Chemistry of Materials最新文献

{"title":"Dual-Acid-Tailored Ionic Covalent Organic Frameworks for High-Temperature Proton Conduction under Anhydrous Conditions and the Practical Opportunities","authors":"Vellaichamy Joseph, Keiichiro Maegawa, Mateusz Wlazło, Marek J. Potrzebowski, Krzysztof Łyczko, Atsushi Nagai","doi":"10.1021/acs.chemmater.5c00016","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00016","url":null,"abstract":"An organic salt (DMAP/Pa-SO₃H) composed of 2,5-diaminiobenzenesulfonic acid (Pa-SO₃H) and dimethylaminopyridine (DMAP) was demonstrated as a linker to construct ionic covalent organic frameworks (iCOFs). The iCOF denoted as TpDMAP/Pa-SO₃H was prepared by the condensation reaction of the triformylphloroglucinol (Tp) building block and DMAP/Pa-SO₃H and offers the potential to accommodate an external proton source (H₃PO₄; PA), enabling the immobilization of PA moieties within the pore structure through a strong ionic hydrogen bonding interaction evidenced by DFT calculations. Furthermore, H₃PO₄-doped iCOF denoted as PA@TpDMAP/Pa-SO₃H proclaimed the advantage of engineering at the linker position, which in turn promotes proton conductivity to 1.56 × 10^–2 S cm^–1 (increased 100-fold as related to PA@TpPa-SO₃H) at 140 °C under anhydrous conditions. Finally, we investigated the adaptability of a dual-acid system in sulfonated poly(ether ether ketone) (SPEEK) membranes, a common acid-modified polymeric material. PA-doped DMAP-modified SPEEK (PA@SPEEK/DMAP) evidenced a 100-fold appreciation of proton conductivity at 120 °C, as compared to bare SPEEK membranes under anhydrous conditions.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"57 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713783","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mussel-Inspired Catechol-Functionalized EVA Elastomers for Specialty Adhesives; Based on Triple Dynamic Network","authors":"Tuhin Subhra Pal, Sagar Kumar Raut, Nikhil K. Singha","doi":"10.1021/acs.chemmater.4c03286","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03286","url":null,"abstract":"Marine mussels secrete adhesive proteins that enable them to bind to various surfaces (like rocks, ship’s hull, piers, etc.) in saline and wet environments. One of the main structural components in these adhesive proteins is the presence of a unique catechol-based amino acid, <span>l</span>-3,4-dihydroxyphenylalanine (DOPA), which is responsible for interfacial binding and the rapid solidification of the proteins. Mimicking this functionality in synthetic polymers yields high-strength adhesives that can be attached to both dry and wet surfaces. In this study, a commercially available epoxy-functionalized elastomer, poly(ethylene-<i>co</i>-vinyl acetate-<i>co</i>-glycidyl methacrylate) (EVA-GMA), was modified with dihydroxycaffeic acid (HCA) via transesterification reaction to prepare catechol-functionalized EVA elastomer which in combination with diboronic acid showed self-healing and recyclable characteristics. The catechol-functionalized elastomers can self-heal both dry and underwater, as the catechols can form hydrogen bonding and coordination complexes with metal ions in both dry and wet environments. The tensile study demonstrated a significant improvement in the mechanical strength due to hydrogen bonding and boronic eater cross-linking. Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) analyses unequivocally confirm the successful formation of covalent boronic ester cross-links along with metal coordination. The stress relaxation behavior of the boronic ester cross-linked EVA-GMA elastomer was examined at various temperatures to assess its dynamic properties. Moreover, boronic ester cross-linked elastomers showed significant self-healing properties (with a healing efficiency of ∼86%) and were monitored by using optical microscopy and tensile analysis. By incorporating boronic ester-based dynamic covalent bonds, metal coordination, and H-bonding into polymer networks, we achieved strong adhesion and their dynamic nature for fast and reversible adhesion. Interestingly, this catechol-functionalized EVA-elastomer-based adhesive showed excellent bonding characteristics toward different surfaces, as analyzed via lap shear test in both dry and wet environments.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"26 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713787","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"LiI-Modified Glass-Ceramic Lithium Thioborate: From Fundamentals to Applications in Solid-State Batteries","authors":"Sarah E. Holmes, Jędrzej Kondek, Pu Zhang, Vasiliki Faka, Jon A. Newnham, Lara M. Gronych, Michael Ryan Hansen, Wolfgang G. Zeier, Yi Cui","doi":"10.1021/acs.chemmater.5c00224","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00224","url":null,"abstract":"Solid-state batteries are an emerging battery technology rivaling lithium-ion batteries, but before commercialization can occur, new classes of solid-state electrolytes (SSEs) must be investigated to better understand the fundamental properties of these materials and to extend the capabilities of fast charging and cycle life. In this work, we investigate glass-ceramic lithium thioborate (LBS) SSEs with the stoichiometry of Li₁₀B₁₀S₂₀ and utilize a rapid synthesis that enables lithium iodide (LiI) modification in Li₁₀B₁₀S₂₀. We study the structures of four materials with varying amounts of LiI using X-ray diffraction, pair distribution function, and solid-state NMR and find that LiI breaks down the B₁₀S₂₀ supertetrahedra that make up the unit cell of Li₁₀B₁₀S₂₀. More LiI increases ionic conductivity by increasing the unit cell volume and the fraction of the glassy phase in the electrolyte. LiI-modified Li₁₀B₁₀S₂₀ as an anode-facing SSE enables all-solid-state batteries to cycle well with theoretical capacities up 6.37 mAh/cm² at 0.1C, validating the relevance of LBS SSEs as separators for solid-state batteries.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"34 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713788","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Influence of “Non-Interacting” Flux Concentration in Metallic Flux Growth Synthesis","authors":"Trent M. Kyrk, Melissa G. Anderson, Gregory T. McCandless, Saul H. Lapidus, Julia Y. Chan","doi":"10.1021/acs.chemmater.5c00139","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00139","url":null,"abstract":"In situ experiments probing the mechanisms of flux growth synthesis above 1100 °C, though challenging, enable direct observation of synthetic pathways, products, and metastable phases. In this study, in situ powder X-ray diffraction of flux growth synthesis up to 1200 °C was employed to investigate the role of Sn flux in the synthesis of praseodymium cobalt germanides. We demonstrate that metallic fluxes, with minimal incorporation into the target compounds, significantly influence the reaction products of flux growth synthesis of intermetallic compounds. The validation of in situ experiments with bulk synthesis is also presented.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"29 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703383","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Enlarged Cleavable Linkages in Shuriken-like Quaternary Ammonium Compounds Providing Safer Bactericides","authors":"Xiao-Qi Xu, Yanji Chu, Zhipeng Liu, Bin Yuan, Yapei Wang","doi":"10.1021/acs.chemmater.5c00202","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00202","url":null,"abstract":"Although they offer great convenience in preventing microbial infections, the nondegradable feature of most commercial quaternary ammonium compounds (QACs) has led to persistent environmental accumulation, raising significant concerns about their detrimental impacts on public and ecological health. In this study, we report a kind of shuriken-like QACs with rapid hydrolysis properties under mild conditions, enabled by the introduction of enlarged cleavable linkages as backbones. Such shuriken-like QACs present potent bactericidal activity owing to the multicationic “heads” yet can be converted to entirely harmless forms of choline and silicone oil after degradation. Both the cytotoxicity assessment and the biosafety evaluation confirm the nontoxic nature of the degradation products. The bactericidal performance in fruit preservation and infection prevention on fabric surfaces further illustrates the broad application prospects of such degradable QACs within the realm of food safety and public health. With the advantages of rapid hydrolysis, environmental friendliness, and low biotoxicity, the concept of an “enlarged cleavable linkage” strategy will pave the way for exploiting a generation of degradable disinfectants that can effectively combat microbial threats while ensuring a minimal ecological footprint.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"93 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703386","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Topological Photoluminescence and Slow Magnetic Relaxation in a Quasi One-Dimensional Stoichiometric Ternary Tb(III) Cyanamide","authors":"Juan Medina-Jurado, Hicham Bourakhouadar, YiXu Wang, Alex J. Corkett, David Enseling, Thomas Jüstel, Richard Dronskowski","doi":"10.1021/acs.chemmater.4c03264","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03264","url":null,"abstract":"Technological advances are intangibly linked to the preparation and description of new solid-state materials. Recently, low-dimensional lanthanide-based systems have received particular attention for their interesting magnetic and luminescent properties. Thus, motivated by the emergence of such “NCN” chemistry, we present the synthesis of the stoichiometric Tb(III) cyanamide Li_<i>x</i>Na_1–<i>x</i>Tb(NCN)₂, which crystallizes in an orthorhombic structure where the magnetic Tb³⁺ ions are arranged in well-separated one-dimensional chains parallel to the <i>c</i> axis. Luminescence studies show phosphor-like behavior with a process of energy migration probed to be one-dimensional due to the large difference in the size of the intra- and interchain transfer probabilities. As a consequence, a long luminescent lifetime of 1.22 ms was observed at 100 K. In contrast, AC magnetic susceptibility studies reveal a slow magnetic relaxation process, with a relaxation time of 4.03 μs, thus establishing a good correlation between the compound’s 1D structure and its luminescent and magnetic properties. This work represents a fine example of a Tb(III)-based solid-state cyanamide compound exhibiting slow magnetic relaxation and slow radiative decay.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"3 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713785","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ordered Cationic Mixing in a 1D Organic–Inorganic Hybrid","authors":"Megan A. Cassingham, Sujeewa N. S. Lamahewage, Yang G. Goh, Alexander G. Squires, Aamani Ponnekanti, Sarah Karabadjakyan, Anna Wapner, Peter I. Djurovich, David O. Scanlon, Aaron J. Rossini, Mark E. Thompson, Brent C. Melot","doi":"10.1021/acs.chemmater.4c02364","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02364","url":null,"abstract":"Hybrid metal halides are a remarkably dynamic family of materials that offer a flexible platform for exploring the novel crystal chemistry that emerges at the intersection of organic and inorganic solids. Herein, we report the discovery of a hybrid that contains two molecules effectively adopting isostructural geometry, (1-NA)PbI₃ and (1-MQ)PbI₃, and our attempts to create solid solutions of the two beyond the 1:1 ratio. Single-crystal X-ray diffraction, combined with solid-state NMR measurements, clearly show that despite having nearly identical steric geometry, the only mixed phase attained was the composition (1-MQ)(1-NA)Pb₂I₆, which exhibits a high degree of order between the two molecules. We propose that this ordering is primarily driven by local molecular dipoles, which ultimately creates a band structure in the blended phase that is highly characteristic of the end members, with little sign of rehybridization between the organic or inorganic components.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"101 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695191","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Correction to “Controlling Thickness of Aurivillius Phase Perovskite Nanosheets Obtained by Delaminating Bi2SrNan–2NbnO3n+3 (n = 2–5) Layered Crystal”","authors":"Keisuke Awaya, Kazuto Hatakeyama, Shintaro Ida","doi":"10.1021/acs.chemmater.5c00609","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00609","url":null,"abstract":"This article has not yet been cited by other publications.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"125 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703526","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Three-Dimensional Covalent Organic Frameworks Containing Diverse Nitrogen Sites for Gold Adsorption","authors":"Ke Li, Douchao Mei, Yin-sheng Liu, Bing Yan","doi":"10.1021/acs.chemmater.4c03404","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03404","url":null,"abstract":"As the study progresses, it becomes more significant to explore the effect of specific active sites in covalent organic frameworks (COFs) on the gold adsorption process. Meanwhile, emerging 3D COFs are potential candidates for the adsorption of gold due to their rich pore and cage structures. In this work, to study the effect of the introduction and position of aromatic Ns on the gold capture, we synthesized three 3D COFs which have good selectivity, immunity to interference, reproducibility, and the potential to recover gold from e-waste. Compared to the COF containing only imine bonds as a blank, the introduction of triazine and pyridine rings resulted in a higher maximum adsorption capacity (2081 mg/g) and a faster adsorption rate (within 10 min), respectively. Theoretical calculations show that the presence of the triazine ring enhances the reduction of Au³⁺ by COF, while the synergistic effect of pyridine N and imine bonding shortens the adsorption time of gold. This work reveals the great potential of 3D COFs for gold adsorption and the roles played by the different types of aromatic Ns on gold capture, providing a reference for enhancing the adsorption performance of 3D COFs on gold.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"34 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695190","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Patterning Technology: From Supporting Role to Main Player in Materials Chemistry","authors":"Han-Bo-Ram Lee","doi":"10.1021/acs.chemmater.5c00419","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00419","url":null,"abstract":"Published as part of &lt;i&gt;Chemistry of Materials&lt;/i&gt; special issue “Precision Patterning”. I recall, when I traveled to Italy, how comfortable I felt browsing items on the shelves of a grocery store (see Figure 1). The neatly and periodically arranged cans and pasta boxes exhibited a satisfying symmetry, adhering to a certain pattern. Like many other scientists, I appreciate symmetry and predictability. Generally, in science and engineering, patterning technology has not received as much attention as other fields, for example those that investigate novel materials’ properties or demonstrate new applications. Instead, patterning technology has often been considered as a type of advance in measurement and device fabrication processes. For instance, the interesting properties and new applications of graphene, which originate from its unique dimensions and atomic structure, attract more interest than the fabrication methods using patterning technology for measurements and demonstrations of graphene’s potential usefulness. Nevertheless, patterning is considered a key technology for commercialization and materials device fabrication. In other words, patterning is akin to arranging pasta sauce cans on shelves in an attractive manner to increase sales rather than changing their taste directly. However, as patterns become smaller, denser, and more complex on a large scale, patterning is evolving into a major player in future research and development. Fundamentally, the purposes of patterning in science and technology can be categorized as follows: 1) to obtain novel properties from interactions within periodic structures and 2) to fabricate repeated structures or devices with a desired level of integration within a given area or space. The first purpose tends to attract interest from scientists, as periodic patterns exhibit fascinating physical properties through their interactions with environmental inputs such as photons and electrons. Plasmonics, for instance, exemplifies the significance of patterning technology (see Fan et al., DOI: 10.1021/acs.chemmater.4c00134). Surface plasmons with periodic quantum dot patterns show great potential for various applications, including sensors, photovoltaics, photocatalysts, and lasers (see Sen et al., DOI: 10.1021/acs.chemmater.4c01090. Additionally, crystalline metal–organic frameworks (MOFs) exhibit novel catalytic properties due to their porosity and periodicity (see Patel et al., DOI: 10.1021/acs.chemmater.4c01137).&lt;named-content content-type=\"anchor\" r type=\"simple\"&gt;&lt;/named-content&gt; The second purpose is important from a manufacturing perspective, as many production processes rely on patterning technology to optimize time, resources, and operational efficiency. As integrated electronic device technology advances, patterning has become an indispensable tool for increasing integration levels, thereby enhancing capacity, speed, and resolution. For example, the number of pixels on a display screen is determined by ","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"35 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695193","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}