Fe-based catalysts are ideal for the oxygen evolution reaction (OER) owing to their earth abundance. However, most of these catalysts are usable only in an alkaline solution because they dissolve at low pH. Therefore, to be sufficiently versatile for large-scale energy conversion and storage devices, they must maintain high activity over a wide pH range. Cl–-stabilized Fe oxyhydroxide, i.e., hollandite-type β-FeOOH(Cl), nanorods have been reported to function in a (nearly) neutral solution with a relatively high activity, which was further improved by heat treatment at ∼200 °C; however, the mechanism underlying this enhancement was poorly understood because of the complicated transformation of β-FeOOH(Cl) to α-Fe2O3 during heating. Therefore, we investigated the structural changes in heat-treated β-FeOOH(Cl) using synchrotron-based X-ray diffraction measurements in addition to several spectroscopic methods and compositional analyses. Structural and compositional analyses, including Rietveld methods, revealed that β-FeOOH(Cl) underwent an indirect phase transformation via a Cl–-enriched β-FeOOH(Cl) intermediate phase at 200 °C before α-Fe2O3 formed. The Cl/Fe ratio of the intermediate phase (0.19) was almost twice that of the initial phase (0.08); furthermore, operando X-ray absorption spectroscopy clarified that the Cl–-enriched β-FeOOH(Cl) phase was stable during the OER even at a high current density of ∼22 mA cm–2. First-principles calculations using β-FeOOH(Cl) supercell models with Cl/Fe = 0.125 and 0.25 revealed that enrichment with Cl– ions increased Cl– diffusivity along the tunnel direction in hollandite, notably increasing the electrical conductivity and diffusion coefficient. Both of these properties could enhance the OER activity of β-FeOOH(Cl) catalysts, in addition to previously proposed structural strain. This finding suggests a structure–activity relationship that can serve as a guideline for broadening the use of β-FeOOH(Cl) OER catalysts.
{"title":"Role of Chloride Ions in the Heat Treatment of β-FeOOH(Cl) Catalysts to Enhance the Oxygen Evolution Reaction Activity","authors":"Takeshi Uyama, Yusuke Noda, Tomiko M. Suzuki, Keita Sekizawa, Naonari Sakamoto, Takamasa Nonaka, Takeshi Morikawa","doi":"10.1021/acs.chemmater.5c00128","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00128","url":null,"abstract":"Fe-based catalysts are ideal for the oxygen evolution reaction (OER) owing to their earth abundance. However, most of these catalysts are usable only in an alkaline solution because they dissolve at low pH. Therefore, to be sufficiently versatile for large-scale energy conversion and storage devices, they must maintain high activity over a wide pH range. Cl<sup>–</sup>-stabilized Fe oxyhydroxide, i.e., hollandite-type β-FeOOH(Cl), nanorods have been reported to function in a (nearly) neutral solution with a relatively high activity, which was further improved by heat treatment at ∼200 °C; however, the mechanism underlying this enhancement was poorly understood because of the complicated transformation of β-FeOOH(Cl) to α-Fe<sub>2</sub>O<sub>3</sub> during heating. Therefore, we investigated the structural changes in heat-treated β-FeOOH(Cl) using synchrotron-based X-ray diffraction measurements in addition to several spectroscopic methods and compositional analyses. Structural and compositional analyses, including Rietveld methods, revealed that β-FeOOH(Cl) underwent an indirect phase transformation via a Cl<sup>–</sup>-enriched β-FeOOH(Cl) intermediate phase at 200 °C before α-Fe<sub>2</sub>O<sub>3</sub> formed. The Cl/Fe ratio of the intermediate phase (0.19) was almost twice that of the initial phase (0.08); furthermore, operando X-ray absorption spectroscopy clarified that the Cl<sup>–</sup>-enriched β-FeOOH(Cl) phase was stable during the OER even at a high current density of ∼22 mA cm<sup>–2</sup>. First-principles calculations using β-FeOOH(Cl) supercell models with Cl/Fe = 0.125 and 0.25 revealed that enrichment with Cl<sup>–</sup> ions increased Cl<sup>–</sup> diffusivity along the tunnel direction in hollandite, notably increasing the electrical conductivity and diffusion coefficient. Both of these properties could enhance the OER activity of β-FeOOH(Cl) catalysts, in addition to previously proposed structural strain. This finding suggests a structure–activity relationship that can serve as a guideline for broadening the use of β-FeOOH(Cl) OER catalysts.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"39 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853782","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}
Transition metal (TM) and rare earth (RE) ion-doped nanoparticles (NPs) are photoluminescent materials of technological relevance in bioimaging, sensing, and light conversion. Fluoride NPs are particularly attractive in this context, since they combine low-energy phonons, high chemical stability, optical transparency, size, and architecture tunability. Yet, nearly all reported colloidal fluoride NPs (e.g., NaYF4 and LiYF4) can only be efficiently doped with RE3+ and not with luminescent TM ions. Herein, we contribute to filling this gap in materials science by reporting Na3InF6 NPs doped with Cr3+ as a model luminescent TM ion. We unveil the heat-driven NP formation mechanism, which involves a cubic-to-monoclinic phase conversion, similarly to the cubic-to-hexagonal phase conversion in NaYF4. Reaction temperatures above 225 °C and reaction time have a limited impact on the NP morphology, while the amount of fluoride precursor and oleylamine grants control over the NP size. After verifying that Na3InF6 NPs show negligible cytotoxicity toward U-87 cell line, we study the optical properties of these NPs upon Cr3+ doping. Temperature-dependent photoluminescence measurements indicate that Cr3+ ions experience a weak crystal field in the Na3InF6 host lattice, while their photoluminescence lifetime varies linearly in the 20–50 °C range. These results set the ground for further studies of photoluminescent TM-doped fluoride NPs, toward their applications in bioimaging, sensing, and light-converting devices.
{"title":"Indium-Based Fluoride Nanoparticles Doped with Chromium for Near-Infrared Luminescence","authors":"Emily Andreato, Nikita Panov, Álvaro Artiga, Viktoriia Osipova, Ute Resch-Genger, Erving Ximendes, Pablo Molina, Patrizia Canton, Riccardo Marin","doi":"10.1021/acs.chemmater.4c03335","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03335","url":null,"abstract":"Transition metal (TM) and rare earth (RE) ion-doped nanoparticles (NPs) are photoluminescent materials of technological relevance in bioimaging, sensing, and light conversion. Fluoride NPs are particularly attractive in this context, since they combine low-energy phonons, high chemical stability, optical transparency, size, and architecture tunability. Yet, nearly all reported colloidal fluoride NPs (e.g., NaYF<sub>4</sub> and LiYF<sub>4</sub>) can only be efficiently doped with RE<sup>3+</sup> and not with luminescent TM ions. Herein, we contribute to filling this gap in materials science by reporting Na<sub>3</sub>InF<sub>6</sub> NPs doped with Cr<sup>3+</sup> as a model luminescent TM ion. We unveil the heat-driven NP formation mechanism, which involves a cubic-to-monoclinic phase conversion, similarly to the cubic-to-hexagonal phase conversion in NaYF<sub>4</sub>. Reaction temperatures above 225 °C and reaction time have a limited impact on the NP morphology, while the amount of fluoride precursor and oleylamine grants control over the NP size. After verifying that Na<sub>3</sub>InF<sub>6</sub> NPs show negligible cytotoxicity toward U-87 cell line, we study the optical properties of these NPs upon Cr<sup>3+</sup> doping. Temperature-dependent photoluminescence measurements indicate that Cr<sup>3+</sup> ions experience a weak crystal field in the Na<sub>3</sub>InF<sub>6</sub> host lattice, while their photoluminescence lifetime varies linearly in the 20–50 °C range. These results set the ground for further studies of photoluminescent TM-doped fluoride NPs, toward their applications in bioimaging, sensing, and light-converting devices.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"23 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-04-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853798","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}
Pub Date : 2025-04-20DOI: 10.1021/acs.chemmater.4c03415
Edwin J. Miller, Ann Baac, Luisa Whittaker-Brooks
Ternary alloying has proven to be an effective method for inducing significant changes in the structural and electronic properties of archetypal 2D metal chalcogenides. In this study, monoclinic TiS3 and triclinic NbS3 were alloyed with Nb (in TiS3) and Ti (in NbS3) to form ternary alloys, resulting in spectroscopically detectable structural modifications. This process not only increases the number of majority charge carriers in both TiS3 and NbS3 frameworks but also enhances the presence of unpaired d electrons in both compounds. These effects are attributed to the population of the 3d band in TiS3 and the depopulation of the Peierls-distorted dz2 orbital in NbS3.
{"title":"Peierls Distortion and Electronic Property Modulation in 2D Metal Chalcogenides via Ternary Alloying of TiS3 and NbS3 Nanobelts","authors":"Edwin J. Miller, Ann Baac, Luisa Whittaker-Brooks","doi":"10.1021/acs.chemmater.4c03415","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03415","url":null,"abstract":"Ternary alloying has proven to be an effective method for inducing significant changes in the structural and electronic properties of archetypal 2D metal chalcogenides. In this study, monoclinic TiS<sub>3</sub> and triclinic NbS<sub>3</sub> were alloyed with Nb (in TiS<sub>3</sub>) and Ti (in NbS<sub>3</sub>) to form ternary alloys, resulting in spectroscopically detectable structural modifications. This process not only increases the number of majority charge carriers in both TiS<sub>3</sub> and NbS<sub>3</sub> frameworks but also enhances the presence of unpaired d electrons in both compounds. These effects are attributed to the population of the 3d band in TiS<sub>3</sub> and the depopulation of the Peierls-distorted d<sub><i>z</i></sub><sup>2</sup> orbital in NbS<sub>3</sub>.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"35 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-04-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853799","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}
Pub Date : 2025-04-18DOI: 10.1021/acs.chemmater.4c03397
Ayushi Tripathi, Trenton James Wolter, Robert J. Twieg, Manos Mavrikakis, Nicholas L. Abbott
Here we address if it is possible to couple changes in liquid crystal (LC) ordering with photocatalytic processes occurring on surfaces to enable the design of photoresponsive materials. We report that ultraviolet (UV) illumination of anatase (101) supporting 4′-n-pentyl-4-biphenylcarbonitrile (5CB) leads to a change in LC ordering driven by photo-oxidation of 5CB to 4′-cyano-4-biphenylcarboxylic acid (CBCA), as confirmed by infrared spectroscopy and mass spectrometry. Specifically, we find that a 0.09 monolayer (ML) surface coverage of the product CBCA on anatase (101) is sufficient to trigger the ordering transition of the LC from planar to homeotropic, thus reporting the transformation with high sensitivity. Additionally, we observe that the LC ordering serves as a reporter of the amount of adsorbed water on anatase (101), a key molecular species involved in the photocatalytic transformation of 5CB. We also demonstrate that the LC film alters the local concentration and structure of water adsorbed on titania, as characterized using infrared spectroscopy and electronic structure calculations. Lastly, the competitive adsorption of water and LC on anatase (101) is reported as a nonmonotonic trend in the rate of photocatalytic transformation of LC as a function of RH levels, a phenomenon captured by the rate of change of LC order. In summary, these results demonstrate that LCs couple to photocatalytic transformations on titania, offering designs of photoresponsive LCs, a novel readout of photocatalytic molecular events and the ability to tune interfacial photocatalytic processes.
{"title":"Responsive Liquid Crystalline Materials Based on Interfacial Photocatalytic Processes","authors":"Ayushi Tripathi, Trenton James Wolter, Robert J. Twieg, Manos Mavrikakis, Nicholas L. Abbott","doi":"10.1021/acs.chemmater.4c03397","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03397","url":null,"abstract":"Here we address if it is possible to couple changes in liquid crystal (LC) ordering with photocatalytic processes occurring on surfaces to enable the design of photoresponsive materials. We report that ultraviolet (UV) illumination of anatase (101) supporting 4′-<i>n</i>-pentyl-4-biphenylcarbonitrile (5CB) leads to a change in LC ordering driven by photo-oxidation of 5CB to 4′-cyano-4-biphenylcarboxylic acid (CBCA), as confirmed by infrared spectroscopy and mass spectrometry. Specifically, we find that a 0.09 monolayer (ML) surface coverage of the product CBCA on anatase (101) is sufficient to trigger the ordering transition of the LC from planar to homeotropic, thus reporting the transformation with high sensitivity. Additionally, we observe that the LC ordering serves as a reporter of the amount of adsorbed water on anatase (101), a key molecular species involved in the photocatalytic transformation of 5CB. We also demonstrate that the LC film alters the local concentration and structure of water adsorbed on titania, as characterized using infrared spectroscopy and electronic structure calculations. Lastly, the competitive adsorption of water and LC on anatase (101) is reported as a nonmonotonic trend in the rate of photocatalytic transformation of LC as a function of RH levels, a phenomenon captured by the rate of change of LC order. In summary, these results demonstrate that LCs couple to photocatalytic transformations on titania, offering designs of photoresponsive LCs, a novel readout of photocatalytic molecular events and the ability to tune interfacial photocatalytic processes.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"61 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143849728","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}
Metal–organic frameworks (MOFs) have become a rising star in the field of materials chemistry and engineering owing to their fascinating physico-chemical properties. The amalgamation of magnetic nanostructures with MOFs allows researchers to design promising hybrid materials with enhanced catalytic activity for desired organic transformations compared to their individual counterparts, facile separability, and reusability. In this contribution, the present work successfully reports the fabrication of a hybrid magnetic metal–organic framework (MMOF) material named Fe3O4/Cu-BTC via a facile hydrothermal approach with ferromagnetic properties and a large specific surface area of about 189.891 m2 g–1. The physico-chemical properties of as-synthesized materials were established via various spectroscopic, microscopic, and physical techniques. The catalytic activity of Fe3O4/Cu-BTC was evaluated for the hydration of nitriles to primary amides, and the catalyst was found to be efficient with up to 99% isolated yield. The catalyst was magnetically recoverable within a time span of 60 s and reusable up to the six catalytic cycles without any significant loss of catalytic activity. Large specific surface area, excellent magnetic retrievability, superior recyclability, and wider functional group tolerance are the outstanding features of this protocol.
{"title":"Fabrication of the Fe3O4/Cu-BTC Metal–Organic Framework Composite: A Magnetically Retrievable Efficient Catalytic Material for Hydration of Nitriles to Amides in Water","authors":"Mayuri Dutta, Jyotismita Bora, Gunjan Hazarika, Nikita Debgupta, Bolin Chetia","doi":"10.1021/acs.chemmater.5c00449","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00449","url":null,"abstract":"Metal–organic frameworks (MOFs) have become a rising star in the field of materials chemistry and engineering owing to their fascinating physico-chemical properties. The amalgamation of magnetic nanostructures with MOFs allows researchers to design promising hybrid materials with enhanced catalytic activity for desired organic transformations compared to their individual counterparts, facile separability, and reusability. In this contribution, the present work successfully reports the fabrication of a hybrid magnetic metal–organic framework (MMOF) material named Fe<sub>3</sub>O<sub>4</sub>/Cu-BTC via a facile hydrothermal approach with ferromagnetic properties and a large specific surface area of about 189.891 m<sup>2</sup> g<sup>–1</sup>. The physico-chemical properties of as-synthesized materials were established via various spectroscopic, microscopic, and physical techniques. The catalytic activity of Fe<sub>3</sub>O<sub>4</sub>/Cu-BTC was evaluated for the hydration of nitriles to primary amides, and the catalyst was found to be efficient with up to 99% isolated yield. The catalyst was magnetically recoverable within a time span of 60 s and reusable up to the six catalytic cycles without any significant loss of catalytic activity. Large specific surface area, excellent magnetic retrievability, superior recyclability, and wider functional group tolerance are the outstanding features of this protocol.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"30 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143847223","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}
The trade-off between maximizing light harvesting efficiency and maintaining high photoredox potentials is still a persistent and fundamental challenge in the field of photocatalysis. Intermediate band semiconductors (IBSCs) offer a promising approach to address the challenge by introducing an additional energy level within the bandgap, enabling simultaneous absorption of low- and high-energy photons while preserving strong redox capabilities. Herein, three kinds of Cu–Fe–S IBSC nanocrystals, i.e., Cu5FeS4 nanodisks (NDs), CuFeS2 NDs, and CuFeS2 octahedrons (Octas), have been controllably synthesized and they exhibit full spectral absorption capability, especially in the near-infrared (NIR) region extending to a wavelength of over 2500 nm. Notably, the Fe content-dependent NIR absorption enhancement has been revealed, originating from the modulation of the IB position within the band, as confirmed by theoretical calculation. These IBSCs can achieve NIR and full-spectrum photocatalytic transformation of 3-nitrostyrene to 3-vinylaniline with excellent conversion and selectivity and also possess broad applicability for various nitrobenzene derivatives. Under full-spectrum irradiation, CuFeS2 Octas exhibit a turnover frequency of up to 13.0 h–1, surpassing most reported nonprecious metal-based photo- and thermocatalysts. This study provides insights into the design of the IBSCs with optimal absorption capability and photoredox potentials, further enhancing the performance of the IBSC-based photocatalysts.
{"title":"Enhancing Near-Infrared Absorption by Modulation the Intermediate Band of Cu–Fe–S Semiconductors for Boosting Photocatalytic Hydrogenation of Nitroarenes","authors":"Feifan Chen, Haixia Liu, Qun Ji, Lijun Hu, Ming-Gang Ju, Fang Cheng, Xue-Jun Wu","doi":"10.1021/acs.chemmater.4c03131","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03131","url":null,"abstract":"The trade-off between maximizing light harvesting efficiency and maintaining high photoredox potentials is still a persistent and fundamental challenge in the field of photocatalysis. Intermediate band semiconductors (IBSCs) offer a promising approach to address the challenge by introducing an additional energy level within the bandgap, enabling simultaneous absorption of low- and high-energy photons while preserving strong redox capabilities. Herein, three kinds of Cu–Fe–S IBSC nanocrystals, i.e., Cu<sub>5</sub>FeS<sub>4</sub> nanodisks (NDs), CuFeS<sub>2</sub> NDs, and CuFeS<sub>2</sub> octahedrons (Octas), have been controllably synthesized and they exhibit full spectral absorption capability, especially in the near-infrared (NIR) region extending to a wavelength of over 2500 nm. Notably, the Fe content-dependent NIR absorption enhancement has been revealed, originating from the modulation of the IB position within the band, as confirmed by theoretical calculation. These IBSCs can achieve NIR and full-spectrum photocatalytic transformation of 3-nitrostyrene to 3-vinylaniline with excellent conversion and selectivity and also possess broad applicability for various nitrobenzene derivatives. Under full-spectrum irradiation, CuFeS<sub>2</sub> Octas exhibit a turnover frequency of up to 13.0 h<sup>–1</sup>, surpassing most reported nonprecious metal-based photo- and thermocatalysts. This study provides insights into the design of the IBSCs with optimal absorption capability and photoredox potentials, further enhancing the performance of the IBSC-based photocatalysts.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"23 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841982","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}
Pub Date : 2025-04-17DOI: 10.1021/acs.chemmater.4c02484
Haozhe Wang, Shuyuan Huyan, Eoghan Downey, Yang Wang, Shane Smolenski, Du Li, Li Yang, Aaron Bostwick, Chris Jozwiak, Eli Rotenberg, Sergey L. Bud’ko, Paul C. Canfield, R.J. Cava, Na Hyun Jo, Weiwei Xie
Nonmagnetic FeNb3Se10 has been demonstrated to be an insulator at ambient pressure through both theoretical calculations and experimental measurements, and it does not host topological surface states. Here, we show that on the application of pressure, FeNb3Se10 transitions to a metallic state at around 3.0 GPa. With a further increase in pressure, its resistivity becomes independent of both temperature and pressure. Its crystal structure is maintained to at least 4.4 GPa.
{"title":"Insulator-to-Metal Transition under High Pressure in FeNb3Se10","authors":"Haozhe Wang, Shuyuan Huyan, Eoghan Downey, Yang Wang, Shane Smolenski, Du Li, Li Yang, Aaron Bostwick, Chris Jozwiak, Eli Rotenberg, Sergey L. Bud’ko, Paul C. Canfield, R.J. Cava, Na Hyun Jo, Weiwei Xie","doi":"10.1021/acs.chemmater.4c02484","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02484","url":null,"abstract":"Nonmagnetic FeNb<sub>3</sub>Se<sub>10</sub> has been demonstrated to be an insulator at ambient pressure through both theoretical calculations and experimental measurements, and it does not host topological surface states. Here, we show that on the application of pressure, FeNb<sub>3</sub>Se<sub>10</sub> transitions to a metallic state at around 3.0 GPa. With a further increase in pressure, its resistivity becomes independent of both temperature and pressure. Its crystal structure is maintained to at least 4.4 GPa.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"582 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143847220","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}
Pub Date : 2025-04-17DOI: 10.1021/acs.chemmater.4c03172
Lionel Zoubritzky, François-Xavier Coudert
Topology is key to the determination of many physical and chemical properties of materials, such as electrical, optical, and magnetic properties, as well as thermal and mechanical behavior. However, despite the growing number of databases of crystalline materials available, there has been very little systematic effort to date to analyze their topology. In this work, we have leveraged recent algorithmic advances in the analysis of chemical bonding and topology determination in order to perform high-throughput analysis of topology of materials on a large-scale database of existing and hypothetical materials, the Materials Project data set of more than 170,000 structures. Beyond the statistical analysis of the most frequent topologies and coordination environments, the publication of these topological data will allow researchers to search for materials by topology and chemical environment, paving the way to enhanced performance in materials screening for applications. We demonstrated two examples of the usefulness of topological considerations in such computational screening.
{"title":"Large-Scale Characterization of Chemical Bonding and Topology in the Materials Project Database","authors":"Lionel Zoubritzky, François-Xavier Coudert","doi":"10.1021/acs.chemmater.4c03172","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03172","url":null,"abstract":"Topology is key to the determination of many physical and chemical properties of materials, such as electrical, optical, and magnetic properties, as well as thermal and mechanical behavior. However, despite the growing number of databases of crystalline materials available, there has been very little systematic effort to date to analyze their topology. In this work, we have leveraged recent algorithmic advances in the analysis of chemical bonding and topology determination in order to perform high-throughput analysis of topology of materials on a large-scale database of existing and hypothetical materials, the Materials Project data set of more than 170,000 structures. Beyond the statistical analysis of the most frequent topologies and coordination environments, the publication of these topological data will allow researchers to search for materials by topology and chemical environment, paving the way to enhanced performance in materials screening for applications. We demonstrated two examples of the usefulness of topological considerations in such computational screening.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"65 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143842011","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}
Pub Date : 2025-04-16DOI: 10.1021/acs.chemmater.4c03173
Leonardo F. Saraiva, Airton G. Bispo-Jr., André L. Costa, Fernando A. Sigoli, Sergio A. M. Lima, Ana M. Pires
Luminescent thermometers (LThs) are particularly suitable for monitoring submicron-scale thermal changes, spurring substantial advances in the field. Compared with the efforts to maximize the performance of LThs by designing novel materials, few advances have been made at the methodological level to exploit classical thermometric essays. Such a viewpoint motivated this study, which sought to combine data analysis algorithms with multiple thermometric parameters to introduce an advanced perspective on postprocessing data methodologies. Specifically, three distinct dimensionality reduction (DR) algorithms were employed: multiple linear regression (MLR), non-negative matrix factorization (NMF), and kernel principal component analysis (k-PCA). These methods were applied to the proof-of-concept SrY2O4:TbIII/IV,EuIII phosphor using the thermal dependence of the thermally coupled levels of EuIII (Δ) and the 5D0 lifetime (τ). Compared to traditional fitting and integration analyses, the DR approach provided enhanced thermometric performance, achieving a sensitivity increase from 0.897% K–1 (using Δ) to 3.68% K–1 (using k-PCA) and reducing temperature uncertainty below 0.03 K (k-PCA). By moving beyond single parametric thermal sensing with DR, these outcomes enable us to push the limits of luminescence thermometry toward unexplored pathways.
{"title":"Dimensionality Reduction Expands the Frontiers of Lanthanide Luminescence Thermometry Beyond Single-Parametric Thermal Sensing","authors":"Leonardo F. Saraiva, Airton G. Bispo-Jr., André L. Costa, Fernando A. Sigoli, Sergio A. M. Lima, Ana M. Pires","doi":"10.1021/acs.chemmater.4c03173","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03173","url":null,"abstract":"Luminescent thermometers (LThs) are particularly suitable for monitoring submicron-scale thermal changes, spurring substantial advances in the field. Compared with the efforts to maximize the performance of LThs by designing novel materials, few advances have been made at the methodological level to exploit classical thermometric essays. Such a viewpoint motivated this study, which sought to combine data analysis algorithms with multiple thermometric parameters to introduce an advanced perspective on postprocessing data methodologies. Specifically, three distinct dimensionality reduction (DR) algorithms were employed: multiple linear regression (MLR), non-negative matrix factorization (NMF), and kernel principal component analysis (k-PCA). These methods were applied to the proof-of-concept SrY<sub>2</sub>O<sub>4</sub>:Tb<sup>III/IV</sup>,Eu<sup>III</sup> phosphor using the thermal dependence of the thermally coupled levels of Eu<sup>III</sup> (Δ) and the <sup>5</sup>D<sub>0</sub> lifetime (τ). Compared to traditional fitting and integration analyses, the DR approach provided enhanced thermometric performance, achieving a sensitivity increase from 0.897% K<sup>–1</sup> (using Δ) to 3.68% K<sup>–1</sup> (using k-PCA) and reducing temperature uncertainty below 0.03 K (k-PCA). By moving beyond single parametric thermal sensing with DR, these outcomes enable us to push the limits of luminescence thermometry toward unexplored pathways.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143842053","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}
Pub Date : 2025-04-16DOI: 10.1021/acs.chemmater.4c02869
Abbas Khan, Eric Quarez, Nicolas Dupré, Eric Gautron, Andrea Balducci, Olivier Crosnier, Thierry Brousse
Design of tailored materials using innovative approaches that allow faster charging/discharging processes could be the key for improvement of electric mobility. In this work, a strategy is developed to modify KNbO3 perovskite structure by partially substituting K+ with La3+ at the A-site of the structure, creating two cation vacancies per substitution in the lattice. Materials with the general formula K1–3xLax□2xNbO3 (with 0 ≤ x ≤ 0.15; □ is an A-site vacancy) have been synthesized by the sol–gel method. With La substitution and creation of artificial vacancies in the structure, KNbO3 became activated for Li+ insertion. The highly substituted K0.55La0.15□0.30NbO3 (30% atomic A-site vacancies) exhibited 164 mAh g–1 at 0.02 A g–1 in the 0.05–3.0 V vs Li+/Li potential window. Ex situ7Li and 93Nb MAS NMR confirmed an increased Li+ insertion in relation to vacancies and corresponding changes in Nb5+ local environment, respectively. In situ X-ray diffraction (XRD) analysis revealed a solid-solution-type storage mechanism with a maximum volume change of only 1.3% upon Li+ insertion for highly substituted material. This accounts for the remarkable capacity retention obtained after 900 cycles at 0.1 A·g–1. Diverged from the classical design of insertion materials, this study presents an alternative approach of creating vacancies without sacrificing the pristine phase, with a possibility to use the not so common class of ABO3-type perovskites as the battery electrode.
{"title":"A-Site Vacancy Engineering in KNbO3 Perovskite for Enhanced Lithium Storage","authors":"Abbas Khan, Eric Quarez, Nicolas Dupré, Eric Gautron, Andrea Balducci, Olivier Crosnier, Thierry Brousse","doi":"10.1021/acs.chemmater.4c02869","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02869","url":null,"abstract":"Design of tailored materials using innovative approaches that allow faster charging/discharging processes could be the key for improvement of electric mobility. In this work, a strategy is developed to modify KNbO<sub>3</sub> perovskite structure by partially substituting K<sup>+</sup> with La<sup>3+</sup> at the A-site of the structure, creating two cation vacancies per substitution in the lattice. Materials with the general formula K<sub>1–3<i>x</i></sub>La<sub><i>x</i></sub>□<sub>2<i>x</i></sub>NbO<sub>3</sub> (with 0 ≤ <i>x</i> ≤ 0.15; □ is an A-site vacancy) have been synthesized by the sol–gel method. With La substitution and creation of artificial vacancies in the structure, KNbO<sub>3</sub> became activated for Li<sup>+</sup> insertion. The highly substituted K<sub>0.55</sub>La<sub>0.15</sub>□<sub>0.30</sub>NbO<sub>3</sub> (30% atomic A-site vacancies) exhibited 164 mAh g<sup>–1</sup> at 0.02 A g<sup>–1</sup> in the 0.05–3.0 V vs Li<sup>+</sup>/Li potential window. <i>Ex situ</i> <sup>7</sup>Li and <sup>93</sup>Nb MAS NMR confirmed an increased Li<sup>+</sup> insertion in relation to vacancies and corresponding changes in Nb<sup>5+</sup> local environment, respectively. <i>In situ</i> X-ray diffraction (XRD) analysis revealed a solid-solution-type storage mechanism with a maximum volume change of only 1.3% upon Li<sup>+</sup> insertion for highly substituted material. This accounts for the remarkable capacity retention obtained after 900 cycles at 0.1 A·g<sup>–1</sup>. Diverged from the classical design of insertion materials, this study presents an alternative approach of creating vacancies without sacrificing the pristine phase, with a possibility to use the not so common class of ABO<sub>3</sub>-type perovskites as the battery electrode.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"4 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837540","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}
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