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}
Ashi Singh, Atiqur Rahman, Srijan Mondal, Mark A Spackman, Bo B Iversen, Sajesh Pynadath Thomas
Mechanically flexible crystals are a rapidly growing class of functional molecular materials. Typically, such flexible crystals are discovered by serendipity. Herein, we have predicted mechanical flexibility in a series of molecular crystals based on a structure screening approach that combines interaction topology and the presence of nitrile×××nitrile interactions – a supramolecular motif hitherto not associated with bending property. Further, we have experimentally validated plastic/elastic bending properties in a series of crystal structures thus predicted. However, four out of five of these crystals showed the bending direction along π∙∙∙π stacking despite the fact that the direction of strongest interaction anisotropy was rendered by the nitrile∙∙∙nitrile interaction motifs. This is contrary to the commonly perceived anisotropy model and underscores the dominant role of dispersion forces over the electrostatically stabilized motifs in dictating the bending phenomena in molecular crystals. The interaction energies of these motifs have been evaluated using accurate structures from X-ray quantum crystallography. Analyses combining elastic tensors, interaction anisotropy indices, thermal expansion studies, and high-pressure simulations quantify the relative roles of the nitrile∙∙∙nitrile motif and π∙∙∙π stacking in mechanical flexibility. Our results point to the possibility of expanding the realm of flexible molecular materials by predictive computational models.
{"title":"Prediction and Validation of Mechanical Flexibility in Molecular Crystals: Dispersion Interactions Dictate Bending","authors":"Ashi Singh, Atiqur Rahman, Srijan Mondal, Mark A Spackman, Bo B Iversen, Sajesh Pynadath Thomas","doi":"10.1002/anie.202424496","DOIUrl":"https://doi.org/10.1002/anie.202424496","url":null,"abstract":"Mechanically flexible crystals are a rapidly growing class of functional molecular materials. Typically, such flexible crystals are discovered by serendipity. Herein, we have predicted mechanical flexibility in a series of molecular crystals based on a structure screening approach that combines interaction topology and the presence of nitrile×××nitrile interactions – a supramolecular motif hitherto not associated with bending property. Further, we have experimentally validated plastic/elastic bending properties in a series of crystal structures thus predicted. However, four out of five of these crystals showed the bending direction along π∙∙∙π stacking despite the fact that the direction of strongest interaction anisotropy was rendered by the nitrile∙∙∙nitrile interaction motifs. This is contrary to the commonly perceived anisotropy model and underscores the dominant role of dispersion forces over the electrostatically stabilized motifs in dictating the bending phenomena in molecular crystals. The interaction energies of these motifs have been evaluated using accurate structures from X-ray quantum crystallography. Analyses combining elastic tensors, interaction anisotropy indices, thermal expansion studies, and high-pressure simulations quantify the relative roles of the nitrile∙∙∙nitrile motif and π∙∙∙π stacking in mechanical flexibility. Our results point to the possibility of expanding the realm of flexible molecular materials by predictive computational models.","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":"143427317","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In this article we report that the air-stable “naked nickel” [Ni(4-CF3stb)3] is a competent catalyst in the catalytic Suzuki-Miyaura cross-coupling reaction (SMC) between heteroaryl bromides and heteroaromatic boron-based nucleophiles. The catalytic system is characterized by its ability to avoid decomposition or deactivation in the presence of multiple Lewis-basic sites. The protocol permits the formation of C‒C bonds between two heteroaryl moieties in the absence of complex exogenous ligands, thus minimizing screening procedures and simplifying reaction setups. This method accommodates combinations of distinct 6-membered heteroaryl bromides and 5- and 6-membered heterocyclic B-based nucleophiles.
{"title":"“Naked Nickel”-Catalyzed Heteroaryl-Heteroaryl Suzuki–Miyaura Coupling","authors":"Rakan Saeb, Byeongdo Roh, Josep Cornella","doi":"10.1002/anie.202424051","DOIUrl":"https://doi.org/10.1002/anie.202424051","url":null,"abstract":"In this article we report that the air-stable “naked nickel” [Ni(4-CF3stb)3] is a competent catalyst in the catalytic Suzuki-Miyaura cross-coupling reaction (SMC) between heteroaryl bromides and heteroaromatic boron-based nucleophiles. The catalytic system is characterized by its ability to avoid decomposition or deactivation in the presence of multiple Lewis-basic sites. The protocol permits the formation of C‒C bonds between two heteroaryl moieties in the absence of complex exogenous ligands, thus minimizing screening procedures and simplifying reaction setups. This method accommodates combinations of distinct 6-membered heteroaryl bromides and 5- and 6-membered heterocyclic B-based nucleophiles.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"80 1 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427321","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In this work, we propose a new Global Optimization Algorithm (GOAT) for molecules and clusters of atoms and show how it can find the global energy minima for both systems without resorting to molecular dynamics (MD). This avoids the potential millions of time-consuming gradient calculations required by a long MD run. Because of that, it can be used with any regular quantum chemical method, even with the costlier hybrid DFT. We showcase its accuracy by running it on various systems, from organic molecules to water clusters, metal complexes, and metal nanoparticles, comparing it with state-of-the-art methods such as the Conformer-Rotamer Ensemble Sampling Tool (CREST). We also discuss its underlying theory and mechanisms for succeeding in challenging cases. GOAT is, in general, more efficient and accurate than previous algorithms in finding global minima and succeeds in cases where others cannot due to the free choice for the Potential Energy Surface (PES).
{"title":"GOAT: A Global Optimization Algorithm for Molecules and Atomic Clusters","authors":"Bernardo de Souza","doi":"10.1002/anie.202500393","DOIUrl":"https://doi.org/10.1002/anie.202500393","url":null,"abstract":"In this work, we propose a new Global Optimization Algorithm (GOAT) for molecules and clusters of atoms and show how it can find the global energy minima for both systems without resorting to molecular dynamics (MD). This avoids the potential millions of time-consuming gradient calculations required by a long MD run. Because of that, it can be used with any regular quantum chemical method, even with the costlier hybrid DFT. We showcase its accuracy by running it on various systems, from organic molecules to water clusters, metal complexes, and metal nanoparticles, comparing it with state-of-the-art methods such as the Conformer-Rotamer Ensemble Sampling Tool (CREST). We also discuss its underlying theory and mechanisms for succeeding in challenging cases. GOAT is, in general, more efficient and accurate than previous algorithms in finding global minima and succeeds in cases where others cannot due to the free choice for the Potential Energy Surface (PES).","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":"143427322","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}
Shengyang Zhong, Dexi Yu, Yuhui Ma, Yuhong Lin, Xiaoyi Wang, Zhenzhen Yu, Meirong Huang, Yidong Hou, Masakazu Anpo, Jimmy C. Yu, Jinshui Zhang, Xinchen Wang
Photocatalytic oxidation of benzene to phenol using molecular O2 is a promising alternative to the traditional cumene process. However, the selectivity toward phenol is often poor due to the ring-opening reaction induced by the superoxide radical (·O2-), which is predominantly produced from the single-electron reduction of O2. Herein, we demonstrate that introducing abundant oxygen vacancies (OVs) on the surface of TiO2 facilitates the activation of O2 through a two-electron reduction process instead of a single-electron reduction. This effectively suppresses the generation of·O2-, thereby reducing phenol decomposition and significantly enhancing the selectivity. In addition, these OVs can trap the electrons to promote chare separation and serve as the adsorption sites for O2 activation. As a result, the introduction of abundant OVs on the surface of TiO2 not only enhances phenol yield but also importantly improves selectivity toward phenol. This finding enriches our understanding of how OVs influence reaction pathways and product selectivity, providing valuable insights for the design and tailoring of OV-rich photocatalysts for selective organic oxygenations.
{"title":"Oxygen Vacancy-Enhanced Selectivity in Aerobic Oxidation of Benzene to Phenol over TiO2 Photocatalysts","authors":"Shengyang Zhong, Dexi Yu, Yuhui Ma, Yuhong Lin, Xiaoyi Wang, Zhenzhen Yu, Meirong Huang, Yidong Hou, Masakazu Anpo, Jimmy C. Yu, Jinshui Zhang, Xinchen Wang","doi":"10.1002/anie.202502823","DOIUrl":"https://doi.org/10.1002/anie.202502823","url":null,"abstract":"Photocatalytic oxidation of benzene to phenol using molecular O2 is a promising alternative to the traditional cumene process. However, the selectivity toward phenol is often poor due to the ring-opening reaction induced by the superoxide radical (·O2-), which is predominantly produced from the single-electron reduction of O2. Herein, we demonstrate that introducing abundant oxygen vacancies (OVs) on the surface of TiO2 facilitates the activation of O2 through a two-electron reduction process instead of a single-electron reduction. This effectively suppresses the generation of·O2-, thereby reducing phenol decomposition and significantly enhancing the selectivity. In addition, these OVs can trap the electrons to promote chare separation and serve as the adsorption sites for O2 activation. As a result, the introduction of abundant OVs on the surface of TiO2 not only enhances phenol yield but also importantly improves selectivity toward phenol. This finding enriches our understanding of how OVs influence reaction pathways and product selectivity, providing valuable insights for the design and tailoring of OV-rich photocatalysts for selective organic oxygenations.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"137 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427323","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}
Dr. Yue Zhou, Dr. Dong Chen, Dr. Wanmiao Gu, Dr. Wentao Fan, Dr. Runguo Wang, Dr. Liang Fang, Dr. Qing You, Dr. Shengli Zhuang, Guoqing Bian, Dr. Lingwen Liao, Ziyan Zhou, Dr. Nan Xia, Prof. Dr. Jun Yang, Prof. Dr. Zhikun Wu
An increasing need for the miniaturization of optoelectronic devices or machines has become evident as we are entering the post-Moore era. One bold conceit is that chemically synthesized nanoparticles (NP) can function as nanodevices or nanomachines. In their Research Article (e202420931), Zhikun Wu, Jun Yang, Nan Xia et al. demonstrate the feasibility by reporting a novel nanocluster with multileveled capacitor-like character, which is identified by a Cd(II) transport from the outershell to the innermost position after charged with NaBH4, as well as some other ways such as NPA charge distribution, voltammetry and electrocatalytic reduction of CO2 to CO. An intra-NP anti-galvanic reduction was found after the migrating of charge carrier.
{"title":"Frontispiece: Chemical Synthesis of ~1 nm Multilevel Capacitor-like Particles with Atomic Precision","authors":"Dr. Yue Zhou, Dr. Dong Chen, Dr. Wanmiao Gu, Dr. Wentao Fan, Dr. Runguo Wang, Dr. Liang Fang, Dr. Qing You, Dr. Shengli Zhuang, Guoqing Bian, Dr. Lingwen Liao, Ziyan Zhou, Dr. Nan Xia, Prof. Dr. Jun Yang, Prof. Dr. Zhikun Wu","doi":"10.1002/anie.202580862","DOIUrl":"https://doi.org/10.1002/anie.202580862","url":null,"abstract":"<p>An increasing need for the miniaturization of optoelectronic devices or machines has become evident as we are entering the post-Moore era. One bold conceit is that chemically synthesized nanoparticles (NP) can function as nanodevices or nanomachines. In their Research Article (e202420931), Zhikun Wu, Jun Yang, Nan Xia et al. demonstrate the feasibility by reporting a novel nanocluster with multileveled capacitor-like character, which is identified by a Cd(II) transport from the outershell to the innermost position after charged with NaBH4, as well as some other ways such as NPA charge distribution, voltammetry and electrocatalytic reduction of CO2 to CO. An intra-NP anti-galvanic reduction was found after the migrating of charge carrier.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"64 8","pages":""},"PeriodicalIF":16.1,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/anie.202580862","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143431287","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}
The diverse valences of iodine enable it with multi-electron transfer capability for energy dense batteries. However, previous studies indicate that the primary I−/I2 redox couple exhibits distinct behaviors depending on electrolyte choice, with the mechanistic basis of aqueous versus nonaqueous systems remaining unclear. Here, we elucidated the solvent effect on iodine redox, particularly focusing on polyiodide formation and their molecular interaction correlations. We validate that a thermodynamically one-step conversion reaction (I2 ↔ I−) occurs in the protic solvents, while it is a two-step transformation (I2 ↔ I3− ↔ I−) in aprotic solvents. This distinction arises from strong electron-donating properties in aprotic solvents that facilitate charge transfer with iodine, promoting complexation with iodide as solvent·I3− species. Conversely, protic solvents form additional hydrogen bonds with iodine, alleviating polarization and reducing interaction with iodide. Furthermore, to address the limitations of single protic electrolytes—characterized by sluggish dissolution-precipitation and slow ion migration rates—we propose a hybrid electrolyte combining water and ethylene glycol. These hybrids enhance iodine redox kinetics, inhibits I3− generation, and modifies the Zn2+ solvation structure to mitigate zinc anode corrosion and dendrite. The Zn-I₂ batteries demonstrates exceptional long-term cycling stability in a wide temperature range, highlighting its potential for practical applications.
{"title":"Solvent Chemistry Manipulated Iodine Redox Thermodynamics For Durable Iodine Batteries","authors":"Tingting Liu, Chengjun Lei, Wei Yang, Huijian Wang, Wenjiao Ma, Jinye Li, Xiao Liang","doi":"10.1002/anie.202422163","DOIUrl":"https://doi.org/10.1002/anie.202422163","url":null,"abstract":"The diverse valences of iodine enable it with multi-electron transfer capability for energy dense batteries. However, previous studies indicate that the primary I−/I2 redox couple exhibits distinct behaviors depending on electrolyte choice, with the mechanistic basis of aqueous versus nonaqueous systems remaining unclear. Here, we elucidated the solvent effect on iodine redox, particularly focusing on polyiodide formation and their molecular interaction correlations. We validate that a thermodynamically one-step conversion reaction (I2 ↔ I−) occurs in the protic solvents, while it is a two-step transformation (I2 ↔ I3− ↔ I−) in aprotic solvents. This distinction arises from strong electron-donating properties in aprotic solvents that facilitate charge transfer with iodine, promoting complexation with iodide as solvent·I3− species. Conversely, protic solvents form additional hydrogen bonds with iodine, alleviating polarization and reducing interaction with iodide. Furthermore, to address the limitations of single protic electrolytes—characterized by sluggish dissolution-precipitation and slow ion migration rates—we propose a hybrid electrolyte combining water and ethylene glycol. These hybrids enhance iodine redox kinetics, inhibits I3− generation, and modifies the Zn2+ solvation structure to mitigate zinc anode corrosion and dendrite. The Zn-I₂ batteries demonstrates exceptional long-term cycling stability in a wide temperature range, highlighting its potential for practical applications.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"137 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427316","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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