Accounts of materials research最新文献

{"title":"Design Strategies, Properties, and Applications toward Cycloarenes and Heterocycloarenes","authors":"Jiangyu Zhu, Rong Zhang, Dongyue An, Yuanhe Gu, Xuefeng Lu, Yunqi Liu","doi":"10.1021/accountsmr.5c00041","DOIUrl":"https://doi.org/10.1021/accountsmr.5c00041","url":null,"abstract":"Cycloarenes, fully benzene-annelated macrocyclic systems with inward-facing carbon–hydrogen bonds, serve as ideal models for defects in graphene, offering great application potential in organic electronics, supramolecular chemistry, and optics. They offer an attractive combination of synthesis challenge, aesthetic appeal, fundamental problems, and potential applications. Initially, the most typical cycloarene, kekulene, was expected to provide a crucial experimental test to determine whether π-electrons are delocalized over the entire molecule or delocalized at the benzenoid rings. This question has captivated synthetic chemists for decades. After numerous failed attempts, Staab and Diederich achieved the first conclusive synthesis of kekulene in 1978. The deshielded inner protons in the <sup>1</sup>H NMR spectrum conclusively demonstrated that the π-electrons in cycloarenes are delocalized at individual benzenoid rings. However, owing to limited synthetic methods, complex reaction routes, and poor solubility of the final products, progress in cycloarene research has been slow. Over the next four decades, only a few contracted or expanded kekulene homologues were reported. Nevertheless, the changes in their chemical structure bring some exciting physicochemical properties. The enlargement of the central ring of kekulene induces a transition from a planar to a saddle-shaped structure, further influencing its electronic and optical properties and unlocking unexpected applications in supramolecular chemistry. Therefore, developing new rational synthetic methods to controllably synthesize structurally diverse cycloarenes is crucial. With the continuous development of synthetic science, in recent years, some functional cycloarenes and heteroatom-embedded heterocycloarenes have been reported. Owing to their unique topological structures, well-defined cavities, and large cyclic conjugated systems, these (hetero)cycloarenes have been applied in fields such as supramolecular chemistry, organic field-effect transistors, and solar cells. However, the limited understanding of the structure–property relationship in (hetero)cycloarenes poses a formidable challenge to their custom synthesis for specific functions. Herein, we review our efforts in the design, synthesis, and applications of cycloarenes and heterocycloarenes. First, we summarize four representative synthetic methods for cycloarenes. Subsequently, we present a comprehensive overview of three molecular design strategies: π-extension, heteroatom embedding, and acceptor moiety insertion, to achieve the molecular structure diversity of cycloarenes. Then, we highlight their synthetic methods, geometries, fundamental optoelectronic properties, and unique applications in ultranarrowband emission, organic transistor devices, and supramolecular chemistry. We also delve into the intrinsic correlations among structures, properties, and applications of these cycloarenes and heterocycloarenes. Finally, we envis","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"183 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713782","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}

{"title":"Nanospace Engineering of Metal–Organic Frameworks for Adsorptive Gas Separation","authors":"Lingshan Gong, Shyam Chand Pal, Yingxiang Ye, Shengqian Ma","doi":"10.1021/accountsmr.5c00006","DOIUrl":"https://doi.org/10.1021/accountsmr.5c00006","url":null,"abstract":"Gas separation is a critical process in the industrial production of chemicals, polymers, plastics, and fuels, which traditionally rely on energy-intensive cryogenic distillation techniques. In contrast, adsorptive separation using porous materials has emerged as a promising alternative, presenting substantial potential for energy savings and improved operational efficiency. Among these materials, metal–organic frameworks (MOFs) have garnered considerable attention due to their unique structural and functional characteristics. MOFs are a class of crystalline porous materials constructed from inorganic metal ions or clusters connected by organic linkers through strong coordination bonds. Their precisely engineered architectures create well-defined nanoscale spaces capable of selectively trapping guest molecules. In contrast to traditional porous materials such as zeolites and activated carbons, emerging MOFs not only demonstrate exceptional capabilities for pore regulation and interior modification through nanospace engineering but also hold great promise as a superior platform for the development of high-performance functional materials. By virtue of the isoreticular principle and building unit assembly strategies in MOF chemistry, precise adjustments to pore structures─including pore size, shape, and surface chemistry─can be readily achieved, making them well-suited for addressing the separation of intractable industrial gas mixtures, particularly those with similar sizes and physicochemical properties.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"9 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723696","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}

{"title":"Engineering Peptide Self-Assembly: Modulating Noncovalent Interactions for Biomedical Applications","authors":"Yaoting Li, Huanfen Lu, Liheng Lu, Huaimin Wang","doi":"10.1021/accountsmr.4c00391","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00391","url":null,"abstract":"Controlling self-assembled peptide nanostructures has emerged as a significant area of research, offering versatile tools for developing functional materials for various applications. This Account emphasizes the essential role of noncovalent interactions, particularly in peptide-based materials. Key forces, such as aromatic stacking and hydrogen bonding, are crucial for promoting molecular aggregation and stabilizing supramolecular structures. Numerous studies demonstrate how these interactions influence the phase transitions and the morphology of self-assembled structures. Recent advances in computational methodologies, including molecular dynamics simulations and machine learning, have significantly enhanced our understanding of self-assembly processes. These tools enable researchers to predict how molecular properties, such as hydrophobicity, charge distribution, and aromaticity, affect assembly behavior. Simulations uncover the energetic landscapes governing peptide aggregation, providing insights into the kinetic pathways and thermodynamic stabilities. Meanwhile, machine learning facilitates the rapid screening of peptide libraries, identifying sequences with optimal self-assembly characteristics, and accelerating material design with tailored functionalities.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"42 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635764","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}

{"title":"Polymer–Nanoparticle Composite Films with Ultrahigh Nanoparticle Loadings Using Capillarity-Based Techniques","authors":"Baekmin Q. Kim, Uiseok Hwang, Hong Huy Tran, Daeyeon Lee","doi":"10.1021/accountsmr.4c00387","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00387","url":null,"abstract":"Polymer–nanoparticle (NP) composites with ultrahigh loadings (more than 50 vol %) of NPs possess exceptional mechanical, transport, and physical properties, making them valuable for various applications. However, producing such polymer–NP composites poses significant challenges due to difficulties associated with mixing and dispersing high fractions of NPs in polymers. A promising approach to overcome these challenges involves infiltrating a polymer into the interstitial pores of a disordered NP packing, resulting in a polymer-infiltrated NP film (PINF). Recently, versatile capillarity-driven techniques have emerged, successfully enabling the production of PINFs. These capillarity-driven techniques allow for the fabrication of homogeneous (fully infiltrated), nanoporous (partially infiltrated), and heterostructured PINFs. Infiltrating polymers into stiff but brittle NP packings increases their toughness, attributed to the formation of polymer bridges between adjacent NPs or interchain entanglements. The physical confinement of polymer within the interstitial pore also enhances thermal stability and heat transfer of PINFs. Additionally, the tunable nanoporosity and heterostructures of PINFs lead to unique optical properties suitable for various practical applications.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"89 3 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143627706","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}

{"title":"Emerging Electrochemical Catalysis on {001}-Facet and Defect-Engineered TiO2 for Water Purification","authors":"Ai-Yong Zhang, Chang Liu, Han-Qing Yu","doi":"10.1021/accountsmr.4c00377","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00377","url":null,"abstract":"Electrochemical water purification and pollutant monitoring have garnered significant attention due to their unique technical advantages. The pursuit of safe, efficient, and economically viable catalysts remains a critical priority. Titanium dioxide (TiO₂), a prototypical transition-metal oxide with substantial industrial importance, is widely recognized as a benchmark catalyst for photochemical reactions. However, its practical application is limited by restricted light absorption and rapid photocarrier recombination. Recently, TiO₂ has emerged as a promising candidate in electrochemical catalysis, particularly in the fields of energy and environmental science. Its atomic and electronic structures can be precisely engineered through advanced techniques such as nanoscale morphology control, polar-facet engineering, guest-metal doping, and structural-defect modulation. This review examines recent advancements in TiO₂-based electrochemical applications, with a focus on water purification and pollutant monitoring.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"69 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143618905","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}

{"title":"Bismuth-Catalyzed Electrochemical Carbon Dioxide Reduction to Formic Acid: Material Innovation and Reactor Design","authors":"Yuqing Luo, Junmei Chen, Na Han, Yanguang Li","doi":"10.1021/accountsmr.4c00386","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00386","url":null,"abstract":"Electrochemical CO₂ reduction reaction (eCO₂RR) has gained increasing attention as a promising strategy to mitigate the negative impacts of CO₂ emission while simultaneously producing valuable chemicals or fuels. By converting CO₂ into energy-rich products using renewable electricity, eCO₂RR provides a sustainable approach to reducing the carbon footprint and promoting a circular carbon economy. Among different reduction products, the formic acid (or formate) is particularly attractive due to its economic viability and diverse industrial applications, making it a key focus for both research and industrial adoption.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"30 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143569851","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}

{"title":"Dislocation Loop Transformation in Metals: Computational Studies, Theoretical Prediction and Future Perspectives","authors":"Cheng Chen, Yiding Wang, Jie Hou, Jun Song","doi":"10.1021/accountsmr.4c00296","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00296","url":null,"abstract":"Dislocation loops (DLs), characterized by closed dislocation lines, are a category of defects of vital importance in determining the mechanical properties of metals, particularly under extreme conditions, such as irradiation, severe plastic deformation, and hydrogen embrittlement. These loops, more intricate than simple dislocations, exhibit far more intricate reaction and evolution pathways arising from the loop type transformation and the associated planar fault transition. This can significantly alter dislocation activities contributing to dislocation channels and complex dislocation networks, which are closely linked to crack initiation and propagation during fracture. Understanding the transformation of DLs is crucial for the development of materials capable of withstanding harsh environments, including those encountered in nuclear reactors, aerospace applications, and hydrogen-rich environments. This Account delves into the computational advancements in studying DL transformations in FCC, HCP, and BCC metals. Traditional simulations often struggle to capture the complexity of DL structures and interactions. To overcome these limitations, a novel computational approach has been developed, enabling precise construction and analysis of DLs. Not only does it automatically account for necessary atom addition or deletion, it is also generic and versatile, applicable for any arbitrary DL morphology with planar fault or fault combination in both pristine metal and complex alloy systems. The new construction approach of DLs provides a critical enabler for studying the transformation of DLs across different crystal structures. In high-symmetry FCC metals, these transformations involve complex unfaulting driven by Shockley and Frank loop interactions, influenced by variations in stress, temperature, and radiation. Meanwhile, HCP metals, with a lower crystal symmetry, exhibit more complex DL transformations due to high anisotropy in the slip systems, variation in Burgers vectors, and different planar faults. Unlike pristine FCC and HCP lattices, ordered intermetallic systems like L1<sub>2</sub>-Ni<sub>3</sub>Al experience a disruption of translational symmetry within the lattice. The ordered nature of these alloys complicates DL interacting with line dislocation, causing asymmetrical shearing and looping mechanisms. BCC metals, in contrast, exhibit different DL evolution due to the lack of stable stacking faults, leading to stronger interactions with impurities such as carbon and hydrogen. In particular, the interaction between DLs and hydrogen in BCC metals is a critical aspect worth investigating as it can cause severe damage in BCC materials under irradiation, hydrogen embrittlement, and intense deformation. This Account highlights the complex nature of DL transformation in metals under extreme environments and recent computational advances. Differences in the evolution of DLs across crystal structures and their interactions with cracks and solute e","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"42 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143546670","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}

{"title":"Direct Optical Lithography: Toward Nondestructive Patterning of Nanocrystal Emitters","authors":"Seongkyu Maeng, Himchan Cho","doi":"10.1021/accountsmr.5c00016","DOIUrl":"https://doi.org/10.1021/accountsmr.5c00016","url":null,"abstract":"Figure 1. (A) Schematic illustration of the main parameters for next-generation display and (B) schematic illustration of strategies for nondestructive direct optical lithography process. Figure 2. Schematic illustrations and methods for the design of (A) photosensitive molecules and (B) ligand post-treatment. Figure 3. Schematic overview of challenges in direct optical lithography. S.M. and H.C. wrote the manuscript. S.M. conducted literature review and prepared figures. H.C. supervised the project. <b>Seongkyu Maeng</b> is currently a Ph.D. candidate in Materials Science and Engineering from Korea Advanced Institute of Science and Technology (KAIST), Republic of Korea. He earned his B.S. (2022) and M.S. (2024) in Materials Science and Engineering from KAIST. His research focuses on the patterning of emissive nanomaterials. <b>Himchan Cho</b> is currently an Associate Professor in the Department of Materials Science and Engineering at Korea Advanced Institute of Science and Technology (KAIST), Republic of Korea. He received his B.S. (2012) and Ph.D. (2016) in Materials Science and Engineering from the Pohang University of Science and Technology (POSTECH), Republic of Korea. Following his doctoral studies, he worked as a postdoctoral scholar at Seoul National University (2016–2018) and the University of Chicago (2018–2021) before he joined KAIST in 2021. His research interests focus on synthesis, patterning, and device applications of metal halide perovskites and colloidal quantum dots. This work was supported by National Research Foundation of Korea (NRF) grants funded by the Ministry of Science and ICT, Korea: RS-2022-NR068226 (2022M3H4A1A04096380) and RS-2024-00416583. This article references 35 other publications. This article has not yet been cited by other publications.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"16 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143538760","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}

{"title":"Facile Strategies for Incorporating Chiroptical Activity into Organic Optoelectronic Devices","authors":"Hanna Lee, Danbi Kim, Jeong Ho Cho, Jung Ah Lim","doi":"10.1021/accountsmr.4c00374","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00374","url":null,"abstract":"Chiral optoelectronics, which utilize the unique interactions between circularly polarized (CP) light and chiral materials, open up exciting possibilities in advanced technologies. These devices can detect, emit, or manipulate light with specific polarization, enabling applications in secure communication, sensing, and data processing. A key aspect of chiral optoelectronics is the ability to generate or detect optical and electrical signals by controlling or distinguishing CP light based on its polarization direction. This capability is rooted in the selective interaction of CP light with the stereogenic (non-superimposable) molecular geometry of chiral substances, wherein the polarization of CP light aligns with the intrinsic asymmetry of the material. Among the diverse chiral materials explored for this purpose, π-conjugated molecules offer special advantages due to their tunable optoelectronic properties, efficient light–matter interactions, and cost-effective processability. Recent advancements in π-conjugated molecule research have demonstrated their ability to generate strong chiroptical responses, thereby paving the way for compact and multifunctional device designs. Building on these unique advantages, π-conjugated molecules have advanced organic electronics into rapidly evolving technological fields. The combination of chiral π-conjugated molecules with organic electronics is anticipated to simplify the fabrication of chiroptical devices, thereby lowering technical barriers and accelerating progress in chiral optoelectronics.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"2 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143532688","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}

{"title":"Engineering Hierarchy to Porous Organic Cages for Biomimetic Catalytic Applications","authors":"Jing-Wang Cui, Si-Hua Liu, Liang-Xiao Tan, Jian-Ke Sun","doi":"10.1021/accountsmr.4c00402","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00402","url":null,"abstract":"In nature, hierarchy is a core organizational principle intricately woven into biological systems, facilitating the compartmentalization of enzymes within living cells. This spatial arrangement enables multistep metabolic reactions to occur simultaneously with remarkable efficiency and precision. Inspired by this, significant progress has been made in artificial biomimetic heterogeneous catalytic systems using porous materials like metal–organic frameworks, porous organic polymers, and zeolites. Among these, molecular cages, with their well-defined cavities, stand out as synthetic models for enzyme-mimic catalysis. They not only provide biomimetic microenvironments for substrate binding, mimicking the highly specific and efficient interactions observed in natural enzymatic systems, but also integrate active centers within confined nanoscale spaces, enabling synergistic functionality. However, research in cage-based biomimetic catalysts has largely focused on tailoring the cavity environment─such as optimizing cavity size, pore geometry, and functional groups on the pore walls─to regulate catalytic processes, while comparatively less attention has been given to the catalytic role of metal centers, akin to the critical function in natural metalloenzymes. While metal nodes in metal–organic cages can act as active sites, their catalytic efficiency may be hindered by coordination saturation. Moreover, the restricted (sub)nanoscale space of molecular cage reactors limits their capacity to host larger active sites or accommodate bulky substrates. Thus, rationally engineering the confined spaces and optimizing the spatial arrangement of active sites within molecular cage-based catalytic systems is essential for advancing the field and unlocking their full potential.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143495901","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}