Chemistry of Materials最新文献

{"title":"Discovering Perovskite-Derived Tungsten Bronzes from In Situ Diffraction of Electrochemical Rubidium and Cesium Intercalation","authors":"Iuliia Neumann, Iuliia Kosolapova, Bertold Rasche","doi":"10.1021/acs.chemmater.4c02900","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02900","url":null,"abstract":"Perovskite-derived tungsten bronzes are formed from tungsten oxide by electrochemical intercalation of all alkali metals from aqueous solutions. In two steps, we yield two different polymorphs, where the first step is reversible and the second step is irreversible. The electrochemical approach affords precise control of the composition, while ex situ X-ray diffraction and particularly in situ X-ray diffraction allow the analysis of the atomic structure. For the heavy alkali metals, rubidium and cesium, the in situ synchrotron X-ray diffraction experiments reveal in sum four new structures and their formation process. The irreversible deintercalation step yields at room temperature, the α-WO₃ phase, a tungsten oxide polymorph which is thermodynamically only stable above 1073 K. Finally, analyzing the full alkali metal series allows us to conclude that the symmetry and structure of the formed bronzes are dictated by the electron count on the tungsten oxide network and the size of the ions plays a negligible role.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142797735","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":"Impact of Photogenerated Charge Carriers on the Stability of the 2D/3D Perovskite Interface","authors":"Zhaojie Zhang, Miu Tsuji, Xin Hu, Tomoyasu Mani, D. Venkataraman","doi":"10.1021/acs.chemmater.4c03015","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03015","url":null,"abstract":"An effective strategy to improve the performance and stability of perovskite solar cells is to deposit a 2D perovskite capping layer on the 3D perovskite. However, when exposed to light, small A-site cations in 3D perovskite exchange with the bulky cations in the 2D layer and degrade the 2D/3D interface. Therefore, to achieve long-term stability in perovskite solar cells, it is important to understand the nature of the photogenerated charge carriers that cause cation migrations at the 2D/3D interface. In this work, we fabricated 2D/3D perovskite stacks on glass, ITO, ITO/PTAA, ITO/PTAA/CuI, and ITO/SnO₂. A combination of grazing incidence X-ray diffraction and steady-state and time-resolved photoluminescence studies reveals the link between the light-induced degradation and the photogenerated charge carrier dynamics. Upon illumination, the stability of the 2D layers follows this trend: ITO/PTAA/CuI ≈ ITO > ITO/PTAA > glass > ITO/SnO₂ (from stable to unstable). This trend suggests that efficiently extracting holes from the 3D layer can improve the stability of the 2D layer. We also found that 2D/3D stacks degrade faster when illuminated from the 2D side instead of the 3D side. Our studies suggest that to achieve a stable 2D/3D interface, hole accumulation in the 3D layer should be avoided, and the exciton density in the 2D layer should be reduced.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"27 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142789859","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":"Using Data-Science Approaches to Unravel Insights for Enhanced Transport of Lithium Ions in Single-Ion Conducting Polymer Electrolytes","authors":"Qinyu Zhu, Yifan Liu, Lauren B. Shepard, Debjyoti Bhattacharya, Susan B. Sinnott, Wesley F. Reinhart, Valentino R. Cooper, Rajeev Kumar","doi":"10.1021/acs.chemmater.4c02432","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02432","url":null,"abstract":"Solid polymer electrolytes have yet to achieve the desired ionic conductivity (&gt;1 mS/cm) near room temperature required for many applications. This target implies the need to reduce the effective energy barriers for ion transport in polymer electrolytes to around 20 kJ/mol. In this work, we combine information extracted from existing experimental results with theoretical calculations to provide insights into ion transport in single-ion conductors (SICs) with a focus on lithium ion SICs. Through the analysis of temperature-dependent ionic conductivity data obtained from the literature, we evaluate different methods of extracting energy barriers for lithium transport. The traditional Arrhenius fit to the temperature-dependent ionic conductivity data indicates that the Meyer–Neldel rule holds for SICs. However, the values of the fitting parameters remain unphysical. Our modified approach based on recent work (<i>Macromolecules</i> <b>2023,</b> <i>56</i>, 15, 6051), which incorporates a fixed pre-exponential factor, reveals that the energy barriers exhibit temperature dependence over a wide range of temperatures. Using this approach, we identify anions leading to the energy barriers &lt;30 kJ/mol, which include trifluoromethane sulfonimide (TFSI), fluoromethane sulfonimide (FSI), and boron-based organic anions. In our efforts to design the next generation of anions, which can exhibit the energy barriers &lt;20 kJ/mol, we have performed density functional theory (DFT) based calculations to connect the chemical structures of boron-based anions via the binding energy of cation (lithium)-anion pairs with the experimentally derived effective energy barriers for ion hopping. Not only have we identified a correlation between the binding energy and the energy barriers, but we also propose a strategy to design new boron-based anions by using the correlation. This combined approach involving experiments and theoretical calculations is capable of facilitating the identification of promising new anions, which can exhibit ionic conductivity &gt;1 mS/cm near room temperature, thereby expediting the development of novel superionic single-ion conducting polymer electrolytes.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"79 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142782617","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":"Chemical Torque in Y14Ag39.3Zn12.1: Unwinding the Disordered Triangles of the Gd14Ag51 Type","authors":"Rie T. Fredrickson, Daniel C. Fredrickson","doi":"10.1021/acs.chemmater.4c02599","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02599","url":null,"abstract":"Elemental substitution is commonly used in materials chemistry to tune the Fermi energy of a compound or impart Chemical Pressure (CP) to atomic environments. In this Article, we illustrate how such substitution can also allow one to tune the relative orientations of geometrical units within a crystal structure, using the Gd₁₄Ag₅₁ structure type as a demonstration. A key feature of this structure type is the presence of hexagonal columns based on the CaPd_5+<i>x</i> structure type, containing triangles of atoms disordered over two orientations. Synthesis and structure solution of a Zn-substituted variant of this structure, Y₁₄Ag_39.3Zn_12.1, reveal that the incorporation of Zn atoms into these triangles leads to their rotation relative to their surroundings. Distinct triangle orientations are found depending on whether they are Ag₃ or Zn₃ units. A DFT-CP analysis of unsubstituted parent compound Y₁₄Ag₅₁ elucidates these observations. The Ag₃ triangles lie within a large hexagon of Y atoms, with each triangle corner being able to gain close contacts with up to two of these Y atoms depending on the orientation. Obtaining an optimal alignment of the Ag₃ triangles with respect to these interactions, however, is prevented by repulsion from other Ag atoms in the columns derived from the CaPd_5+<i>x</i> type. Instead, the triangles are twisted toward the Y neighbors with larger negative CP features. The replacement of Ag atoms with smaller Zn atoms provides the opportunity to relieve these packing tensions, allowing the triangles to turn to a position that better optimizes their interactions with the surrounding Y atoms. These results point to simple guidelines for identifying, with CP analysis, rigid units within structures that may be manipulated through elemental substitution.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"82 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142782623","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 Postsynthetic Ligand Exchange in ZIF-7 on Gate-Opening Pressure and CO2/CH4 Mixture Separation","authors":"Lukas W. Bingel, Jack D. Evans, Taehun Kim, Joseph K. Scott, Krista S. Walton","doi":"10.1021/acs.chemmater.4c01815","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01815","url":null,"abstract":"The targeted development of adsorbents tailored for specific separation tasks offers an opportunity to optimize selectivity, energy usage, and cycling. One instance of such a separation challenge is presented by biogas, a renewable energy source primarily composed of methane and carbon dioxide. The field of flexible metal–organic frameworks (MOFs) has garnered significant attention from researchers due to their potential for gas storage and capture applications. The adsorbate-dependent threshold pressure for the phase transition in these MOFs indicates potential for selective gas separation. The incorporation of functionalized ligands in these systems results in two notable effects: the introduction of specific adsorption sites on the internal surface as well as a modification of the flexible gate-opening behavior. Here, we conducted a comparison among different nitrogen-containing ligands (2-aminobenzimidazole, benzotriazole, and 5-azabenzimidazole) incorporated into the flexible MOF ZIF-7. These linkers include a nitrogen atom either in a heterocycle or as an attached functional group. The aim was to evaluate their performance for carbon dioxide–methane separation in a simulated biogas scenario. We further synthesized additional derivatives of the best-performing material, featuring the 5-azabenzimidazole ligand in varying quantities. Breakthrough experiments conducted under actual mixture conditions reveal that there is an optimal ligand exchange point (10%) facilitating the phase transition without significantly enhancing methane adsorption. Density functional theory simulations confirm that increased functionalization led to an easier phase transition due to heightened stability of the open phase resulting from additional hydrogen bonding, coupled with a weakened collapsed phase. To assess the effectiveness of this most-promising material, its performance was compared to the baseline ZIF-7 adsorbent using pressure swing adsorption (PSA) simulations. The enhanced surface affinity toward carbon dioxide, along with a sharper isotherm step and narrower hysteresis, translated to increased selectivity, faster cycling, and reduced process costs due to decreased energy input as shown by optimization opportunities of the high-pressure feed step.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"79 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142782690","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":"(3-CF3pyH)2(3-CF3py)Pb3I8: A Three-Dimensional Metal Halide Inorganic Framework with Distinctive Kagomé Bands","authors":"Rafaela Maria Giappa, Nikita I. Selivanov, Anna Yu. Samsonova, Apostolos Pantousas, Ioannis N. Remediakis, Yury V. Kapitonov, Alexei V. Emeline, Georgios Kopidakis, Constantinos C. Stoumpos","doi":"10.1021/acs.chemmater.4c02076","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02076","url":null,"abstract":"The structural diversity inherent in hybrid organic–inorganic metal halides as a function of the organic cation template can give access to numerous semiconducting materials featuring distinct polyhedral connectivity patterns. Beyond the common corner-sharing pattern of halide perovskites, different motifs can be accessed via the use of bulky and asymmetric templates, which can break the corner-sharing pattern. In this work, we report on the synthesis and characterization of a novel three-dimensional hybrid metal halide network, (3-CF₃pyH)₂(3-CF₃py)Pb₃I₈, featuring a buckled decorated honeycomb lattice arising from the corner-connected arrangement of [Pb₃I₈]^2– clusters. The compound is an indirect bandgap semiconductor with a bandgap of E_g = 2.6 eV that exhibits photoluminescence via a trap-assisted mechanism at 77 K. The inorganic cluster topology governs the electronic properties of the material, whereas the perovskite-like corner connectivity of the clusters gives rise to dispersive bands along certain crystallographic directions. The unprecedented appearance of distinctive Kagomé bands, emerging in the DFT calculated band structure of the idealized crystal structure, renders this material a promising candidate for advanced optoelectronic applications.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"199 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142782585","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":"Elucidating the Impact of Cis–Trans Organic Structure Directing Agent Isomer Ratios on the Aluminum Distribution Within SSZ-39","authors":"Charles E. Umhey, Jiawei Guo, Zheng Cui, Daniel F. Shantz, Ambarish Kulkarni, Jean-Sabin McEwen","doi":"10.1021/acs.chemmater.4c02175","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02175","url":null,"abstract":"Despite their widespread use, the mechanisms governing the synthesis of zeolite catalysts are still poorly understood. A notable example of this problem is the uncertainty surrounding the influence of synthesis conditions on the placement of Al atoms in the zeolite framework, which determines the active sites available for catalytic species. In this work, the role of the <i>cis</i> to <i>trans</i> isomer ratio of the OSDA <i>N</i>,<i>N</i>-dimethyl-3-5-dimethylpiperidinium on the energetics of 26 distinct Al pair distributions in SSZ-39 is examined both in the presence and absence of Na using density functional theory calculations. The initial orientation of the OSDA was found to have a significant impact on the final energies present, necessitating the screening of a large number of initial orientations with force field calculations and single point DFT calculations. Ground state energies were found to vary significantly with the ratio of <i>cis</i> to <i>trans</i> OSDAs with a Boltzmann distribution revealing the most likely Al pair distributions shift from sharing the same 8 membered rings to sharing the same double 6-membered rings to having no shared subunits as one increases the amount of <i>cis</i> OSDA present within the framework. The presence of Na was found to favor Al pair distributions where both Als occupied the same 6-membered ring. When an implicit solvent model was used to evaluate ground state energies the ideal Na sites shifted from 6-membered rings to empty SSZ-39 cages while OSDA positions and orientations remained largely the same. To provide insight on how kinetic factors may influence Al distributions, formation energies we calculated for connected double 6-membered rings. These formation energies revealed a preference for Al pairs to occupy the same 4-membered ring, which indicates kinetic and thermodynamic control may lead to different Al distributions in SSZ-39.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"1 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142788683","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":"Hybrid Materials for Electrochemical Energy Storage","authors":"Christopher Choi, Yunkai Luo, Aaron Reed, Grace Whang, Bruce Dunn","doi":"10.1021/acs.chemmater.4c02203","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02203","url":null,"abstract":"Hybrid materials hold significant promise for a variety of applications due to their customizable properties and functionalities that can be readily tailored by selecting specific elements and altering material compositions. In this review, we highlight the emerging potential of hybrid materials in energy storage applications, particularly as electrode and electrolyte materials. We describe model hybrid energy storage materials composed of organic and inorganic constituents. An overview of representative hybrid materials including metal–organic frameworks (MOFs), intercalated layered materials, and ionogels is provided with an emphasis on their material and functional properties enabled by hybridization.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"4 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142782618","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":"Targeted Delivery of siRNA-Gemcitabine Oligonucleotide Chimeras for High-Efficacy Synergistic Treatment of Pancreatic Cancer","authors":"Ri Huang, Hong Du, Liang Cheng, Ning Zhao, Peizhuo Zhang, Fenghua Meng, Zhiyuan Zhong","doi":"10.1021/acs.chemmater.4c02335","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02335","url":null,"abstract":"Pancreatic cancer (PC) stands for the most intractable malignancy. Gemcitabine (GEM) is one of the few approved first-line treatments for PC patients. The fast clearance, demanded high dosage, and existence of drug resistance have, nevertheless, posed not only a significant limitation to its clinical efficacy but also serious toxicity concerns. <i>KRAS^G12D</i> mutation is identified as a key driver in many PC patients, and its expression level shows a correlation with drug resistance and mortality. Here, we explored <i>KRAS</i>^<i>G12D</i> siRNA-gemcitabine oligonucleotide chimeras (<i>siKRAS</i>-G<i>_n</i>) as a dual prodrug that was designed to specifically silence <i>KRAS</i>^<i>G12D</i> gene and sensitize PC cells to GEM for the synergistic treatment of PC. <i>siKRAS</i>-G<i>_n</i> conjugates with 1, 2, 3, 4, or 5 units of GEM were synthesized and delivered using cRGD-decorated polymersomes. Interestingly, the proapoptotic activity of <i>siKRAS</i>-G<i>_n</i> was shown to highly depend on the number of GEM, in which three GEM units (<i>siKRAS</i>-G₃) were found to be optimal and induced strong apoptosis of PANC-1 cells (apoptosis rate: 64.2%). In contrast, minimal cell apoptosis was discerned for <i>siKRAS</i>, <i>siKRAS</i>-G₁, <i>siKRAS</i>-G₂, and free GEM (9-fold of that in <i>siKRAS</i>-G₃). <i>siKRAS</i>-G₃, while showing similar <i>KRAS</i> mRNA silencing ability to <i>siKRAS</i>, markedly enhanced the downregulation of <i>KRAS</i> protein <i>in vitro</i> and <i>in vivo</i>. Accordingly, <i>siKRAS</i>-G₃ significantly outperformed <i>siKRAS</i> and <i>siScramble</i>-G₃ in both tumor inhibition and survival benefits. The targeted delivery of the <i>siKRAS</i>-gemcitabine prodrug conjugate has emerged as an appealing treatment for pancreatic cancer.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"27 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142782621","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":"Discovery of Copolymer Resins with Optimal Viscosity–Toughness–Heat Resistance Trade-Offs via the Material Genome Approach","authors":"Xuan Jiang, Xiangfei Ye, Liangshun Zhang, Jiaping Lin","doi":"10.1021/acs.chemmater.4c02920","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02920","url":null,"abstract":"Accelerated discovery of polymer materials for specific applications requires the achievement of multiple, sometimes competing design objectives. Vast chemical space and the absence of well-established structure–processing–property relationships have considerably challenged the accelerated discovery of polymer materials. Herein, taking high-performance copolymer resins as an example, we propose a generalizable pipeline that integrates the screening of molecular structures, experimental validation of properties, and chemical interpretability to address both of these challenges. By means of the material genome paradigm, machine learning models are established for the structure–property relationship in conjunction with the additional viscosity for the evaluation of processing performance. Importantly, molecules of copolymer resins with low viscosity, high toughness, and high heat resistance are designed for a large search space. Experimental studies further verify that the newly designed copolymer resins possess excellent comprehensive performance, which cannot be achieved through time-consuming trial-and-error design methods. In addition, gene analysis is employed to interpret the structure–processing–property relationships of copolymer resins. The machine-learning-assisted material genome pipeline proposed in this work provides a promising strategy for the accelerated design of molecular structures in a large search space and for the understanding of structure–property relationships from data-informed perspectives.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"27 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142777282","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}