Chemistry of Materials最新文献

{"title":"A Field Guide to Materials with Axis-Dependent Conduction Polarity","authors":"Tianze Song, Joshua E. Goldberger","doi":"10.1021/acs.chemmater.5c01707","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c01707","url":null,"abstract":"Most electronic materials uniformly exhibit either dominant p- or n-type conduction along all crystallographic directions. However, there is an emerging class of materials in which either dominant p- or n-type conduction is observed depending on the crystallographic direction. This phenomenon is referred to as axis-dependent conduction polarity (ADCP) and has been experimentally detected across many different classes of materials. In this Review, we start by establishing the band structure origins and signatures of this phenomenon. Then, we thoroughly detail each material in which ADCP has been observed. We provide a chemical understanding of why ADCP occurs in these materials and show that closely related isostructural and isoelectronic phases will also exhibit this effect. This zoological survey of ADCP materials will serve as an important reference as electronic device concepts exploiting this effect arise.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"93 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145141110","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":"Elucidation of the Solution Synthesis and Growth of Non-Noble Metal TE3-Type Intermetallics (T = Fe, Co; E = Ga, In)","authors":"Devin J. Boski, Ryan C. Ross, Emil A. Hernandez-Pagan","doi":"10.1021/acs.chemmater.5c01494","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c01494","url":null,"abstract":"Due to challenging synthetic routes, non-noble metal intermetallic nanomaterials are seldom studied despite having promising thermoelectric, magnetic, and catalytic properties. To initiate these materials’ further study, we present a facile, quick, and modifiable solution-based procedure for the synthesis of FeGa₃, CoGa₃, CoIn₃, and Fe_0.5Co_0.5Ga₃, which are characterized by pXRD, TEM, SEM, EDS, ICP-MS, and XPS. Reaction insights for these isostructural intermetallics demonstrate a reliance on long-chain secondary amines, fast injection rates, as well as select aluminum hydride reductants, such as diisobutylaluminum hydride (DIBAL-H), whereas other strong reductants like alkoxyaluminum hydrides and borohydrides inhibit the formation of Ga-containing intermetallics. Our results suggest that these reactions can be tailored to proceed through either a coreduction or rapid amalgamation (seeded growth) mechanism, in which liquid Ga nanoseeds are formed, followed by rapid diffusion of the first-row transition metals, leading to crystallization of a thermodynamically stable intermetallic. These results lay foundational groundwork for accessing and understanding other underexplored non-noble metal intermetallic nanomaterials, and we believe it may be succeeded by further developments to improve control over composition, morphology, and thus physical properties.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"42 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145141069","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":"Design Principles in Engineering of Multigrain Nanocatalysts via Multiscale Electronic Structure Characterization","authors":"Min Gee Cho, Colin Ophus, Jung-Hoon Lee, Inchul Park, Dong Young Chung, Jeong Hyun Kim, Dokyoon Kim, Yung-Eun Sung, Kisuk Kang, Mary C. Scott, A. Paul Alivisatos, Taeghwan Hyeon, Myoung Hwan Oh","doi":"10.1021/acs.chemmater.5c01154","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c01154","url":null,"abstract":"Engineering grain boundary (GB) strain provides a promising pathway to tune the catalytic properties of nanocrystals. However, structural heterogeneity from random grain orientation and geometry has limited clear structure–property correlations. Here, we utilize a multigrain Co₃O₄/Mn₃O₄ core/shell nanocrystal platform as a model system to systematically investigate how geometric misfit strain at GBs serves as catalytically active sites for the oxygen reduction reaction. Through precise subnanometer-level control over grain morphology and by integrating multiscale electronic structure characterization, we identify the electronic structural signature of GB defects and establish a direct correlation between localized strain fields and modified electronic states. Strain modulation at GBs alters the e_g orbital energy levels, with elongation along the <i>z</i>-axis combined with shear strain stabilizing the e_g states, in contrast to the destabilization observed under pure shear strain. This stabilization mechanism enhances the electrocatalytic activity and selectivity of strained GBs compared with strain-relaxed grain surfaces. Furthermore, we reveal that GBs exhibit a radial strain gradient, producing a spatial energy shift that further modulates local electronic structures, as resolved through the classification of electron energy loss spectroscopy data. Together, these findings demonstrate that geometric misfit strain enables precise tuning of grain geometry and the resulting electronic structures, offering a robust strategy for engineering next-generation nanocatalysts.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"1 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145133881","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":"Carbonate Formation during Nickel Hydroxide Precipitation Reduces Pseudocapacitive Performance","authors":"Anja Siher, Ksenija Maver, Iztok Arčon, Andraž Mavrič","doi":"10.1021/acs.chemmater.5c01467","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c01467","url":null,"abstract":"Nickel hydroxide (Ni(OH)₂) is a promising pseudocapacitive material owing to its high theoretical capacitance and reversible Ni²⁺/Ni³⁺ redox activity. Here we demonstrate that carbonate incorporation during hydrothermal synthesis is the key structural factor limiting its electrochemical performance. Ni(OH)₂ was prepared using hexamethylenetetramine (HMT) and urea at different synthesis temperatures, and carbonate incorporation was quantified by XRD, FTIR, Raman, TGA-MS, and CaCO₃ precipitation. HMT-derived samples at a low temperature (80 °C) formed a turbostratic α-phase with interlayer water, delivering the highest specific capacitance (∼870 F g^–1 at 1 A g^–1) and excellent cycling stability (92–96% retention after 1000 cycles). In contrast, increasing the synthesis temperature promoted carbonate incorporation and crystallization into nickel carbonate hydroxide, reducing the interlayer spacing and surface area and increasing charge-transfer resistance. Urea-derived samples incorporated carbonate at all synthesis temperatures, yielding phases with capacitances an order of magnitude lower than those of HMT analogues. Electrochemical impedance spectroscopy confirmed that carbonate incorporation blocks redox-active sites and hinders ion/electron transport. These results provide a quantitative mechanistic understanding of how carbonate formation governs transition metal layered hydroxide performance, establishing guidelines for optimizing hydrothermal synthesis of pseudocapacitive electrodes.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"107 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145141068","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":"Artificial Intelligence Guided Search for Chalcogenide Hybrid Inorganic/Organic Polymers Comonomers","authors":"Maliheh Shaban Tameh, Veaceslav Coropceanu, Thomas A. R. Purcell","doi":"10.1021/acs.chemmater.5c01059","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c01059","url":null,"abstract":"Chalcogenide hybrid inorganic/organic polymers (CHIPs) have the potential to revolutionize infrared (IR) optics and create sustainable and recyclable devices. CHIPs combine elemental sulfur with organic comonomers via inverse vulcanization to create a high-sulfur-content polymer, with optical properties that rival state-of-the-art inorganic solids with the processability and recyclability of plastic materials. However, the optimal comonomer for these applications remains unknown. This work presents a gradient-boosted tree model that determines which comonomers merit further consideration as high-performing CHIPs materials. After training models on previously calculated IR absorption data, we apply them to a larger set of 960,966 molecules from the GDB data set and validate the predictions for both highly transparent molecules and a set of 1000 randomly selected molecules. We then look at the 199,511 molecule subset of the expanded search space with chemical moieties eligible for inverse vulcanization and found 2942 possible comonomers predicted to have better optical properties than the state-of-the-art comonomer stillene. Finally, we calculate the optical properties of all 2942 comonomers in the gas phase and in a configuration to approximate the polymer films to find a set of target comonomers.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"28 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145133877","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":"Autonomous Discovery of Polymer Electrolyte Formulations with Warm-Start Batch Bayesian Optimization","authors":"Jurğis Ruža, Michael A. Stolberg, Sawyer Cawthern, Jeremiah A. Johnson, Yang Shao-Horn, Rafael Gómez-Bombarelli","doi":"10.1021/acs.chemmater.5c01209","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c01209","url":null,"abstract":"Solid polymer electrolytes are a promising class of materials to enable next-generation Li-based batteries. They offer highly tunable properties, scalable processing conditions, and increased safety. However, current solid polymer electrolytes do not have sufficient ionic conductivity for room-temperature battery applications. The discovery of novel polymers and the optimization of polymer-salt formulations with high ionic conductivity are critical bottlenecks in developing new polymer-based batteries. Programmable laboratories driven by machine learning algorithms have been proposed to power accelerated discovery cycles. Here we demonstrate a closed-loop, machine-learning driven Bayesian optimization pipeline for optimizing a dry polymer electrolyte composed of poly(ϵ-caprolactone) (PCL) electrolyte with one of 18 lithium salts. We use previously collected literature data to warm-start our optimization and achieve high performance while following through with a novel high-exploration batch-based sampling method. Formulations chosen by the sampling method were mixed, cast, dried, and characterized on an autonomous high-throughput polymer electrolyte platform. After five batches of optimization conducted in just over a month, we discovered formulations with ionic conductivity that were on par with top-performing poly(ethylene oxide) electrolytes, the standard of the field.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"21 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145141067","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 Site Determination Signals of Eu3+ for Tracking Structural Phase Transition in Terbium-Rich TbSc3(BO3)4 Borate","authors":"Nan Yang, Junhao Li, Haiyong Ni, Pengpeng Dai","doi":"10.1021/acs.chemmater.5c01611","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c01611","url":null,"abstract":"Phase transitions exert profound effects on luminescent behavior, while conversely, luminescence can serve as an effective probe for monitoring phase transitions. Trivalent europium ions (Eu³⁺) are well-known lattice probes since their nondegenerate ⁵<i>D</i>₀–⁷<i>F</i>₀ transition directly reflects the number of nonequivalent crystallographic sites in host materials. However, the emission intensity of the ⁵<i>D</i>₀–⁷<i>F</i>₀ transition in general compounds is typically too weak for reliable detection under ambient conditions. Herein, La³⁺ and Eu³⁺ codoped terbium-rich TbSc₃(BO₃)₄ phosphor was prepared and studied for the first time. Through efficient energy transfer from Tb³⁺ to Eu³⁺, the newly generated peak of Eu³⁺ occupying the LaSc₃(BO₃)₄ phase can be distinctly observed in lattice site resolution spectra, evidencing the phase transition induced by the small amount of La³⁺. Considering that a small amount of Eu³⁺ in the LaSc₃(BO₃)₄ phase can hardly give detectable emission intensity of the ⁵<i>D</i>₀–⁷<i>F</i>₀ transition, the enlarged site resolution ability can be ascribed to an efficient Tb³⁺→Eu³⁺ energy transfer inside the LaSc₃(BO₃)₄ phase. In other words, the phase tolerance of TbSc₃(BO₃)₄ by LaSc₃(BO₃)₄ prompts the enlarged site resolution ability of Eu³⁺ in this terbium-rich inorganic compound. This discovery may propose a complementary spectroscopic approach for tracking structural transformations.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"63 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145141070","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":"Structural Engineering in Polyoxovanadate–Organic Cages toward Photocatalytic Synthesis of Benzimidazoles","authors":"Ke-Wei Tong, Shi-Ru Xiong, Xue-Ying Jiang, Meng-Yu Li, Yan-Hu Wang, Chao-Qin Chen, Jing Du, Peng Yang","doi":"10.1021/acs.chemmater.5c02060","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02060","url":null,"abstract":"Photocatalytic fabrication of fine chemicals provides a sustainable method of development for the pharmaceutical industry. At present, optimizing the performance of photocatalysts via precise structural engineering at the atomic level is of the utmost importance. To unleash the potential of structurally editable polyoxovanadate–organic cages (POV-MOCs) as photocatalytic materials, herein, a family of five POV-MOCs were scaffolded by a cross combination of {V₆X} (X = SO₄^2–, PhPO₃^2–, and NH₂PhAsO₃^2–) vertices and benzo-2,1,3-thiadiazole-functionalized carboxylate linkers. Along with the structural evolution from capsule to cuboid-type topology as well as the heterogroup modification of the vertex, the photophysical properties of POV-MOCs could be regulated precisely. The structurally optimized POV-MOCs demonstrated prominent photocatalytic activity in the oxidative synthesis of benzimidazoles, which are medicinally important. Thanks to the teamwork of experimental and theoretical studies, a possible reaction mechanism that involves O₂^•– has been proposed and validated. The unveiled structure–function relationship provides an effective route to customize POV-MOC-based photocatalysts for a broader range of sustainable applications.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"89 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145141092","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":"Mechanistic Insights into Hydride Incorporation in BaZr1–xInxO3−δ-Based Perovskite Oxyhydrides","authors":"Takuya Takahashi, Hajime Toriumi, Genki Kobayashi, Takashi Saito, Kazuhiro Mori, SeongWoo Jeong, Hiroki Habazaki, Yoshitaka Aoki","doi":"10.1021/acs.chemmater.5c01482","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c01482","url":null,"abstract":"Metal oxyhydrides have emerged as promising candidates for next-generation electrochemical devices due to their unique combination of hydride (H^–) ion conductivity and catalytic activity for carbon dioxide and nitrogen reduction. However, their limited stability under ambient hydrogen pressure (<i>p</i>_H2) poses a significant challenge. In this study, we demonstrated that BaZr_1–<i>x</i>In_<i>x</i>O_{3–0.5<i>x</i>} (BZI) undergoes topochemical transformation into a thermodynamically stable oxyhydride phase under ambient <i>p</i>_H2 across a broad composition range. Indium-rich compositions (<i>x</i> = 0.5, 0.6, and 0.7) successfully formed oxyhydrides─BaZr_0.5In_0.5O_2.25H_0.5, BaZr_0.4In_0.6O_2.18H_0.23, and BaZr_0.3In_0.7O_2.17H_0.11─via the sequential formation of oxygen vacancy (V_O) and subsequent H^– ion incorporation. Conversely, the Zirconium-rich composition (<i>x</i> = 0.3) formed only V_O and stabilized as an oxygen-deficient phase, BaZr_0.7In_0.3O_2.70, without hydride uptake. Combined experimental and density functional theory (DFT) analyses reveal that the extent of In reduction, reflected by an increase of the Fermi level following V_O donor formation, governs the thermodynamic driving force for H^– incorporation. DFT results show that a greater initial Fermi energy rise facilitates greater H^– uptake, which subsequently lowers Fermi energy upon H^– incorporation, establishing an equilibrium determined by defect formation energetics. Furthermore, DFT and <i>in situ</i> X-ray absorption spectroscopy confirm that the oxyhydride phase preferentially forms neutral oxygen vacancies (V_O^×) during dehydrogenation, in contrast to the commonly assumed doubly charged species (V_O^••). This reversible transformation between a pure oxyhydride and an oxyhydride–electride phase, dependent on <i>p</i>_H2, highlights the tunable defect chemistry and electronic structure of perovskite oxyhydrides and offers new design principles for stable and fast hydride ion conductors.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"41 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145133878","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":"Chemically Robust Functionalized MOF/Polymer Composite for Selective Sequestration of Higher-Valent Actinides from Simulated Nuclear Waste","authors":"Dipanjan Majumder, Sahel Fajal, Nayan Sarkar, Arijit Sengupta, Writakshi Mandal, Mandar M. Shirolkar, Sujit K. Ghosh","doi":"10.1021/acs.chemmater.5c01870","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c01870","url":null,"abstract":"Due to the increasing global demand for energy, the development of nuclear energy becomes crucial because of its low carbon emission and high energy density output. Thorium and uranium are the main raw materials and energy resources for nuclear fission industries, and their improper disposal may cause a serious threat to the ecosystem. Herein, we strategically designed and fabricated a functionalized MOF/polymer composite via the in situ formation of a cross-linked polymer inside the cavity of MIL-101. The porous composite with high chemical and radiation stability and suitable functionality can extract Th(IV), Pu(IV), and U(VI) from highly acidic nuclear waste. The synthesized MOF/polymer hybrid adsorbents exhibit a maximum capacity of 823 mg/g and 679 mg/g, achieving a high distribution coefficient (<i>K</i>_d) of 2.48 × 10⁵ and 1.64 × 10⁵ mLg^–1 for Th(IV) and U(VI), respectively, in the presence of other competing ions. This study not only shows the great potential of hybrid porous materials but also provides a fundamental approach to designing a functionalized adsorbent for extraction of higher-valent actinides, aiming toward sustainable development, CO₂ free energy, and environmental remediation.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"29 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145127530","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}