Chemistry of Materials最新文献

{"title":"Machine Learning Models for High Explosive Crystal Density and Performance","authors":"Jack V. Davis, Frank W. Marrs, Marc J. Cawkwell, Virginia W. Manner","doi":"10.1021/acs.chemmater.4c01978","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01978","url":null,"abstract":"The rate of discovery of new explosives with superior energy density and performance has largely stalled. Rapid property prediction through machine learning has the potential to accelerate the discovery of new molecules by screening of large numbers of molecules before they are ever synthesized. To support this goal, we assembled a 21,000-molecule database of experimentally synthesized molecules containing energetic functional groups. Using a combination of experimental density measurements and high throughput electronic structure and atomistic calculations, we calculated detonation velocities and pressures for all 21,000 compounds. Using these values, we trained machine learning models for the prediction of density, detonation velocity and detonation pressure. Notably, our model for crystal density surpassed the accuracy of all current models and decreased the root-mean square error (RMSE) of the previous best model by 20%. This improvement in model performance relative to past works is attributed to our handling of chiral-specified Simplified Molecular-Input Line-Entry System (SMILES) strings and introduction of a new molecular descriptor, MolDensity. To elucidate descriptor importance, we evaluated interpretable descriptors in terms of importance and compared the accuracy of a statistics-driven machine learning model against a model comprised of descriptors typically assumed to control material density. The inexpensive, yet highly accurate predictions from our models should enable creation of future artificial intelligence (AI) models that are able to screen large numbers (>10⁶) of compounds to find the highest performing compounds in terms of crystal density, detonation velocity and detonation pressure.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142596745","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":"Machine Learning-Based Prediction of Proton Conductivity in Metal–Organic Frameworks","authors":"Seunghee Han, Byoung Gwan Lee, Dae-Woon Lim, Jihan Kim","doi":"10.1021/acs.chemmater.4c02368","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02368","url":null,"abstract":"Recently, metal–organic frameworks (MOFs) have demonstrated their potential as solid-state electrolytes in proton exchanged membrane fuel cells. However, the number of MOFs reported to exhibit proton conductivity remains limited, and the mechanisms underlying this phenomenon have not been fully elucidated, complicating the design of proton-conductive MOFs. In response, we developed a comprehensive database of proton-conductive MOFs and applied machine learning techniques to predict their proton conductivity. Our approach included the construction of both descriptor-based and transformer-based models. Notably, the transformer-based transfer learning (Freeze) model performed the best with a mean absolute error (MAE) of 0.91, suggesting that the proton conductivity of MOFs can be estimated within 1 order of magnitude using this model. Additionally, we employed feature importance and principal component analysis to explore the factors influencing the proton conductivity. The insights gained from our database and machine learning model are expected to facilitate the targeted design of proton-conductive MOFs.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142588835","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":"Recent Advances of High-Entropy Intermetallics for Electrocatalysis","authors":"Qian Zhang, Min Song, Guanyu Luo, Tao Shen, Hanyu Hu, Deli Wang","doi":"10.1021/acs.chemmater.4c02151","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02151","url":null,"abstract":"High-entropy intermetallics (HEIs) combining the advantages of ordered intermetallics and high-entropy alloys have been considered as highly promising candidates for electrocatalysis. Nevertheless, the comprehension and rational design of HEI electrocatalysts still lack a systematic summary. In this Review, we summarize the recent advances in HEI electrocatalysts and their applications in energy conversion reactions for the advancement of efficient electrocatalysts. At first, we propose the underlying thermodynamic mechanism and design principles of HEI electrocatalysts. After that, various synthetic strategies for HEI electrocatalysts are introduced. Furthermore, we highlight representative catalytic examples in important electrocatalytic reactions, such as the liquid fuel oxidation reaction (FOR), the oxygen reduction reaction (ORR), the hydrogen evolution reaction (HER), and so on. Finally, current issues and future perspectives on HEI electrocatalysts are presented.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142588921","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":"MnRhBi3: A Cleavable Antiferromagnetic Metal","authors":"Eleanor M. Clements, Dmitry Ovchinnikov, Parul R. Raghuvanshi, Valentino R. Cooper, Satoshi Okamoto, Andrew D. Christianson, Joseph A. M. Paddison, Brenden R. Ortiz, Stuart Calder, Andrew F. May, Xiaodong Xu, Jiaqiang Yan, Michael A. McGuire","doi":"10.1021/acs.chemmater.4c02671","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02671","url":null,"abstract":"Cleavable metallic antiferromagnets may be of use for low-dissipation spintronic devices; however, few are currently known. Here we present orthorhombic MnRhBi₃ as one such compound and present a thorough study of its physical properties. Exfoliation is demonstrated experimentally, and the cleavage energy and electronic structure are examined by density functional theory calculations. It is concluded that MnRhBi₃ is a van der Waals-layered material that cleaves easily between neighboring Bi layers and that the Bi atoms have lone pairs extending into the van der Waals gaps. A series of four phase transitions are observed below room temperature, and neutron diffraction shows that at least two of the transitions involve the formation of antiferromagnetic order. Anomalous thermal expansion points to a crystallographic phase transition and/or strong magnetoelastic coupling. This work reveals a complex phase evolution in MnRhBi₃ and establishes this cleavable antiferromagnetic metal as an interesting material for studying the interplay of structure, magnetism, and transport in the bulk and ultrathin limits, as well as the role of lone pair electrons in interface chemistry and proximity effects in van der Waals heterostructures.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142588834","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":"Unveiling Surface Chemistry of Ultrafast-Sintered LLZO Solid-State Electrolytes for High-Performance Li-Garnet Solid-State Batteries","authors":"Huanyu Zhang, Matthias Klimpel, Krzysztof Wieczerzak, Romain Dubey, Faruk Okur, Johann Michler, Lars P.H. Jeurgens, Dmitry Chernyshov, Wouter van Beek, Kostiantyn V. Kravchyk, Maksym V. Kovalenko","doi":"10.1021/acs.chemmater.4c02351","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02351","url":null,"abstract":"Ultrafast (UF) sintering emerges as a game-changing sintering methodology for fabricating Li₇La₃Zr₂O₁₂ (LLZO) solid-state electrolytes, representing a pivotal stride toward the advancement and prospective commercialization of Li-garnet solid-state batteries. Despite its widespread use in the fabrication of LLZO ceramics, the chemical composition of the UF-sintered LLZO surface remains largely unexplored. This study presents an in-depth analysis of the surface chemistry of UF-sintered LLZO using comprehensive techniques, including depth-profiling X-ray photoelectron spectroscopy (XPS) and focused-ion-beam time-of-flight secondary ion mass spectroscopy (FIB-TOF-SIMS). Our investigation uncovers a striking difference between the surface of UF-sintered and conventionally sintered LLZO, revealing predominant surface contamination by Li₂O up to ca. 40 nm depth in the case of UF processing. Comparative synchrotron X-ray diffraction data during UF and conventional sintering elucidate the origin of surface contamination. We propose a viable solution to this issue through an additional heat treatment (HT) step at 900 °C after UF sintering, as corroborated by XPS and FIB-TOF-SIMS measurements. Furthermore, we present a comparative assessment of the electrochemical performance of Li/LLZO/Li symmetric cells based on UF-sintered LLZO pellets, both with and without the post-HT step, underscoring the pivotal role of an uncontaminated LLZO surface.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580535","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":"Oxidation Kinetics of Magnetite Nanoparticles: Blocking Effect of Surface Ligands and Implications for the Design of Magnetic Nanoheaters","authors":"Juan M. Orozco-Henao, Francisco L. Alí, Julio C. Azcárate, Leonardo D. Robledo Candia, Gustavo Pasquevich, Pedro Mendoza Zélis, Benedikt Haas, Katrina Coogan, Holm Kirmse, Christoph T. Koch, Carolina Vericat, Gabriel C. Lavorato, Mariano H. Fonticelli","doi":"10.1021/acs.chemmater.4c01959","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01959","url":null,"abstract":"Magnetite (Fe₃O₄) nanoparticles (NPs) are nowadays extensively used in biomedical, environmental, and catalytic applications. However, magnetite is known to oxidize to maghemite (γ-Fe₂O₃), leading to changes in the physical properties of the NPs. The factors that modulate such transformation and, particularly, the role of surface capping are often overlooked. In this work, we have studied monodisperse Fe₃O₄ NPs synthesized by organic phase methods with sizes between 9 and 28 nm and we report on the oxidation kinetics of stable NP colloids in organic and aqueous media. The fraction of Fe₃O₄ in the as-prepared NPs was found to depend on their size but, in contrast to usual assumptions, monochromated electron energy loss spectroscopy results reveal that the Fe²⁺ concentration is homogeneous across nonstoichiometric nanocrystals, without evidence of a core/shell structure with a γ-Fe₂O₃ outer layer. Additionally, we show that typical ligand-exchange procedures employed to remove oleate capping from the surface lead to partially oxidized NPs, indicating that surface ligands play a key role in hindering the oxidation reaction. To elucidate the effect of the capping agent in the redox transformation, we demonstrate that the oxidation process is notably slowed for NPs with increasing oleate coverages. Then, we interpreted these findings quantitatively by considering the coupling between the surface reactivity and diffusion of cations within the oxide. Finally, we demonstrate the remarkable impact of the oxidation process on the magnetic properties of the NPs and on their heating efficiencies under radio frequency magnetic fields. Overall, our results shed light on the importance of the design of iron oxide-based nanomaterials with increased chemical stability and greater control of their physical properties, which are key aspects for their successful application.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580534","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":"Accelerating the Discovery of New, Single Phase High Entropy Ceramics via Active Learning","authors":"Calen J. Leverant, Jacob A. Harvey","doi":"10.1021/acs.chemmater.4c00303","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c00303","url":null,"abstract":"High-entropy ceramics have garnered interest due to their remarkable hardness, compressive strength, thermal stability, and fracture toughness; yet the discovery of new high-entropy ceramics (out of a tremendous number of possible elemental permutations) still largely requires costly, inefficient, trial-and-error experimental and computational approaches. The entropy forming ability (EFA) factor was recently proposed as a computational descriptor that positively correlates with the likelihood that a 5-metal high-entropy carbide (HECs) will form the desired single phase, homogeneous solid solution; however, discovery of new compositions is computationally expensive. If you consider 8 candidate metals, the HEC EFA approach uses 49 optimizations for each of the 56 unique 5-metal carbides, requiring a total of 2744 costly density functional theory calculations. Here, we describe an orders-of-magnitude more efficient active learning (AL) approach for identifying novel HECs. To begin, we compared numerous methods for generating composition-based feature vectors (e.g., magpie and mat2vec), deployed an ensemble of machine learning (ML) models to generate an average and distribution of predictions, and then utilized the distribution as an uncertainty. We then deployed an AL approach to extract new training data points where the ensemble of ML models predicted a high EFA value or was uncertain of the prediction. Our approach has the combined benefit of decreasing the amount of training data required to reach acceptable prediction qualities and biases the predictions toward identifying HECs with the desired high EFA values, which are tentatively correlated with the formation of single phase HECs. Using this approach, we increased the number of 5-metal carbides screened from 56 to 15,504, revealing 4 compositions with record-high EFA values that were previously unreported in the literature. Our AL framework is also generalizable and could be modified to rationally predict optimized candidate materials/combinations with a wide range of desired properties (e.g., mechanical stability, thermal conductivity).","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142588863","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":"Atomic-Scale Polar Helix in Inorganic Crystals","authors":"Jan Langmann, Georg Eickerling, Lilian Prodan, Alexander A. Tsirlin, Maximilian Winkler, Sándor Bordács, Vladimir Tsurkan, Istvan Kézsmárki","doi":"10.1021/acs.chemmater.4c02060","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02060","url":null,"abstract":"Chiral structures, noncentrosymmetric objects with a given handedness, emerge on all scales in nature. The most well-known chiral form, <i>the helix</i>, has numerous materializations not only on the microscopic scale (DNA, cholesteric liquid crystals, and spin helices) but also on macroscopic and even cosmological scales. The ongoing quest for new types of chiral structures is fueled by a wide range of fascinating phenomena observed in chiral materials, such as nonreciprocal transport and optical processes, electro-optical effects, and chiral amplification and induction. Here, we report a novel route to chirality in antipolar GaTa₄Se₈ crystals, where the rotation of the electric polarization vector through the unit cell traces out a helix. The determination of atomic positions using X-ray diffraction combined with ab initio calculations reveals that quasi-molecular Ta₄Se₄ clusters distort upon a phase transition and evoke significant local electric polarization within structural layers of the unit cell. This polarization is found to rotate in 90° steps between neighboring layers, either clockwise or anticlockwise. A similar analysis performed on two archetypal chiral compounds, α-quartz and tellurium, implies that antipolar crystals with screw-axis symmetry may generally host atomic-scale polarization helices with emergent functionalities.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580105","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":"Effects of A’-Site Cation Structure on the Stability of 2D Tin Halide Perovskites","authors":"Tareq Hossain, Harindi R. Atapattu, Henry Pruett, Md Tawabur Rahman, Kevin R. Pedersen, Aron J. Huckaba, Sean R. Parkin, Kenneth R. Graham","doi":"10.1021/acs.chemmater.4c01251","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01251","url":null,"abstract":"Two-dimensional halide perovskites (2D-HPs) are of significant interest for their applications in optoelectronic devices. Part of this increased interest in 2D-HPs stems from their increased stability relative to their three-dimensional (3D) counterparts. Here, the origin of higher stability in 2D-HPs is mainly attributed to the bulky ammonium cation layers, which can act as a blocking layer against moisture and oxygen ingression and ion diffusion. While 2D-HPs have demonstrated increased stability, it is not clear how the structure of the ammonium ions impacts material stability. Herein, we investigate how the structure of ammonium cations, including three <i>n</i>-alkyl ammoniums, phenethylammonium (PEA) and five PEA derivatives, anilinium (An), benzylammonium (BzA), and cyclohexylmethylammonium (CHMA), affects the crystal structure and air, water, and oxygen stability of 2D tin halide perovskites (2D-SnHPs). We find that stability is influenced by several factors, including the molecular packing and intermolecular interactions in the organic layer, steric effects around the ammonium group, the orientation distribution of the 2D sheets, and the hydrophobicity of the perovskite film surface. With superior hydrophobicity, strong interactions between organic molecules, and a high extent of parallel oriented inorganic sheets, the 2-(4-trifluoromethyl-phenyl)-ethylammonium (4-TFMPEA) ion forms the most stable 2D-SnHP among the 12 ammonium cations investigated.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142574617","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":"Ultra-Thin Cation Exchange Membranes: Sulfonated Polyamide Thin-Film Composite Membranes with High Charge Density","authors":"Claudio A. Ruiz-Torres, Jiahao Zhu, Jocelyn A. Riet, Niher R. Sarker, Sara Abu-Obaid, Kevin D. Yuan, Charles-François de Lannoy, Jay R. Werber","doi":"10.1021/acs.chemmater.4c02270","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02270","url":null,"abstract":"Advancements in membrane technology are crucial for electrochemical separations, such as ion exchange, and pressure-driven processes, such as nanofiltration (NF). This study introduces high-charge-density sulfonated polyamide thin-film composite membranes fabricated via interfacial polymerization using disulfonated monomers, resulting in ultra-thin (∼50 nm) films that serve as nanofiltration (NF) membranes or cation exchange membranes (CEMs). Post-modifications enabled precise control over membrane chemistry, enhancing CEM properties such as ion exchange capacity, water uptake, and fixed charge concentration. The high charge density led to ion selectivity in NF via the Donnan exclusion mechanism, facilitating effective separation of monovalent and divalent ions. The incorporation of sulfonic acids within an ultra-thin polyamide matrix significantly reduced the resistance for ion and proton transport, enabling high in-plane conductivities (Na⁺: &gt;80 mS cm^–1, H₃O⁺: &gt;200 mS cm^–1) comparable to state-of-the-art polymer-based CEMs. Furthermore, the nanoscale thickness of these membranes dramatically enhanced ionic and proton conductance, achieving area conductance values 4 to 6 orders of magnitude higher than those of conventional thick CEMs. This enhancement is primarily attributed to the ultra-thin design of our sulfonated polyamide membrane, setting a new benchmark for the design and fabrication of highly conductive membranes, and laying the groundwork for future enhancements of ion conductive membranes for water purification and energy applications.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142579963","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}