydrogen peroxide (H2O2) synthesis by the dual-channel mechanisms of oxygen reduction reaction (ORR) and water oxidation reaction (WOR). In pure water and O2 atmosphere, the H2O2 production rate (HPR) of iTPPy-COF after 1 h reaction is as high as 7955 μmol g-1 h-1. Even though in air, its HPR value still reaches 6249 μmol g-1 h-1. Moreover, it is found that changing the arm lengths and ratios of pyridine to benzene ring in the frameworks significantly affects the photocatalytic capability. The structure-property relationship is investigated in terms of the variations of electronic structures through the theoretical simulations and measurements of photophysical parameters such as fluorescence lifetimes, photocurrent intensities, and impedances of charge transfer, which presents new insights into the engineering of multipyridine-based cationic COFs for highly efficient H2O2 photosynthesis.
{"title":"Terpyridine- and Quarterpyridine-Based Cationic Covalent Organic Frameworks for Visible-Light-Catalytic H2O2 Synthesis","authors":"Jun Zhang, Fei Xue, Zhonggang Wang","doi":"10.1002/anie.202425617","DOIUrl":"https://doi.org/10.1002/anie.202425617","url":null,"abstract":"This paper presents multipyridine-containing covalent organic frameworks (COFs) with precisely defined position and number of pyridinium cationic groups. Specifically, three terpyridine- and quarterpyridine-based trialdehydes were synthesized, and utilized as the starting monomers to polymerize with trimethylpyridinium bromide to yield vinylene-linked iTPy-COF, iTPPy-COF and iQPPy-COF, respectively. Thus constructed donor-acceptor cationic COFs exhibit considerably high light-visible catalytic efficiency for hydrogen peroxide (H2O2) synthesis by the dual-channel mechanisms of oxygen reduction reaction (ORR) and water oxidation reaction (WOR). In pure water and O2 atmosphere, the H2O2 production rate (HPR) of iTPPy-COF after 1 h reaction is as high as 7955 μmol g-1 h-1. Even though in air, its HPR value still reaches 6249 μmol g-1 h-1. Moreover, it is found that changing the arm lengths and ratios of pyridine to benzene ring in the frameworks significantly affects the photocatalytic capability. The structure-property relationship is investigated in terms of the variations of electronic structures through the theoretical simulations and measurements of photophysical parameters such as fluorescence lifetimes, photocurrent intensities, and impedances of charge transfer, which presents new insights into the engineering of multipyridine-based cationic COFs for highly efficient H2O2 photosynthesis.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"52 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435646","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}
Xie Zhang, Jimmy-Xuan Shen, Mark E Turiansky, Chris G Van de Walle
Toxicity remains one of the major challenges that prevent Pb-based halide perovskites from widespread utilization. Ideally, non-toxic alternatives can be identified while still maintaining the superior power conversion efficiency of the Pb-based perovskite solar cells. Using the currently most promising candidate, the Sn-based halide perovskites, as an example, we show that a trade-off exists between toxicity and efficiency in the Sn- versus Pb-based halide perovskites. Indeed, the dominant nonradiative recombination center in the Sn-based halide perovskites differs from the one in its Pb-based counterparts, resulting in the nonradiative capture coefficient in CsSnI3 being an order of magnitude higher than that in CsPbI3. We attribute this difference to the band alignment. Our results indicate that development of halide perovskites beyond the Pb and Sn bases is essential for efficient yet environmentally friendly perovskite solar cells.
{"title":"Trade-Off Between Toxicity and Efficiency in Tin versus Lead Based Halide Perovskites.","authors":"Xie Zhang, Jimmy-Xuan Shen, Mark E Turiansky, Chris G Van de Walle","doi":"10.1002/anie.202500557","DOIUrl":"https://doi.org/10.1002/anie.202500557","url":null,"abstract":"<p><p>Toxicity remains one of the major challenges that prevent Pb-based halide perovskites from widespread utilization. Ideally, non-toxic alternatives can be identified while still maintaining the superior power conversion efficiency of the Pb-based perovskite solar cells. Using the currently most promising candidate, the Sn-based halide perovskites, as an example, we show that a trade-off exists between toxicity and efficiency in the Sn- versus Pb-based halide perovskites. Indeed, the dominant nonradiative recombination center in the Sn-based halide perovskites differs from the one in its Pb-based counterparts, resulting in the nonradiative capture coefficient in CsSnI3 being an order of magnitude higher than that in CsPbI3. We attribute this difference to the band alignment. Our results indicate that development of halide perovskites beyond the Pb and Sn bases is essential for efficient yet environmentally friendly perovskite solar cells.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":" ","pages":"e202500557"},"PeriodicalIF":16.1,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143447790","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}
Cellulose derivatives represent a promising natural chiral platform for creating circularly polarized luminescence (CPL) materials owing to their excellent processability and structural diversity. However, achieving full‐color and white CPL emissions based on cellulose derivatives remains challenging. The present work reports the first success in achieving full‐color and white CPL emissions leveraging chirality transmission and amplification from cellulose derivative to achiral helical polymer. Importantly, such chirality transfer displays a dependence on the hydrogen bond accepting ability of solvent, making it effortless to precisely regulate chiral intensity by single or combined solvents. Moreover, the induced chirality in helical polymer is further transferred to the introduced racemic fluorescent dyes, resulting in full‐color and white‐light CPL emissions with a maximum luminescence dissymmetry factor (glum) and photoluminescence quantum yield (PLQY) up to 1.5×10−2 and 62.9%, respectively. Further spatially separating the chiral and fluorescent components allows inversion of CPL handedness and precise modulation of CPL intensity. Notably, circularly polarized white organic light‐emitting diodes and chiral logic gate with multiple information outputs are successfully developed. This work gives an impetus to construct cellulosic chiroptical materials, offering more insights into chirality transfer between biomacromolecules and synthetic helical polymers.
{"title":"Solvent‐Dependent Chirality Transmission and Amplification from Cellulose Derivative to Achiral Helical Polymer for Achieving Full‐Color and White Circularly Polarized Luminescence","authors":"Hai Zhong, Biao Zhao, Jianping Deng","doi":"10.1002/anie.202418463","DOIUrl":"https://doi.org/10.1002/anie.202418463","url":null,"abstract":"Cellulose derivatives represent a promising natural chiral platform for creating circularly polarized luminescence (CPL) materials owing to their excellent processability and structural diversity. However, achieving full‐color and white CPL emissions based on cellulose derivatives remains challenging. The present work reports the first success in achieving full‐color and white CPL emissions leveraging chirality transmission and amplification from cellulose derivative to achiral helical polymer. Importantly, such chirality transfer displays a dependence on the hydrogen bond accepting ability of solvent, making it effortless to precisely regulate chiral intensity by single or combined solvents. Moreover, the induced chirality in helical polymer is further transferred to the introduced racemic fluorescent dyes, resulting in full‐color and white‐light CPL emissions with a maximum luminescence dissymmetry factor (glum) and photoluminescence quantum yield (PLQY) up to 1.5×10−2 and 62.9%, respectively. Further spatially separating the chiral and fluorescent components allows inversion of CPL handedness and precise modulation of CPL intensity. Notably, circularly polarized white organic light‐emitting diodes and chiral logic gate with multiple information outputs are successfully developed. This work gives an impetus to construct cellulosic chiroptical materials, offering more insights into chirality transfer between biomacromolecules and synthetic helical polymers.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"49 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435464","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}
Classical aza-Reformatsky reaction generally involves excess reductants. Herein, we developed a visible light-induced catalytic asymmetric aza-Reformatsky reaction via a chiral Lewis acid-assisted direct excitation of imines without additional reductants, enabling the carbon–iodine bond cleavage of iododifluoromethyl ketones and the subsequent enantioselective radical coupling. This protocol provided an ingenious access to chiral β-amino ketones containing a gem-difluorine moiety. The mechanistic studies including radical trapping experiment, electron paramagnetic resonance experiment, cyclic voltammetry experiment and spectroscopic analysis rationalized the reaction process.
{"title":"Reductant-Free Enantioselective Aza-Reformatsky Reaction Enabled by Synergistic Visible Light Photocatalysis and Lewis Acid Catalysis","authors":"Mingyi Jiang, Zengcheng Yu, Linhan Yang, Fei Wang, Weidi Cao, Xiaohua Liu, Xiaoming Feng","doi":"10.1002/anie.202500756","DOIUrl":"https://doi.org/10.1002/anie.202500756","url":null,"abstract":"Classical aza-Reformatsky reaction generally involves excess reductants. Herein, we developed a visible light-induced catalytic asymmetric aza-Reformatsky reaction via a chiral Lewis acid-assisted direct excitation of imines without additional reductants, enabling the carbon–iodine bond cleavage of iododifluoromethyl ketones and the subsequent enantioselective radical coupling. This protocol provided an ingenious access to chiral β-amino ketones containing a gem-difluorine moiety. The mechanistic studies including radical trapping experiment, electron paramagnetic resonance experiment, cyclic voltammetry experiment and spectroscopic analysis rationalized the reaction process.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"10 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435649","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}
Present design and application of perovskite oxide catalysts assume lattice oxygen redox (LOR) mechanisms that depend on lattice oxygen activity without consideration of the entire redox cycle. Herein, using in situ characterizations and theoretical calculations, we uncover a hole-mediated LOR cycle on p-type Sr-deficient SrFeO3–δ (SFO-Srv) perovskites in CO oxidation reaction. Sr vacancies activate surface lattice oxygen of SFO-Srv and promote formation of highly covalent Fe(4–x)+-O(2–x)– sites. In situ electrical conductivity measurement demonstrates that holes directly participate in the entire LOR cycle, and are reversibly consumed and regenerated in reducing/oxidizing atmosphere via Fe(4–x)+-O(2–x)– sites of SFO-Srv. Hole-mediated LOR in SFO-Srv, as revealed by in situ soft X-ray absorption spectroscopy, occurs through changing in covalency of Fe-O bonds, O 2p hole state, and electron density of Fe sites. 18O2 labeling experiment further confirms an improved Mars-van Krevelen pathway in the hole-mediated LOR cycle, which accounts for a ten-times enhancement of SFO-Srv for CO reaction rate over that of SFO alone.
{"title":"Hole-Mediated Lattice Oxygen Redox Design for Perovskite Oxide Catalysts","authors":"Xinbo Li, Xiyang Wang, Yaowen Wang, Jingze Shao, Yimin A. Wu, Subhajit Jana, Haozhe Liu, Yue Peng, Zhiyao Wu, Zhen Li, Yingge Cong, Yawen Zhang, Guangshe Li, Liping Li","doi":"10.1002/anie.202424347","DOIUrl":"https://doi.org/10.1002/anie.202424347","url":null,"abstract":"Present design and application of perovskite oxide catalysts assume lattice oxygen redox (LOR) mechanisms that depend on lattice oxygen activity without consideration of the entire redox cycle. Herein, using in situ characterizations and theoretical calculations, we uncover a hole-mediated LOR cycle on p-type Sr-deficient SrFeO3–δ (SFO-Srv) perovskites in CO oxidation reaction. Sr vacancies activate surface lattice oxygen of SFO-Srv and promote formation of highly covalent Fe(4–x)+-O(2–x)– sites. In situ electrical conductivity measurement demonstrates that holes directly participate in the entire LOR cycle, and are reversibly consumed and regenerated in reducing/oxidizing atmosphere via Fe(4–x)+-O(2–x)– sites of SFO-Srv. Hole-mediated LOR in SFO-Srv, as revealed by in situ soft X-ray absorption spectroscopy, occurs through changing in covalency of Fe-O bonds, O 2p hole state, and electron density of Fe sites. 18O2 labeling experiment further confirms an improved Mars-van Krevelen pathway in the hole-mediated LOR cycle, which accounts for a ten-times enhancement of SFO-Srv for CO reaction rate over that of SFO alone.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"49 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435687","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}
Selina Reigl, Alexander Van Driessche, Tomasz M. Stawski, Sebastian Koltzenburg, Werner Kunz, Matthias Kellermeier
Calcium sulfate, and especially its hemihydrate form (bassanite), is crucial in the construction industry, primarily used as a hydraulic binder in cements, mortars, and wallboards. Because of the rapid transformation of bassanite into thermodynamically stable gypsum (calcium sulfate dihydrate) upon contact with water, natural deposits of the hemihydrate are scarce, rendering it one of the most extensively produced inorganic materials worldwide. Currently, bassanite is derived from mined or waste gypsum through a thermal dehydration process, which is energy‐intensive and costly. As sustainability has become a key target for industrial processes and products, a series of studies aiming to increase the energy efficiency and reduce the carbon footprint of bassanite production was published recently. Two primary approaches are pursued: conversion of gypsum and direct precipitation of bassanite from solution. In both cases, organic solvents, (specific) additives and/or elevated temperatures have been used to control the activity/availability of water in the reaction medium and thus direct phase selection towards the hemihydrate. This review offers a comprehensive overview of alternative bassanite production methods, critically examining their benefits, potential downsides, and overall impact on the sustainability of industrial‐scale calcium sulfate hemihydrate use.
{"title":"Sustainable Pathways for the Synthesis of Calcium Sulfate Hemihydrate","authors":"Selina Reigl, Alexander Van Driessche, Tomasz M. Stawski, Sebastian Koltzenburg, Werner Kunz, Matthias Kellermeier","doi":"10.1002/anie.202415161","DOIUrl":"https://doi.org/10.1002/anie.202415161","url":null,"abstract":"Calcium sulfate, and especially its hemihydrate form (bassanite), is crucial in the construction industry, primarily used as a hydraulic binder in cements, mortars, and wallboards. Because of the rapid transformation of bassanite into thermodynamically stable gypsum (calcium sulfate dihydrate) upon contact with water, natural deposits of the hemihydrate are scarce, rendering it one of the most extensively produced inorganic materials worldwide. Currently, bassanite is derived from mined or waste gypsum through a thermal dehydration process, which is energy‐intensive and costly. As sustainability has become a key target for industrial processes and products, a series of studies aiming to increase the energy efficiency and reduce the carbon footprint of bassanite production was published recently. Two primary approaches are pursued: conversion of gypsum and direct precipitation of bassanite from solution. In both cases, organic solvents, (specific) additives and/or elevated temperatures have been used to control the activity/availability of water in the reaction medium and thus direct phase selection towards the hemihydrate. This review offers a comprehensive overview of alternative bassanite production methods, critically examining their benefits, potential downsides, and overall impact on the sustainability of industrial‐scale calcium sulfate hemihydrate use.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"4 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427086","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}
Yubin He, Peng Zhao, Lei Wang, Yaqi Jing, Yanhe Li, Huolin L. Xin
Solid polymer electrolytes (SPEs) are widely recognized as promising candidates for enabling solid‐state lithium metal batteries (SSLMBs) with improved safety, high energy density, and extended cycling life. The traditional perspective posits that increasing the mechanical modulus of SPEs enhances their capacity to regulate Li0 deposition and suppress dendrite penetration. However, this study reveals a distinct failure mechanism: a rigid SPE with a high storage modulus suffers from delamination‐induced cell failure due to its inability to accommodate the volumetric changes of the Li0 anode. To address these limitations, we developed a hierarchical SPE incorporating an adhesive adaptation layer (AAL) positioned between the Li0 anode and the rigid SPE. The AAL combines strong adhesive strength, effectively mitigating delamination, with flowability, allowing it to eliminate interfacial voids and defects. Structural characterization via Cryo‐TEM and SEM demonstrates that this hierarchical design facilitates uniform, dense, and whisker‐free Li0 deposition, in sharp contrast to the uneven and porous morphology observed with the rigid SPE alone. Furthermore, the enhanced interfacial stability promotes the formation of an inorganic‐enriched SEI layer, contributing to long‐term cycling stability. As a result, the H‐SPE exhibits superior electrochemical performance, achieving 87% capacity over 960 cycles when paired with high‐loading (1.6 mAh/cm2) NMC622 cathode.
{"title":"An Adhesive Adaptation Layer Mitigates the Interfacial Instabilities of Rigid Polymer Electrolyte","authors":"Yubin He, Peng Zhao, Lei Wang, Yaqi Jing, Yanhe Li, Huolin L. Xin","doi":"10.1002/anie.202424304","DOIUrl":"https://doi.org/10.1002/anie.202424304","url":null,"abstract":"Solid polymer electrolytes (SPEs) are widely recognized as promising candidates for enabling solid‐state lithium metal batteries (SSLMBs) with improved safety, high energy density, and extended cycling life. The traditional perspective posits that increasing the mechanical modulus of SPEs enhances their capacity to regulate Li0 deposition and suppress dendrite penetration. However, this study reveals a distinct failure mechanism: a rigid SPE with a high storage modulus suffers from delamination‐induced cell failure due to its inability to accommodate the volumetric changes of the Li0 anode. To address these limitations, we developed a hierarchical SPE incorporating an adhesive adaptation layer (AAL) positioned between the Li0 anode and the rigid SPE. The AAL combines strong adhesive strength, effectively mitigating delamination, with flowability, allowing it to eliminate interfacial voids and defects. Structural characterization via Cryo‐TEM and SEM demonstrates that this hierarchical design facilitates uniform, dense, and whisker‐free Li0 deposition, in sharp contrast to the uneven and porous morphology observed with the rigid SPE alone. Furthermore, the enhanced interfacial stability promotes the formation of an inorganic‐enriched SEI layer, contributing to long‐term cycling stability. As a result, the H‐SPE exhibits superior electrochemical performance, achieving 87% capacity over 960 cycles when paired with high‐loading (1.6 mAh/cm2) NMC622 cathode.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"49 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427122","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}
Alexander Roseborough, Lev N. Zakharov, Ryan Loughran, Christopher A. Colla, May Nyman
Many industrial separations of chemically‐similar elements are achieved by solvent extraction, exploiting differences in speciation and solubility across aqueous‐organic interfaces. We recently identified [OM4(OH)6(SCN)12]4‐ (OM4, M=Zr/HfIV) tetrahedral oxoclusters as the main species in industrial processes that produce nuclear‐grade Zr and Hf from crude ore. However, isostructural/isoelectronic OM4‐oxoclusters do not explain selective extraction of Hf into the organic phase. Here we have characterized heterometal Hf‐Zr clusters in solution and the solid‐state yielding key information about their fundamentally different chemistry that engenders separation. Clusters prepared with both ammonium (industrial process) and tetramethylammonium counter cations revealed that 1) heterometal clusters (instead of a mixture of homometal clusters) assemble, and 2) Hf‐rich OM4 selectively precipitates over Zr‐rich OM4, providing a separation process that does not require an organic extractant. Mass spectrometry, small‐angle X‐ray scattering, solution‐state 1H nuclear magnetic resonance (NMR) spectroscopy, and solid‐state 17O NMR evidence both mixed‐metal speciation and selective Hf‐precipitation. Raman spectroscopy suggests greater Zr‐ligand lability than Hf‐ligand lability, consistent with higher aqueous solubility of Zr‐rich clusters, enabling both extraction and precipitation‐based separation. Fundamentally, we also identify a key difference between these chemically similar elements that has enabled diversification of Zr‐polyoxocation chemistry over the last decade, while Hf‐polyoxocation chemistry lags.
{"title":"Aqueous Zr/HfIV‐Oxo Cluster Speciation and Separation","authors":"Alexander Roseborough, Lev N. Zakharov, Ryan Loughran, Christopher A. Colla, May Nyman","doi":"10.1002/anie.202421819","DOIUrl":"https://doi.org/10.1002/anie.202421819","url":null,"abstract":"Many industrial separations of chemically‐similar elements are achieved by solvent extraction, exploiting differences in speciation and solubility across aqueous‐organic interfaces. We recently identified [OM4(OH)6(SCN)12]4‐ (OM4, M=Zr/HfIV) tetrahedral oxoclusters as the main species in industrial processes that produce nuclear‐grade Zr and Hf from crude ore. However, isostructural/isoelectronic OM4‐oxoclusters do not explain selective extraction of Hf into the organic phase. Here we have characterized heterometal Hf‐Zr clusters in solution and the solid‐state yielding key information about their fundamentally different chemistry that engenders separation. Clusters prepared with both ammonium (industrial process) and tetramethylammonium counter cations revealed that 1) heterometal clusters (instead of a mixture of homometal clusters) assemble, and 2) Hf‐rich OM4 selectively precipitates over Zr‐rich OM4, providing a separation process that does not require an organic extractant. Mass spectrometry, small‐angle X‐ray scattering, solution‐state 1H nuclear magnetic resonance (NMR) spectroscopy, and solid‐state 17O NMR evidence both mixed‐metal speciation and selective Hf‐precipitation. Raman spectroscopy suggests greater Zr‐ligand lability than Hf‐ligand lability, consistent with higher aqueous solubility of Zr‐rich clusters, enabling both extraction and precipitation‐based separation. Fundamentally, we also identify a key difference between these chemically similar elements that has enabled diversification of Zr‐polyoxocation chemistry over the last decade, while Hf‐polyoxocation chemistry lags.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"49 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427084","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}
Kristóf Garami, Nikolett Péczka, László Petri, Zoltán Orgován, Tímea Imre, Tamás Langó, Zoltán Szabó, Pál Szabó, György Miklós Keserű, Péter Ábrányi-Balogh
Photoaffinity labeling is a widely used methodology for interrogating small molecule‐protein interactions. However, these applications are limited by the few photo‐cross‐linkers that typically modify the affinity and the binding mode of the original ligand. Here, we report the development of new target agnostic photoaffinity warheads, sulfohydrazones that form a reactive carbene upon UV irradiation. Careful optimization of the reaction conditions allowed us to effectively label five different amino acid residues in proteins. Our approach turned biologically relevant hydrazones and sulfohydrazones to intrinsically irreversible covalent binders without structural modifications by photoactivation as demonstrated on monoamine oxidase A (MAO‐A) enzyme and STAT5b (Signal transducer and activator of transcription 5b) transcription factor. Sulfohydrazones are readily accessible by transforming the corresponding carbonyl group of a ligand or a suitable tag that extends the application domain of the method for any ligands exemplified by conditional labelling of the acetylcholine esterase enzyme and the oncogenic mutant of GTP‐ase KRasG12D.
{"title":"Target agnostic photoaffinity labelling by sulfonylhydrazones","authors":"Kristóf Garami, Nikolett Péczka, László Petri, Zoltán Orgován, Tímea Imre, Tamás Langó, Zoltán Szabó, Pál Szabó, György Miklós Keserű, Péter Ábrányi-Balogh","doi":"10.1002/anie.202408701","DOIUrl":"https://doi.org/10.1002/anie.202408701","url":null,"abstract":"Photoaffinity labeling is a widely used methodology for interrogating small molecule‐protein interactions. However, these applications are limited by the few photo‐cross‐linkers that typically modify the affinity and the binding mode of the original ligand. Here, we report the development of new target agnostic photoaffinity warheads, sulfohydrazones that form a reactive carbene upon UV irradiation. Careful optimization of the reaction conditions allowed us to effectively label five different amino acid residues in proteins. Our approach turned biologically relevant hydrazones and sulfohydrazones to intrinsically irreversible covalent binders without structural modifications by photoactivation as demonstrated on monoamine oxidase A (MAO‐A) enzyme and STAT5b (Signal transducer and activator of transcription 5b) transcription factor. Sulfohydrazones are readily accessible by transforming the corresponding carbonyl group of a ligand or a suitable tag that extends the application domain of the method for any ligands exemplified by conditional labelling of the acetylcholine esterase enzyme and the oncogenic mutant of GTP‐ase KRasG12D.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"4 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427169","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}
Recycling gold from electronic waste represents a sustainable and environmentally friendly strategy for both resource recovery and waste reduction. In this study, we designed an innovative and highly stable porous aromatic framework (PAF)/polymer composite, PAF-147/polydopamine (PDA), as an efficient adsorbent for selective gold recovery for the first time. The maximum gold adsorption capacity of PAF-147/PDA reached 1700 mg·g⁻¹. Furthermore, it could rapidly extract over 95% of gold from solutions in a pH range of 0-10 within just 2 minutes. Importantly, as a real application demonstration, the PAF-147/PDA composite selectively recovered 99% of gold from the leachate of discarded central processing units. When the recovered Au-containing composite was applied to electrocatalytic CO2 reduction, the Faradaic efficiency for CO production exceeded 95% across acidic, neutral, and alkaline electrolytes, outperforming most reported gold-based catalysts due to the cooperation effect of the composite and Au. This work opens a new way for the combination of selective gold recovery from electronic waste with highly efficient CO2 conversion.
{"title":"Selective Gold Recycling from Electronic Waste Using a Highly Stable Porous Aromatic Framework/Polymer and Its Application for CO2 Electroreduction","authors":"Tianwei Xue, Guangkuo Xu, Chengbin Liu, Ruiqing Li, Yanyin Wu, Yuyu Guo, Shan Gong, Zeyu Shao, Xiangcheng Cai, Haoyu Zou, Linxiao Cui, Jia Zhao, Zhihong Gao, Shuliang Yang, Jun Li, Buxing Han, Li Peng","doi":"10.1002/anie.202500092","DOIUrl":"https://doi.org/10.1002/anie.202500092","url":null,"abstract":"Recycling gold from electronic waste represents a sustainable and environmentally friendly strategy for both resource recovery and waste reduction. In this study, we designed an innovative and highly stable porous aromatic framework (PAF)/polymer composite, PAF-147/polydopamine (PDA), as an efficient adsorbent for selective gold recovery for the first time. The maximum gold adsorption capacity of PAF-147/PDA reached 1700 mg·g⁻¹. Furthermore, it could rapidly extract over 95% of gold from solutions in a pH range of 0-10 within just 2 minutes. Importantly, as a real application demonstration, the PAF-147/PDA composite selectively recovered 99% of gold from the leachate of discarded central processing units. When the recovered Au-containing composite was applied to electrocatalytic CO2 reduction, the Faradaic efficiency for CO production exceeded 95% across acidic, neutral, and alkaline electrolytes, outperforming most reported gold-based catalysts due to the cooperation effect of the composite and Au. This work opens a new way for the combination of selective gold recovery from electronic waste with highly efficient CO2 conversion.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"10 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427326","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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