Angewandte Chemie International Edition最新文献

{"title":"Eliminating Hydrogen Fluoride through Piperidine-Doped Separators for Stable Li Metal Batteries with Nickel-Rich Cathodes.","authors":"Luoyi Ding, Yuanmao Chen, Yeliang Sheng, Xinyang Yue, Zheng Liang","doi":"10.1002/anie.202411933","DOIUrl":"10.1002/anie.202411933","url":null,"abstract":"<p><p>Hydrofluoric acid (HF)-induced electrode and interfacial structure degeneration poses a significant challenge for high-voltage lithium metal batteries (LMBs). To address this issue, we propose a separator strategy that involves decorating a regular polyethylene (PE) separator with molecular sieves (TW) impregnated with piperidine (PI). The porous structure of the TW serves as a reaction chamber for PI and HF. As a result, the HF content in the controlled electrolyte with 500 ppm H₂O (ELE-500) is notably reduced when using TW@PI-PE separators, thereby shielding nickel-rich cathodes from HF etching. Simultaneously, due to the hydrolysis of Li salts, and the inertness of PI towards H₂O, a uniform lithium fluoride (LiF)-rich solid electrolyte interphase can form on the Li metal anode, further mitigating dendrite formation. The lifespan of the symmetric Li cell using the TW@PI-PE separator is doubled in ELE-500, exhibiting stable 500-hour cycles at 3 mA cm^-2 and 3 mAh cm^-2. Additionally, with the effective limitation of transition metal (TM) dissolution, the 4.6-V LMBs employing a LiNi_0.8Co_0.1Mn_0.1O₂ cathode maintain an 81 % capacity retention over 100 cycles, even in ELE-1000. The innovative TW@PI system presented here offers a fresh perspective for future research aimed at eliminating HF in LMBs.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":" ","pages":"e202411933"},"PeriodicalIF":16.1,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142102475","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}

{"title":"Operando Stable Palladium Hydride Nanoclusters Anchored on Tungsten Carbides Mediate Reverse Hydrogen Spillover for Hydrogen Evolution.","authors":"Hao Fan, Qian Qian Yang, Song Ru Fang, Yi Ning Xu, Yao Lv, Hao Yang Lin, Miao Yu Lin, Ji Kai Liu, Yi Xiao Wu, Hai Yang Yuan, Sheng Dai, Peng Fei Liu, Hua Gui Yang","doi":"10.1002/anie.202412080","DOIUrl":"10.1002/anie.202412080","url":null,"abstract":"<p><p>Proton exchange membrane (PEM) electrolysis holds great promise for green hydrogen production, but suffering from high loading of platinum-group metals (PGM) for large-scale deployment. Anchoring PGM-based materials on supports can not only improve the atomic utilization of active sites but also enhance the intrinsic activity. However, in practical PEM electrolysis, it is still challenging to mediate hydrogen adsorption/desorption pathways with high coverage of hydrogen intermediates over catalyst surface. Here, operando generated stable palladium (Pd) hydride nanoclusters anchored on tungsten carbide (WC_x) supports were constructed for hydrogen evolution in PEM electrolysis. Under PEM operando conditions, hydrogen intercalation induces formation of Pd hydrides (PdH_x) featuring weakened hydrogen binding energy (HBE), thus triggering reverse hydrogen spillover from WC_x (strong HBE) supports to PdH_x sites, which have been evidenced by operando characterizations, electrochemical results and theoretical studies. This PdH_x-WC_x material can be directly utilized as cathode electrocatalysts in PEM electrolysis with ultralow Pd loading of 0.022 mg cm^-2, delivering the current density of 1 A cm^-2 at the cell voltage of ~1.66 V and continuously running for 200 hours without obvious degradation. This innovative strategy via tuning the operando characteristics to mediate reverse hydrogen spillover provide new insights for designing high-performance supported PGM-based electrocatalysts.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":" ","pages":"e202412080"},"PeriodicalIF":16.1,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142131342","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}

{"title":"Drug Discovery and Screening Tool Development for Tauopathies by Focusing on Pathogenic Tau Repeat 3 Oligomers.","authors":"Soljee Yoon, Hye Yun Kim, Sohui Park, Minhae Cha, Kyeonghwan Kim, Songmin Lee, JiMin Kim, Saeyun Bhang, YoungSoo Kim","doi":"10.1002/anie.202411942","DOIUrl":"10.1002/anie.202411942","url":null,"abstract":"<p><p>Comprehending early amyloidogenesis is essential for the development of effective therapeutic strategies. In tauopathies like Alzheimer's disease (AD), the abnormal accumulation of tau protein is initiated by pathological tau seeds. Mounting evidence implies that the microtubule binding domain, consisting of three to four repeats, plays a pivotal role in this process, yet the exact region driving the formation of pathogenic species needs to be further scrutinized. Here, we chemically synthesized individual tau repeats to identify those exhibiting pathogenic prion-like characteristics. Notably, repeat 3 (R3) displayed a remarkable propensity to polymerize, form toxic filaments, and induce cognitive impairment, even in the absence of an aggregation-promoting inducer, highlighting its physiological relevance. Additionally, oligomeric R3 was identified as a particularly pathological form, prompting the establishment of a screening platform. Through screening, tolcapone was found to possess therapeutic efficacy against pathological tau aggregates in PS19 transgenic mice. This screening platform provides a valuable avenue for identifying compounds that selectively interact with peptides implicated in the progression of tauopathies.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":" ","pages":"e202411942"},"PeriodicalIF":16.1,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142306731","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}

{"title":"Electrodriven ATP Synthesis via Integration of a Reconstructed Thylakoid Membrane","authors":"Lijing Chang, Huijuan Cui, Weisong Liu, Yi-Heng P. Job Zhang, Lingling Zhang","doi":"10.1002/anie.202421120","DOIUrl":"https://doi.org/10.1002/anie.202421120","url":null,"abstract":"Nature produces ATP, the energy currency, by converting solar energy (photophosphorylation) and chemical energy (substrate‐level phosphorylation and oxidative phosphorylation). Green electricity, as a significant and sustainable energy carrier, plays a crucial role in achieving a carbon‐neutral society. In this work, we established and verified a novel electrodriven phosphorylation method. Spinach thylakoid membranes (TMs), enriched with ATPases, were isolated and constructed into planar TMs (pTMs) on a proton exchange membrane (PEM), effectively imparting the traditional PEM with the biological function of ATP regeneration. Following the optimization of TMs concentration and incubation time, the biological PEM was integrated into a two‐compartment electrochemical cell, where ATP was successfully synthesized by ATPase of pTMs, triggered by the proton gradient potential generated during electrochemical water splitting. When a constant voltage of 3 V was applied to the electrochemical cells, ATP was synthesized at a rate of 3.16 μM min‐1μgChl‐1, approximately twice the rate of ΔpH‐driven ATP synthesis. This design offers substantial potential for green energy applications in in vitro biotransformation (ivBT) systems.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"36 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142825042","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}

{"title":"A Clean One-Pot Synthesis of Structurally Ordered Linear, Monocyclic, and Bicyclic Oligosiloxanes.","authors":"Yoshihiro Shinohara, Makiko Hatori, Hiroshi Yamashita, Masayasu Igarashi, Kazuhiko Sato, Norihisa Fukaya, Shigeru Shimada","doi":"10.1002/anie.202412808","DOIUrl":"10.1002/anie.202412808","url":null,"abstract":"<p><p>A highly selective cross-coupling reaction between Si-OAc (AcO=acetoxy) and Si-OH compounds that generates unsymmetrical and symmetrical oligosiloxanes concurrent with the release of acetic acid has been developed. The high selectivity arises from the reactivity difference that depends on the varying number of acetoxy groups present, thus facilitating a clean one-pot synthesis of oligosiloxanes. For instance, the reactions of di-, tri-, or tetraacetoxysilanes with silanols furnish acetoxy-containing di- and trisiloxanes in high yield. Two equivalents of tetraacetoxysilane can react with various silanediols to form 1,1,1,3,3,3-hexaacetoxytrisiloxanes, which subsequently react with a second molecule of a silanediol to selectively afford 1,1,3,3-tetraacetoxycyclotetrasiloxanes. The cyclotetrasiloxanes further react with a third molecule of silanediol to provide unprecedented bicyclic pentasiloxanes with acetoxy groups at the bridgehead silicon atoms. Applications of the acetoxy-containing products as efficient surface-treatment agents and new building blocks for highly heat-resistant materials are demonstrated.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":" ","pages":"e202412808"},"PeriodicalIF":16.1,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142034577","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}

{"title":"The Asymmetrical Fe-O-Se Bonds in Fe₂O(SeO₃)₂ Boosting Bifunctional Oxygen Electrocatalytic Performance for Zinc-Air Battery.","authors":"Hui-Min Xu, Kai-Hang Yue, Lian-Jie Song, Hong-Cheng Zhang, Hong-Rui Zhu, Zhi-Jie Zhang, Gao-Ren Li","doi":"10.1002/anie.202412025","DOIUrl":"10.1002/anie.202412025","url":null,"abstract":"<p><p>Zinc-air batteries (ZABs) have the advantages of high energy density and rich zinc raw materials. It is a low-cost, green and sustainable energy storage device. At present, one of the key technologies that hinder the large-scale application of ZABs is the design and fabrication oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) bifunctional catalysts with excellent performance, especially the non-platinum-based catalysts. Here N-doped carbon-coated Fe-based selenium oxide catalyst Fe₂O(SeO₃)₂/Fe₃C@NC with high performance has been fabricated by a one-step pyrolysis and then the electrochemical oxidization. The experimental results confirmed that the existence of Fe-O-Se bonds in Fe₂O(SeO₃)₂ crystal phase of Fe₂O(SeO₃)₂/Fe₃C@NC, and the Fe-O-Se bonds could obviously enhance ORR and OER catalytic performance of Fe₂O(SeO₃)₂/Fe₃C@NC. Density functional theoretical calculations (DFT) confirmed that the Fe₂O(SeO₃)₂ in Fe₂O(SeO₃)₂/Fe₃C@NC had a higher d-band center of Fe atom and a lower p-orbital coupling degree with its own lattice O atom than Fe₂O₃, which leads to Fe site of Fe₂O(SeO₃)₂ being more likely to adsorb external oxygen intermediates. The Fe-O-Se bonds in Fe₂O(SeO₃)₂ results in the modification of coordination environment of Fe atoms and optimizes the adsorption energy of Fe site for oxygen intermediates. Compared with Fe₂O₃/Fe₃C@NC, the Fe₂O(SeO₃)₂/Fe₃C@NC showed the obvious enhancements of ORR/OER catalytic activities with a half-wave potential of 0.91 V for ORR in 0.1 M KOH electrolyte and a low overpotential of 345 mV for OER at 10 mA cm^-2 in a 1.0 M KOH electrolyte. The peak power density and specific capacity of Fe₂O(SeO₃)₂/Fe₃C@NC-based ZABs are higher than those of Pt/C+RuO₂-ZABs. The above results demonstrate that the asymmetrical Fe-O-Se bonds in Fe₂O(SeO₃)₂ plays a key role in improving the bifunctional catalytic activities of ORR/OER for ZABs.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":" ","pages":"e202412025"},"PeriodicalIF":16.1,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142124299","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}

{"title":"Halogen Bonding Initiated Difunctionalization of [1.1.1]Propellane via Photoinduced Polarity Match Additions.","authors":"Liang Yi, Deshen Kong, Ajit Prabhakar Kale, Rawan Alshehri, Huifeng Yue, Amir Gizatullin, Bholanath Maity, Rajesh Kancherla, Luigi Cavallo, Magnus Rueping","doi":"10.1002/anie.202411961","DOIUrl":"10.1002/anie.202411961","url":null,"abstract":"<p><p>Bicyclo[1.1.1]pentane (BCP), recognized as a bioisostere for para-disubstituted benzene, has gained widespread interest in drug development due to its ability to enhance the physicochemical properties of pharmaceuticals. In this work, we introduce a photoinduced, halogen bonding-initiated, metal-free strategy for synthesizing various BCP derivatives. This method involves the generation of nucleophilic α-aminoalkyl radicals via halogen-bonding adducts. These undergo selective radical addition to [1.1.1]propellane, yielding electrophilic BCP radicals that subsequently participate in polarity-matched additions, culminating in the difunctionalization of bicyclopentane. The versatility and practicality of this metal-free approach are underscored by its broad substrate scope, which includes late-stage functionalization and a series of valuable transformations, all conducted under mild reaction conditions.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":" ","pages":"e202411961"},"PeriodicalIF":16.1,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142078569","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}

{"title":"Long-Term Autotrophic Growth and Solar-to-Chemical Conversion in Shewanella Oneidensis MR-1 through Light-Driven Electron Transfer.","authors":"Yan Shi, Kejing Zhang, Jianxin Chen, Bingtian Zhang, Xun Guan, Xin Wang, Tong Zhang, Han Song, Long Zou, Xiangfeng Duan, Haichun Gao, Zhang Lin","doi":"10.1002/anie.202412072","DOIUrl":"10.1002/anie.202412072","url":null,"abstract":"<p><p>Members of the genus Shewanella are known for their versatile electron accepting routes, which allow them to couple decomposition of organic matter to reduction of various terminal electron acceptors for heterotrophic growth in diverse environments. Here, we report autotrophic growth of Shewanella oneidensis MR-1 with photoelectrons provided by illuminated biogenic CdS nanoparticles. This hybrid system enables photosynthetic oscillatory acetate production from CO₂ for over five months, far exceeding other inorganic-biological hybrid system that can only sustain for hours or days. Biochemical, electrochemical and transcriptomic analyses reveal that the efficient electron uptake of S. oneidensis MR-1 from illuminated CdS nanoparticles supplies sufficient energy to stimulate the previously overlooked reductive glycine pathway for CO₂ fixation. The continuous solar-to-chemical conversion is achieved by photon induced electric recycling in sulfur species. Overall, our findings demonstrate that this mineral-assisted photosynthesis, as a widely existing and unique model of light energy conversion, could support the sustained photoautotrophic growth of non-photosynthetic microorganisms in nutrient-lean environments and mediate the reversal of coupled carbon and sulfur cycling, consequently resulting in previously unknown environmental effects. In addition, the hybrid system provides a sustainable and flexible platform to develop a variety of solar products for carbon neutrality.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":" ","pages":"e202412072"},"PeriodicalIF":16.1,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142091240","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}

{"title":"Machine Learning-Aided Discovery of Low-Pt High Entropy Intermetallic Compounds for Electrochemical Oxygen Reduction Reaction.","authors":"Longhai Zhang, Xu Zhang, Changsheng Chen, Jiaxi Zhang, Weiquan Tan, Zhihang Xu, Ziying Zhong, Li Du, Huiyu Song, Shijun Liao, Ye Zhu, Zhen Zhou, Zhiming Cui","doi":"10.1002/anie.202411123","DOIUrl":"10.1002/anie.202411123","url":null,"abstract":"<p><p>Advancing the design of cathode catalysts to significantly maximize platinum utilization and augment the longevity has emerged as a formidable challenge in the field of fuel cells. Herein, we rationally design a high entropy intermetallic compound (HEIC, Pt(FeCoNiCu)₃) for catalyzing oxygen reduction reaction (ORR) by an efficient machine learning stategy, where crystal graph convolutional neural networks are employed to expedite the multicomponent design. Based on a dataset generated from first-principles calculations, the model can achieve a high prediction accuracy with mean absolute errors of 0.003 for surface strain and 0.011 eV atom^-1 for formation energy. In addition, we identify two chemical features (atomic size difference and mixing enthalpy) as new descriptors to explore advanced ORR catalysts. The carbon supported Pt(FeCoNiCu)₃ catalyst with small particle size is successfully synthesized by a freeze-drying-annealing technology, and exhibits ultrahigh mass activity (4.09 A mg_Pt ^-1) and specific activity (7.92 mA cm^-2). Meanwhile, The catalyst also shows significantly enhanced electrochemical stability which can be ascribed to the sluggish diffussion effect in the HEIC structure. Beyond offering a promising low-Pt electrocatalysts for fuel cell cathode, this work offers a new paradigm to rationally design advanced catalysts for energy storage and conversion devices.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":" ","pages":"e202411123"},"PeriodicalIF":16.1,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142379631","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}

{"title":"Controllable Graphene/MoS₂ Heterointerfaces by Perpendicular Surface Functionalization.","authors":"Qing Cao, Jiajun Dai, Zhuting Hao, Beate Paulus, Siegfried Eigler, Xin Chen","doi":"10.1002/anie.202415922","DOIUrl":"10.1002/anie.202415922","url":null,"abstract":"<p><p>Surface chemistry and interface interactions profoundly influence the properties of two-dimensional (2D) materials and heterostructures. Therefore, developing methods to precisely control surfaces and interfaces is crucial for harnessing the properties and functions of 2D materials and heterostructures. Here, we developed a facile approach to tuning the interface distance and properties of graphene/MoS₂ heterostructures (G/MoS₂) by varying the functional groups attached to the surface of graphene bottom layer. We systematically investigated how different functionalized graphene bottom layers affect the interlayer distance, coupling between the interlayers, and optical properties of resulting G/MoS₂ heterostructures. Our findings indicate that both the size and electron-withdrawing/donating properties of functional groups are pivotal in regulating charge transport properties, with size playing a particularly decisive role. Our approach demonstrates an efficient and flexible pathway to regulate the interlayer spacing and charge transport, highlighting the potential of engineering interface chemistry in optimizing properties of van der Waals heterostructures.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":" ","pages":"e202415922"},"PeriodicalIF":16.1,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142602506","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}