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)PbBr<sub>3</sub> and (AzrH)PbCl<sub>3</sub> (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)PbBr<sub>3</sub> 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}
{"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 (κ<sub>lat</sub>) 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 κ<sub>lat</sub> 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 κ<sub>lat</sub> 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 κ<sub>lat</sub>, 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}
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 <i>M</i>-elements beyond titanium and <i>A</i>-elements beyond aluminum, oxidize is lacking. Therefore, we synthesized two <i>A</i>-site solid solutions (gallium and germanium as the <i>A</i>-elements) based on chromium and vanadium as <i>M</i>-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 <i>M</i>- and <i>A</i>-elements on the oxidation behavior: phases with Cr on the <i>M</i>-site have higher oxidation stability than with V, and solid solutions Cr<sub>2</sub>Ga<sub>1–<i>x</i></sub>Ge<sub><i>x</i></sub>C have improved oxidation resistance compared to the individual phases Cr<sub>2</sub>GaC and Cr<sub>2</sub>GeC.","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}
Noa Azaria, Danielle Schweke, Lee Shelly, Shmuel Hayun
{"title":"Correction to “Effect of La Addition to Ceria on the Oxygen Storage Capacity and the Energetics of Water Adsorption”","authors":"Noa Azaria, Danielle Schweke, Lee Shelly, Shmuel Hayun","doi":"10.1021/acs.chemmater.5c01187","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c01187","url":null,"abstract":"The following statement was inadvertently omitted from the Acknowledgments in the originally published article: N.A. sincerely thanks Maisam Nassar for her valuable assistance in testing the OSC of doped ceria and in the preparation of Figure 6 during her B.Sc. studies. This article has not yet been cited by other publications.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"61 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144260621","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":"Spiky and Dendritic Microparticles: Design, Synthesis, and Emerging Applications","authors":"Yijiang Mu, Hong Huy Tran, Daeyeon Lee","doi":"10.1021/acs.chemmater.5c00674","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00674","url":null,"abstract":"Microparticles with long surface protrusions, either as rigid spikes or flexible dendrites, represent a unique class of colloidal materials. Their chemical and structural features give rise to properties and functions that differ fundamentally from those of similarly shaped nanoparticles, with applications in drug delivery, biofilm disruption, and adhesive technologies. Their distinctive spiky or dendritic morphologies alter interparticle interactions, and regulate particle–environment interactions. Synthesizing these particles is inherently challenging, as colloidal particles naturally favor smooth surfaces to minimize surface energy. This review highlights key synthetic strategies, including seeded growth, emulsion-templated synthesis, and polymer precipitation under turbulent shear. We describe the particles produced via these processes and their applications, and discuss future challenges and opportunities in this emerging field.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"6 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144269246","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}
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 CsPbI<sub>3</sub> 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-CsPbI<sub>3</sub> is not fully understood, especially at the atomic level. Here, we investigate the effect on iodide migration of incorporating different cations (including Sn<sup>2+</sup>, Ba<sup>2+</sup>, and Cu<sup>2+</sup>) into γ-CsPbI<sub>3</sub>, focusing on maintaining an inorganic phase rather than doping with molecular organic ions. Through a combination of <i>ab initio</i> 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}
Andrey A. Shults, Alexandra C. Koziel, Joshua D. Caldwell, Janet E. Macdonald
{"title":"Decomposition of Selenourea in Various Solvents: Red versus Gray Selenium in the Synthesis of Iron Selenide Nanoparticles","authors":"Andrey A. Shults, Alexandra C. Koziel, Joshua D. Caldwell, Janet E. Macdonald","doi":"10.1021/acs.chemmater.4c03430","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03430","url":null,"abstract":"Selenourea is a useful reagent for the synthesis of metal chalcogenides. Its low decomposition temperature allows it to bypass the usual harsh conditions used in nanoparticle synthesis. Here, we show that selenourea decomposes differently based on its chemical environment, a phenomenon that can be used for the phase control of iron selenide nanoparticles. Two solvents (oleylamine and oleic acid) were tested for their interactions with selenourea to control the phase of iron selenides as they are ubiquitous in nanocrystal synthesis. It was found that in the presence of oleylamine, selenourea decomposes into red selenium resulting in the formation of Fe<sub>7</sub>Se<sub>8</sub>. When combined with oleic acid, selenourea decomposes into gray selenium, resulting in the formation of FeSe<sub>2</sub>. In this report, allotropes have been identified as phase-determining intermediates in nanocrystal synthesis.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"88 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144252804","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":"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)<sub>2</sub>SbBr<sub>5</sub>·CH<sub>2</sub>Cl<sub>2</sub> with a unique matrix that allows for the control of the size and shape of its glass. The luminescent properties of both the (ITP)<sub>2</sub>SbBr<sub>5</sub>·CH<sub>2</sub>Cl<sub>2</sub> 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]<sup>+</sup> and [SbBr<sub>5</sub>]<sup>2–</sup> units during melting, explaining the high thermal stability of the glass. The structure and optical properties of (ITP)<sub>2</sub>SbBr<sub>5</sub>·CH<sub>2</sub>Cl<sub>2</sub> 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}
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}
{"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}