Angewandte Chemie最新文献_第8页

Leveraging Iron in the Electrolyte to Improve Oxygen Evolution Reaction Performance: Fundamentals, Strategies, and Perspectives

Angewandte Chemie Pub Date : 2025-01-14 DOI: 10.1002/ange.202423071

Haiyan Li, Yuwei Zhang, Yubo Chen, Yang Li, Zhongjian Li, Bin Yang, Qinghua Zhang, Jianguo Lu, Lecheng Lei, Zhichuan J. Xu, Yang Hou

{"title":"Leveraging Iron in the Electrolyte to Improve Oxygen Evolution Reaction Performance: Fundamentals, Strategies, and Perspectives","authors":"Haiyan Li, Yuwei Zhang, Yubo Chen, Yang Li, Zhongjian Li, Bin Yang, Qinghua Zhang, Jianguo Lu, Lecheng Lei, Zhichuan J. Xu, Yang Hou","doi":"10.1002/ange.202423071","DOIUrl":"https://doi.org/10.1002/ange.202423071","url":null,"abstract":"Electrochemical water splitting is a pivotal technology for storing intermittent electricity from renewable sources into hydrogen fuel. However, its overall energy efficiency is impeded by the sluggish oxygen evolution reaction (OER) at the anode. In the quest to design high-performance anode catalysts for driving the OER under non-acidic conditions, iron (Fe) has emerged as a crucial element. Although the profound impact of adventitious electrolyte Fen+ species on OER catalysis had been reported forty years ago, recent interest in tailoring the electrode-electrolyte interface has spurred studies on the controlled introduction of Fe ions into the electrolyte to improve OER performance. During the catalytic process, scenarios where the rate of Fen+ deposition on a specific host material outruns that of dissolution pave the way for establishing highly efficient and dynamically stable electrochemical interfaces for long-term steady operation. This review systematically summarizes recent endeavors devoted to elucidating the behaviors of in situ Fe(aq.) incorporation, the role of incorporated Fe sites in the OER, and critical factors influencing the interplay between the electrode surface and Fe ions in the electrolyte environment. Finally, unexplored issues related to comprehensively understanding and leveraging the dynamic exchange of Fen+ at the interface for improved OER catalysis are summarized.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 8","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143431346","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Observation of the Smallest Three-Dimensional Neutral Boron Cluster

Angewandte Chemie Pub Date : 2025-01-14 DOI: 10.1002/ange.202419089

Cong-Qiao Xu, Tiantong Wang, Chong Wang, Xin-Ran Dong, Huijun Zheng, Ya Zhao, Li-Li Pan, Jiayue Yang, Weiqing Zhang, Guorong Wu, Hua Xie, Gang Li, Jun Li, Ling Jiang, Xueming Yang, Lai-Sheng Wang

{"title":"Observation of the Smallest Three-Dimensional Neutral Boron Cluster","authors":"Cong-Qiao Xu, Tiantong Wang, Chong Wang, Xin-Ran Dong, Huijun Zheng, Ya Zhao, Li-Li Pan, Jiayue Yang, Weiqing Zhang, Guorong Wu, Hua Xie, Gang Li, Jun Li, Ling Jiang, Xueming Yang, Lai-Sheng Wang","doi":"10.1002/ange.202419089","DOIUrl":"https://doi.org/10.1002/ange.202419089","url":null,"abstract":"Despite major progress in the investigation of boron cluster anions, direct experimental study of neutral boron clusters remains a significant challenge because of the difficulty in size selection. Here we report a size-specific study of the neutral B9 cluster using threshold photoionization with a tunable vacuum ultraviolet free electron laser. The ionization potential of B9 is measured to be 8.45±0.02 eV and it is found to have a heptagonal bipyramid D7h structure, quite different from the planar molecular wheel of the B9- anionic cluster. Chemical bonding analyses reveal superior stability of the bipyramidal structure arising from delocalized σ and π bonding interactions within the B7 ring and between the B7 ring and the capping atoms. Photoionization of B9 breaks the single-electron B-B bond of the capping atoms, which undergo off-axis distortion to enhance interactions with the B7 ring in the singlet ground state of B9+. The single-electron B-B bond of the capping atoms appears to be crucial in stabilizing the D7h structure of B9. This work opens avenues for direct size-dependent experimental studies of a large variety of neutral boron clusters to explore the stepwise development of network structures.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 8","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143431351","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Kinetic Control of Self-Assembly Pathway in Dual Dynamic Covalent Polymeric Systems

Angewandte Chemie Pub Date : 2025-01-14 DOI: 10.1002/ange.202424147

Ling Liu, Dr. Yuanxin Deng, Da-Hui Qu, Prof. Dr. Ben L. Feringa, Prof. Dr. He Tian, Jun.-Prof. Dr. Qi Zhang

{"title":"Kinetic Control of Self-Assembly Pathway in Dual Dynamic Covalent Polymeric Systems","authors":"Ling Liu, Dr. Yuanxin Deng, Da-Hui Qu, Prof. Dr. Ben L. Feringa, Prof. Dr. He Tian, Jun.-Prof. Dr. Qi Zhang","doi":"10.1002/ange.202424147","DOIUrl":"https://doi.org/10.1002/ange.202424147","url":null,"abstract":"Kinetically controlled self-assembly is garnering increasing interest in the field of supramolecular polymers and materials, yet examples involving dynamic covalent exchange remain relatively unexplored. Here we report an unexpected dynamic covalent polymeric system whose aqueous self-assembly pathway is strongly influenced by the kinetics of evaporation of water. The key design is to integrate dual dynamic covalent bonds—including disulfide bonds and boroxine/borate—into a dynamic equilibrium system of monomers, polymers, and materials. This dual dynamic covalent design allows polymer growth and crosslinking to occur with the same spatiotemporal characteristics, governed solely by solvent evaporation. We found that a single building block can assemble into two distinct types of polymeric materials, each characterized by unique crosslinking topologies, orders, solubility, and macroscopic properties. The dual dynamic nature of the materials imparts them with intrinsic reconfigurability, such as interfacial repairability and close-loop chemical recyclability.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 9","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143475432","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Building Three-Dimensional Complexity by Intramolecular 2-Aminoallyl Cation−Diene (4+3) Cycloaddition

Angewandte Chemie Pub Date : 2025-01-14 DOI: 10.1002/ange.202423405

Lulu Shen, Tianzhu Qin, Chongling Jiao, Prof. Dr. Weiwei Zi

引用次数: 0

A photosynthesis-derived bionic system for sustainable biosynthesis

Angewandte Chemie Pub Date : 2025-01-13 DOI: 10.1002/ange.202414981

Na Chen, Ruichen Shen, Tianpei He, Jing Xi, Rui Zhao, Na Du, Yangbing Yang, Lilei Yu, Quan Yuan

{"title":"A photosynthesis-derived bionic system for sustainable biosynthesis","authors":"Na Chen, Ruichen Shen, Tianpei He, Jing Xi, Rui Zhao, Na Du, Yangbing Yang, Lilei Yu, Quan Yuan","doi":"10.1002/ange.202414981","DOIUrl":"https://doi.org/10.1002/ange.202414981","url":null,"abstract":"“Cell factory” strategy based on microbial anabolism pathways offers an intriguing alternative to relieve the dependence on fossil fuels, which are recognized as the main sources of CO2 emission. Typically, anabolism of intracellular substance in cell factory requires the consumption of sufficient reduced nicotinamide adenine dinucleotide /nicotinamide adenine dinucleotide phosphate NAD(P)H and adenosine triphosphate ATP. However, it is of great challenge to modify the natural limited anabolism and to increase the insufficient level of NAD(P)H and ATP to optimum concentrations without causing metabolic disorder. Inspired by the natural photosynthesis process in which NAD(P)H and ATP can both be produced through the coupled electron-proton transfer processes driven by sunlight, herein we designed a light-driven bionic system composed of three modules including photo-induced electron module, electron transfer channel module and proton gradient module. The proposed strategy of light-driven bionic system enables for achieving simultaneous and controllable supplies of NAD(P)H and ATP, thus facilitating both highly efficient CO2 fixation and biomanufacturing. The proposed light-driven bionic system design strategy in this work might pave new sustainable ways for reducing power and energy regeneration to optimize microbial metabolism, offering intriguing alternatives for CO2 emission mitigation and high-value chemical biomanufacturing.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 7","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143380752","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Zero-Valent Copper Catalysis Enables Regio- and Stereoselective Difunctionalization of Alkynes

Angewandte Chemie Pub Date : 2025-01-13 DOI: 10.1002/ange.202418901

Aishwarya Prakash, Suma Basappa, Rajashri R. Urkude, Ravindra Jangir, Rajendra S. Dhayal, Shubhankar Kumar Bose

{"title":"Zero-Valent Copper Catalysis Enables Regio- and Stereoselective Difunctionalization of Alkynes","authors":"Aishwarya Prakash, Suma Basappa, Rajashri R. Urkude, Ravindra Jangir, Rajendra S. Dhayal, Shubhankar Kumar Bose","doi":"10.1002/ange.202418901","DOIUrl":"https://doi.org/10.1002/ange.202418901","url":null,"abstract":"The development of a metallic copper-based catalyst system remains a significant challenge. Herein, we report the synthesis of highly stable, active, and reusable Cu0 catalyst for the carboboration of alkynes using carbon electrophiles and bis(pinacolato)diboron (B2pin2) as chemical feedstocks to afford di- and trisubstituted vinylboronate esters in a regio- and stereoselective manner with appreciable turnover number (TON) of up to 2535 under mild reaction conditions. This three-component coupling reaction works well with a variety of substituted electrophiles and alkynes with broad functional group tolerance. In addition, a wide range of terminal and challenging internal alkynes were efficiently converted into hydroborated products in up to >99 % yield with excellent regioselectivity in the absence of carbon electrophiles. X-ray photoelectron spectroscopy and X-ray absorption near-edge spectroscopy (XANES) analysis confirm that the oxidation state of the copper in the catalyst is zero. The broad range of organic transformations, effectiveness, and recyclability of this Cu0 catalyst are the major achievements that provide an environmentally friendly route for the efficient production of tri- and tetrasubstituted olefins, key intermediates in organic synthesis. The gram-scale reaction and synthetic transformations further highlights the usefulness of these methods.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 8","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143431125","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Organoboron-Functionalized Metal-Organic Nanosheets for Highly Efficient CO2 Fixation Mediated by Frustrated Lewis Pairs

Angewandte Chemie Pub Date : 2025-01-13 DOI: 10.1002/ange.202416497

Dr. Cheng-Xia Chen, Haiping Wang, Dr. Hassan Rabaâ, Dr. Yang-Yang Xiong, Dr. Peter VanNatta, Dr. Zhang-Wen Wei, Prof. Abdullah M. Al-Enizi, Prof. Ayman Nafady, Prof. Shengqian Ma

{"title":"Organoboron-Functionalized Metal-Organic Nanosheets for Highly Efficient CO2 Fixation Mediated by Frustrated Lewis Pairs","authors":"Dr. Cheng-Xia Chen, Haiping Wang, Dr. Hassan Rabaâ, Dr. Yang-Yang Xiong, Dr. Peter VanNatta, Dr. Zhang-Wen Wei, Prof. Abdullah M. Al-Enizi, Prof. Ayman Nafady, Prof. Shengqian Ma","doi":"10.1002/ange.202416497","DOIUrl":"https://doi.org/10.1002/ange.202416497","url":null,"abstract":"Converting CO2 to high-value fine chemicals represents one of the most promising approaches to combat global warming and subsequently achieve a sustainable carbon cycle. Herein, we contribute an organoboron functionalized ultra-thin metal-organic nanosheet (MON), termed TCPB-Zr-NS, featuring an abundance of exposed Lewis acidic B and formate sites, which can effectively promote CO2 conversion upon the addition of Lewis basic o-phenylenediamines. Compared with the prototypical 3D analogue TCPB-Zr-3D, the resultant TCPB-Zr-NS showcases dramatically improved catalytic activity for the cyclization of o-phenylenediamine as a result of the highly exposed active sites and efficient substrates/products diffusion. Strikingly, the incorporation of Lewis acidic B sites into ultra-thin Zr-based MON (Zr-MON) not only promotes the highly efficient CO2 conversion, but also enhances the recyclability/durability of catalysts. Additionally, the underlying catalytic mechanism has been well established by the comprehensive experiments and theoretical calculations, unveiling a formate-assisted frustrated Lewis pairs (FLP) mediated catalytic pathway. This work opens up a new avenue to heterogeneous FLP-based catalysts for small molecule activation and beyond.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 7","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143380686","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Copper-Catalysed Electrochemical CO2 Methanation via the Alloying of Single Cobalt Atoms

Angewandte Chemie Pub Date : 2025-01-13 DOI: 10.1002/ange.202417008

Jiawei Li, Miaojin Wei, Bifa Ji, Sunpei Hu, Jing Xue, Donghao Zhao, Haoyuan Wang, Chunxiao Liu, Yifan Ye, Jilong Xu, Jie Zeng, Ruquan Ye, Yongping Zheng, Tingting Zheng, Chuan Xia

{"title":"Copper-Catalysed Electrochemical CO2 Methanation via the Alloying of Single Cobalt Atoms","authors":"Jiawei Li, Miaojin Wei, Bifa Ji, Sunpei Hu, Jing Xue, Donghao Zhao, Haoyuan Wang, Chunxiao Liu, Yifan Ye, Jilong Xu, Jie Zeng, Ruquan Ye, Yongping Zheng, Tingting Zheng, Chuan Xia","doi":"10.1002/ange.202417008","DOIUrl":"https://doi.org/10.1002/ange.202417008","url":null,"abstract":"The electrochemical reduction of carbon dioxide (CO2) to methane (CH4) presents a promising solution for mitigating CO2 emissions while producing valuable chemical feedstocks. Although single-atom catalysts have shown potential in selectively converting CO2 to CH4, their limited active sites often hinder the realization of high current densities, posing a selectivity-activity dilemma. In this study, we developed a single-atom cobalt (Co) doped copper catalyst (Co1Cu) that achieved a CH4 Faradaic efficiency exceeding 60 % with a partial current density of −482.7 mA cm−2. Mechanistic investigations revealed that the incorporation of single Co atoms enhances the activation and dissociation of H2O molecules, thereby lowering the energy barrier for the hydrogenation of *CO intermediates. In situ spectroscopic experiments and density functional theory simulations further demonstrated that the modulation of the *CO adsorption configuration, with stronger bridge-binding, favours deep reduction to CH4 over the C−C coupling or CO desorption pathways. Our findings underscore the potential of Co1Cu catalysts in overcoming the selectivity-activity trade-off, paving the way for efficient and scalable CO2-to-CH4 conversion technologies.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 8","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143431563","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Digital and Tunable Genetically Encoded Tension Sensors Based on Engineered Coiled-Coils

Angewandte Chemie Pub Date : 2025-01-13 DOI: 10.1002/ange.202407359

Shuhong Liu, Jinchan Liu, Alexander Foote, Hiroaki Ogasawara, Sarah Al Abdullatif, Prof. Victor S. Batista, Prof. Khalid Salaita

{"title":"Digital and Tunable Genetically Encoded Tension Sensors Based on Engineered Coiled-Coils","authors":"Shuhong Liu, Jinchan Liu, Alexander Foote, Hiroaki Ogasawara, Sarah Al Abdullatif, Prof. Victor S. Batista, Prof. Khalid Salaita","doi":"10.1002/ange.202407359","DOIUrl":"https://doi.org/10.1002/ange.202407359","url":null,"abstract":"Genetically encoded tension sensors (GETSs) allow for quantifying forces experienced by intracellular proteins involved in mechanotransduction. The vast majority of GETSs are comprised of a FRET pair flanking an elastic “spring-like” domain that gradually extends in response to force. Because of ensemble averaging, the FRET signal generated by such analog sensors conceals forces that deviate from the average, and hence it is unknown if a subset of proteins experience greater magnitudes of force. We address this problem by developing digital GETSs comprised of coiled-coils (CCs) with tunable mechanical thresholds. We validate the mechanical response of CC digital probes using thermodynamic stability prediction, AlphaFold2 modeling, steered molecular dynamics simulations, and single-molecule force spectroscopy. Live cell measurements using optimized CC tension sensors that are inserted into vinculin demonstrate that 13 % of this mechanosensor experiences forces >9.9 pN within focal adhesions. This reveals greater magnitudes of vinculin force than had previously been reported and demonstrates that CC tension sensors enable more facile and precise tension measurements in living systems.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 8","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143431564","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Integrating Enzymes with Reticular Frameworks To Govern Biocatalysis

Angewandte Chemie Pub Date : 2025-01-13 DOI: 10.1002/ange.202421192

Linjing Tong, Prof. Dr. Siming Huang, Prof. Guosheng Chen, Prof. Gangfeng Ouyang

{"title":"Integrating Enzymes with Reticular Frameworks To Govern Biocatalysis","authors":"Linjing Tong, Prof. Dr. Siming Huang, Prof. Guosheng Chen, Prof. Gangfeng Ouyang","doi":"10.1002/ange.202421192","DOIUrl":"https://doi.org/10.1002/ange.202421192","url":null,"abstract":"Integrating enzymes with reticular frameworks offers promising avenues for access to functionally tailorable biocatalysis. This Minireview explores recent advances in enzyme-reticular framework hybrid biocomposites, focusing on the utilization of porous reticular frameworks, including metal-organic frameworks, covalent-organic frameworks, and hydrogen-bonded organic frameworks, to regulate the reactivity of an enzyme encapsulated inside mainly by pore infiltration and in situ encapsulation strategies. We highlight how pore engineering and host-guest interfacial interactions within reticular frameworks create tailored microenvironments that substantially impact the mass transfer and enzyme conformation, leading to biocatalytic rate enhancement, or imparting enzymes with non-native biocatalytic functions, including substrate selectivity and new activity. Additionally, the feasibility of leveraging the photothermal effect of a framework to optimize the local reaction temperature and photoelectric effect to elicit diverse photoenzyme-coupled reactions is also summarized in detail, which can expand the functional repertoire of biocatalytic transformations under light irradiation. This Minireview underscores the potential of reticular frameworks as tunable and reliable platforms to govern biocatalysis, offering pathways for engineering sustainable, efficient, and selective biocatalytic reactors in pharmaceutical, environmental, and energy-related applications.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 8","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143431123","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0