High-entropy alloys (HEAs), composed of five or more principal elements in near-equiatomic ratios, have emerged as transformative electrocatalysts for energy conversion due to their exceptional compositional flexibility, thermodynamic stability, and tunable surface chemistry. This review authoritatively analyzes recent advances in HEA-based electrocatalysts for reactions, including hydrogen evolution (HER), hydrogen oxidation (HOR), oxygen evolution (OER), and oxygen reduction (ORR), crucial to water electrolyzers, fuel cells, and metal–air batteries (MABs). Fundamental aspects governing HEA formation (configurational entropy, lattice distortion, and sluggish diffusion) are outlined alongside synthetic strategies. The electrochemical performance of HEAs in acidic and alkaline media is critically discussed, emphasizing structure–activity–stability correlations and multielement synergistic effects. Despite major progress, challenges persist in compositional precision, identification of active sites, and large-scale fabrication. The review concludes by outlining future research directions toward the rational design of HEA electrocatalysts for efficient, scalable, and sustainable energy technologies.
{"title":"High-Entropy Alloy-Catalyzed Bifunctional Electrocatalysis of H2 and O2 Involving Reactions","authors":"Neha Clare Minj, Sneha Mittal, Sandeep Yadav, Balakumaran Kamaraj, Pracheta Trivedi, Shivani Saraswat, Krishanu Biswas, Ligang Feng, Suguru Noda, Anantharaj Sengeni","doi":"10.1021/acs.chemmater.5c02763","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02763","url":null,"abstract":"High-entropy alloys (HEAs), composed of five or more principal elements in near-equiatomic ratios, have emerged as transformative electrocatalysts for energy conversion due to their exceptional compositional flexibility, thermodynamic stability, and tunable surface chemistry. This review authoritatively analyzes recent advances in HEA-based electrocatalysts for reactions, including hydrogen evolution (HER), hydrogen oxidation (HOR), oxygen evolution (OER), and oxygen reduction (ORR), crucial to water electrolyzers, fuel cells, and metal–air batteries (MABs). Fundamental aspects governing HEA formation (configurational entropy, lattice distortion, and sluggish diffusion) are outlined alongside synthetic strategies. The electrochemical performance of HEAs in acidic and alkaline media is critically discussed, emphasizing structure–activity–stability correlations and multielement synergistic effects. Despite major progress, challenges persist in compositional precision, identification of active sites, and large-scale fabrication. The review concludes by outlining future research directions toward the rational design of HEA electrocatalysts for efficient, scalable, and sustainable energy technologies.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"107 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135338","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}
Melanin-like nanoparticles (MLNPs) hold great promise for biomedical applications, yet their controlled synthesis under mild conditions remains challenging. Here, we present a hydrogen bond-mediated liquid–liquid phase separation (LLPS) strategy to fabricate functional MLNPs with tunable physicochemical properties. Coacervates are formed through hydrogen bonding between hydrogen bond donor polyphenols and hydrogen bond acceptor polymers, providing a dynamic and mild environment for nanostructure formation. Leveraging this hydrogen bond-stabilized coacervate as a soft template, we synthesized monodisperse MLNPs via oxidative polymerization of coacervates. The resulting nanoparticles feature precise size control and abundant surface functionalities, enabling drug loading via electrostatic interactions, hydrogen bonding, π-π stacking, and metal-ion coordination. These multifunctional properties support diverse biomedical applications, including drug delivery, imaging, and enzyme-mimetic catalytic therapy. This work establishes a scalable and versatile platform for engineering MLNPs via hydrogen bond-driven LLPS templating, opening up opportunities for translational nanomedicine.
{"title":"Hydrogen Bond Mediated Phase Separation of Phenolic-Based Compounds for the Preparation of Melanin-like Nanoparticles","authors":"Han Yang, Yihao Gan, Xinxin Han, Dandan Ren, Aixin Song, Zhiliang Gao, Peiyu Zhang","doi":"10.1021/acs.chemmater.5c02681","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02681","url":null,"abstract":"Melanin-like nanoparticles (MLNPs) hold great promise for biomedical applications, yet their controlled synthesis under mild conditions remains challenging. Here, we present a hydrogen bond-mediated liquid–liquid phase separation (LLPS) strategy to fabricate functional MLNPs with tunable physicochemical properties. Coacervates are formed through hydrogen bonding between hydrogen bond donor polyphenols and hydrogen bond acceptor polymers, providing a dynamic and mild environment for nanostructure formation. Leveraging this hydrogen bond-stabilized coacervate as a soft template, we synthesized monodisperse MLNPs via oxidative polymerization of coacervates. The resulting nanoparticles feature precise size control and abundant surface functionalities, enabling drug loading via electrostatic interactions, hydrogen bonding, π-π stacking, and metal-ion coordination. These multifunctional properties support diverse biomedical applications, including drug delivery, imaging, and enzyme-mimetic catalytic therapy. This work establishes a scalable and versatile platform for engineering MLNPs via hydrogen bond-driven LLPS templating, opening up opportunities for translational nanomedicine.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"58 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146129461","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 : 2026-02-07DOI: 10.1021/acs.chemmater.5c02860
Tori Cox, Volodymyr Gvozdetskyi, Nisaga Prathibhani Wanigasekara, Zhen Zhang, Genevieve Amobi, Kaden Osborn, Zeina Miari, Julia V. Zaikina
K3Cd12Sb10 was discovered using an unconventional hydride synthetic route, whereas the temperature conditions were rationalized from in situ powder X-ray diffraction. K3Cd12Sb10 can be synthesized in the single-phase form through the hydride method at relatively low temperatures (723 K). K3Cd12Sb10 melts incongruently at 794 K and has a narrow synthesizability window (691–794 K), as determined by in situ high-temperature diffraction and differential scanning calorimetry. Because of its limited thermal stability, suitable crystals for single-crystal X-ray diffraction are unavailable; the crystal structure of K3Cd12Sb10 was solved from high-resolution synchrotron powder X-ray diffraction data. K3Cd12Sb10 crystallizes in a new structure type (space group Ia3̅d, a = 18.09301(1) Å, V = 5922.87(1) Å3, Z = 8), adding another syngony for the previously reported ternary K–Cd–Sb compounds. By merging unconventional synthesis with in situ high-temperature monitoring, this study pushes the boundaries of materials discovery, revealing a clathrate-like phase with a novel structure type and hinting at vast structural diversity across other antimonide systems.
{"title":"Adding Another Syngony to the K–Cd–Sb System: Synthesis, Structure, and Properties of Cubic, Clathrate-Like K3Cd12Sb10","authors":"Tori Cox, Volodymyr Gvozdetskyi, Nisaga Prathibhani Wanigasekara, Zhen Zhang, Genevieve Amobi, Kaden Osborn, Zeina Miari, Julia V. Zaikina","doi":"10.1021/acs.chemmater.5c02860","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02860","url":null,"abstract":"K<sub>3</sub>Cd<sub>12</sub>Sb<sub>10</sub> was discovered using an unconventional hydride synthetic route, whereas the temperature conditions were rationalized from in situ powder X-ray diffraction. K<sub>3</sub>Cd<sub>12</sub>Sb<sub>10</sub> can be synthesized in the single-phase form through the hydride method at relatively low temperatures (723 K). K<sub>3</sub>Cd<sub>12</sub>Sb<sub>10</sub> melts incongruently at 794 K and has a narrow synthesizability window (691–794 K), as determined by in situ high-temperature diffraction and differential scanning calorimetry. Because of its limited thermal stability, suitable crystals for single-crystal X-ray diffraction are unavailable; the crystal structure of K<sub>3</sub>Cd<sub>12</sub>Sb<sub>10</sub> was solved from high-resolution synchrotron powder X-ray diffraction data. K<sub>3</sub>Cd<sub>12</sub>Sb<sub>10</sub> crystallizes in a new structure type (space group <i>Ia</i>3̅<i>d</i>, <i>a</i> = 18.09301(1) Å, <i>V</i> = 5922.87(1) Å<sup>3</sup>, <i>Z</i> = 8), adding another syngony for the previously reported ternary K–Cd–Sb compounds. By merging unconventional synthesis with in situ high-temperature monitoring, this study pushes the boundaries of materials discovery, revealing a clathrate-like phase with a novel structure type and hinting at vast structural diversity across other antimonide systems.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"107 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135342","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 : 2026-02-07DOI: 10.1021/acs.chemmater.5c02941
Olufemi S. Araoyinbo, Amirhossein Zareihassangheshlaghi, Md Sahab Uddin, Mehak Ghafoor, Kaya Wei, Susan E. Latturner
Reactions of silicon with europium and ytterbium were carried out in Mg/Zn eutectic flux to synthesize complex metal silicides. Depending on the ratios of Eu and Yb reactant used, observed products were Yb2MgSi2 (when no Eu was used), Eu2Yb2.7Mg9.3Si7 (with more Yb than Eu reacted), and Eu5(Eu1–xYbx)3Mg16Si12 (with more Eu than Yb). The latter two compounds form in the Zr2Fe12P7 (P-6) and Ho5Ni19P12 (P-62m) structure types, and are charge-balanced Zintl phases. Density of states calculations show that the consistently observed composition of Eu2Yb2.7Mg9.3Si7 is electronically stabilized. Magnetic susceptibility measurements show europium and ytterbium are both divalent; highly anisotropic ferromagnetic ordering of Eu2+ moments is observed at low temperature. Thermoelectric measurements indicate that site mixing of cations lowers thermal conductivity, and that Eu6.72Yb1.28Mg15.56Zn0.44Si12 has the most promising thermoelectric behavior with a zT = 0.14 at 400 K and potential for use at high temperatures.
{"title":"Thermoelectric and Magnetic Behavior of (Eu/Yb/Mg)2Si Zintl Phases Grown in Magnesium-Based Flux","authors":"Olufemi S. Araoyinbo, Amirhossein Zareihassangheshlaghi, Md Sahab Uddin, Mehak Ghafoor, Kaya Wei, Susan E. Latturner","doi":"10.1021/acs.chemmater.5c02941","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02941","url":null,"abstract":"Reactions of silicon with europium and ytterbium were carried out in Mg/Zn eutectic flux to synthesize complex metal silicides. Depending on the ratios of Eu and Yb reactant used, observed products were Yb<sub>2</sub>MgSi<sub>2</sub> (when no Eu was used), Eu<sub>2</sub>Yb<sub>2.7</sub>Mg<sub>9.3</sub>Si<sub>7</sub> (with more Yb than Eu reacted), and Eu<sub>5</sub>(Eu<sub>1–<i>x</i></sub>Yb<sub><i>x</i></sub>)<sub>3</sub>Mg<sub>16</sub>Si<sub>12</sub> (with more Eu than Yb). The latter two compounds form in the Zr<sub>2</sub>Fe<sub>12</sub>P<sub>7</sub> (<i>P</i>-6) and Ho<sub>5</sub>Ni<sub>19</sub>P<sub>12</sub> (<i>P</i>-62<i>m</i>) structure types, and are charge-balanced Zintl phases. Density of states calculations show that the consistently observed composition of Eu<sub>2</sub>Yb<sub>2.7</sub>Mg<sub>9.3</sub>Si<sub>7</sub> is electronically stabilized. Magnetic susceptibility measurements show europium and ytterbium are both divalent; highly anisotropic ferromagnetic ordering of Eu<sup>2+</sup> moments is observed at low temperature. Thermoelectric measurements indicate that site mixing of cations lowers thermal conductivity, and that Eu<sub>6.72</sub>Yb<sub>1.28</sub>Mg<sub>15.56</sub>Zn<sub>0.44</sub>Si<sub>12</sub> has the most promising thermoelectric behavior with a zT = 0.14 at 400 K and potential for use at high temperatures.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"126 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146129462","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 : 2026-02-06DOI: 10.1021/acs.chemmater.5c03475
Anna Vigolo, Valeria Vanoli, Luca Laugeni, Carlos Pavón, Rossana Pasquino, Edmondo M. Benetti, Franca Castiglione, Francesca Lorandi
Graft polymers with oligo(ethylene glycol) (OEG) side chains and poly(meth)acrylate backbones have been commonly studied as polymer electrolytes (PEs) owing to the ability of oligoether segments to coordinate Li+ ions. However, when poly[oligo(ethylene glycol) methyl ether methacrylate]s (P(OEG)MAs) are synthesized from commercial macromonomers, these are structurally polydisperse, as OEG segments feature a broad distribution of lengths. Herein, we investigate the influence of side-chain heterogeneity on Li-ion transport by comparing structurally polydisperse P(OEG)MAs with analogous graft polymers with homogeneous architecture, generated from discrete macromonomer feeds obtained through flash chromatography. Ionic conductivity was found to increase with increasing side-chain dispersity. For structurally polydisperse P(OEG)MAs, enhancing side-chain heterogeneity resulted in greater salt dissociation and higher ionic conductivity at relatively high salt contents. These trends are uncorrelated with differences in thermal properties, rheology, and polymer diffusivity, indicating that ion transport is not governed by overall polymer dynamics. Dispersity of side chains thus emerges as a determinant for Li-ion transport in PEs based on P(OEG)MAs. However, this effect is lost when backbone flexibility increases, i.e., when polymethacrylates are substituted with more flexible polyacrylate counterparts. By elucidating how side-chain heterogeneity and backbone flexibility affect ion transport, this work provides guidance for the rational design of graft PEs.
{"title":"Structural Dispersity as a Determinant of Li-Ion Transport in Ethylene-Oxide-Based Graft Polymer Electrolytes","authors":"Anna Vigolo, Valeria Vanoli, Luca Laugeni, Carlos Pavón, Rossana Pasquino, Edmondo M. Benetti, Franca Castiglione, Francesca Lorandi","doi":"10.1021/acs.chemmater.5c03475","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c03475","url":null,"abstract":"Graft polymers with oligo(ethylene glycol) (OEG) side chains and poly(meth)acrylate backbones have been commonly studied as polymer electrolytes (PEs) owing to the ability of oligoether segments to coordinate Li<sup>+</sup> ions. However, when poly[oligo(ethylene glycol) methyl ether methacrylate]s (P(OEG)MAs) are synthesized from commercial macromonomers, these are structurally polydisperse, as OEG segments feature a broad distribution of lengths. Herein, we investigate the influence of side-chain heterogeneity on Li-ion transport by comparing structurally polydisperse P(OEG)MAs with analogous graft polymers with homogeneous architecture, generated from discrete macromonomer feeds obtained through flash chromatography. Ionic conductivity was found to increase with increasing side-chain dispersity. For structurally polydisperse P(OEG)MAs, enhancing side-chain heterogeneity resulted in greater salt dissociation and higher ionic conductivity at relatively high salt contents. These trends are uncorrelated with differences in thermal properties, rheology, and polymer diffusivity, indicating that ion transport is not governed by overall polymer dynamics. Dispersity of side chains thus emerges as a determinant for Li-ion transport in PEs based on P(OEG)MAs. However, this effect is lost when backbone flexibility increases, i.e., when polymethacrylates are substituted with more flexible polyacrylate counterparts. By elucidating how side-chain heterogeneity and backbone flexibility affect ion transport, this work provides guidance for the rational design of graft PEs.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"302 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122367","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 : 2026-02-06DOI: 10.1021/acs.chemmater.5c03153
Gentoku Kido, Hiroto Ueki, Megumi Okazaki, Jun Kikkawa, Koji Kimoto, Ryosuke Nishikubo, Akinori Saeki, Kazuhiko Maeda
Mixed-anion compounds offer unique functionalities unattainable with single-anion materials, yet rational morphology control remains largely unexplored. Here, we report a Lewis acid–base-driven strategy that enables low-temperature, solution-phase morphology control of the oxyfluoride photocatalyst Pb2Ti2O5.4F1.2 (PTOF). A microwave-assisted solvothermal method with monoethanolamine (MEA) was used to tune the particle morphology and size via the precursor-solution pH, which was adjusted by the addition of formic acid or acetic acid. PTOF, an A2B2X6X′0.5-type pyrochlore with intrinsic anion vacancies (X′2, 4d site), has exposed {111} facets composed of alternating Pb-rich and Ti-rich layers. Lewis basic MEA is proposed to bind selectively to undercoordinated, strongly acidic Pb2+ sites adjacent to Ti4+ and vacancies on Ti-rich {111} facets, suppressing growth along the surface direction and stabilizing these facets, thereby driving anisotropic crystal growth and forming plate-like nanoparticles. At pH 10 (formic acid), PTOF nanoparticles (∼30 nm) with a specific surface area of 37 m2 g–1 were obtained. Compared with an analogous PTOF synthesized by a conventional solid–state reaction, the optimized sample exhibited ∼29-fold higher H2 evolution activity in an aqueous solution containing dissolved disodium ethylenediaminetetraacetate under visible-light (λ > 400 nm) with the aid of a Pt cocatalyst. Lewis acid–base-directed facet stabilization is thus shown to be a promising approach for the rational morphological design of mixed-anion oxyfluorides via solution processing.
{"title":"Lewis Acid–Base-Driven Anisotropic Crystal Growth of Pyrochlore Pb2Ti2O5.4F1.2 with Enhanced Visible-Light H2 Evolution Activity","authors":"Gentoku Kido, Hiroto Ueki, Megumi Okazaki, Jun Kikkawa, Koji Kimoto, Ryosuke Nishikubo, Akinori Saeki, Kazuhiko Maeda","doi":"10.1021/acs.chemmater.5c03153","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c03153","url":null,"abstract":"Mixed-anion compounds offer unique functionalities unattainable with single-anion materials, yet rational morphology control remains largely unexplored. Here, we report a Lewis acid–base-driven strategy that enables low-temperature, solution-phase morphology control of the oxyfluoride photocatalyst Pb<sub>2</sub>Ti<sub>2</sub>O<sub>5.4</sub>F<sub>1.2</sub> (PTOF). A microwave-assisted solvothermal method with monoethanolamine (MEA) was used to tune the particle morphology and size via the precursor-solution pH, which was adjusted by the addition of formic acid or acetic acid. PTOF, an <i>A</i><sub>2</sub><i>B</i><sub>2</sub><i>X</i><sub>6</sub><i>X</i>′<sub>0.5</sub>-type pyrochlore with intrinsic anion vacancies (<i>X</i>′2, 4d site), has exposed {111} facets composed of alternating Pb-rich and Ti-rich layers. Lewis basic MEA is proposed to bind selectively to undercoordinated, strongly acidic Pb<sup>2+</sup> sites adjacent to Ti<sup>4+</sup> and vacancies on Ti-rich {111} facets, suppressing growth along the surface direction and stabilizing these facets, thereby driving anisotropic crystal growth and forming plate-like nanoparticles. At pH 10 (formic acid), PTOF nanoparticles (∼30 nm) with a specific surface area of 37 m<sup>2</sup> g<sup>–1</sup> were obtained. Compared with an analogous PTOF synthesized by a conventional solid–state reaction, the optimized sample exhibited ∼29-fold higher H<sub>2</sub> evolution activity in an aqueous solution containing dissolved disodium ethylenediaminetetraacetate under visible-light (λ > 400 nm) with the aid of a Pt cocatalyst. Lewis acid–base-directed facet stabilization is thus shown to be a promising approach for the rational morphological design of mixed-anion oxyfluorides via solution processing.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"76 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146129537","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}
Magnetoelectric effect is a coupling phenomenon between magnetism and dielectric properties that occurs in noncentrosymmetric magnetic materials. This effect can be extended to the response to electromagnetic waves, i.e., light, in materials and is referred to as the optical magnetoelectric (OME) effect. The OME effect can give rise to fascinating optical properties, such as propagation-direction-dependent light absorption, known as nonreciprocal directional dichroism. In this study, we prepared single crystals of a polar and ferromagnetic two-dimensional organic–inorganic hybrid perovskite (2D-OIHP) copper chloride, (ClBA)2CuCl4 (where ClBA+ = 4-chlorobenzylammonium ion), with sufficient size for optical measurements, and successfully detected the OME effect by measuring the difference in light absorption between opposite propagation directions. These results suggest that 2D-OIHPs are a promising class of materials for developing emergent functionalities unique to noncentrosymmetric systems.
{"title":"Optical Magnetoelectric Effect in a Polar Ferromagnetic Two-Dimensional Organic–Inorganic Hybrid Perovskite","authors":"Po-Jung Huang, Gyeongoh Noh, Shojiro Kimura, Kouji Taniguchi","doi":"10.1021/acs.chemmater.5c03048","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c03048","url":null,"abstract":"Magnetoelectric effect is a coupling phenomenon between magnetism and dielectric properties that occurs in noncentrosymmetric magnetic materials. This effect can be extended to the response to electromagnetic waves, i.e., light, in materials and is referred to as the optical magnetoelectric (OME) effect. The OME effect can give rise to fascinating optical properties, such as propagation-direction-dependent light absorption, known as nonreciprocal directional dichroism. In this study, we prepared single crystals of a polar and ferromagnetic two-dimensional organic–inorganic hybrid perovskite (2D-OIHP) copper chloride, (ClBA)<sub>2</sub>CuCl<sub>4</sub> (where ClBA<sup>+</sup> = 4-chlorobenzylammonium ion), with sufficient size for optical measurements, and successfully detected the OME effect by measuring the difference in light absorption between opposite propagation directions. These results suggest that 2D-OIHPs are a promising class of materials for developing emergent functionalities unique to noncentrosymmetric systems.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"76 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146129463","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 : 2026-02-04DOI: 10.1021/acs.chemmater.5c03245
Jinpeng Liu,Hongmei Mu,Junchao Huang,Yuhua Wang
Rigid polyurethane foam (RPUF) is a versatile thermal and acoustic barrier material with high flammability, which raises severe safety concerns and necessitates an effective flame retardant (FR). Compared to the single FR system, organic/inorganic flame-retardant composites with the synergistic effect show better performance in both flame retardancy. While the synergistic effect is always considered among FRs and does not include the polymer matrix, it obtains limited effectiveness. Our work prepared an extender for PU foam, which contains accessible phenyl side groups that can interact with modified expandable graphite through intercalation to construct a synergistic effect between the polymer matrix and the inorganic FR. With a total additive content of 21.9%, the LOI and UL-94 ratings increased to 37% and V-0 level, respectively, which shows the greatest improvement compared to other expandable graphite systems and only induces small fluctuations in physicochemical performances. The designed FRs fulfill the major requirements of current standards on RPUF, and they also show a great practicality for future large-scale production.
{"title":"Flame-Retardant Synergism through Chemical Intercalation for Rigid Polyurethane Foam by Using Intrinsic/inorganic Combination","authors":"Jinpeng Liu,Hongmei Mu,Junchao Huang,Yuhua Wang","doi":"10.1021/acs.chemmater.5c03245","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c03245","url":null,"abstract":"Rigid polyurethane foam (RPUF) is a versatile thermal and acoustic barrier material with high flammability, which raises severe safety concerns and necessitates an effective flame retardant (FR). Compared to the single FR system, organic/inorganic flame-retardant composites with the synergistic effect show better performance in both flame retardancy. While the synergistic effect is always considered among FRs and does not include the polymer matrix, it obtains limited effectiveness. Our work prepared an extender for PU foam, which contains accessible phenyl side groups that can interact with modified expandable graphite through intercalation to construct a synergistic effect between the polymer matrix and the inorganic FR. With a total additive content of 21.9%, the LOI and UL-94 ratings increased to 37% and V-0 level, respectively, which shows the greatest improvement compared to other expandable graphite systems and only induces small fluctuations in physicochemical performances. The designed FRs fulfill the major requirements of current standards on RPUF, and they also show a great practicality for future large-scale production.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"20 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111129","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}
Lead-free bismuth ferrite–barium titanate (BF–BT) relaxor ferroelectrics have emerged as promising candidates for high-strain actuator applications, yet the fundamental link between their nanoscale structure and macroscopic electromechanical performance remains elusive. This study overcomes this challenge by demonstrating that controlled A-site La3+ doping in 0.7(Bi0.95La0.05)FeO3–0.3BaTiO3 (BLF–BT) directly engineers a local structural environment characterized by chemical disorder and localized stress fields. Through local structure analysis and simulations, we reveal that La doping introduces A-site chemical heterogeneity and lattice mismatch, enhancing FeO6 octahedral distortions and local structural fluctuations. This pronounced local disorder suppresses long-range rhombohedral order, fostering a pseudocubic matrix populated by interacting randomly oriented polar nanoregions. These structural modifications create a flattened energy landscape that facilitates nearly isotropic and low-barrier polarization reorientation under an electric field. The resultant cooperative switching of these highly responsive nanodomains, the inherent lattice strain from local distortions, yields substantial unipolar strain of 0.35%, representing a 200% enhancement over undoped BF–BT. This work provides a definitive structural mechanism for giant strain in lead-free relaxors and establishes a design principle for activating large electromechanical responses through targeted local disorder.
{"title":"Engineering Giant Strain in Bismuth Ferrite–Barium Titanate Relaxor Ferroelectrics via A-Site Driven Local Structural Disorder","authors":"Zhanpeng Li, Xiaoming Shi, Xianghong Zhou, Yuxuan Yang, Zhi Tan, Chao Wu, Qihang Tang, Yang Zhang, Haijun Wu, Ting Zheng, Shujun Zhang, Jiagang Wu","doi":"10.1021/acs.chemmater.5c03265","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c03265","url":null,"abstract":"Lead-free bismuth ferrite–barium titanate (BF–BT) relaxor ferroelectrics have emerged as promising candidates for high-strain actuator applications, yet the fundamental link between their nanoscale structure and macroscopic electromechanical performance remains elusive. This study overcomes this challenge by demonstrating that controlled A-site La<sup>3+</sup> doping in 0.7(Bi<sub>0.95</sub>La<sub>0.05</sub>)FeO<sub>3</sub>–0.3BaTiO<sub>3</sub> (BLF–BT) directly engineers a local structural environment characterized by chemical disorder and localized stress fields. Through local structure analysis and simulations, we reveal that La doping introduces A-site chemical heterogeneity and lattice mismatch, enhancing FeO<sub>6</sub> octahedral distortions and local structural fluctuations. This pronounced local disorder suppresses long-range rhombohedral order, fostering a pseudocubic matrix populated by interacting randomly oriented polar nanoregions. These structural modifications create a flattened energy landscape that facilitates nearly isotropic and low-barrier polarization reorientation under an electric field. The resultant cooperative switching of these highly responsive nanodomains, the inherent lattice strain from local distortions, yields substantial unipolar strain of 0.35%, representing a 200% enhancement over undoped BF–BT. This work provides a definitive structural mechanism for giant strain in lead-free relaxors and establishes a design principle for activating large electromechanical responses through targeted local disorder.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"46 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116210","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 : 2026-02-04DOI: 10.1021/acs.chemmater.5c03128
Volkan Kilinc,Linawati Sutrisno,Joel Henzie,Emmanuel Picheau,Yusuke Yamauchi,Katsuhiko Ariga,Jonathan P. Hill
Controlling the large-scale assembly of charged biopolymers is a fundamental challenge in materials chemistry. Here, we report a chemical strategy that uses disulfide-linked single-stranded DNA (ssDNA) dimers as unique building blocks to drive the hierarchical self-assembly of functional DNA microstructures. Formed from short, random-sequence oligomers, these dimers first organize into DNA-salt composite nanobead condensates, which then serve as scaffolds for the assembly of uniform, microrod-shaped DNA condensates called DNA-pod condensates. The key innovation of this work is the material’s unique, cooperative structural transition. Upon thermal stimulation (>60 °C), dsDNA-pod condensates undergo a rapid exfoliation into an expanded ssDNA network, a process driven by significant gains in configurational entropy and the relief of electrostatic repulsion. This establishes an accessible strategy for creating stimuli-responsive DNA materials through a chemistry-driven, sequence-independent pathway. We further demonstrate that these materials act as robust host matrices for encapsulating guest molecules like doxorubicin.
{"title":"Hierarchical Self-Assembly of Disulfide-Linked Single-Stranded DNA into Stimuli-Responsive Pods","authors":"Volkan Kilinc,Linawati Sutrisno,Joel Henzie,Emmanuel Picheau,Yusuke Yamauchi,Katsuhiko Ariga,Jonathan P. Hill","doi":"10.1021/acs.chemmater.5c03128","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c03128","url":null,"abstract":"Controlling the large-scale assembly of charged biopolymers is a fundamental challenge in materials chemistry. Here, we report a chemical strategy that uses disulfide-linked single-stranded DNA (ssDNA) dimers as unique building blocks to drive the hierarchical self-assembly of functional DNA microstructures. Formed from short, random-sequence oligomers, these dimers first organize into DNA-salt composite nanobead condensates, which then serve as scaffolds for the assembly of uniform, microrod-shaped DNA condensates called DNA-pod condensates. The key innovation of this work is the material’s unique, cooperative structural transition. Upon thermal stimulation (>60 °C), dsDNA-pod condensates undergo a rapid exfoliation into an expanded ssDNA network, a process driven by significant gains in configurational entropy and the relief of electrostatic repulsion. This establishes an accessible strategy for creating stimuli-responsive DNA materials through a chemistry-driven, sequence-independent pathway. We further demonstrate that these materials act as robust host matrices for encapsulating guest molecules like doxorubicin.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"215 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111130","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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