Angewandte Chemie International Edition最新文献_第9页

Efficient Methane Purification Using a Robust and Recoverable Hydrogen-Bonded Organic Framework

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-02-03 DOI: 10.1002/anie.202500970

Yabing He, Shengjie Lin, Ye Liang, Peiren Ke, Limin Wang, Deli Chen, Lin Zhang

{"title":"Efficient Methane Purification Using a Robust and Recoverable Hydrogen-Bonded Organic Framework","authors":"Yabing He, Shengjie Lin, Ye Liang, Peiren Ke, Limin Wang, Deli Chen, Lin Zhang","doi":"10.1002/anie.202500970","DOIUrl":"https://doi.org/10.1002/anie.202500970","url":null,"abstract":"Efficient separation and purification of methane is a key step in promoting its wide application as an environmentally friendly energy carrier and an important chemical raw material. Development of single solid adsorbents simultaneously combining robust structure, high separation capacity, and easy performance recovery is highly desired but quite a challenge for realizing methane depuration. In the present study, we report an ultramicroporous hydrogen-bonded organic framework compound constructed from a tetracyano bithiophene-functionalized ligand. Similar to the acting principle of enzymes, multisite supramolecular interactions endow the material with not only extraordinary chemical stability in wide pH range including 12 M HCl and 20 M NaOH solutions but also highly selective recognition of acetylene and carbon dioxide over methane. The packing densities and adsorption selectivities toward acetylene and carbon dioxide are the highest reported for the hydrogen-bonded organic framework materials. Dynamic breakthrough experiments demonstrate its highly efficient methane purification ability from binary and even ternary mixed gases, with not only methane productivities up to 2.34 mol kg-1 but also moderate regeneration energy. Furthermore, the title compound can be easily regenerated in almost quantitative yield via simple rato-evaporation of its dichloromethane solution once its activity is attenuated or lost.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"66 2 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143076838","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}

引用次数: 0

Identical Grain Atomic Force Microscopy Elucidates Facet-dependent Restructuring of Copper for CO2 Electroreduction

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-02-03 DOI: 10.1002/anie.202424530

Hui Wang, Laurens Mandemaker, Jim De Ruiter, Xuang Yu, Ward van der Stam, Bert Marc Weckhuysen

{"title":"Identical Grain Atomic Force Microscopy Elucidates Facet-dependent Restructuring of Copper for CO2 Electroreduction","authors":"Hui Wang, Laurens Mandemaker, Jim De Ruiter, Xuang Yu, Ward van der Stam, Bert Marc Weckhuysen","doi":"10.1002/anie.202424530","DOIUrl":"https://doi.org/10.1002/anie.202424530","url":null,"abstract":"Studies on the catalyst restructuring during the electrochemical CO2 reduction reaction (eCO2RR) are limited and mostly focused on Cu (001) or (111) single crystals as model systems. A comprehensive overview of the dynamic restructuring of the different Cu facets is lacking. Here, we first reveal the facet-dependent restructuring of polycrystalline Cu electrodes through electron backscatter diffraction (EBSD) and identical grain atomic force microscopy (AFM). This combined analysis provides new insights into the evolution of crystal domains (EBSD) and surface topography (AFM) at varying conditions (e.g., applied potential and oxidative-reductive pulses). The statistic slope distribution function was applied to study the restructuring asymmetry on five Cu facets (i.e., planar vs. atom stepped). We find that planar Cu (001) shows a square-shaped morphology after eCO2RR with a 4-fold asymmetry restructuring behavior, while triangular features dominate on Cu (111), evidenced by surface changes with 3-fold asymmetry. 2-fold restructuring is observed for Cu (114), (212), and (124) with atom steps, resulting in forming elongated structures. Therefore, the restructuring is dominated by the asymmetry of its facet lattice structure (i.e., planar vs. atom-stepped). This work underscores the potential of combining techniques to elucidate the relationship between surface restructuring and crystal facets on different length scales.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"25 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143084064","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}

引用次数: 0

Switchable Polymerization from Monomer Mixtures to Synthesize Oxygen-Rich Block Copolymers with Dual Recyclability and Degradability

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-02-03 DOI: 10.1002/anie.202424856

Di Xie, Zhi-Hua Jia, Yan-Li Zhang, Xin-Lei Cai, Long-Nv Liu, Guan-Wen Yang, Xiaohui Kang, Xianming Zhang, Yao-Yao Zhang

{"title":"Switchable Polymerization from Monomer Mixtures to Synthesize Oxygen-Rich Block Copolymers with Dual Recyclability and Degradability","authors":"Di Xie, Zhi-Hua Jia, Yan-Li Zhang, Xin-Lei Cai, Long-Nv Liu, Guan-Wen Yang, Xiaohui Kang, Xianming Zhang, Yao-Yao Zhang","doi":"10.1002/anie.202424856","DOIUrl":"https://doi.org/10.1002/anie.202424856","url":null,"abstract":"Switchable catalysis from monomer mixtures has been emerging as a powerful technique to synthesize various useful block copolymers, yet represents a significant challenge in polymer chemistry. Herein, we present the synthesis of well-defined polyacetal/polycarbonate block copolymers through switchable polymerization from mixtures of terminal epoxides, internal epoxides, o-phthalaldehyde (OPA) and CO2. The exclusive chemoselectivity of terminal epoxide or internal epoxide was achieved by controlling the reaction atmosphere. The dynamic equilibrium of acetal anion and alkoxy anion is the key to the successful switch from terminal epoxides/OPA copolymerization to internal epoxides/CO2 copolymerization. Computational studies elucidated the kinetic and thermodynamic preferences underlying this selective polymerization. The acid/base labile nature of the block copolymers enables their sequence-controlled chemical recycling/degradation. These novel polyacetal/polycarbonate block copolymers with facilely sequence-controlled polymerization/depolymerization capabilities will enable their further tailored applications and contribute to the development of a circular plastic economy.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"1 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143076842","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}

引用次数: 0

Mass Activity Elucidation of Cobalt-Based Oxygen Evolution Catalysts Utilizing Depth-Resolved Spectroscopy in the Presence of Various Cations with Chloride

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-02-03 DOI: 10.1002/anie.202501579

Hiroki Komiya, Keisuke Obata, Oki Sekizawa, Kiyofumi Nitta, Ke Xu, Melody Wada, Kazuhiro Takanabe

{"title":"Mass Activity Elucidation of Cobalt-Based Oxygen Evolution Catalysts Utilizing Depth-Resolved Spectroscopy in the Presence of Various Cations with Chloride","authors":"Hiroki Komiya, Keisuke Obata, Oki Sekizawa, Kiyofumi Nitta, Ke Xu, Melody Wada, Kazuhiro Takanabe","doi":"10.1002/anie.202501579","DOIUrl":"https://doi.org/10.1002/anie.202501579","url":null,"abstract":"The oxygen evolution reaction (OER) in water electrolysis is a kinetically sluggish reaction that requires catalysts with high electrocatalytic activity. Cobalt oxide (CoOx) is among the best performing OER catalysts and has been reported to have “bulk activity” with active sites distributed within the material. Herein, we examined the distribution of OER activity over μg cm−2 loaded CoOx deposited on anti-corrosive Ti substrate in 1 M KOH with and without various cations with chloride (X-Cl, X = Li, Na, K). Depth-resolved X-ray absorption spectroscopy and depth-profiling X-ray photoelectron spectroscopy were employed. In a thin sample with ~20 nm thickness, uniform oxidation was observed, but a thicker sample with ~80 nm thickness had active oxidized phases close to the surface and an unexpected inactive Co0 phase concurrently occupying about three-quarters of the CoOx layer in the depth direction, which accounted for the mass activity loss. The formation of Co0 in the bulk is attributed to the galvanic replacement reaction between CoOx and the metallic Ti substrate, which is not observed on the carbon substrate. Operando Raman spectroscopy demonstrated that the type of cations rather than Cl− impacts the OER performance likely due to their interaction with superoxo species.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"50 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143076846","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}

引用次数: 0

High-Density Catalytic Sites Grafting on 2D-Metal Oxides for Acceptorless Alcohol Dehydrogenation

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-02-03 DOI: 10.1002/anie.202423169

Yurim Hong, Nitee Kumari, Junwon Kim, Ankur Maji, Min Gyu Kim, Kyu-Min Jo, Si-Young Choi, Ji Hoon Shim, In Su Lee

{"title":"High-Density Catalytic Sites Grafting on 2D-Metal Oxides for Acceptorless Alcohol Dehydrogenation","authors":"Yurim Hong, Nitee Kumari, Junwon Kim, Ankur Maji, Min Gyu Kim, Kyu-Min Jo, Si-Young Choi, Ji Hoon Shim, In Su Lee","doi":"10.1002/anie.202423169","DOIUrl":"https://doi.org/10.1002/anie.202423169","url":null,"abstract":"Installing well-defined high density single-atomic catalyst (SAC) sites is highly desired for the synergistic cooperative effect in efficient chemical synthesis but elusive to synthesize due to unavoidable atomic segregation into clusters or particulates. We implemented a 2D-nanoconfined SAC grafting strategy. Inside a bilayer silica envelope, single metal hydroxide layer, pre-loaded with the catalytic metal (Pt, Pd, Ir) precursors, underwent controlled thermal conversion to the homogeneously embedded SACs decorated onto the in-situ generated 1 nm-thin transition metal oxide (TMO) nanosheet. Ultranarrow confined slit-space exclusively availed laterally emerging cation vacancies of TMO host, as atomic scale sockets to capture SACs within 2D-plane while vertically restricting the atomic aggregation into nanoparticulates. High density SACs stably decorated on isolated TMO nanosheet, could be obtained in a controllable manner. Well-defined SACs on TMO were conveniently employed for acceptorless dehydrogenation of a variety of alcohols with quite high activities outperforming reported catalysts. In-depth, mechanistic investigation revealed the dramatic enhancement in acceptorless dehydrogenation reaction rates by following distinct reaction pathways (concerted or stepwise) depending on the density of SACs cooperativity effect. Such advantageous effect is distinct from the reactions on isolated metal sites in low-density SACs or nanoparticle surface.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"17 3 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143084061","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}

引用次数: 0

Selective Hydrogenolysis of Biomass-Derived Aromatic Alcohols over 2D-Mo2COx MXene by a Reversible Redox-Relay Mechanism

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-02-03 DOI: 10.1002/anie.202500881

Yangye Hu, Jianxin Cai, Guoqiang Sheng, Zepeng Zhao, Yong Liu, Shuting Liu, Shaobo Tu, Yajie Tian, Haijiao Lu, Jun Wang, Shuguang Deng, Qiang Deng

{"title":"Selective Hydrogenolysis of Biomass-Derived Aromatic Alcohols over 2D-Mo2COx MXene by a Reversible Redox-Relay Mechanism","authors":"Yangye Hu, Jianxin Cai, Guoqiang Sheng, Zepeng Zhao, Yong Liu, Shuting Liu, Shaobo Tu, Yajie Tian, Haijiao Lu, Jun Wang, Shuguang Deng, Qiang Deng","doi":"10.1002/anie.202500881","DOIUrl":"https://doi.org/10.1002/anie.202500881","url":null,"abstract":"Selective CH2–OH hydrogenolysis of biomass-derived aromatic alcohols to produce methyl aromatics is crucial for synthesizing sustainable fuels and chemicals; yet traditional metal–acid bifunctional catalysis possesses significant challenges owing to its complex reaction network. Herein, a 2D-Mo2COx MXene was fabricated, demonstrating an efficient hydrogenolysis of 5-hydroxymethyl furfural into 5-methyl furfural, achieving an impressive yield (99.5%) at the mild reaction temperature of 90°C. Catalytic mechanism investigations reveal that 2D-Mo2COx facilitate the activation and cleavage of the CH2–OH bond through a redox mechanism, driven by the strong CH2–OH affinity of the Mo–Mo metallic plane. In the absence of H2, hydrogen from O–H group is the source for methyl formation from CH2–OH. Under a H2 atmosphere, H2 is activated to remove residual oxygen species, boosting selective hydrogenolysis while suppressing furan and CH=O hydrogenation. Furthermore, the catalyst exhibited broad universality for synthesizing methyl aromatics from various furfuryl alcohols, benzyl alcohols, and hydroxycyclopentenones. This study presents a novel redox-relay mechanism in advanced MXene catalysis, offering a straightforward hydrogenolysis pathway for challenging substrates.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"37 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143084065","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}

引用次数: 0

Transient Dangling Active Sites of Fe(III)-N-C Single-Atom Catalyst for Efficient Electrochemical CO2 Reduction Reaction

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-02-03 DOI: 10.1002/anie.202424150

Yun-Ze Qiu, Xiao-Meng Liu, Wenying Li, Jun Li, Hai Xiao

{"title":"Transient Dangling Active Sites of Fe(III)-N-C Single-Atom Catalyst for Efficient Electrochemical CO2 Reduction Reaction","authors":"Yun-Ze Qiu, Xiao-Meng Liu, Wenying Li, Jun Li, Hai Xiao","doi":"10.1002/anie.202424150","DOIUrl":"https://doi.org/10.1002/anie.202424150","url":null,"abstract":"The Fe single-atom catalyst (SAC) with an oxidation state of III anchored on the N-doped carbon substrate (Fe(III)-N-C) delivers superior activity for catalyzing the electrochemical CO2 reduction reaction (eCO2RR) to produce CO, but its mechanism remains contentious and the commonly adopted FeN4-C model is not a conformant model for Fe(III)-N-C but for Fe(II)-N-C. Herein, employing the grand-canonical ensemble modeling with the density functional theory method benchmarked against the high-level wavefunction theory method, we first identify the conformant model for Fe(III)-N-C to be FeN1C3-C, and we then unveil that the Fe(III)N1C3-C SAC generates a novel type of dangling active site transiently under working conditions, in which the Fe single-atom leaves from the anchoring site by breaking all the Fe-C bonds but retains a stable binding to the substrate by the Fe-N bond. Thus, we further elucidate that this flexible dangling active site of Fe(III)-N-C renders a convoluted reaction network with facile CO2 activation, which delivers superior activity for eCO2RR. Our findings provide a novel understanding of the structure-activity relationship for Fe-N-C and concrete insights into the design of highly active SACs.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"47 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143084076","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}

引用次数: 0

Chemical Energy Lights Up Europium-Based Ultra-bright Afterglow for Bioanalysis Application

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-02-03 DOI: 10.1002/anie.202423791

Yuetian Pei, Yiwei Fan, Kuangshi Sun, Donghao Hu, Yawei Liu, Jiamiao Yin, Lei Chen, Ming Xu, Weigang Yan, Xin Liu, Fuyou Li

{"title":"Chemical Energy Lights Up Europium-Based Ultra-bright Afterglow for Bioanalysis Application","authors":"Yuetian Pei, Yiwei Fan, Kuangshi Sun, Donghao Hu, Yawei Liu, Jiamiao Yin, Lei Chen, Ming Xu, Weigang Yan, Xin Liu, Fuyou Li","doi":"10.1002/anie.202423791","DOIUrl":"https://doi.org/10.1002/anie.202423791","url":null,"abstract":"Photochemical afterglow materials are gaining great attention for the property to continuously emit light after the excitation source is removed. However, their limited luminescence quantum yield (QY) and brightness hinder the use in biological applications. In this study, we introduce a novel photochemical afterglow system that combines a newly designed photoenergy cache unit (PCU) with an emitter through coordination covalent bonds. The PCU boasts a dark state to significantly emit photons only through chemiexcitation in the process of photochemical reactions, facilitating direct energy transfer to the emitter and resulting in bright afterglow. The related mechanisms further guided us to achieve the highest reported afterglow luminescence quantum yield of 27.5%. The system can be encapsulated and dispersed in aqueous solutions for in vivo bioimaging in living mice under mild and simple conditions (low concentration, low excitation power, short excitation time, short exposure time), and also for in vitro diagnostic through lateral flow immunoassay, enabling the highly sensitive detection of the inflammatory biomarker serum amyloid A (SAA) and demonstrating excellent correlation with clinical test results. This study offers new insights into enhancing luminescence QY and brightness of afterglow, highlighting the potential of such systems for further biomedical applications.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"47 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143076835","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}

引用次数: 0

Insights into the Electrolyte Hydrolysis and Its Impacts on the Interfacial Chemistry of a Li+-Intercalated Anode during High-Temperature Calendar Aging

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-02-02 DOI: 10.1002/anie.202425491

Yu Zhang, Zhen-Zhen Shen, Yanyan Zhang, Min Niu, Liwei Dong, Wen-Peng Wang, Di-Xin Xu, Ge Li, Ling-Yan Jiang, Fuyi Wang, Rui Wen, Chunhui Yang, Jia-Yan Liang, Sen Xin, Yu-Guo Guo

{"title":"Insights into the Electrolyte Hydrolysis and Its Impacts on the Interfacial Chemistry of a Li+-Intercalated Anode during High-Temperature Calendar Aging","authors":"Yu Zhang, Zhen-Zhen Shen, Yanyan Zhang, Min Niu, Liwei Dong, Wen-Peng Wang, Di-Xin Xu, Ge Li, Ling-Yan Jiang, Fuyi Wang, Rui Wen, Chunhui Yang, Jia-Yan Liang, Sen Xin, Yu-Guo Guo","doi":"10.1002/anie.202425491","DOIUrl":"https://doi.org/10.1002/anie.202425491","url":null,"abstract":"Calendar aging occurring during high-temperature storage has long plagued practical realization of long-life, high-safety lithium-ion batteries (LIBs). Generally, the aging process is ascribed to the hydrolysis reaction of fluorine-containing electrolyte salt that generates hydrofluoric acid and chemically corrodes the anode surface. Nevertheless, the underlying mechanism about electrolyte degradation, HF generation and surface corrosion remains concealed for various electrolytes. In this work, we employed in situ liquid time-of-flight secondary ion mass spectroscopy to resolve the chemical evolution during high-temperature calendar aging in the bulk of the electrolyte and at the anode/electrolyte interface. Two conventional salts, LiPF6 and Li bis(fluorosulfonyl)imide (LiFSI), were employed for comparison. We identify that the high-temperature hydrolysis of LiPF6 preferentially occurs when the anion aggregates ([PF6+LiPF6]-) are attacked by trace H2O. HPO2F2, HF and LiF are generated and assist formation of an inorganics-rich solid electrolyte interphase (SEI), improving anode stability against parasitic reactions. The LiFSI-based electrolyte does not involve hydrolysis, which facilities the formation of an organics-rich SEI. Nevertheless, the SEI does not passivate the anode surface and could induce severe corrosions via electron tunneling at a high temperature. Our work offers original insights into rational design of electrolyte and interface for high-energy, long-calendar-life LIBs.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"38 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143077139","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}

引用次数: 0

Precise Regulation of Intra-Nanopore Charge Microenvironment in Covalent Organic Frameworks for Efficient Monovalent Cation Transport

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-02-02 DOI: 10.1002/anie.202420333

Guoxing Jiang, Wenwu Zou, Zhaoyuan Ou, Weifeng Zhang, Junlang Huo, Shengguang Qi, Liming Wang, Li Du

{"title":"Precise Regulation of Intra-Nanopore Charge Microenvironment in Covalent Organic Frameworks for Efficient Monovalent Cation Transport","authors":"Guoxing Jiang, Wenwu Zou, Zhaoyuan Ou, Weifeng Zhang, Junlang Huo, Shengguang Qi, Liming Wang, Li Du","doi":"10.1002/anie.202420333","DOIUrl":"https://doi.org/10.1002/anie.202420333","url":null,"abstract":"Charged channels are considered an effective design for achieving efficient monovalent cation transport; however, it remains challenging to establish a direct relationship between charge microenvironments and ionic conductivity within the pores. Herein, we report a series of crystalline covalent organic frameworks (COFs) with identical skeletons but different charge microenvironments and explore their intra-pore charge-driven ion transport performance and mechanism differences. We found that the charged nature determines ion-pair action sites, modes, host-guest interaction, thereby influencing the dissociation efficiency of ion pairs, the hopping ability of cations, and the effective carrier concentration. The order of transport efficiency for Li+, Na+, and H+ follows anion > zwitterion > cation > neutrality. Ionic COFs exhibit up to 11-fold higher ionic conductivity than neutral COFs. Notably, the ionic conductivity of anionic COF achieves 2.0×10-4 S cm-1 for Li+ at 30°C and 3.8×10-2 S cm-1 for H+ at 160°C, surpassing most COF-based ionic conductors. This COF platform for efficient ion migration and stable battery cycling in lithium-metal quasi-solid-state batteries has also been verified as proof of concept. This work offers new insights into the development and structure-activity relationship studies of the next generation of solid-state ionic conductors.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"84 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143077141","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}

引用次数: 0