Chemistry of Materials最新文献

{"title":"Pressure-Induced Conglomerate to Racemate Transformation in a One-Dimensional Disulfide-Based Lead Halide","authors":"Wenbo Qiu, Weilong He, Yu Liu, Boyang Fu, Weiyi Wang, Jiangang He, Luhong Wang, Haozhe Liu, Weizhao Cai","doi":"10.1021/acs.chemmater.5c00335","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00335","url":null,"abstract":"Controlling the molecular chirality under external pressure is particularly challenging in low-dimensional hybrid halides, as the constrained structure and strong hydrogen bonding hinder significant conformational changes in bulky organic molecules. Here, by incorporating flexible disulfide-based molecules into the one-dimensional (1D) PbI₅ framework, the chiral hybrid halide [NH₃(CH₂)₂S–S(CH₂)₂NH₃]PbI₅·H₃O undergoes a transformation from conglomerate to racemate at a hydrostatic pressure of approximately 0.10 GPa. This reversible acentric-to-centric transformation is accompanied by the second-harmonic generation (SHG) “on–off” switching and significant conformational changes in the cystamine cations within the structure. In the high-pressure racemic phase, two enantiomers with left- and right-handed conformers (M- and P-helicity) coexist within the lattice structure and their deformations under compression resemble those of a compressed mechanical spring, ultimately leading to considerable distortions of the 1D zigzag PbI₅ chains through strong organic–inorganic H···I interactions. Furthermore, both experimental and theoretical results reveal that the unique phase transformation induces minor alterations in the electronic structures and optical bandgaps. Our findings provide insights into the manipulation of molecular chirality and SHG properties in hybrid halides by introducing flexible organic molecules into inorganic frameworks.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"26 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723697","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":"Manipulation of Charged Porous Cages as Tunable Platforms for Strong Gas Adsorption","authors":"Meaghan M. Deegan, Alexandra M. Antonio, Kyle J. Korman, Andrew A. Ezazi, Kaushalya Korathotage, Merissa N. Morey, Jahidul Hoq, Duleeka Dissanayake, Dewni D. Fernando, Glenn P. A. Yap, David C. Powers, Eric D. Bloch","doi":"10.1021/acs.chemmater.4c02269","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02269","url":null,"abstract":"Metal–organic frameworks (MOFs) have long been explored for their tunable structures and applications in gas separation and catalysis, yet systems capable of engaging in metal-to-ligand π-backbonding remain scarce. Expanding beyond MOFs, our study leverages porous coordination cages (PCCs) as modular building blocks to construct highly tunable porous salts. By incorporating coordinatively unsaturated, π-basic ruthenium sites within charged PCCs, we achieve selective and reversible carbon monoxide chemisorption, a property rarely observed in hybrid porous materials. We further demonstrate that nonporous molecular ruthenium complexes can be incorporated as charge-balancing counterions, yielding materials with tailored porosities and adsorption properties. These findings introduce a strategy for designing porous salts that integrate molecular reactivity with tunable porosity, offering promising avenues for next-generation separations, sensing, and catalysis. Our approach bridges molecular design principles with material functionality, expanding the toolkit for designing adaptive porous materials beyond traditional MOFs.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"11 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723698","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":"In-Situ Study of Heterogeneous Crystal Growth of Gold Nanoparticles on Hematite Facets","authors":"Xiang Wang, Sichuang Xue, Xin Qi, Duo Song, Lili Liu, Yatong Zhao, Ping Chen, Maria L. Sushko, Kevin M. Rosso, Xin Zhang","doi":"10.1021/acs.chemmater.5c00065","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00065","url":null,"abstract":"Although significant research has been conducted on metal nanoparticles, a notable gap persists in understanding the fundamental principles governing their crystallization and stability, particularly when deposited on heterogeneous supports. Most current studies focus on specific systems, such as single nanocrystalline facet, which limits the broader understanding of how these processes are influenced by various factors, such as interactions with the facet-dependent crystalline supports. Gaining deeper insights into these mechanisms could lead to the development of more robust and efficient catalytic systems, sensors, and nanomaterials for other advanced applications across various industries. To address this gap, our study focuses on the in-depth examination of the crystallization process of gold (Au) nanoparticles on hematite (104) and (001) facets through in situ transmission electron microscopy (TEM) observation. Our findings reveal the existence of three distinct crystal growth pathways in hematite-supported Au nanoparticles: Ostwald ripening, particle coalescence, and disordered intermediate-phase-mediated growth where particle coalescence plays a dominant role in the sintering process. Furthermore, analysis of crystal growth kinetics on different facets of hematite substrate highlights a facet-dependent behavior. Hematite (001) effectively stabilizes Au nanoparticles and suppresses their sintering more effectively than (104) facets. This enhanced stabilization is attributed to the lower surface energy and stronger interaction between Au and the hematite (001) facet. Density functional theory (DFT) calculations, in conjunction with molecular dynamics (MD) simulations, provide valuable insight into heterogeneous coarsening of Au nanoparticles on hematite. Our research significantly contributes to the understanding of facet-dependent growth of metal nanoparticles on hematite nanocrystals and offers guidelines for selecting hematite-supported heterogeneous catalysts.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"125 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713784","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":"Wearable Thermal Energy Storage Polymeric Materials via the Progressive Phase Change Strategy of Crystalline Bottlebrush Polysiloxane Networks","authors":"Jiahao Ma, Tian Ma, Yanyun Li, Qiguang Liu, Jue Cheng, Junying Zhang","doi":"10.1021/acs.chemmater.5c00005","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00005","url":null,"abstract":"Flexible polymeric solid–solid phase change materials (PCMs) have garnered continuous attention owing to their potential for thermal management in flexible/wearable devices and their non-leakage characteristics. However, it is still a big challenge to obtain polymeric solid–solid PCMs with both flexibility and high latent heat. In this study, bottlebrush phase change polysiloxane networks with alkyl side chains of different lengths (Si-X) are prepared through a one-step grafting cross-linking process. The influence of the length of the grafting chain on the mechanical and thermomechanical properties, phase change behavior, rheological characteristics, and thermal stability of materials is systematically studied. Furthermore, the concept of progressive phase change is proposed by cografting of crystalline side chains with multiple lengths in bottlebrush polysiloxane networks, which reduces the dense packing of crystals. The resulting network (Si-ODDT-70) exhibits excellent latent heat (Δ<i>H</i>_m = 128.0 J/g; Δ<i>H</i>_f = 129.1 J/g) and elongation at break values exceeding 200 and 450% at room and body temperatures, respectively. In addition, Si-ODDT-70 can be freely coiled, rolled, cut, and repaired with UV light at room temperature. Besides, the recyclable, stretchable/bendable, and multiresponsive phase change composites are obtained by combining the liquid metal/graphene paper with Si-ODDT-70. The first proposed cografting strategy offers a solution to unify the flexibility and high latent heat of PCMs, which will further enrich bottlebrush polymer network topology structures and guide the future design of flexible polymeric PCMs.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"59 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723699","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":"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}