Chemistry of Materials最新文献

{"title":"Fluorescence Lifetime Imaging Microscopy: Advances in Materials Science Research","authors":"Fariyad Ali, Subhankar Kundu","doi":"10.1021/acs.chemmater.5c00666","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00666","url":null,"abstract":"Controlling formation dynamics and tuning micro- or nanoscale structures are crucial to designing materials with desired properties for specific applications. Thus, visualization of the structures and probing of the <i>in situ</i> formation mechanisms of molecular materials are quite important, although challenging. Recently, fluorescence lifetime imaging microscopy (FLIM) has emerged as a valuable complementary, robust, and noninvasive technique along with conventional imaging tools to unravel the nanoscale morphology and dynamics of fluorescent or fluorophore-tagged molecular materials. This Review emphasizes the growing importance of FLIM in exploring the salient aspects of various materials, including semiconductor nanocrystals, molecular self-assembly, polymers, and metal–organic frameworks. The fundamental features of FLIM and its applications decipher the dynamic self-assembly process, the growth kinetics of and mechanistic insights into polymers, and the phase purity in metal–organic frameworks. Additionally, this work also highlights the use of FLIM as a complementary tool along with intensity-correlation techniques in photoluminescence blinking and photon antibunching to resolve many unreciprocated facts in the field of semiconductor nanocrystals. Beyond presenting up-to-date knowledge in the field, we outline the potential future directions of FLIM for developing different materials and improving existing ones. This advancement paves the way for further opportunities in materials science research and applications.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"25 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144146274","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":"Breaking Barriers in Zeolite Synthesis via ZnO-Assisted Interzeolite Conversion for Enhanced Catalysis","authors":"Mostafa Torka Beydokhti, Gleb Ivanushkin, Ibrahim Khalil, Ahmed Sajid, Juna Bae, Aram Bugaev, Thibaut Donckels, Dieter Plessers, Michiel Dusselier","doi":"10.1021/acs.chemmater.5c00431","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00431","url":null,"abstract":"Interzeolite Conversion (IZC) can overcome kinetic hurdles toward exceptional phases by taking advantage of the selective dissolution of crystalline ones. Controlled dissolution of a siliceous mordenite (MOR) in the presence of ZnO enables us to ‘catch’ a zincosilicate ferrierite (FER) topology. Structural characterization proves that defect engineering achieved from a mild post-treatment can tune composition and properties ranging from a Zn-containing FER with Si/Al and Si/Zn ratios of 170 and 36 to a high-silica FER with a Si/Al ratio of 170 and Si/Zn ratio of 700, which is challenging to reach from one-step synthesis in hydroxide media. The extent of acid washing can regulate the framework Zn species toward a Lewis acid catalyst and an almost nonacidic high-silica counterpart. Along the way, we provide ample new insights into the influence and role of zinc heteroatom on the kinetics of IZC. Due to the custom textural properties obtained by IZC, post-treatment, and also by exhibiting Lewis acidity with less Bro̷nsted acidity, Zn-FER shows enhanced selectivity and long lifetime for dimethyl ether (DME) production in the CO₂ hydrogenation to hydrocarbons reaction.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"2 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144154062","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":"Modifying Inorganic Structure through Hydration in Vapor Phase Infiltrated AlOxHy-PIM-1 Hybrid Membranes: Implications for Solvent Stability, Permeance, and Selectivity","authors":"Benjamin C. Jean, Yi Ren, Ian Slagle, Ryan P. Lively, Faisal M. Alamgir, Mark D. Losego","doi":"10.1021/acs.chemmater.4c03453","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03453","url":null,"abstract":"Vapor-phase infiltration (VPI) presents a promising approach to enhancing the stability of organic membranes in organic solvents while maintaining critical properties, such as membrane permeance and selectivity. However, the precise chemical structure of the infiltrated inorganics and their impact on solvent stability remain poorly understood, limiting efforts to improve VPI treated hybrid membrane technology for organic solvent reverse osmosis (OSRO). This study uses X-ray absorption spectroscopy alongside X-ray photoelectron spectroscopy (XPS) to elucidate the inorganic cluster structure within PIM-1/AlO_<i>x</i>H_<i>y</i>. By analyzing the H₂O ratio via XPS and assessing the first and second shell Al coordination numbers from Al K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy, we propose that aluminum oxyhydroxide tends to form nonlinear networked structures. X-ray absorption near-edge spectroscopy (XANES) analysis confirms a predominantly six-coordinate structure in the first shell, while EXAFS analysis of the second shell reveals the presence of three aluminum atoms, suggesting clusters significantly larger than simple dimers or trimers, similar to larger aluminum hydroxide and oxyhydroxide crystal structures. Furthermore, we demonstrate that postprocessing techniques, such as dehydration and rehydration, can be utilized to control this network structure and membrane permeance and selectivity without compromising solvent stability.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"17 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144146315","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":"Mechanically Reinforced Nanocomposite Hydrogels and Advanced Applications in Biosensing and Bioelectronics","authors":"Dongdong Lu, Yongyan Mo, Shuo Sun, Qiangwei Wang, Ziteng Wu, Wenkai Wang, Mingning Zhu","doi":"10.1021/acs.chemmater.5c00498","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00498","url":null,"abstract":"Nanocomposite hydrogels, as emerging multifunctional and flexible materials, have garnered significant attention in biosensing and bioelectronic applications due to their outstanding mechanical properties and diverse functional features. By integration of nanomaterials with hydrogel matrices, the mechanical properties are significantly enhanced while their softness and high-water content are maintained, making them particularly suitable for applications in flexible sensors, artificial muscles, and tissue engineering. This Review summarizes the latest advancements in nanocomposite hydrogels, with a focus on the mechanisms and effects of mechanical property enhancement as well as the characteristics of interactions between hydrogel matrices and nanomaterials. The applications in biosensors and bioelectronic devices are also discussed. There are four types of nanofillers included: polymeric nano/microgels, carbon-based nanoparticles, silicon-based nanoparticles, and metallic or metal oxide nanoparticles. Representative case studies are carefully selected, with a detailed discussion of their fabrication methods, mechanical enhancements, advantages, and limitations. Finally, the prospects and challenges of nanocomposite hydrogels in biosensor and wearable device applications are explored.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"25 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144137212","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":"Liquid–Liquid Interface-Based Thiocyanate Surface Treatment for Bright and Stable CsPbBr3 Nanocrystals","authors":"Rachel Lifer, Nathan Rafisiman, Saar Shaek, Arghyadeep Basu, Yaron Kauffmann, Nicholas G. Pavlopoulos, Ivano E. Castelli, Lev Chuntonov, Yehonadav Bekenstein","doi":"10.1021/acs.chemmater.5c00803","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00803","url":null,"abstract":"Enhancing the efficiency and stability of lead halide perovskite devices is crucial to their practical application. Previous treatments with thiocyanate (SCN^–) have demonstrated significant improvements in the photoluminescence quantum yield (PLQY) and stability of CsPbBr₃ nanocrystals (NCs), but the underlying mechanisms remain partially unresolved. Addressing the challenge of low SCN^– solubility in traditional nonpolar solvents, our study introduces a urea-ammonium thiocyanate (UAT)-based ionic liquid surface treatment. This method facilitates a higher SCN^– loading by creating a liquid–liquid interface that is compatible with the organic colloidal suspension, preventing NC degradation, and achieving near-unity PLQY. Utilizing transmission electron microscopy techniques, we present atomic resolution evidence that thiocyanate-treated surfaces are rich in sulfur and display structural dilation of the lattice spacing of 3%. This supports that thiocyanate acts as a pseudohalide and binds to Pb cations on the NC surfaces. As a result, the treated NCs show enhanced stability against ionic substitution while maintaining the perovskite structure intact. Our findings provide conclusive evidence that the primary mechanism of performance enhancement is the passivation of surface traps attributed to bromide vacancies rather than the scavenging of excess lead cation. This surface treatment method slows ion migration, a prominent challenge in photovoltaics, offering a significant advancement in the development of perovskite-based devices.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"26 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-05-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144133674","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":"Synthesis, Characterization, and Thermolysis Studies of Binary Malondialdehydate Complexes of Copper(II) and Palladium(II)","authors":"Nathan D. Edmonsond, Vincent J. Flores, Gregory S. Girolami","doi":"10.1021/acs.chemmater.5c00568","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00568","url":null,"abstract":"An improved preparation of the malondialdehydate (mda) salt Na(mda)(H₂O) is reported; also described are preparations of copper(II) and palladium(II) complexes of mda and its 2-phenylmalondialdehydate (2-Ph-mda) analog. Crystal structures of Na(mda)(H₂O), Cu(mda)₂, Cu(2-Ph-mda)₂, Pd(mda)₂, and Pd(2-Ph-mda)₂ are described, along with nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) data. Cu(mda)₂ and Pd(mda)₂ deposit metallic thin films at 130 °C under chemical vapor deposition (CVD) conditions. Mechanistic studies show that Cu(mda)₂ transforms to copper metal by means of a ligand fragmentation pathway that involves carbon–carbon bond scission reactions.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"31 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122663","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":"Glass-Ceramic Lithium Thiophosphate Electrolytes with Enhanced Conductivity and (Chemo)mechanical Properties for All-Solid-State Batteries","authors":"Jingui Yang, Mareen Schaller, Gennady Cherkashinin, Ruizhuo Zhang, Sylvio Indris, Daniel Alves Dalla Corte, Aleksandr Kondrakov, Torsten Brezesinski, Florian Strauss","doi":"10.1021/acs.chemmater.5c00234","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00234","url":null,"abstract":"Solid-state batteries (SSBs) based on inorganic solid electrolytes (SEs) possibly offer enhanced energy and power densities, along with increased safety, compared to state-of-the-art rechargeable batteries using liquid organic electrolytes. However, the stiffness and brittle nature of inorganic SEs can complicate cell fabrication and lead to the (chemo)mechanical failure of SSBs during operation. In the past, the design of SEs has mainly focused on optimizing the ionic conductivity and (electro)chemical stability. However, to mitigate detrimental (chemo)mechanical degradation in SSBs, due to electrode volume and morphology changes upon charge and discharge, the mechanical properties of SEs also need to be considered in their development. In this regard, glass-ceramic SEs offer a reduced hardness but often suffer from rather low ionic conductivities. Herein we systematically investigate the effect of LiI additive and annealing temperature on phase composition and charge-transport properties of a series of SEs with the general composition of 4.25Li₂S–0.75P₂S₅–1.5SiS₂–<i>x</i>LiI (0 ≤ <i>x</i> ≤ 2). We demonstrate that the glass-ceramic material (LPSI-GC) with <i>x</i>(LiI) = 1.25 achieves a high room-temperature ionic conductivity of 4.38 mS cm^–1 and further exhibits favorable mechanical properties owing to the combination of crystalline <i>t</i>-Li_10.5P_1.5Si_1.5S₁₂ and I-rich amorphous phases. When implemented in SSBs together with a layered Ni-rich oxide cathode material, the LPSI-GC SE enables stable cycling for over 100 cycles, although (electro)chemical decomposition, detected by X-ray photoelectron spectroscopy, is evident. Collectively, our results demonstrate that glass-ceramic SEs allow for simultaneous optimization of the ionic conductivity and mechanical properties, thus enabling long-term SSB operation.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"59 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122768","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":"A Copper-Rich Multinary Iodido Bismuthate with Cationic Ligands and Broad Red Emission","authors":"Jakob Möbs, Philip Klement, Lukas Gümbel, Paula Epure, Florian Weigend, Sangam Chatterjee, Johanna Heine","doi":"10.1021/acs.chemmater.5c00306","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00306","url":null,"abstract":"Lead halide perovskites and related hybrid metal halides exhibit exceptional semiconductor properties, enabling diverse applications in photovoltaics, solid-state lighting, and photocatalysis. Multinary halido metalates, combining multiple metals, offer unique opportunities to tune the optical and electronic properties of these materials for specific applications. Here, we present the synthesis and characterization of (Hpiz)₄BiCu₄I₁₁·2MeCN (piz = piperazine), the most copper-rich molecular iodido bismuthate reported to date, featuring a Cu/Bi ratio of 4:1. It extends the “all-in-one” design concept of halido cuprates with cationic ligands to multinary systems and exhibits a low optical band gap of 1.82 eV (681 nm) and broad red photoluminescence centered at 1.69 eV (735 nm), making it a promising candidate for light-harvesting and near-infrared emission applications. Quantum chemical analyses attribute the reduced band gap to strong electronic interactions between Cu(I) and Bi(III). Additionally, the monometallic analogs (H₂piz)CuI₃ and (H₂piz)Bi₂I₈ reveal the role of heterometallic interactions in modulating the optical properties. This study provides valuable insights into the design of copper–bismuth iodide systems, enriching the library of hybrid materials with customized semiconductor characteristics.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"56 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144130122","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":"Non-Covalent Interactions and Helical Packing in Thiophene-Phenylene Copolymers: Tuning Solid-State Ordering and Charge Transport for Organic Field-Effect Transistors","authors":"Manikanta Makala, Zhuang Xu, Shamil Saiev, Xiaojuan Ni, Sina Sabury, Veaceslav Coropceanu, Jean-Luc Brédas, Ying Diao, John R. Reynolds, Oana D. Jurchescu, Anna M. Österholm","doi":"10.1021/acs.chemmater.5c00631","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00631","url":null,"abstract":"In this study, we introduce two thiophene-phenylene-thiophene (TPT) polymers designed to leverage noncovalent intramolecular interactions to regulate main-chain conformation and enhance solid-state ordering. By incorporating unsubstituted thiophene (T) or bithiophene (2T) units, we reveal striking divergence in the thermal, morphological, and optoelectronic properties of the resulting films, facilitated by these noncovalent interactions. Using a combination of computational and experimental approaches, we show that annealing yields remarkably different polymer conformations and, consequently, charge transport properties. TPT-T undergoes a significant structural transformation, adopting a more planar backbone conformation and a highly crystalline, edge-on molecular orientation. In contrast, the introduction of a single additional thiophene unit in TPT-2T leads to a more isotropic molecular orientation with a slight preference for face-on alignment, resulting in a heterogeneous film structure that hinders charge transport despite achieving tighter molecular packing. Remarkably, despite being composed of achiral components, TPT-2T develops chirality upon annealing, indicating the formation of a helical conformation. Organic field-effect transistor measurements reveal that the well-ordered alignment in annealed TPT-T films results in higher charge carrier mobility and a narrower distribution of mobility values than in TPT-2T. These findings provide critical insights into the structure–property relationships of conjugated polymers, offering guidance for optimizing molecular design and processing strategies for high-performance organic electronic materials.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"6 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144122653","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":"High-Pressure States of the Au25 Cluster","authors":"Camino Martín-Sánchez, Khadijetou Ahmed Ethmane, Abolfazl Ziarati, Daniele Rosa-Gastaldo, Michal Swierczewski, Arnulf Rosspeintner, Thomas Bürgi","doi":"10.1021/acs.chemmater.5c00755","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00755","url":null,"abstract":"In the present work, the effects of pressure on the electronic, vibrational, and structural properties of neutral and negatively charged Au₂₅(SR)₁₈ clusters are investigated up to 15 GPa combining UV–vis absorption and Raman spectroscopy. We show that Au₂₅(SR)₁₈ clusters undergo three structural transitions in the 0–15 GPa range located at around 0.8, 6, and 11 GPa. Results indicate that these phase transitions are intrinsic to the M₂₅(SR)₁₈ structure and independent of the pressurization conditions, type of ligand, and charge state. The reported Raman measurements show that vibrational spectroscopy is a powerful tool for structural tracking of atomically precise metal nanoclusters under the application of pressure.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"34 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144114487","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}