Pub Date : 2026-01-27DOI: 10.1021/acs.chemmater.5c02547
Mgcini Keith Phuthi, Pin-Wen Guan, Russell J. Hemley, Venkatasubramanian Viswanathan
Metal hydrides can be tuned to have a diverse range of properties and can find applications in hydrogen storage and superconductivity. Developing methods to control the synthesis of hydrides can open up alternative pathways to design hydride compounds with the desired properties. We introduced the idea of utilizing electrochemistry as an additional tuning knob, and in this work, we study the synthesis of binary metal hydrides using high pressure, electrochemistry, and combined pressure electrochemistry. Using density functional theory calculations, we predict the phase diagrams of selected transition metal hydrides under combined pressure and electrochemical conditions and demonstrate that the approach agrees well with the experimental observations for most phases. We use the phase diagrams to determine trends in the stability of binary metal hydrides of scandium, yttrium, and lanthanum as well as discuss the hydrogen–metal charge transfer at different pressures. Furthermore, we predict a diverse range of vanadium and chromium hydrides that could potentially be synthesized by using pressure electrochemistry. These predictions highlight the value of exploring pressure electrochemistry as a pathway to hydride synthesis.
{"title":"Stability and Structure of Binary Metal Hydrides under Pressure, Electrochemical Potential, and Combined Pressure Electrochemistry","authors":"Mgcini Keith Phuthi, Pin-Wen Guan, Russell J. Hemley, Venkatasubramanian Viswanathan","doi":"10.1021/acs.chemmater.5c02547","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02547","url":null,"abstract":"Metal hydrides can be tuned to have a diverse range of properties and can find applications in hydrogen storage and superconductivity. Developing methods to control the synthesis of hydrides can open up alternative pathways to design hydride compounds with the desired properties. We introduced the idea of utilizing electrochemistry as an additional tuning knob, and in this work, we study the synthesis of binary metal hydrides using high pressure, electrochemistry, and combined pressure electrochemistry. Using density functional theory calculations, we predict the phase diagrams of selected transition metal hydrides under combined pressure and electrochemical conditions and demonstrate that the approach agrees well with the experimental observations for most phases. We use the phase diagrams to determine trends in the stability of binary metal hydrides of scandium, yttrium, and lanthanum as well as discuss the hydrogen–metal charge transfer at different pressures. Furthermore, we predict a diverse range of vanadium and chromium hydrides that could potentially be synthesized by using pressure electrochemistry. These predictions highlight the value of exploring pressure electrochemistry as a pathway to hydride synthesis.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"58 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146057053","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 : 2026-01-26DOI: 10.1021/acs.chemmater.5c02927
Mengling Liu,Wenxian Zhang,Jinyang Zhao,Lei Hua,Zhongjie Ren,Shouke Yan,Xiaoli Sun
Polyvinylidene fluoride (PVDF) is valued for its chemical stability and ease of processing, but its natural formation of the nonpolar α-phase limits its ability to adopt the electroactive β- and γ-phases required for applications like sensors and energy harvesters. Existing methods to create these functional phases are expensive and inefficient or degrade material performance. To address this, we develop a scalable approach by chemically attaching poly(tert-butyl acrylate) (PtBA) chains to PVDF by using controlled polymerization (ATRP). This modification selectively adjusts the molecular conformation of main chains via interactions on side chains and main chains, lowering energy barriers during phase transitions from the α- to γ-phase and boosting the formation of the γ-phase during thermal processing. The optimized material shows a 16-fold increase in γ-phase nuclei compared to unmodified PVDF. The resulting films achieve a piezoelectric response (d33 = 85 pC/N) that is 7 times stronger than that of pure PVDF, retain high crystallinity, and reduce production costs compared to traditional methods. These insights enable precise control over PVDF’s structure, overcoming long-standing challenges in scaling up electroactive polymers. Our strategy bridges lab-scale innovation with industrial needs, advancing PVDF toward practical uses in flexible electronics, self-powered sensors, and energy-harvesting devices.
{"title":"Grafting-Induced Conformational Engineering Breaks Polarization Barriers in PVDF for High-Temperature Piezoelectrics","authors":"Mengling Liu,Wenxian Zhang,Jinyang Zhao,Lei Hua,Zhongjie Ren,Shouke Yan,Xiaoli Sun","doi":"10.1021/acs.chemmater.5c02927","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02927","url":null,"abstract":"Polyvinylidene fluoride (PVDF) is valued for its chemical stability and ease of processing, but its natural formation of the nonpolar α-phase limits its ability to adopt the electroactive β- and γ-phases required for applications like sensors and energy harvesters. Existing methods to create these functional phases are expensive and inefficient or degrade material performance. To address this, we develop a scalable approach by chemically attaching poly(tert-butyl acrylate) (PtBA) chains to PVDF by using controlled polymerization (ATRP). This modification selectively adjusts the molecular conformation of main chains via interactions on side chains and main chains, lowering energy barriers during phase transitions from the α- to γ-phase and boosting the formation of the γ-phase during thermal processing. The optimized material shows a 16-fold increase in γ-phase nuclei compared to unmodified PVDF. The resulting films achieve a piezoelectric response (d33 = 85 pC/N) that is 7 times stronger than that of pure PVDF, retain high crystallinity, and reduce production costs compared to traditional methods. These insights enable precise control over PVDF’s structure, overcoming long-standing challenges in scaling up electroactive polymers. Our strategy bridges lab-scale innovation with industrial needs, advancing PVDF toward practical uses in flexible electronics, self-powered sensors, and energy-harvesting devices.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"7 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146045000","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 : 2026-01-26DOI: 10.1021/acs.chemmater.5c02867
A. K. M. Ashiquzzaman Shawon,George Yumnam,Hsin Wang,Qiang Zhang,Douglas L. Abernathy,Michael E. Manley,Jose L. Mendoza-Cortes,Raphaël P. Hermann,Alexandra Zevalkink
AMX Zintl compounds with the hexagonal ZrBeSi structure have gained significant attention for their remarkable vacancy tolerance and low thermal conductivity. Their 2D honeycomb sublattice, composed of M–X covalent bonds, is believed to contribute to high anharmonicity and unusual thermal transport properties. In this study, we explore the temperature-dependent polymorphism of YbCuBi as a model system to investigate the relationship between the structure and elastic and thermal transport properties in AMX Zintls. YbCuBi undergoes a structural transition from the “flat” Cu–Bi layers in the ZrBeSi structure to corrugated layers in the LiGaGe structure below 410 K, resulting in a distortion of its centrosymmetric structure. To probe the effects of this crystallographic transition, we employ inelastic neutron scattering and temperature-dependent resonant ultrasound spectroscopy. These experimental findings, coupled with first-principles calculations and thermal conductivity measurements, allow us to elucidate a direct relationship between corrugation of the honeycomb lattice and the observed changes in elastic and thermal transport properties. These insights can be extended to other Zintl phases with similar structure types, providing a platform for the rational design of functional materials with tailored thermal properties.
{"title":"Leveraging Polymorphism in YbCuBi to Map Transport and Elastic Properties","authors":"A. K. M. Ashiquzzaman Shawon,George Yumnam,Hsin Wang,Qiang Zhang,Douglas L. Abernathy,Michael E. Manley,Jose L. Mendoza-Cortes,Raphaël P. Hermann,Alexandra Zevalkink","doi":"10.1021/acs.chemmater.5c02867","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02867","url":null,"abstract":"AMX Zintl compounds with the hexagonal ZrBeSi structure have gained significant attention for their remarkable vacancy tolerance and low thermal conductivity. Their 2D honeycomb sublattice, composed of M–X covalent bonds, is believed to contribute to high anharmonicity and unusual thermal transport properties. In this study, we explore the temperature-dependent polymorphism of YbCuBi as a model system to investigate the relationship between the structure and elastic and thermal transport properties in AMX Zintls. YbCuBi undergoes a structural transition from the “flat” Cu–Bi layers in the ZrBeSi structure to corrugated layers in the LiGaGe structure below 410 K, resulting in a distortion of its centrosymmetric structure. To probe the effects of this crystallographic transition, we employ inelastic neutron scattering and temperature-dependent resonant ultrasound spectroscopy. These experimental findings, coupled with first-principles calculations and thermal conductivity measurements, allow us to elucidate a direct relationship between corrugation of the honeycomb lattice and the observed changes in elastic and thermal transport properties. These insights can be extended to other Zintl phases with similar structure types, providing a platform for the rational design of functional materials with tailored thermal properties.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"49 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146044981","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 : 2026-01-26DOI: 10.1021/acs.chemmater.5c02122
Olga E. Eremina,Emad L. Izake,Cristina Zavaleta,Priyanka Dey,Olga E. Eremina,Emad L. Izake,Cristina Zavaleta,Priyanka Dey,Olga E. Eremina,Emad L. Izake,Cristina Zavaleta,Priyanka Dey
Understanding how small aromatic ligands bind to noble-metal surfaces is critical for engineering plasmonic nanomaterials for sensing, catalysis, and biomedical applications. Here, we systematically investigate how nitrogen heteroatoms─and their positional placement within fused bicyclic molecules (Bm)─govern anchoring, orientation, and functionalization on colloidal gold nanoparticles (AuNPs). Surface-enhanced Raman scattering (SERS) is used as an in situ probe of adsorption motifs, while density functional theory (DFT) calculations quantify adsorption energies, preferred geometries, and chemical enhancement contributions using a Au20 cluster model. The Bm library comprises (i) a non-nitrogen thiolated reference (2-naphthalenethiol, 2-NT), (ii) thiolated nitrogen-containing quinolinethiols (2-QTH and 8-QTH), and (iii) nonthiolated nitrogen-functionalized naphthols (AN, NN, and NNA). Combined theoretical and experimental analyses reveal how molecular architecture controls binding strength, adsorption geometry, colloidal stability, and SERS performance. Three distinct interaction regimes emerge: strong bidentate anchoring for 2-QTH via cooperative Au–S and Au–N coordination (∼2.3 Å), monodentate π-stacking for 2-NT and 8-QTH (∼2.5 Å), and weak physisorption for nonthiols (∼3.2 Å). We further introduce a transferable descriptor, D*χ, linking molecular energetics with surface affinity and functionalization density. Overall, the results demonstrate that nitrogen positioning critically determines molecule–gold interactions and provide quantitative design rules for robust ligand anchoring and stable plasmonic interfaces.
{"title":"Nitrogen Positioning in Bicyclic Aromatic Ligands Governs Binding to Nano-Gold: A Curious Case of Quinolinethiol","authors":"Olga E. Eremina,Emad L. Izake,Cristina Zavaleta,Priyanka Dey,Olga E. Eremina,Emad L. Izake,Cristina Zavaleta,Priyanka Dey,Olga E. Eremina,Emad L. Izake,Cristina Zavaleta,Priyanka Dey","doi":"10.1021/acs.chemmater.5c02122","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02122","url":null,"abstract":"Understanding how small aromatic ligands bind to noble-metal surfaces is critical for engineering plasmonic nanomaterials for sensing, catalysis, and biomedical applications. Here, we systematically investigate how nitrogen heteroatoms─and their positional placement within fused bicyclic molecules (Bm)─govern anchoring, orientation, and functionalization on colloidal gold nanoparticles (AuNPs). Surface-enhanced Raman scattering (SERS) is used as an in situ probe of adsorption motifs, while density functional theory (DFT) calculations quantify adsorption energies, preferred geometries, and chemical enhancement contributions using a Au20 cluster model. The Bm library comprises (i) a non-nitrogen thiolated reference (2-naphthalenethiol, 2-NT), (ii) thiolated nitrogen-containing quinolinethiols (2-QTH and 8-QTH), and (iii) nonthiolated nitrogen-functionalized naphthols (AN, NN, and NNA). Combined theoretical and experimental analyses reveal how molecular architecture controls binding strength, adsorption geometry, colloidal stability, and SERS performance. Three distinct interaction regimes emerge: strong bidentate anchoring for 2-QTH via cooperative Au–S and Au–N coordination (∼2.3 Å), monodentate π-stacking for 2-NT and 8-QTH (∼2.5 Å), and weak physisorption for nonthiols (∼3.2 Å). We further introduce a transferable descriptor, D*χ, linking molecular energetics with surface affinity and functionalization density. Overall, the results demonstrate that nitrogen positioning critically determines molecule–gold interactions and provide quantitative design rules for robust ligand anchoring and stable plasmonic interfaces.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"117 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146044982","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}
Achieving precise and controllable drug release remains a significant challenge for hydrogel dressings. In this study, the hydrogel network was modified with functionalized cyclodextrin to enhance its thermal responsiveness and shrinkage capacity. Additionally, cuttlefish ink nanoparticles were incorporated as a natural photothermal agent to enable precise temperature regulation. As a result, the modified hydrogel exhibited controllable drug release behavior within a temperature range of 36 to 46.5 °C. Under this strategy, a shrinkage ratio of 60.54% and gallic acid release rate of 85.17% were achieved. Furthermore, the hydrogel demonstrated antibacterial performance (>90%), high biocompatibility (cell viability >90%), and significant antioxidant activity. This hydrogel system shows significant potential for application in intelligent drug delivery platforms, infected wound dressings, and combined photothermal therapy.
{"title":"Photothermal-Responsive Supramolecular-Driven Hydrogel for Controlled Drug Release","authors":"Wanqi Li,Qinqin Cui,Xu Fei,Yao Li,Cong Wang,Sheng Cheng,Longquan Xu,Wanqi Li,Qinqin Cui,Xu Fei,Yao Li,Cong Wang,Sheng Cheng,Longquan Xu","doi":"10.1021/acs.chemmater.5c02786","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02786","url":null,"abstract":"Achieving precise and controllable drug release remains a significant challenge for hydrogel dressings. In this study, the hydrogel network was modified with functionalized cyclodextrin to enhance its thermal responsiveness and shrinkage capacity. Additionally, cuttlefish ink nanoparticles were incorporated as a natural photothermal agent to enable precise temperature regulation. As a result, the modified hydrogel exhibited controllable drug release behavior within a temperature range of 36 to 46.5 °C. Under this strategy, a shrinkage ratio of 60.54% and gallic acid release rate of 85.17% were achieved. Furthermore, the hydrogel demonstrated antibacterial performance (>90%), high biocompatibility (cell viability >90%), and significant antioxidant activity. This hydrogel system shows significant potential for application in intelligent drug delivery platforms, infected wound dressings, and combined photothermal therapy.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"44 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146044980","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}
Visible-light-driven N2 reduction into NH4+ emerges as a promising approach for nitrogen fixation. However, the low efficiency of electron–hole separation and the multielectron transfer processes hamper the efficiency of N2 photoreduction. In this work, a potential p–n heterojunction of Ru@Ni-MOF@H–C3N4 was designed by valence control of the Ni2+/3+ node in Ni-MOF to facilitate the separation of photogenerated carriers. Ni-MOFs containing the Ni2+/3+/sulfhydryl ligand as an amphoteric semiconductor and H–C3N4 with a hollow sphere structure as an n-type semiconductor were successfully assembled as a p–n heterojunction, and Ru nanoparticles were introduced into the MOF shell on H–C3N4 as the active sites of N2 reduction. The microstructure was investigated by XAFS to understand the valence state and coordination environment of the p–n heterojunction. The built-in electric field and the Fermi level for the Ru@Ni-MOF@H–C3N4 p–n heterojunction were explored by UPS results. Ru@Ni-MOF@H–C3N4 possesses very high N2 photoreduction activity to target NH4+ (123.2 μmol g–1 h–1) and very high OER activity, indicating that the p–n heterojunction has both N2 reduction and H2O oxidation active sites. This work highlights the construction of MOF-based p–n heterojunctions through valence control of the Ni2+/3+ node and tunes charge separation and electron transmission through the built-in electron field for enhancing the N2 photoreduction performance.
{"title":"Designing Metal–Organic Framework-Based Ru@Ni-MOF@H–C3N4p–n Heterojunction through Valence Control of Metal Ions for Visible-Light Nitrogen Fixation","authors":"Chuanjiao Wang,Banglun Sun,Xiaona Zhao,Changan Hou,Yi Ping,Danhong Wang,Chuanjiao Wang,Banglun Sun,Xiaona Zhao,Changan Hou,Yi Ping,Danhong Wang,Chuanjiao Wang,Banglun Sun,Xiaona Zhao,Changan Hou,Yi Ping,Danhong Wang","doi":"10.1021/acs.chemmater.5c02465","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02465","url":null,"abstract":"Visible-light-driven N2 reduction into NH4+ emerges as a promising approach for nitrogen fixation. However, the low efficiency of electron–hole separation and the multielectron transfer processes hamper the efficiency of N2 photoreduction. In this work, a potential p–n heterojunction of Ru@Ni-MOF@H–C3N4 was designed by valence control of the Ni2+/3+ node in Ni-MOF to facilitate the separation of photogenerated carriers. Ni-MOFs containing the Ni2+/3+/sulfhydryl ligand as an amphoteric semiconductor and H–C3N4 with a hollow sphere structure as an n-type semiconductor were successfully assembled as a p–n heterojunction, and Ru nanoparticles were introduced into the MOF shell on H–C3N4 as the active sites of N2 reduction. The microstructure was investigated by XAFS to understand the valence state and coordination environment of the p–n heterojunction. The built-in electric field and the Fermi level for the Ru@Ni-MOF@H–C3N4 p–n heterojunction were explored by UPS results. Ru@Ni-MOF@H–C3N4 possesses very high N2 photoreduction activity to target NH4+ (123.2 μmol g–1 h–1) and very high OER activity, indicating that the p–n heterojunction has both N2 reduction and H2O oxidation active sites. This work highlights the construction of MOF-based p–n heterojunctions through valence control of the Ni2+/3+ node and tunes charge separation and electron transmission through the built-in electron field for enhancing the N2 photoreduction performance.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"143 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146044999","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 : 2026-01-26DOI: 10.1021/acs.chemmater.5c03125
Yutong Lin, Jiawei Lin, Fangmei Fu, Jingqi Chen, Pan Wang, Lingling Mao
Fluorescence lifetime thermometry is used for noncontact temperature sensing applications. However, conventional materials are limited by low luminescence efficiency and thermal sensitivity. Herein, we synthesized a series of Zn and alkaline earth (Ae) metal based bimetallic halides, Ae(L)6ZnBr4 (Ae = Ca, Sr; L = tetramethyl-urea (TMU) or dimethyl-propylene-urea (DMPU)), exhibiting blue emission upon UV excitation. Based on systematic optical characterizations and theoretical calculations, we revealed that the blue emission originates from the radiative recombination of singlet states of [Ae(L)6]2+ complexes and self-trapped excitons, accompanied by an energy transfer process from [Ae(L)6]2+ to [ZnBr4]2–. Altering the ligand from TMU to DMPU can suppress phonon-assisted nonradiative recombination, resulting in increased enhancement in quantum yields (up to 64.3% for Sr(DMPU)6ZnBr4). The luminescence mechanism involving multiple photophysical processes of these hybrids offers suitable temperature sensitivity for lifetime thermometers. The composite film based on Sr(DMPU)6ZnBr4 achieves a relative sensitivity of 9.66% K–1, along with excellent stability during repeated heating–cooling cycles. This work provides a viable strategy for developing high-efficiency blue-light emitters and underscores the potential of Zn-based bimetallic halides for high-sensitivity remote thermometry.
荧光寿命测温法用于非接触式温度传感应用。然而，传统材料受限于低发光效率和热敏性。本文合成了一系列Zn和碱土（Ae）金属基双金属卤化物Ae(L)6ZnBr4 （Ae = Ca, Sr; L =四甲基脲（TMU）或二甲基丙烯脲（DMPU）），在紫外激发下表现出蓝色发射。基于系统的光学表征和理论计算，我们发现蓝色辐射来自于[Ae(L)6]2+配合物和自捕获激子的单重态辐射复合，伴随着从[Ae(L)6]2+到[ZnBr4]2 -的能量传递过程。将配体从TMU改变为DMPU可以抑制声子辅助的非辐射重组，导致量子产率的提高（Sr(DMPU)6ZnBr4高达64.3%）。这些杂化体的发光机制涉及多个光物理过程，为终身温度计提供了合适的温度灵敏度。基于Sr(DMPU)6ZnBr4的复合薄膜的相对灵敏度为9.66% K-1，并且在反复加热-冷却循环中具有优异的稳定性。这项工作为开发高效蓝光发射器提供了可行的策略，并强调了锌基双金属卤化物用于高灵敏度远程测温的潜力。
{"title":"Bright Blue-Emitting Hybrid Bimetallic Halides: Enabling Highly Sensitive Remote Thermometry via Swift Luminescent Response","authors":"Yutong Lin, Jiawei Lin, Fangmei Fu, Jingqi Chen, Pan Wang, Lingling Mao","doi":"10.1021/acs.chemmater.5c03125","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c03125","url":null,"abstract":"Fluorescence lifetime thermometry is used for noncontact temperature sensing applications. However, conventional materials are limited by low luminescence efficiency and thermal sensitivity. Herein, we synthesized a series of Zn and alkaline earth (<i>Ae</i>) metal based bimetallic halides, <i>Ae</i>(<i>L</i>)<sub>6</sub>ZnBr<sub>4</sub> (<i>Ae</i> = Ca, Sr; <i>L</i> = tetramethyl-urea (TMU) or dimethyl-propylene-urea (DMPU)), exhibiting blue emission upon UV excitation. Based on systematic optical characterizations and theoretical calculations, we revealed that the blue emission originates from the radiative recombination of singlet states of [<i>Ae</i>(<i>L</i>)<sub>6</sub>]<sup>2+</sup> complexes and self-trapped excitons, accompanied by an energy transfer process from [<i>Ae</i>(<i>L</i>)<sub>6</sub>]<sup>2+</sup> to [ZnBr<sub>4</sub>]<sup>2–</sup>. Altering the ligand from TMU to DMPU can suppress phonon-assisted nonradiative recombination, resulting in increased enhancement in quantum yields (up to 64.3% for Sr(DMPU)<sub>6</sub>ZnBr<sub>4</sub>). The luminescence mechanism involving multiple photophysical processes of these hybrids offers suitable temperature sensitivity for lifetime thermometers. The composite film based on Sr(DMPU)<sub>6</sub>ZnBr<sub>4</sub> achieves a relative sensitivity of 9.66% K<sup>–1</sup>, along with excellent stability during repeated heating–cooling cycles. This work provides a viable strategy for developing high-efficiency blue-light emitters and underscores the potential of Zn-based bimetallic halides for high-sensitivity remote thermometry.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"28 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146048702","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 : 2026-01-26DOI: 10.1021/acs.chemmater.5c02330
Tori Cox,Volodymyr Gvozdetskyi,Zeina Miari,Kaden Osborn,Arka Sarkar,Philip Yox,Balaranjan Selvaratnam,Shiya Chen,Yang Sun,Arthur Mar,Julia V. Zaikina,Tori Cox,Volodymyr Gvozdetskyi,Zeina Miari,Kaden Osborn,Arka Sarkar,Philip Yox,Balaranjan Selvaratnam,Shiya Chen,Yang Sun,Arthur Mar,Julia V. Zaikina
Antimonides are attractive candidates for thermoelectric materials, but like other intermetallic compounds, their compositions and structures are not easy to predict, and once predicted, they may be difficult to synthesize. Three new ternary antimonides in the K–Cd–Sb system were discovered through a multifaceted approach that involves (i) use of a machine learning algorithm to pinpoint the compositional regions with low formation energy, (ii) rapid experimental compositional screening aided by the hydride route, and (iii) determination of optimal synthesis temperature from in situ high-temperature powder X-ray diffraction data. Various experimental compositions were screened efficiently through the use of KH instead of elemental K as the starting material, which allows greater compositional control and faster reactions through more rapid diffusion. Furthermore, a simple machine learning model was developed to classify ternary K-containing intermetallics according to denser network vs more open (clathrate, layer, and channel) structures and to identify compositional regions in which phases are likely to adopt open structures. This synergistic approach results in the synthesis of compositionally similar but structurally distinct antimonides: monoclinic K2Cd3Sb4 with a layered structure, tetragonal K3Cd11Sb8 with K+ filling channels in the [CdSb] framework, and hexagonal clathrate-like K3Cd17Sb14 with K+ in the center of 20-vertex polyhedral [CdSb] cages. The compositions of the three K–Cd–Sb compounds are nearly charge-balanced, and their chemical bonding can be rationalized by the Zintl concept. Low-temperature transport property measurements reveal that the electrical resistivity and thermopower change over several orders of magnitude from a semiconductor for hexagonal K3Cd17Sb14 to a heavily doped semiconductor for monoclinic K2Cd3Sb4. All three compounds exhibit low thermal conductivity, attributed to the disordered structures made of heavy Cd and Sb atoms. The strategy presented here can be expanded to other systems for the targeted discovery of new inorganic solids.
{"title":"Combining Compositional Screening via Hydride Route, Machine Learning, and In Situ Diffraction to Discover Antimonides in the K–Cd–Sb System","authors":"Tori Cox,Volodymyr Gvozdetskyi,Zeina Miari,Kaden Osborn,Arka Sarkar,Philip Yox,Balaranjan Selvaratnam,Shiya Chen,Yang Sun,Arthur Mar,Julia V. Zaikina,Tori Cox,Volodymyr Gvozdetskyi,Zeina Miari,Kaden Osborn,Arka Sarkar,Philip Yox,Balaranjan Selvaratnam,Shiya Chen,Yang Sun,Arthur Mar,Julia V. Zaikina","doi":"10.1021/acs.chemmater.5c02330","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02330","url":null,"abstract":"Antimonides are attractive candidates for thermoelectric materials, but like other intermetallic compounds, their compositions and structures are not easy to predict, and once predicted, they may be difficult to synthesize. Three new ternary antimonides in the K–Cd–Sb system were discovered through a multifaceted approach that involves (i) use of a machine learning algorithm to pinpoint the compositional regions with low formation energy, (ii) rapid experimental compositional screening aided by the hydride route, and (iii) determination of optimal synthesis temperature from in situ high-temperature powder X-ray diffraction data. Various experimental compositions were screened efficiently through the use of KH instead of elemental K as the starting material, which allows greater compositional control and faster reactions through more rapid diffusion. Furthermore, a simple machine learning model was developed to classify ternary K-containing intermetallics according to denser network vs more open (clathrate, layer, and channel) structures and to identify compositional regions in which phases are likely to adopt open structures. This synergistic approach results in the synthesis of compositionally similar but structurally distinct antimonides: monoclinic K2Cd3Sb4 with a layered structure, tetragonal K3Cd11Sb8 with K+ filling channels in the [CdSb] framework, and hexagonal clathrate-like K3Cd17Sb14 with K+ in the center of 20-vertex polyhedral [CdSb] cages. The compositions of the three K–Cd–Sb compounds are nearly charge-balanced, and their chemical bonding can be rationalized by the Zintl concept. Low-temperature transport property measurements reveal that the electrical resistivity and thermopower change over several orders of magnitude from a semiconductor for hexagonal K3Cd17Sb14 to a heavily doped semiconductor for monoclinic K2Cd3Sb4. All three compounds exhibit low thermal conductivity, attributed to the disordered structures made of heavy Cd and Sb atoms. The strategy presented here can be expanded to other systems for the targeted discovery of new inorganic solids.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"217 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146044979","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 : 2026-01-24DOI: 10.1021/acs.chemmater.5c02228
Kosaku Ohishi, Satoshi Ogawa, Hisanori Yamane, Saburo Hosokawa, Zi Lang Goo, Kunihisa Sugimoto, Miwa Saito, Teruki Motohashi
Here, we report the synthesis and characterization of melilite-type A2MnC2O7 (A = Sr, Ba; C = Si, Ge) and the discovery of its unconventional oxygen storage and release properties. Unlike conventional Mn-containing oxygen storage materials driven by the Mn2+/Mn3+ redox couple, Ba2MnGe2O7+δ (BMG) does not require highly reducing atmospheres for oxygen release and exhibits reversible oxygen storage/release under oxygen-rich conditions at moderate temperatures (200–500 °C). Comprehensive compositional and structural analyses utilizing X-ray absorption spectroscopy, synchrotron in situ powder X-ray diffraction, single-crystal X-ray diffraction, and powder neutron diffraction revealed that the oxygen storage/release processes involve changes in the local coordination environment. Specifically, MnO4 tetrahedra in the reduced phase change into MnO5 trigonal bipyramids in the oxidized phase, accompanied by a distinct transformation from the fundamental melilite-type structure of Ba2MnGe2O7 (tetragonal, space group P4̅21m) to a 5a × 5a × 1c superstructure of Ba2MnGe2O7.455(4) (tetragonal, P4̅). BMG exhibits a maximum oxygen storage capacity of δ ≈ 0.45 and, notably, develops a distinctive blue color upon oxygen storage. This characteristic response suggests promising potential for various oxygen-related applications, such as oxygen sensors and oxygen-sensitive inorganic pigments.
本文报道了melilite型A2MnC2O7 （A = Sr, Ba; C = Si, Ge）的合成和表征，并发现了其非常规的氧储存和释放特性。与传统的由Mn2+/Mn3+氧化还原对驱动的含锰储氧材料不同，Ba2MnGe2O7+δ (BMG)不需要高还原气氛来释放氧，并且在中等温度（200-500℃）的富氧条件下表现出可逆的氧储存/释放。利用x射线吸收光谱、同步加速器原位粉末x射线衍射、单晶x射线衍射和粉末中子衍射等手段进行的综合成分和结构分析表明，氧的储存/释放过程涉及局部配位环境的变化。具体来说，还原相中的MnO4四面体在氧化相中转变为MnO5三角双棱体，并伴随着Ba2MnGe2O7的基本千晶石型结构（四方，空间群P4′21m）向Ba2MnGe2O7.455(4)的上层结构（四方，P4′）的明显转变。BMG的最大储氧能力δ≈0.45，在储氧过程中呈现出独特的蓝色。这种特性响应表明了各种氧相关应用的潜力，例如氧传感器和氧敏感无机颜料。
{"title":"Unconventional Oxygen Storage/Release Properties of Melilite-Type Ba2MnGe2O7+δ Associated with Complex Structural Transformation","authors":"Kosaku Ohishi, Satoshi Ogawa, Hisanori Yamane, Saburo Hosokawa, Zi Lang Goo, Kunihisa Sugimoto, Miwa Saito, Teruki Motohashi","doi":"10.1021/acs.chemmater.5c02228","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02228","url":null,"abstract":"Here, we report the synthesis and characterization of melilite-type <i>A</i><sub>2</sub>Mn<i>C</i><sub>2</sub>O<sub>7</sub> (<i>A</i> = Sr, Ba; <i>C</i> = Si, Ge) and the discovery of its unconventional oxygen storage and release properties. Unlike conventional Mn-containing oxygen storage materials driven by the Mn<sup>2+</sup>/Mn<sup>3+</sup> redox couple, Ba<sub>2</sub>MnGe<sub>2</sub>O<sub>7+δ</sub> (BMG) does not require highly reducing atmospheres for oxygen release and exhibits reversible oxygen storage/release under oxygen-rich conditions at moderate temperatures (200–500 °C). Comprehensive compositional and structural analyses utilizing X-ray absorption spectroscopy, synchrotron in situ powder X-ray diffraction, single-crystal X-ray diffraction, and powder neutron diffraction revealed that the oxygen storage/release processes involve changes in the local coordination environment. Specifically, MnO<sub>4</sub> tetrahedra in the reduced phase change into MnO<sub>5</sub> trigonal bipyramids in the oxidized phase, accompanied by a distinct transformation from the fundamental melilite-type structure of Ba<sub>2</sub>MnGe<sub>2</sub>O<sub>7</sub> (tetragonal, space group <i>P</i>4̅2<sub>1</sub><i>m</i>) to a 5<i>a</i> × 5<i>a</i> × 1<i>c</i> superstructure of Ba<sub>2</sub>MnGe<sub>2</sub>O<sub>7.455(4)</sub> (tetragonal, <i>P</i>4̅). BMG exhibits a maximum oxygen storage capacity of δ ≈ 0.45 and, notably, develops a distinctive blue color upon oxygen storage. This characteristic response suggests promising potential for various oxygen-related applications, such as oxygen sensors and oxygen-sensitive inorganic pigments.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"214 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146034102","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 : 2026-01-23DOI: 10.1021/acs.chemmater.5c02430
Elana J. Cope, Alicia Lancaster, Zöe M. Johnson, Matthias T. Agne
Thermal management in solid-state technologies such as batteries, microprocessors, thermal barrier coatings, superconductors, fuel cells, and more depends on understanding phonons, the quantum vibrations of atoms described by lattice dynamics. Anharmonicity, the nonlinear dependence of interatomic forces on displacement, governs key properties like thermal conductivity and thermal expansion. Mode Grüneisen parameters quantify this anharmonicity by assessing phonon frequency shifts with lattice deformations, linking microscopic vibrations to macroscopic thermal behavior. Previously, Grüneisen parameters have been correlated to atomic coordination environments, but the fundamental roles of atomic structure and crystal chemistry in phonon anharmonicity have yet to be fully discerned. Herein, an analysis of the vibrational structures and mode Grüneisen parameters of nine alkali halide rock salt structures demonstrates the importance of phonon eigenvectors in anharmonic analysis. A mode-matching algorithm is developed that allows for direct comparison of their anharmonicities, where materials with similar mode shapes are found to have similar mode anharmonicities. This suggests that eigenvector alignment relative to structural motifs plays a central role in determining the distribution and magnitude of phonon anharmonicity. Thus, materials design will greatly benefit from a combined consideration of atomic structure and bonding in tuning anharmonic properties of solids.
{"title":"Structural Origins of Phonon Anharmonicity in Alkali Halide Rock Salt Structures","authors":"Elana J. Cope, Alicia Lancaster, Zöe M. Johnson, Matthias T. Agne","doi":"10.1021/acs.chemmater.5c02430","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c02430","url":null,"abstract":"Thermal management in solid-state technologies such as batteries, microprocessors, thermal barrier coatings, superconductors, fuel cells, and more depends on understanding phonons, the quantum vibrations of atoms described by lattice dynamics. Anharmonicity, the nonlinear dependence of interatomic forces on displacement, governs key properties like thermal conductivity and thermal expansion. Mode Grüneisen parameters quantify this anharmonicity by assessing phonon frequency shifts with lattice deformations, linking microscopic vibrations to macroscopic thermal behavior. Previously, Grüneisen parameters have been correlated to atomic coordination environments, but the fundamental roles of atomic structure and crystal chemistry in phonon anharmonicity have yet to be fully discerned. Herein, an analysis of the vibrational structures and mode Grüneisen parameters of nine alkali halide rock salt structures demonstrates the importance of phonon eigenvectors in anharmonic analysis. A mode-matching algorithm is developed that allows for direct comparison of their anharmonicities, where materials with similar mode shapes are found to have similar mode anharmonicities. This suggests that eigenvector alignment relative to structural motifs plays a central role in determining the distribution and magnitude of phonon anharmonicity. Thus, materials design will greatly benefit from a combined consideration of atomic structure and bonding in tuning anharmonic properties of solids.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"2 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146022083","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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