Chemistry of Materials最新文献

Aziridinium 3D Perovskites: Toward Semiconducting Films with Tunable Band Gaps 三维叠氮钙钛矿：具有可调带隙的半导体薄膜

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2025-06-13 DOI: 10.1021/acs.chemmater.5c00671

Olesia I. Kucheriv, Hanna R. Petrosova, Valerii Y. Sirenko, Oleksandr A. Semenikhin, Maryam Choghaei, Klaus Meerholz, Selina Olthof, Il’ya A. Gural’skiy

{"title":"Aziridinium 3D Perovskites: Toward Semiconducting Films with Tunable Band Gaps","authors":"Olesia I. Kucheriv, Hanna R. Petrosova, Valerii Y. Sirenko, Oleksandr A. Semenikhin, Maryam Choghaei, Klaus Meerholz, Selina Olthof, Il’ya A. Gural’skiy","doi":"10.1021/acs.chemmater.5c00671","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00671","url":null,"abstract":"Halide organic–inorganic perovskites are used as highly efficient semiconducting layers in photovoltaic and optoelectronic devices. However, the selection of known 3D organic–inorganic perovskites that have been processed into thin films is very limited. Here, we offer a route toward thin films of (AzrH)PbBr3 and (AzrH)PbCl3 (AzrH = aziridinium). The aziridinium perovskite films were deposited via a solution-based approach and make a contribution toward extension of the set of functional halide perovskite thin films. The developed procedure allows achieving thin films that keep the perovskite crystal structure up to 60 °C as confirmed by X-ray diffraction measurements. UV–vis absorption and photoluminescence measurements show that these bromide and chloride containing aziridinium perovskites form semiconducting thin films with optical band gaps of 2.40 and 3.20 eV and display emission at 545 and 407 nm, respectively. Interestingly, (AzrH)PbBr3 thin films show an increased value of Stokes shift at room temperature (up to 80 meV) that makes this material promising for applications where reabsorption has to be avoided. UV and inverse photoelectron spectroscopies yield energy level positions that are in good agreement with calculations by density functional theory. This work uncovers the potential of aziridinium-based perovskite thin films regarding their semiconducting properties, thus widening the range of perovskites suitable for optoelectronic applications.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"4 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-06-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144278857","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}

引用次数: 0

Pauling’s Third Rule as a Guide for Designing Low Thermal Conducting Chalcogenides 鲍林第三法则作为设计低导热硫族化合物的指南

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2025-06-12 DOI: 10.1021/acs.chemmater.5c01050

Riddhimoy Pathak, Mridul Krishna Sharma, Kanishka Biswas

{"title":"Pauling’s Third Rule as a Guide for Designing Low Thermal Conducting Chalcogenides","authors":"Riddhimoy Pathak, Mridul Krishna Sharma, Kanishka Biswas","doi":"10.1021/acs.chemmater.5c01050","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c01050","url":null,"abstract":"Linus Pauling’s third empirical rule, which describes the destabilizing effect of shared polyhedral units in crystal structures, now provides a novel basis for understanding and predicting lattice thermal conductivity (κlat) in extended solids. In this perspective, we investigate ∼65 ternary metal chalcogenides with corner-shared (CS), edge-shared (ES), or face-shared (FS) polyhedral units, uncovering a monotonous decline in κlat as polyhedral connectivity shifts from CS to ES to FS in the structure. This trend arises from increasing cationic repulsion, leading to local lattice instability and enhanced phonon scattering in structures particularly having either ES or FS polyhedra. Comparative analysis of metal chalcogenides having the same constituent atoms further validates that materials possessing ES and FS configurations consistently exhibit lower κlat than materials having CS subunits. While a few exceptions exist, our findings establish Pauling’s third rule as a chemical guide for identifying materials with intrinsically ultralow κlat, a key requirement for high thermoelectric performance. We believe that this insight would accelerate the discovery of efficient thermoelectric materials by leveraging fundamental crystal chemistry principles.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"17 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144269245","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}

引用次数: 0

Influence of the M- and A-Elements on the Oxidation Stability of Solid Solution MAX Phases V2Ga1–xGexC and Cr2Ga1–xGexC M-和a -元素对固溶MAX相V2Ga1-xGexC和Cr2Ga1-xGexC氧化稳定性的影响

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2025-06-12 DOI: 10.1021/acs.chemmater.5c00888

Suneet Kale, Alexander E. Sedykh, Prajna Bhatt, Aysha A. Riaz, Pardeep K. Thakur, Tien-Lin Lee, Anna Regoutz, Maren Lepple, Christina S. Birkel

{"title":"Influence of the M- and A-Elements on the Oxidation Stability of Solid Solution MAX Phases V2Ga1–xGexC and Cr2Ga1–xGexC","authors":"Suneet Kale, Alexander E. Sedykh, Prajna Bhatt, Aysha A. Riaz, Pardeep K. Thakur, Tien-Lin Lee, Anna Regoutz, Maren Lepple, Christina S. Birkel","doi":"10.1021/acs.chemmater.5c00888","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00888","url":null,"abstract":"MAX phase carbides have attracted much attention due to their unique combination of metallic and ceramic properties, making them promising materials for high-temperature applications. Understanding how the materials fail is a crucial step in working toward implementing them into devices outside of the laboratory setting. Their stability toward oxidation at high temperatures, while also being electronically and thermally conductive, sets MAX phases apart from other materials. Some aluminum-containing compounds form a protective alumina layer that contributes to the oxidation resistance of the respective MAX phase. However, a broader understanding of how other MAX phases, especially those with M-elements beyond titanium and A-elements beyond aluminum, oxidize is lacking. Therefore, we synthesized two A-site solid solutions (gallium and germanium as the A-elements) based on chromium and vanadium as M-elements by high-temperature solid-state syntheses. Their composition, structural properties, and bonding characteristics are investigated by synchrotron powder X-ray diffraction, electron microscopy with elemental analysis, and Raman and X-ray photoelectron spectroscopy. Thermal analysis reveals the influence of the M- and A-elements on the oxidation behavior: phases with Cr on the M-site have higher oxidation stability than with V, and solid solutions Cr2Ga1–xGexC have improved oxidation resistance compared to the individual phases Cr2GaC and Cr2GeC.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"26 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144269241","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}

引用次数: 0

Correction to “Effect of La Addition to Ceria on the Oxygen Storage Capacity and the Energetics of Water Adsorption” 对“La加入铈对储氧能力和水吸附力的影响”的修正

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2025-06-11 DOI: 10.1021/acs.chemmater.5c01187

Noa Azaria, Danielle Schweke, Lee Shelly, Shmuel Hayun

引用次数: 0

Spiky and Dendritic Microparticles: Design, Synthesis, and Emerging Applications 刺状和树突状微粒：设计、合成和新兴应用

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2025-06-11 DOI: 10.1021/acs.chemmater.5c00674

Yijiang Mu, Hong Huy Tran, Daeyeon Lee

引用次数: 0

Ion Migration and Dopant Effects in the Gamma-CsPbI3 Perovskite Photovoltaic Material: Atomistic Insights through Ab Initio and Machine Learning Methods γ - cspbi3钙钛矿光伏材料中的离子迁移和掺杂效应：通过从头算和机器学习方法的原子性见解

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2025-06-10 DOI: 10.1021/acs.chemmater.5c00503

Allison Nicole Arber, Vikram, Felix C. Mocanu, M. Saiful Islam

{"title":"Ion Migration and Dopant Effects in the Gamma-CsPbI3 Perovskite Photovoltaic Material: Atomistic Insights through Ab Initio and Machine Learning Methods","authors":"Allison Nicole Arber, Vikram, Felix C. Mocanu, M. Saiful Islam","doi":"10.1021/acs.chemmater.5c00503","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00503","url":null,"abstract":"Inorganic halide perovskites such as CsPbI3 are attracting increasing attention for solar cell and optoelectronic applications. Ion migration is known to be an important factor in perovskite behavior, but the impact of cation dopants on iodide diffusion in the room-temperature orthorhombic γ-CsPbI3 is not fully understood, especially at the atomic level. Here, we investigate the effect on iodide migration of incorporating different cations (including Sn2+, Ba2+, and Cu2+) into γ-CsPbI3, focusing on maintaining an inorganic phase rather than doping with molecular organic ions. Through a combination of ab initio and machine learning (ML) techniques, our results show that the simulated structure, band gap, and ion migration energies are in good agreement with experimental data. We find that partial Pb-site substitution does not have a major suppressing effect on iodide ion transport, which is important for guiding future doping work. An ML interatomic potential model was derived for large-scale simulations (∼80 ns) of the pristine and Sn-doped materials, which reveal iodide diffusion paths along the Pb–I octahedral edges with no correlated cation motion. Structural analysis indicates an ordered cation sublattice but disorder in the anion sublattice, indicative of high iodide ion mobility similar to fast-ion conductors.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"36 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144260682","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}

引用次数: 0

Decomposition of Selenourea in Various Solvents: Red versus Gray Selenium in the Synthesis of Iron Selenide Nanoparticles 硒脲在不同溶剂中的分解：合成硒化铁纳米颗粒中的红硒与灰硒

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2025-06-10 DOI: 10.1021/acs.chemmater.4c03430

Andrey A. Shults, Alexandra C. Koziel, Joshua D. Caldwell, Janet E. Macdonald

引用次数: 0

Molecular Dynamics of Crystal-to-Glass Transition in Zero-Dimensional Organic–Inorganic Hybrid Halide (ITP)2SbBr5·CH2Cl2 for Multifunctional Application 零维有机-无机杂化卤化物（ITP）2SbBr5·CH2Cl2晶体到玻璃转变的分子动力学及其多功能应用

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2025-06-06 DOI: 10.1021/acs.chemmater.5c00854

Chenyang Zhang, Yuexiao Pan, Wenxia Zhang, Haitao Tang, Yihong Ding, Qianqian Lin

{"title":"Molecular Dynamics of Crystal-to-Glass Transition in Zero-Dimensional Organic–Inorganic Hybrid Halide (ITP)2SbBr5·CH2Cl2 for Multifunctional Application","authors":"Chenyang Zhang, Yuexiao Pan, Wenxia Zhang, Haitao Tang, Yihong Ding, Qianqian Lin","doi":"10.1021/acs.chemmater.5c00854","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00854","url":null,"abstract":"The molecular dynamics of organic–inorganic hybrid halide (OIHH) materials during phase transitions are of utmost importance for their practical applications. In this study, we obtained a novel zero-dimensional (0D) OIHH material (ITP)2SbBr5·CH2Cl2 with a unique matrix that allows for the control of the size and shape of its glass. The luminescent properties of both the (ITP)2SbBr5·CH2Cl2 crystal and glass exhibit photoluminescence quantum yields (PLQYs) of 82.13% and 36.23%, respectively. DFT calculation shows that the indirect band gap of the sample is 2.44 eV. AIMD simulations confirm the structural retention of [ITP]+ and [SbBr5]2– units during melting, explaining the high thermal stability of the glass. The structure and optical properties of (ITP)2SbBr5·CH2Cl2 are thoroughly investigated, revealing its potential as a high-performance scintillator with superior light output and spatial resolution in X-ray imaging, as well as its effectiveness in agricultural lighting technology.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"33 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144229145","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}

引用次数: 0

Pivotal Role of Nanoparticle Distribution on Agile Steering of Magnetic Microrobots 纳米颗粒分布在磁性微机器人敏捷转向中的关键作用

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2025-06-06 DOI: 10.1021/acs.chemmater.5c00290

Sukyoung Won, Mingeun Kim, Jaeyong Lee, Young Joon Ko, Kijun Yang, Hee Eun Lee, Yong Ju Kim, Jong Hoon Jung, Jin Kon Kim, Kyu Hyun, Jeong Jae Wie

{"title":"Pivotal Role of Nanoparticle Distribution on Agile Steering of Magnetic Microrobots","authors":"Sukyoung Won, Mingeun Kim, Jaeyong Lee, Young Joon Ko, Kijun Yang, Hee Eun Lee, Yong Ju Kim, Jong Hoon Jung, Jin Kon Kim, Kyu Hyun, Jeong Jae Wie","doi":"10.1021/acs.chemmater.5c00290","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00290","url":null,"abstract":"Magnetic microrobots can be spatiotemporally steered by manipulating external magnetic fields, achieving rapid locomotion. However, for high-speed magnetic microrobots, steering stability is crucial to control actuation speeds along predetermined trajectories. Herein, we discover that nanoscale distribution of magnetic nanoparticles is key to ensuring the steering stability of agile magnetic microrobots. A model system comprising two different processing methods is implemented to induce either macroscopic phase separation or nanoscale distribution of nanoparticles within thermoplastic nanocomposites-based magnetic microrobots. The dispersive and distributive mixing of magnetic nanoparticles is evaluated via systematic investigation on magnetic, thermal, and rheological properties. According to the spatial distribution states of the magnetic nanoparticles, magnetic microrobots exhibit stark differences in motion uniformity and trajectory regularity during agile pivoting motion. Our findings elucidate the correlations among nanocomposite processing, nanoparticle distribution, physical properties, and magnetic actuation, providing valuable insights for designing stimuli-responsive miniaturized robots with enhanced locomotion control.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"18 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144229102","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}

引用次数: 0

Feature-Extended Descriptor Construction for Prediction of Consecutive Elementary Reaction Energies in Methane Oxidation 甲烷氧化中连续基本反应能预测的特征扩展描述符构造

IF 8.6 2区材料科学

Chemistry of Materials Pub Date : 2025-06-06 DOI: 10.1021/acs.chemmater.5c00930

Wangqiang Lin, Fangting Liu, Zhilong Song, Yehui Zhang, Qionghua Zhou, Chongyi Ling, Qiang Li, Jinlan Wang

{"title":"Feature-Extended Descriptor Construction for Prediction of Consecutive Elementary Reaction Energies in Methane Oxidation","authors":"Wangqiang Lin, Fangting Liu, Zhilong Song, Yehui Zhang, Qionghua Zhou, Chongyi Ling, Qiang Li, Jinlan Wang","doi":"10.1021/acs.chemmater.5c00930","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00930","url":null,"abstract":"Conventional descriptor construction approaches are fundamentally limited by their narrow focus on predicting adsorption energies for structurally similar intermediates, failing to address the complexity of real catalytic systems involving multiple active sites and elementary reactions. To overcome these limitations, we develop a general feature extension approach that systematically expands descriptor functionality through two key innovations: structure extension for diverse active sites and reaction extension for consecutive elementary reactions, enabled by comparative analysis of active site characteristics. Applying this approach to methane oxidation to methanol with three consecutive elementary reactions and six possible active sites (totaling 1,026 metal-exchanged zeolite catalysts), we successfully mapped the complete reaction pathways, identified optimal bimetallic catalysts (including experimentally verified Ag and Cu bimetallic active sites), and extracted fundamental structure–activity relationships. Proof-of-concept verification supports the generalizability of the feature extension approach, establishing a paradigm shift in descriptor discovery that transcends traditional single-site/single-step limitations and offering a powerful framework for complex catalytic pathway analysis and rational catalyst design.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"40 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144229146","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}

引用次数: 0