Angewandte Chemie International Edition最新文献

Electrochemical Alkyl Displacement of Thioethers for Streamlined Trideuteromethylation. 流线型三氘甲基化中硫醚的电化学烷基置换。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-07-24 DOI: 10.1002/anie.202512612

Hongshuai Chen,Yanghao Yin,Guoqing Wang,Xiao Xiao,Xuefeng Jiang,Minghao Feng

{"title":"Electrochemical Alkyl Displacement of Thioethers for Streamlined Trideuteromethylation.","authors":"Hongshuai Chen,Yanghao Yin,Guoqing Wang,Xiao Xiao,Xuefeng Jiang,Minghao Feng","doi":"10.1002/anie.202512612","DOIUrl":"https://doi.org/10.1002/anie.202512612","url":null,"abstract":"Deuterated compounds exhibit significant pharmacokinetic advantages and have been widely applied in drug discovery. Trideuteromethyl-containing compounds represent a substantial portion of both approved deuterated drugs and those in development. Traditional approaches to incorporate trideuterated methyl group with trideuterated methyl sources (such as iodomethane-d3, dimethyl sulfate-d6) require preactivated synthetic precursor, limiting the application for the late-stage trideuteromethyl group incorporation of pharmaceutical molecules. Herein, we develop an electrochemical approach for late-stage trideuteromethyl incorporation of thioether by using stoichiometric methanol-d4 as the trideuteromethyl isotopic source via a sulfide alkyl displacement. This protocol features operational simplicity, selectivity, and scalability, enabling direct alkyl modification of various aryl alkyl sulfides as well as gram-scale production of trideuteromethyl drugs without the need for synthetic precursors. Mechanistic studies show that the in-situ generated sulfonium salt was the key intermediate. A series of control experiments reveals that alkanes as the departing moiety are the key to alkyl displacement and precise late-stage trideuteration.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"25 1","pages":"e202512612"},"PeriodicalIF":16.6,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144693249","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

Correction to "Cell-Active, Arginine-Targeting Irreversible Covalent Inhibitors for Nonkinases and Kinases". 对“非激酶和激酶的细胞活性、精氨酸靶向不可逆共价抑制剂”的更正。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-07-24 DOI: 10.1002/anie.202515279

引用次数: 0

Efficient Hydrogen Sulfide Separation from Carbon Dioxide Achieved by Carbonyl-Functionalized Ionic Liquids for Natural Gas Upgrading. 羰基功能化离子液体在天然气改造中的高效硫化氢分离

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-07-24 DOI: 10.1002/anie.202504337

Mingzhen Shi,Guoao Li,Hangzhi Wu,Hailong Ning,Hongchao Lan,Xiaomin Zhang,Shuhua Li,Youting Wu

{"title":"Efficient Hydrogen Sulfide Separation from Carbon Dioxide Achieved by Carbonyl-Functionalized Ionic Liquids for Natural Gas Upgrading.","authors":"Mingzhen Shi,Guoao Li,Hangzhi Wu,Hailong Ning,Hongchao Lan,Xiaomin Zhang,Shuhua Li,Youting Wu","doi":"10.1002/anie.202504337","DOIUrl":"https://doi.org/10.1002/anie.202504337","url":null,"abstract":"Natural gas upgrading requires efficient separation of H2S from CO2, another acidic impurity, to enhance gas utilization efficiency and enable resource recovery from waste streams. While significant advancements have been achieved in separating H2S from CH4, the selective removal of H2S from CO2 remains a formidable challenge due to their similar physicochemical properties. Herein, we report a breakthrough strategy utilizing reversible nucleophilic addition reaction between carbonyl group and H2S, departing from conventional acid-base interaction-based liquid-phase capture processes. Through comprehensive characterization using nuclear magnetic resonance (NMR) and Fourier transform infrared (FT-IR) spectroscopy, we confirmed the formation of nucleophilic addition products between the designed carbonyl-functionalized ionic liquids (ILs) and H2S. Dispersion-corrected DFT calculations revealed that the nucleophilic addition products facilitate secondary H2S capture through two distinct approaches: 1) conformational matching and 2) dissociation of H2S into [HS]⁻ species. The unique cascade H2S sorption mechanism demonstrates exceptional affinity for H2S, endowing the [6ca]-derived ILs with unprecedented high H2S capacities and record-breaking H2S/CO2 selectivities (67-89 at 1.0 bar and 229-319 at 0.1 bar), surpassing previously reported values. Combined with energy-efficient regeneration cycles, these findings establish a new paradigm for H2S/CO2 separation with significant potential for natural gas valorization.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"75 1","pages":"e202504337"},"PeriodicalIF":16.6,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144693341","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

Platinum-Catalysed Hydrofluorination of Alkynes at Room Temperature Promoted by a Fluoride Shuttle. 室温下铂催化炔的氟化反应。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-07-23 DOI: 10.1002/anie.202512181

Ouchan He,Froze Jameel,Hannah Flammang,Smrithi Suresh Babu,Martin Kaupp,Thomas Braun

{"title":"Platinum-Catalysed Hydrofluorination of Alkynes at Room Temperature Promoted by a Fluoride Shuttle.","authors":"Ouchan He,Froze Jameel,Hannah Flammang,Smrithi Suresh Babu,Martin Kaupp,Thomas Braun","doi":"10.1002/anie.202512181","DOIUrl":"https://doi.org/10.1002/anie.202512181","url":null,"abstract":"Hydrofluorination of alkynes provides a synthetic route to access fluoroalkenes, a class of compounds with wide applications in chemical research. Herewith, we describe an exceptional hydrofluorination process of alkynes catalysed by Pt(II) complexes at room temperature. Various Pt(II) dichloride complexes bearing chelating phosphines were synthesised and studied towards their catalytic behaviour. Mechanistic investigations suggest the involvement of a dicationic Pt(II) bis(alkyne) species as well as a cationic ß-fluorovinyl Pt(II) complex in the catalytic cycle. Remarkably, the hydrofluorination is enabled by fluorinated anions. The corresponding acids BF3, HF as well as PF5 act as fluoride shuttles to allow for an outer-sphere fluorination of the metal-bound substrate. Detailed DFT analyses for BF3 show that the hydrofluorination is mediated by complexes between the fluorinated anion and HF. This lowers the hydrofluorination barriers sufficiently to outcompete the simultaneously occurring, more exergonic cyclisation of two coordinated alkynes to a structurally characterised cycloallyl complex. The catalytic system can be applied to a wide substrate scope to generate fluoroalkenes bearing bulky alkyl, aryl and electron withdrawing groups, such as ester and carbonyl substituents.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"1 1","pages":"e202512181"},"PeriodicalIF":16.6,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144684096","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

Atomic Metal‒Nonmetal Catalytic Pair Cooperatively Drives Efficient Enzyme-Mimetic Catalysis. 原子金属-非金属催化对协同驱动高效的模拟酶催化。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-07-23 DOI: 10.1002/anie.202508651

Zheye Zhang,Fuhua Li,Shibo Xi,Lewen Zheng,Xiaozhe Wang,Baojie Du,Xiao Chi,Zhongxin Chen,Hong Bin Yang,Lishuang Zhang,Dongsheng Li,Bin Liu,Liping Li,Peng Chen

{"title":"Atomic Metal‒Nonmetal Catalytic Pair Cooperatively Drives Efficient Enzyme-Mimetic Catalysis.","authors":"Zheye Zhang,Fuhua Li,Shibo Xi,Lewen Zheng,Xiaozhe Wang,Baojie Du,Xiao Chi,Zhongxin Chen,Hong Bin Yang,Lishuang Zhang,Dongsheng Li,Bin Liu,Liping Li,Peng Chen","doi":"10.1002/anie.202508651","DOIUrl":"https://doi.org/10.1002/anie.202508651","url":null,"abstract":"Single-atom catalysts with maximum atom utilization and well-defined coordination environments are promising alternatives to natural enzymes. However, their catalytic performance in enzymatic reactions is intrinsically restricted by the scaling relations, which impose an inherent trade-off between substrate adsorption/activation and product desorption. Here we report atomically dispersed manganese‒sulfur (Mn─S) catalytic pairs with strong electronic coupling that integratively drive enzymatic catalysis, in which the S atom not only modulates the electronic structure of the adjacent Mn site to promote substrate adsorption and activation, but also functions as the secondary catalytic site for stabilizing oxygenated intermediates and facilitating product desorption. Consequently, this metal‒nonmetal dual-site cooperation enables simultaneous optimization of both adsorption/activation and desorption processes, leading to remarkably enhanced catalytic activity. As a potential application, the Mn─S catalytic pairs with coupled catalase-, peroxidase-, and oxidase-mimicking activities are successfully demonstrated for synergistic tumor catalytic therapy. This work establishes a paradigm for the rational design of highly efficient artificial enzymes through catalytic pair engineering.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"47 1","pages":"e202508651"},"PeriodicalIF":16.6,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144684254","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

Insight into how PETase Functions at the Solid-Liquid Interface and an Activity-Stability Trade-Off. 洞察PETase如何在固液界面起作用和活性-稳定性权衡。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-07-23 DOI: 10.1002/anie.202511131

Shuang Chen,Ekram Akram,Hui Liang,Weili Qiao,Yifei Zhang,Shozeb Haider,Yufei Cao

{"title":"Insight into how PETase Functions at the Solid-Liquid Interface and an Activity-Stability Trade-Off.","authors":"Shuang Chen,Ekram Akram,Hui Liang,Weili Qiao,Yifei Zhang,Shozeb Haider,Yufei Cao","doi":"10.1002/anie.202511131","DOIUrl":"https://doi.org/10.1002/anie.202511131","url":null,"abstract":"Enzymatic degradation of poly(ethylene terephthalate) (PET) has garnered considerable interest in plastic recycling efforts. However, the underlying molecular mechanism governing PETase-catalyzed PET depolymerization at the solid-liquid interface remains elusive, hampering the rational design of highly efficient enzymes. Here, we comprehensively elucidate the catalytic pathway of PETase, detailing steps from initial enzyme adsorption at the PET interface, subsequent substrate fragment capture, conformational refinement, to the ultimate cleavage of ester bonds. We uncover an intrinsic trade-off between the activity and stability of the enzyme's PET-binding loops, which negatively impacts overall PET degradation efficiency. By strategically reshaping the loop dynamics of PETase, we successfully overcome this compromise, simultaneously enhancing both enzymatic activity and structural stability. Collectively, this work provides critical insights into PETase functionality at solid-liquid interfaces and establishes valuable guidelines for the rational design of efficient plastic-degrading enzymes.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"35 1","pages":"e202511131"},"PeriodicalIF":16.6,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144684253","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

Alkali Metal Cations Impact the Selectivity of Radical-Mediated Electrochemical C─H Chlorination. 碱金属阳离子对自由基介导的电化学C─H氯化选择性的影响。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-07-23 DOI: 10.1002/anie.202509115

Bo Wu,Ruihu Lu,Tenghui Yuan,Beijing Cai,Bingqing Wang,Bote Zhao,Shibo Xi,Ziyun Wang,Yanwei Lum

{"title":"Alkali Metal Cations Impact the Selectivity of Radical-Mediated Electrochemical C─H Chlorination.","authors":"Bo Wu,Ruihu Lu,Tenghui Yuan,Beijing Cai,Bingqing Wang,Bote Zhao,Shibo Xi,Ziyun Wang,Yanwei Lum","doi":"10.1002/anie.202509115","DOIUrl":"https://doi.org/10.1002/anie.202509115","url":null,"abstract":"Electrochemistry offers a promising route toward facilitating organic transformation reactions in a sustainable manner. However, there are often a multitude of factors at play; hence, it can be unclear how operating conditions can be rationally tuned to optimize selectivity. Here, we demonstrate how the identity of alkali metal cations in the electrolyte can control the selectivity of electrochemical C─H chlorination. Specifically, we obtained a 90.3% Faradaic efficiency with KCl as compared to 78.4% with LiCl for the conversion of cyclohexane to chlorocyclohexane at 1000 mA using an IrOx electrode. Electron paramagnetic resonance spectroscopy experiments indicate a greater propensity for Cl- oxidation to generate Cl radicals in the order: K+ > Na+ > Li+. This leads to an increase in the selectivity toward the chlorination of cyclohexane and a concomitant decrease in competitive Cl2 formation. Density functional theory calculations and in situ Raman spectroscopy experiments indicate that this is likely due to a decrease in *Cl binding energy on IrOx in the presence of K+. These findings highlight the important role of alkali metal cations, which can be a key consideration for designing electrochemical organic synthesis systems.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"15 1","pages":"e202509115"},"PeriodicalIF":16.6,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144684257","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

Atorvastatin-Loaded Mineralized Vaccine Reprograms Endosomal Trafficking to Amplify STING-Driven Cancer Immunotherapy. 负载阿托伐他汀的矿化疫苗重编程内体运输以增强sting驱动的癌症免疫治疗。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-07-23 DOI: 10.1002/anie.202503749

Yuhan Yang,Wei Long,Xiangyu Pei,Shangfei Li,Bowen Fu,Hao Zhai,Xiaoyi Zhang,Ying Wan,Yayun Peng,Ting Cai

{"title":"Atorvastatin-Loaded Mineralized Vaccine Reprograms Endosomal Trafficking to Amplify STING-Driven Cancer Immunotherapy.","authors":"Yuhan Yang,Wei Long,Xiangyu Pei,Shangfei Li,Bowen Fu,Hao Zhai,Xiaoyi Zhang,Ying Wan,Yayun Peng,Ting Cai","doi":"10.1002/anie.202503749","DOIUrl":"https://doi.org/10.1002/anie.202503749","url":null,"abstract":"Dendritic cell (DC)-targeted nanovaccines offer great promise for cancer immunotherapy but are severely limited by premature lysosomal degradation of antigens, which reduces cross-presentation efficacy. Here, we report a facile yet effective biomineralization strategy to construct nanovaccine (OVA-ATV@MnO₂) that co-delivers ovalbumin (OVA) and atorvastatin (ATV) within MnO₂ matrix. The ATV-mediated nanovaccine reprograms endosomal trafficking by inhibiting the mevalonate (MVA) pathway, thereby delaying endosomal maturation and preventing antigen diversion to degradative lysosomes. This intervention significantly enhances antigen preservation and MHC-I presentation in DCs. Simultaneously, the MnO₂ framework not only stabilizes the vaccine nanostructure but also releases Mn2⁺ ions as an adjuvant to potently activate the cGAS-STING pathway, amplifying DC maturation and antitumor T-cell priming. In vivo studies demonstrate that the nanovaccine induces robust tumor regression, suppresses metastasis, and establishes durable prophylactic immunity. By synergistically rewiring intracellular antigen trafficking and amplifying STING-mediated immune activation, this mineralized vaccine platform provides a transformative strategy for precise cancer immunotherapy.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"52 1","pages":"e202503749"},"PeriodicalIF":16.6,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144684262","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

Hydrogen-Bonding-Assisted Assembly of Stable High-Nuclearity Copper(I)-Alkyne Nanoclusters for X-Ray Scintillation. 用于x射线闪烁的稳定高核铜-炔纳米团簇的氢键辅助组装。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-07-23 DOI: 10.1002/anie.202507412

Bao-Liang Han,Fahri Alkan,Zhi-Rui Yuan,Paritosh Mahato,Zhi Wang,Chen-Ho Tung,Di Sun

{"title":"Hydrogen-Bonding-Assisted Assembly of Stable High-Nuclearity Copper(I)-Alkyne Nanoclusters for X-Ray Scintillation.","authors":"Bao-Liang Han,Fahri Alkan,Zhi-Rui Yuan,Paritosh Mahato,Zhi Wang,Chen-Ho Tung,Di Sun","doi":"10.1002/anie.202507412","DOIUrl":"https://doi.org/10.1002/anie.202507412","url":null,"abstract":"The construction of high-nuclearity, atomically precise copper(I)-alkyne nanoclusters remains a formidable challenge due to their high reactivity and strong aggregation tendency. Here, we report a hydrogen-bonding-assisted assembly strategy that enables the ambient-condition synthesis of two robust copper(I)-alkyne nanoclusters. Single-crystal X-ray diffraction reveals the different core structures including [(C2)8@Cu50] (Cu50) and [(C2)10@Cu56] (Cu56). Both clusters feature distinctive metal shells stabilized by synergistic Cu─C/O coordination interactions and an extensive outer-layer hydrogen-bonding network between the hydroxyl groups of 2-methyl-3-butyn-2-ol and CF3COO- ligands, enhancing molecular rigidity and inoxidizability. Notably, Cu50 displays strong yellow phosphorescence and prominent X-ray-excited luminescence (XEL). More significantly, it represents the first high-nuclearity copper nanocluster to be processed into a scintillator film, which exhibits promising X-ray imaging performance. The present work not only establishes a generalizable hydrogen-bond-assisted assembly strategy for constructing stable, high-nuclearity copper(I)-alkyne nanoclusters, but also demonstrates their practical applicability in X-ray scintillation, providing new insights into the synthetic design and functional diversification of nanocluster-based materials.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"12 1","pages":"e202507412"},"PeriodicalIF":16.6,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144684097","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

Asymmetric Coordinated Single-Atom Catalysts Offering Zero-Order Sulfur Redox Kinetics for High Performance Li-S Batteries. 不对称配位单原子催化剂为高性能锂电池提供零级硫氧化还原动力学。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-07-23 DOI: 10.1002/anie.202510212

Xianghua Kong,Yifan Li,Guolei Cai,Wenchao Liu,Junjie Xu,Chuanfeng Liu,Guikai Zhang,Yilin Wang,Zhiyu Lu,Jing Zhang,Xiaojun Wu,Dawei Zhang,Hao Luo,Song Jin,Hengxing Ji

{"title":"Asymmetric Coordinated Single-Atom Catalysts Offering Zero-Order Sulfur Redox Kinetics for High Performance Li-S Batteries.","authors":"Xianghua Kong,Yifan Li,Guolei Cai,Wenchao Liu,Junjie Xu,Chuanfeng Liu,Guikai Zhang,Yilin Wang,Zhiyu Lu,Jing Zhang,Xiaojun Wu,Dawei Zhang,Hao Luo,Song Jin,Hengxing Ji","doi":"10.1002/anie.202510212","DOIUrl":"https://doi.org/10.1002/anie.202510212","url":null,"abstract":"Accelerating the sluggish sulfur redox kinetics through electrocatalysis has been regarded as one of the key factors to achieve Li-S batteries of cell-level energy densities exceeding 600 Wh kg-1. Though single-atom catalysts (SACs), typically with symmetric M-N4 coordination structures have demonstrated attractive electrocatalytic performance in Li-S batteries, herein we discovered that an asymmetric-coordinated metal center distinctly shifts sulfur redox reaction (SRR) kinetics-from first-order (concentration-dependent) behavior in the symmetric-coordinated SACs-to zero-order (surface-saturated) kinetics, highlighting fundamentally altered reaction pathways, leading to a concurrent polysulfide conversion. Experimental and theoretical studies on the Ni atom-based SACs showed that symmetry breaking raises the Ni d-band center, enabling a monodentate-to-bidentate Li2S4 adsorption transition, which strengthens polysulfide adsorption and shifts the rate-limiting step from sluggish solid-solid transformation (Li2S2 → Li2S) to a more favorable liquid-solid conversion (Li2S4 → Li2S2), effectively lowering the overall energy barrier of the SRR process. Consequently, Li-S cells employing Ni-NPG, a SACs with asymmetric Ni-N3P1 coordination, achieved a specific capacity of 877 mAh g-1 at 4 C. Even under a high sulfur loading of 6 mg cm-2, the cell retained 92% of its capacity after 200 cycles at 0.2 C, outperforming conventional SACs with symmetric coordination structures.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"4 1","pages":"e202510212"},"PeriodicalIF":16.6,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144684099","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