Accounts of materials research最新文献

{"title":"Porous Crystalline Frameworks as Ion-Conducting Solid-State Electrolytes","authors":"Hongwei Chen, Chenji Hu, Xiaoqing Zhang, Liwei Chen","doi":"10.1021/accountsmr.4c00156","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00156","url":null,"abstract":"Room-temperature Li⁺ conductors have been intensively revisited to develop high-safety solid-state batteries. While promising inorganic Li⁺ solid-state electrolytes (SSEs) with competitive ionic conductivity have been demonstrated, their practical applications are still hindered by manufacturing technology, cost constraints, and internal battery interfaces. Advances in the design and synthesis of periodic frameworks over the past decade have created a new platform for designing SSEs. These porous crystalline frameworks feature open channels that can be tailored into ion-hopping sites and guest-accessible voids, both essential for SSE construction. Framework-based SSEs uniquely merge the advantages of inorganic crystal-like ordered structures and the design flexibility of organic molecules, distinguishing them significantly from traditional inorganic or organic SSEs. Enhancing ionic conduction and exploring potential applications are two critical factors driving the rapid advancement of framework-based SSEs.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142178232","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":"Functional Covalent Organic Frameworks: Design Principles to Potential Applications","authors":"Yusran Yusran, Bo Miao, Shilun Qiu, Qianrong Fang","doi":"10.1021/accountsmr.4c00195","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00195","url":null,"abstract":"Covalent organic frameworks (COFs) represent an emerging class of crystalline porous polymers synthesized by linking predesigned organic building units into targeted repetitive networks. The unique features of COFs stem from their modular synthesis, allowing for precise control over the chemical composition and functionalization on both the skeleton and the pore walls. Topologically, COFs are defined not by their chemical nature but by the symmetry and dimensions of the building units, resulting in 2D and 3D structures with distinct surface areas, pore architectures, and arrangements of functional moieties. The combination of predesigned organic units into geometries results in frameworks that can be precisely controlled and modified. This control is vital for applications requiring materials with specific pore sizes, surface areas, and functional group distributions. Particularly, COFs show great potential in the field of gas storage and separation, energy storage and conversion, catalysis, sensing, environmental remediation, and many more. Hence, an effective designed approach to incorporate various functional properties into the structures is pivotal to manipulate the functional properties and potential applications of COFs.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142178234","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":"Electrically Stable Self-Assembled Monolayers Achieved through Repeated Surface Exchange of Molecules","authors":"Jiung Jang, Gyu Don Kong, Hyo Jae Yoon","doi":"10.1021/accountsmr.4c00190","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00190","url":null,"abstract":"Self-assembled monolayers (SAMs) are two-dimensional molecular ensembles. In molecular electronics, SAMs serve as active components for exploring structure-tunneling relationships due to their easy and simple fabrication and atomic-detailed (supra)molecular modifications. Single-component pure SAMs are commonly incorporated into tunneling junctions. However, pure SAMs are defective to some extent, which results in low electrical breakdown voltages and allows access to narrow bias windows through the junctions. Narrow bias windows ultimately limit the possible charge-transport channels to shallow molecular orbital energy levels such as the highest occupied molecular orbital (HOMO) or lowest unoccupied molecular orbital (LUMO), making it difficult to investigate charge transport through deeper molecular orbital (MO) energy levels such as sub-HOMOs and post-LUMOs.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142043308","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":"Component Engineering in Multinary Alloyed I-III-VI Type Semiconductor Nanocrystals for Photoluminescence and Electroluminescence","authors":"Lijin Wang, Zhe Yin, Aiwei Tang","doi":"10.1021/accountsmr.4c00161","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00161","url":null,"abstract":"Display technologies have been developed in an unprecedented way in the past one hundred years. The evolution of display technologies is remarkable, progressing from the initial cathode ray tube and rear projection technology to the second-generation advancements of plasma and liquid crystal displays. Now, with the ongoing development of light-emitting diodes (LEDs) technology, including organic LEDs (OLEDs) and quantum dot LEDs (QD-LEDs), we are looking forward to a transition toward mini-LED, micro-LED, and nano-LED technologies. This evolution is gradually rendering displays thinner, more convenient, high-definition, highly luminous, and cost-effective. At present, commercially available OLEDs technology is afflicted with drawbacks such as intricate solution processing, difficulties in achieving efficient mass production, and suboptimal stability, limiting its widespread adoption. QD-LEDs serve as a perfect complement to the limitations of OLEDs and demonstrate a large potential for application in the next generation of displays. Quantum dots (QDs) are nanocrystals (NCs) with a size of 1–10 nm. Since the 1980s, researchers have studied and developed these magic tiny particles. At present, Cd-based materials have been extensively studied, resulting in red-, green-, and blue-LEDs devices approaching or surpassing theoretical external quantum efficiency limits. And the lifetime of Cd-based LEDs has reached commercial standards expected for blue-LEDs. However, the intrinsic toxicity of Cd element limits their further development. In the past decades, several Cd-free QDs have been developed and extensively researched, including III-V type InP QDs, perovskite QDs, I-III-VI type QDs, II-VI type ZnSe QDs, carbon dots, and so on. Among these Cd-free QDs, I-III-VI type semiconductor nanocrystals demonstrate remarkable potential due to facile synthesis, large tunable luminescence range, and solution processability. Moreover, owing to its distinctive nonstoichiometric composition, the luminescence peak position can be readily tuned from the blue to near-infrared by means of straightforward component engineering. This Account presents an overview of the I-III-VI type NCs, starting with the photoluminescent properties regulated by component engineering. Interestingly, narrow-band emission can also be realized through component engineering. Then the construction of light-emitting diodes based on these materials is discussed, encompassing wide-band and narrow-band emission. Additionally, interface engineering is adopted for balancing carrier injection to enhance electroluminescent properties. Moreover, taking advantage of the wide-band emission characteristics of I-III-VI type NCs, white LEDs with high color rendering index can be fabricated by incorporating other blue-emitting materials. Finally, the present challenges and prospective solutions are proposed to propel the advancement of I-III-VI type NCs with high expectations.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142013983","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":"Chemical Mechanisms and Biological Effects of Chiral Nanomaterials","authors":"Gaoyang Wang, Aihua Qu, Maozhong Sun, Jun Xu, Hua Kuang","doi":"10.1021/accountsmr.4c00158","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00158","url":null,"abstract":"Chirality exerts significant roles in biological systems and physiological processes; amino acids, sugars, peptides with multilevel structures, macromolecular proteins, and nucleic acids are all known to exhibit a single chiral structure. The characteristics of intrinsic chirality in a biological system determine the specificity of interactions between biomolecules and also influence a series of key processes in biological systems. Consequently, investigating chirality and the biogenesis of life is critical if we are to understand how the human body works. Although the influential role of chiral materials on biological processes has been investigated for several decades, the specific relationships between chirality and biological functionality have yet to be determined. In order to elucidate the specific role played by chirality in living processes, researchers have tended to focus on three essential aspects: (1) the origin of chirality and breaking the symmetry of life; (2) the amplification of chirality and the realization of high levels of homogeneous chirality in living systems, and (3) chirality transfer mechanisms in <i>vivo</i>.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141992067","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":"Heterogeneous Integration of Diamond","authors":"Oliver A. Williams, Soumen Mandal, Jerome A. Cuenca","doi":"10.1021/accountsmr.4c00126","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00126","url":null,"abstract":"The heterogeneous integration of materials offers new paradigms in many extreme applications, where single materials cannot solve the problem alone. Diamond has a plethora of superlative properties that make it attractive in a diverse array of applications, such as its unique combination of unrivalled thermal conductivity combined with high electrical impedance; single photon emission at room temperature; superlative acoustic wave velocity, and Debye temperature. Most of these properties are directly related to diamond’s atomically dense lattice of light carbon atoms, which has consequences such as difficulty in doping diamond n-type and low thermal coefficient of thermal expansion. This last property presents a significant problem for the growth of diamond on nondiamond materials as the linear coefficients of thermal expansion of other materials are often several times larger than diamond.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141994703","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":"Diamond Homoepitaxial Growth Technology toward Wafer Fabrication, Atomically Controlled Surfaces, and Low Resistivity","authors":"Kimiyoshi Ichikawa, Tsubasa Matsumoto, Takao Inokuma, Satoshi Yamasaki, Christoph E. Nebel, Norio Tokuda","doi":"10.1021/accountsmr.4c00123","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00123","url":null,"abstract":"Strong covalent bonds provide diamond with superior properties such as higher thermal conductivity, electron/hole mobilities, and wider bandgap than those of other semiconductors. This makes diamonds promising for next-generation power devices, optoelectronics, quantum technologies, and sensors. However, there are still challenges in realizing practical diamond electronic applications. Key issues include controlling the microwave plasma chemical vapor deposition (MPCVD) growth process to achieve a large size, smooth surfaces, and desired conductivity. Standard semiconductor processing techniques like polishing and ion implantation also need improvement for diamonds. This Account outlines three MPCVD growth technologies being investigated at Kanazawa University to address these challenges.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141986683","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":"[Au23(SR)16]−: A Stepping Stone towards the Rational Design of Atomically Precise Metal Nanoclusters","authors":"Saniya Gratious, Eyyakkandy Nida Nahan, Rongchao Jin, Sukhendu Mandal","doi":"10.1021/accountsmr.4c00205","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00205","url":null,"abstract":"Atomically precise metal nanoclusters (MNCs) have revolutionized the field of nanoscience and material chemistry with their well-defined structure, quantum confinement effect, and distinctive physicochemical properties. They have opened up new avenues for applications in diverse fields such as biomedicine, renewable energy devices, catalysis, chemical sensing, etc. These metal NCs with a size range of 1–3 nm stand out from the conventional nanoparticles (1–100 nm) due to the quantum confinement effect, which is absent in the polydisperse nanoparticles. Over the past few decades, a populous library of metal NCs with different metals, such as Au, Ag Cu, and their alloys, has been established. Of all these NCs, the molecularly pure [Au₂₃(CHT)₁₆]⁻ NC (CHT = S-<i>c</i>-C₆H₁₁) is emerging as a potential nanomaterial with a unique structure and properties and is being used as a precursor for various transformation studies. This [Au₂₃(CHT)₁₆]⁻ NC has an Au₁₅ bipyramidal kernel, which can be viewed as an Au₁₃ cuboctahedron capped with two hub Au atoms, protected by a pair of trimeric and monomeric staple motifs and four bridging thiolates. This unique structure of [Au₂₃(CHT)₁₆]⁻ NC gives rise to interesting properties such as photoluminescence (PL) and catalysis. In this Account, we focus on the recent advances in the methods and types of different structural transformations carried out on the [Au₂₃(CHT)₁₆]⁻ NC and their detailed mechanistic insights. These postsynthetic modifications have proven to be efficient strategies to induce structural changes, tune the physicochemical properties, and tailor them for promising applications. We have divided the transformation chemistry of [Au₂₃(CHT)₁₆]⁻ NC into three sections. In the first section, we discuss various types of metal-exchange-induced transformation reactions carried out on the [Au₂₃(CHT)₁₆]⁻ NC with different heterometal ions to achieve bimetallic NCs with various degrees of alloying and multiple alloying sites, whereas the second section deals with the various ligand-exchange-induced transformation reactions of [Au₂₃(CHT)₁₆]⁻ NC, exploring the intriguing ligand effects on the NC structure and properties. Transformation reactions under other conditions, such as irradiation, oxidation, reduction, and change of solvent, are discussed in the last section. A detailed investigation into the mechanistic insights is also discussed to illustrate the driving force and other fundamentals of these transformations. Finally, we outline the future perspectives of the deep exploration of the transformation methods of [Au₂₃(CHT)₁₆]⁻ NC that can advance the NC research. We hope this Account will prompt the nanoscie","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141910553","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":"Synthesis, Processing, and Use of Isotopically Enriched Epitaxial Oxide Thin Films","authors":"Tiffany C. Kaspar, Yingge Du","doi":"10.1021/accountsmr.3c00148","DOIUrl":"https://doi.org/10.1021/accountsmr.3c00148","url":null,"abstract":"Isotopic engineering has emerged as a key approach to study the nucleation, diffusion, phase transitions, and reactions of materials at an atomic level. It aims to uncover mass transport pathways, kinetics, and operational and failure mechanisms of functional materials and devices. Understanding these phenomena leads to deeper insights into important physical processes, such as the transport of ions in energy conversion and storage devices and the role of active sites and supports during heterogeneous catalytic reactions. Likewise, isotopic engineering is being pursued as a means of modifying functionality to enable future technological applications. In this Account, we summarize our recent work employing isotope labeling (e.g., ¹⁸O₂ and ⁵⁷Fe) during thin film synthesis and postgrowth processing to reveal growth mechanisms, defect chemistry, and elemental diffusion under working and extreme conditions. Isotope-resolved analysis techniques with nanometer-scale spatial resolution, such as time-of-flight secondary ion mass spectrometry and atom probe tomography, facilitate the accurate quantification of isotopic placement and concentration in our well-defined heterostructures with precisely positioned, isotope-enriched layers. By measuring the nanometer-scale redistribution between natural abundance and isotopically enriched oxygen layers during the deposition of Fe₂O₃ and Cr₂O₃ by molecular beam epitaxy, we identified intermixing processes driven by surface adatoms occurring both at the film growth surface and within the first few layers below the surface. Further insights into synthesis mechanisms were gained by studying the tungsten oxide thin films grown by evaporating WO₃ powder in the presence of background ¹⁸O₂, revealing minimal incorporation of background oxygen during the film formation process. Thermal and radiation-enhanced diffusion in epitaxial Fe and Cr oxides were precisely tracked using ¹⁸O and ⁵⁷Fe tracer layers incorporated into model epitaxial oxide thin films. This approach has allowed us to access thermal diffusion behavior at lower temperatures than previously measured, revealing a potential changeover in diffusion mechanism. Understanding radiation-enhanced diffusion in model oxides that represent the surface layers on the structural components of nuclear reactors informs our understanding of their corrosion behavior under irradiation. Isotopic labeling can also provide unique insights into the surface exchange reactions and defect chemistry of electrocatalysts. For instance, tracking the change in ¹⁸O concentration at the surface of an epitaxial LaNiO₃ thin film after the electrocatalytic oxygen evolution reaction revealed the participation of lattice oxygen, confirming a hypothesis that had been proposed previously. Lastly, we highlight a new direction wherein we perform i","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141910552","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":"Water Molecule as a Dynamic Cross-Linker for Creating Multifunctional Poly(ionic liquid) Porous Membranes","authors":"Yue Shao, Hong Wang","doi":"10.1021/accountsmr.4c00130","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00130","url":null,"abstract":"Supramolecular polyelectrolyte porous membranes (SPPMs), which structurally integrate supramolecular material properties, electrolyte characteristics and pore confinement effects into a membrane, represent an exciting class of materials targeted for a broad range of applications in modern science and technology. However, owing to the intrinsic water solubility of conventional polyelectrolytes and the complex bonding mode arising from their charged nature, a long-standing challenge in the field has been the development of reliable preparation methods for fabricating high-quality SPPMs with controllable pore architectures and programmable functionalities. There have been a few characteristic attempts at achieving SPPMs. One involves layer-by-layer assembly of polyelectrolyte species through the strategic utilization of “orthogonal” noncovalent interactions; the other involves self-assembly of amphiphilic polyelectrolyte block copolymers, forming SPPMs. However, considering the multiple tedious preparation steps, the use of large amounts of organic solvents, and/or expensive precursors, these approaches suffer from some inherent limitations for the scalable preparation of SPPMs. Undoubtedly, direct assembly of polyelectrolytes in water to produce SPPMs is a priority because of its eco-friendly nature and ease of scaling up.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141892148","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}