{"title":"Biphen[n]arene-Based Supramolecular Materials","authors":"Zhixue Liu, Junyi Chen, Chunju Li","doi":"10.1021/accountsmr.5c00071","DOIUrl":"https://doi.org/10.1021/accountsmr.5c00071","url":null,"abstract":"Macrocycles play pivotal roles in supramolecular chemistry and materials science because of their distinctive molecular recognition capabilities and versatile applications in self-assembly. However, traditional macrocycles, such as cyclodextrins, calixarenes, cucurbiturils, and pillararenes, have inherent limitations in terms of cavity size and structural variety, which restrict their ability to encapsulate guest molecules of varying sizes and their potential in constructing multifunctional materials. To address these challenges, our group has developed a simple, universal, and modular strategy for constructing functional macrocycles, termed biphen[<i>n</i>]arenes. This approach leverages structure- or function-oriented modular replacement of reactive, functional, and linking modules. Therefore, biphen[<i>n</i>]arenes with customized cavity size and molecule depth can effectively encapsulate guests from small molecules to biomacromolecules. On the other hand, different from modification of side chains, incorporation of functional primitives into the biphen[<i>n</i>]arene scaffold can leave active sites on both edges to induce additional moieties to improve recognition potency or integrate extra application functionality. These characteristics provide significant advantages in the construction of diverse supramolecular materials.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"3 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144114500","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":"Machine Learning Assisted Material Discovery: A Small Data Approach","authors":"Qionghua Zhou, Xinyu Chen, Jinlan Wang","doi":"10.1021/accountsmr.1c00236","DOIUrl":"https://doi.org/10.1021/accountsmr.1c00236","url":null,"abstract":"The data-driven paradigm, represented by the famous machine learning paradigm, is revolutionizing the way materials are discovered. The inductive nature of the data-driven approach gives it great speed of prediction but also brings with it a heavy reliance on material data. However, unlike its success with text and images, which are supported by big data, materials data tend to be small data. Building a large database of materials is a good solution but not a permanent one. The cost of materials data is much higher than that of text or images, and the size of the materials database at this stage is far from sufficient. We will continue to face a shortage of materials data for a long time to come, making small data approaches necessary for machine learning based materials discovery.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"21 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122766","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}
Kostiantyn V. Kravchyk, Matthias Klimpel, Huanyu Zhang, Maksym V. Kovalenko
{"title":"Electrochemical Performance of Li Metal Anodes in Conjunction with LLZO Solid-State Electrolyte","authors":"Kostiantyn V. Kravchyk, Matthias Klimpel, Huanyu Zhang, Maksym V. Kovalenko","doi":"10.1021/accountsmr.5c00124","DOIUrl":"https://doi.org/10.1021/accountsmr.5c00124","url":null,"abstract":"Figure 1. Depiction of published data on the electrochemical cycling of a Li metal anode in conjunction with an LLZO solid electrolyte in a Li/LLZO/Li symmetric cell configuration. Detailed information for each data point shown in Figure 1 can be found in Supporting Information Table S1. The blue circle represents the electrochemical performance of a Panasonic NCR18650GA Li-ion battery with 6.9 mAh cm<sup>–2</sup> electrodes operated at a discharge current density of 20 mA cm<sup>–2</sup> (2.9 C) and capable of retaining at least 80% of its initial capacity over 300 cycles (equivalent to a cumulative capacity of 2.1 Ah cm<sup>–2</sup>). The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/accountsmr.5c00124. Supporting Tables S1–S4 and Figures S1, S2 (PDF) Electrochemical\u0000Performance of Li Metal Anodes in\u0000Conjunction with LLZO Solid-State Electrolyte <span> 0 </span><span> views </span> <span> 0 </span><span> shares </span> <span> 0 </span><span> downloads </span> Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html. <b>Kostiantyn V. Kravchyk</b> obtained his Ph.D. degree from Vernadsky Institute of General and Inorganic Chemistry of the Ukrainian National Academy of Sciences in 2009. Then, he completed postdoctoral research at the University of Le Mans (France), the University of Nantes (France), and ETH Zurich and Empa (Swiss Federal Laboratories for Materials Science and Technology). He now works as a senior scientist at ETH Zurich and Empa in the Functional Inorganic Materials group of Prof. Maksym Kovalenko. His research interests include all-solid-state Li-ion batteries, novel concepts for electrochemical energy storage and novel materials for Li-ion and post-Li-ion batteries. <b>Matthias Klimpel</b> obtained his Bachelor’s degree from RWTH Aachen University in 2019 and his Master’s degree from Ludwig Maximilian University Munich in 2022. He is currently pursuing his PhD under the supervision of Prof. Maksym Kovalenko at ETH Zurich. <b>Huanyu Zhang</b> obtained his Bachelor of Science in Chemistry from Wuhan University in 2018 and his Master’s in Chemical Engineering and Biotechnology from École Polytechnique Fédérale de Lausanne (EPFL) in 2020. He is currently pursuing his PhD at ETH Zurich under the supervision of Prof. Maksym Kovalenko. <b>Maksym V. Kovalenko</b> studied chemistry at Chernivtsi National University (Ukraine) and then continued his studies at the Johannes Kepler University Linz (Austria), earning his Ph.D. degree in 2007 with professor Dr. Wolfgang Heiss. Subsequently, he joined the University of Chicago for postdoctoral tra","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"11 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-05-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144104312","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":"Derivative Chemistry of Ag29 Nanoclusters","authors":"Honglei Shen, Xi Kang, Manzhou Zhu","doi":"10.1021/accountsmr.5c00083","DOIUrl":"https://doi.org/10.1021/accountsmr.5c00083","url":null,"abstract":"Metal nanoclusters represent a unique class of nanomaterials with monodisperse sizes, atomically precise structures, and rich physicochemical properties, and they find wide applications in optics, catalysis, and biomedicine. The strong quantum size effects and discrete electronic energy levels endow metal nanoclusters with structure-dependent properties, where any perturbation of their compositions or structures induces significant variations in their properties. This makes the research of metal nanoclusters particularly exciting but also challenging, as small changes in their atomic composition or arrangement can result in substantial differences in their behavior. As a result, the study of metal nanoclusters follows a node-style research pattern, wherein major breakthroughs often lead to new insights into their structural and functional properties. However, despite these advances, the systematic exploration of these materials remains highly challenging. In recent years, there has been increasing interest in the development of unified theoretical models that can predict and control the properties of metal nanoclusters, potentially making them ideal candidates for programmable nanomaterials. Key examples of well-studied nanoclusters include Au<sub>25</sub>(SR)<sub>18</sub> and Ag<sub>44</sub>(SR)<sub>30</sub>, which have provided valuable insights into the fundamental principles of metal nanocluster chemistry. Nevertheless, given the vast differences observed among various cluster frameworks, there is an urgent need to develop new models and explore versatile approaches for the preparation of nanoclusters with tunable functionalities. In this regard, our research group has focused on advancing the derivative chemistry of Ag<sub>29</sub>-templated nanoclusters.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"334 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-05-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144104308","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":"Chemically Inert Atomic Passivation Shell for Stable Semiconductor Nanocrystals","authors":"Congyang Zhang, Zhichun Li, Mingming Liu, Qun Wan, Weilin Zheng, Liang Li","doi":"10.1021/accountsmr.4c00366","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00366","url":null,"abstract":"The 2023 Nobel Prize in Chemistry has recognized the important discovery and development of QDs. Colloidal semiconductor nanocrystals (NCs), known as quantum dots (QDs), have attracted increased attention for a wide range of potential applications, such as displays, lighting, photovoltaics, and biological imaging, because of their high quality and size-dependent optical properties. To obtain high-quality semiconductor NCs with reduced surface defects and boosted photoluminescence emission, semiconductor shell-based surface engineering is a commonly used strategy. However, the terminated semiconductor surface is likely not immune to photodegradation or chemical degradation behavior. Insulating matrix encapsulation was demonstrated to be an alternative way to resolve the stability issue, but the bulk and insulating feature of the matrix could restrain the electrical activity and solution processability for device applications of NCs. As a compromise, the chemically inert atomic passivation shell (CIAPS) could be the ideal approach to break the above-mentioned trade-off and promote practical optoelectronic applications. The CIAPS on semiconductor NCs can protect the NCs from the surrounding environment physically and isolate photogenerated excitons from the external photochemical reactions while maintaining access to charge injection or transport for device applications.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"41 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144087962","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":"Phenothiazine Polymers as Versatile Electrode Materials for Next-Generation Batteries","authors":"Birgit Esser, Isabel H. Morhenn, Michael Keis","doi":"10.1021/accountsmr.5c00053","DOIUrl":"https://doi.org/10.1021/accountsmr.5c00053","url":null,"abstract":"Organic battery electrode materials are key enablers of different postlithium cell chemistries. As a p-type compound with up to two reversible redox processes at relatively high potentials of 3.5 and 4.1 V vs. Li/Li<sup>+</sup>, phenothiazine is an excellently suited redox-active group. It can easily be functionalized and incorporated into polymeric structures, a prerequisite to obtain insolubility in liquid battery electrolytes. Phenothiazine tends to exhibit π-interactions (π*−π*-interactions) to stabilize its radical cationic form, which can increase the stability of the oxidized form but can also strongly influence its cycling performance as a battery electrode material. In recent years, we investigated a broad range of phenothiazine-based polymers as battery electrode materials, providing insight into the effect of π-interactions on battery performance, leading to design principles for highly functional phenothiazine-based polymers, and enabling the investigation of full cells. We observed that π-interactions are particularly expressed in “mono”-oxidized forms of poly(3-vinyl-<i>N</i>-methylphenothiazine) (PVMPT) and are enabled in the battery electrode due to the solubility of oxidized PVMPT in many carbonate-based liquid electrolytes. PVMPT dissolves during charge and is redeposited during discharge as a stable film on the positive electrode, however, still retaining half of its charge. This diminishes its available specific capacity to half of the theoretical value. We followed three different strategies to mitigate dissolution and inhibit the formation of π-interactions in order to access the full specific capacity for the one-electron process: Adjusting the electrolyte composition (type and ratio of cyclic vs. linear carbonate), encapsulating PVMPT in highly porous conductive carbons or cross-linking the polymer to X-PVMPT. All three strategies are excellently suited to pursue full-cell concepts using PVMPT or X-PVMPT as positive electrode material. The extent of π-interactions could also be modified by structural changes regarding the polymer backbone (polystyrene or polynorbornene) or exchanging the heteroatom sulfur in phenothiazine by oxygen in phenoxazine. By changing the molecular design and attaching electron-donating methoxy groups to the phenothiazine units, its second redox process can be reversibly enabled, even in carbonate-based electrolytes. Studies by us as well as others provided a selection of high-performing phenothiazine polymers. Their applicability was demonstrated as positive electrode in full cells of different configurations, including dual-ion battery cells using an inorganic or organic negative electrode, anion-rocking-chair cells as examples of all-organic batteries, or even an aluminum battery with a performance exceeding that of aluminum-graphite battery cells. In changing the design concept to conjugated phenothiazine polymers, a higher intrinsic semiconductivity can result, enabling the use of a lesser amo","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"58 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144087959","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":"Chemistry of Two-Dimensional Materials for Sustainable Energy and Catalysis","authors":"Xiao Wang, Wei Gu, Pratteek Das, Chenyang Li, Zhong-Tao Li, Zhong-Shuai Wu","doi":"10.1021/accountsmr.4c00406","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00406","url":null,"abstract":"Two-dimensional (2D) materials form a large and diverse family of materials with extremely rich compositions, ranging from graphene to complex transition metal derivatives. They exhibit unique physical, chemical, and electronic properties, making 2D materials highly promising in the fields of sustainable energy storage and electrocatalysis. Although significant progress has been made in the design and performance optimization of 2D materials, challenges persist, particularly in energy storage and electrocatalysis. A key issue is the restacking or aggregation of these materials in the powder form, which hinders ion transport and reduces their overall performance by limiting the effective surface area. In this Account, we delve into the latest advancements made by our team in the chemistry of 2D materials toward sustainable electrochemical energy storage and catalysis. We begin by highlighting some of the representative 2D materials developed by our team, such as fluorine-modified graphene and transition metal telluride nanosheets. These materials, with their atomic-scale thickness, offer significant advantages over traditional bulk materials by circumventing issues such as limited active surface area, extended ion transport pathways, and complex manufacturing processes, thereby providing innovative approaches for the development of high-performance materials. Next, the key synthesis strategies that have been pivotal in our research are summarized. Techniques such as electrochemical exfoliation, solid-state lithiation and exfoliation, and ion-adsorption chemical strategies have enabled precise control over the ionic and electronic conductivities, lateral dimensions, and internal atomic configurations of 2D materials. These methodologies not only facilitate the preparation of 2D materials with tailored properties, but also support the scalable production of high-quality materials. Furthermore, we outline the broad applications of 2D energy materials across various domains. In alkali-based batteries, these materials have been instrumental in enhancing battery performance, including extending the cycle life and improving the charge–discharge efficiency. They also contribute to increased energy and power densities in aqueous-based batteries and supercapacitor–battery hybrid devices. In the realm of metal-free anodes, they play a crucial role in inhibiting metal dendrite growth, thereby enhancing battery safety. Additionally, in energy catalysis, they demonstrate superior catalytic activity, promoting efficient energy conversion. In microscale electrochemical energy storage devices, they meet the demands for high power and energy density, propelling the advancement of miniaturized energy storage solutions. Lastly, we address the critical challenges confronting 2D energy materials and offer a perspective on future directions. While significant progress has been achieved in 2D material research, challenges persist in synthesis, performance optimization, a","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"28 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143945993","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":"Surface-Active Catalysts for Interfacial Gas–Liquid–Solid Reactions","authors":"Kang Wang, Badri Vishal, Marc Pera-Titus","doi":"10.1021/accountsmr.5c00026","DOIUrl":"https://doi.org/10.1021/accountsmr.5c00026","url":null,"abstract":"Multiphase reactions combining gas and liquid phases and a solid catalyst are widespread in the chemical industry. The reactions are typically affected by the low gas solubility in liquids and poor mass transfer from the gas phase to the liquid, especially for fast reactions, leading to much lower activity than the intrinsic catalytic activity. In practice, high pressure, temperature, and cosolvents are required to increase the gas solubility and boost the reaction rate. Gas–liquid–solid (G-L-S) microreactors based on particle-stabilized (Pickering) foams rather than conventional surfactant-stabilized foams can increase the contact between the gas and liquid phases, together with surface-active catalytic particles, and dramatically accelerate G-L-S reactions. Unlike surfactants, surface-active catalytic particles can be recycled and reused and reduce coalescence, Ostwald ripening, and aggregation by adsorbing selectively at the G-L interface, promoting stability.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"29 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-05-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143930641","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}
Hengrui Zhang, Alexandru B. Georgescu, Suraj Yerramilli, Christopher Karpovich, Daniel W. Apley, Elsa A. Olivetti, James M. Rondinelli, Wei Chen
{"title":"Emerging Microelectronic Materials by Design: Navigating Combinatorial Design Space with Scarce and Dispersed Data","authors":"Hengrui Zhang, Alexandru B. Georgescu, Suraj Yerramilli, Christopher Karpovich, Daniel W. Apley, Elsa A. Olivetti, James M. Rondinelli, Wei Chen","doi":"10.1021/accountsmr.5c00011","DOIUrl":"https://doi.org/10.1021/accountsmr.5c00011","url":null,"abstract":"The increasing demands of sustainable energy, electronics, and biomedical applications call for next-generation functional materials with unprecedented properties. Of particular interest are emerging materials that display exceptional physical properties, making them promising candidates for energy-efficient microelectronic devices. As the conventional Edisonian approach becomes significantly outpaced by growing societal needs, emerging computational modeling and machine learning methods have been employed for the rational design of materials. However, the complex physical mechanisms, cost of first-principles calculations, and the dispersity and scarcity of data pose challenges to both physics-based and data-driven materials modeling. Moreover, the combinatorial composition–structure design space is high-dimensional and often disjoint, making design optimization nontrivial.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"10 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143910162","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":"Vat Photopolymerization 3D Printing of Conductive Nanocomposites","authors":"David Tilve-Martinez, Philippe Poulin","doi":"10.1021/accountsmr.5c00060","DOIUrl":"https://doi.org/10.1021/accountsmr.5c00060","url":null,"abstract":"Recent years have witnessed a surge in efforts to integrate electrically conductive nanomaterials into photopolymer-based additive manufacturing (AM), driven by the growing demand for multifunctional 3D-printing. While several AM techniques have been adapted to process conductive composites, Digital Light Processing (DLP) stands out for its high-resolution and fast-curing capabilities. However, it poses a central limitation: the requirement for optical transparency in the printing resin, which is compromised by the incorporation of conventional conductive fillers. This Account highlights the advances in overcoming three fundamental challenges in the field: (i) How can conductive nanocomposites be printed by DLP without compromising resolution? (ii) How can high electrical conductivity be achieved at low filler content? (iii) What is the origin of anisotropic conductivity in printed objects, and how can it be mitigated?","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"13 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143897596","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}