Lixiang Wang, Yu Zhang, Xiao Liu, Xin Wen, Xusheng Wang, Lang Pei, Shicheng Yan, Zhigang Zou
Photothermal catalytic CO 2 reduction offers a promising route for full‐spectrum carbon recycling. While high‐entropy oxides (HEO) show potential as photothermal catalysts, their efficiency is often limited by uncoordinated kinetics in CO 2 activation, active proton formation via H 2 O dissociation, and proton migration. Herein, a grain boundaries (GB) engineering strategy is reported to tailor HEO, constructing adjacent asymmetric redox dual sites that simultaneously promote CO 2 activation and proton feeding. Using (CoCrFeMnNi) 3 O 4 HEO nanosheets, it is found that a high density of GB induces electronic redistribution and promotes asymmetric oxygen vacancies (Vo) formation, creating abundant polarized Fe−Vo−Cr−O motifs. Specifically, electron‐deficient Fe centers function as Lewis acid sites, accelerating H 2 O activation to yield active proton, while adjacent photogenerated electron‐rich Cr─O clusters primarily adsorb CO 2 via a bridging mode. Furthermore, the photothermal effect of (CoCrFeMnNi) 3 O 4 HEO catalysts leads to a substantial elevation of the catalyst surface temperature, reaching ≈198 °C, synergistically optimizes the thermodynamics and kinetics of the proton‐coupled electron transfer process. Consequently, the GB‐rich HEO catalysts achieve impressive CH 4 and CO yield rates of 677.7 and 957.2 µmol g −1 h −1 , respectively, with a notable apparent quantum yield of 0.38% at 420 nm, highlighting their significant advantage in CO 2 photoreduction.
{"title":"Tailoring High‐Entropy Oxide via Grain Boundary Engineering to Establish Adjacent Asymmetric Redox Sites for Full‐Spectrum Photothermal Catalytic CO 2 Reduction","authors":"Lixiang Wang, Yu Zhang, Xiao Liu, Xin Wen, Xusheng Wang, Lang Pei, Shicheng Yan, Zhigang Zou","doi":"10.1002/smll.202513596","DOIUrl":"https://doi.org/10.1002/smll.202513596","url":null,"abstract":"Photothermal catalytic CO <jats:sub>2</jats:sub> reduction offers a promising route for full‐spectrum carbon recycling. While high‐entropy oxides (HEO) show potential as photothermal catalysts, their efficiency is often limited by uncoordinated kinetics in CO <jats:sub>2</jats:sub> activation, active proton formation via H <jats:sub>2</jats:sub> O dissociation, and proton migration. Herein, a grain boundaries (GB) engineering strategy is reported to tailor HEO, constructing adjacent asymmetric redox dual sites that simultaneously promote CO <jats:sub>2</jats:sub> activation and proton feeding. Using (CoCrFeMnNi) <jats:sub>3</jats:sub> O <jats:sub>4</jats:sub> HEO nanosheets, it is found that a high density of GB induces electronic redistribution and promotes asymmetric oxygen vacancies (Vo) formation, creating abundant polarized Fe−Vo−Cr−O motifs. Specifically, electron‐deficient Fe centers function as Lewis acid sites, accelerating H <jats:sub>2</jats:sub> O activation to yield active proton, while adjacent photogenerated electron‐rich Cr─O clusters primarily adsorb CO <jats:sub>2</jats:sub> via a bridging mode. Furthermore, the photothermal effect of (CoCrFeMnNi) <jats:sub>3</jats:sub> O <jats:sub>4</jats:sub> HEO catalysts leads to a substantial elevation of the catalyst surface temperature, reaching ≈198 °C, synergistically optimizes the thermodynamics and kinetics of the proton‐coupled electron transfer process. Consequently, the GB‐rich HEO catalysts achieve impressive CH <jats:sub>4</jats:sub> and CO yield rates of 677.7 and 957.2 µmol g <jats:sup>−1</jats:sup> h <jats:sup>−1</jats:sup> , respectively, with a notable apparent quantum yield of 0.38% at 420 nm, highlighting their significant advantage in CO <jats:sub>2</jats:sub> photoreduction.","PeriodicalId":228,"journal":{"name":"Small","volume":"115 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145732021","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}
Ming‐Di Gao, Chao‐Yang Guan, Jia‐Yao Wang, Jin‐Ying Qi, Nan‐Nan Deng
Soft materials capable of responding to diverse environmental stimuli are fundamental to advancing soft robotics and intelligent biomedical devices, enabling adaptive, life‐like functions. Here, multimodal photothermal adaptability is reported in azobenzene‐conjugated DNA condensates assembled via liquid‐liquid phase separation (LLPS). These coacervates exhibit a striking temperature‐dependent inversion of their photo‐response: at elevated temperatures, the liquid‐like droplets deform under visible light and dissolve under ultraviolet (UV) light, whereas at lower temperatures, the gel‐like condensates are reshaped by UV light while remaining inert to visible light. This unique bidirectional control is attributed to the synergy of confined azobenzene photochemistry within DNA duplexes and a pronounced isomer‐dependent shift in the system's glass transition and melting temperatures. This platform of multi‐responsive photofluids opens new avenues for applications demanding exquisite spatiotemporal control.
{"title":"Thermally Switchable Photoactivity in Azobenzene‐Functionalized DNA Condensates","authors":"Ming‐Di Gao, Chao‐Yang Guan, Jia‐Yao Wang, Jin‐Ying Qi, Nan‐Nan Deng","doi":"10.1002/adma.202518318","DOIUrl":"https://doi.org/10.1002/adma.202518318","url":null,"abstract":"Soft materials capable of responding to diverse environmental stimuli are fundamental to advancing soft robotics and intelligent biomedical devices, enabling adaptive, life‐like functions. Here, multimodal photothermal adaptability is reported in azobenzene‐conjugated DNA condensates assembled via liquid‐liquid phase separation (LLPS). These coacervates exhibit a striking temperature‐dependent inversion of their photo‐response: at elevated temperatures, the liquid‐like droplets deform under visible light and dissolve under ultraviolet (UV) light, whereas at lower temperatures, the gel‐like condensates are reshaped by UV light while remaining inert to visible light. This unique bidirectional control is attributed to the synergy of confined azobenzene photochemistry within DNA duplexes and a pronounced isomer‐dependent shift in the system's glass transition and melting temperatures. This platform of multi‐responsive photofluids opens new avenues for applications demanding exquisite spatiotemporal control.","PeriodicalId":114,"journal":{"name":"Advanced Materials","volume":"10 1","pages":""},"PeriodicalIF":29.4,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145732036","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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 : 2025-12-13DOI: 10.1016/j.apsusc.2025.165575
Xiaoye Fan, Haiou Liang, Xingwei Sun, Man Zhang, Tong Xu, Jie Bai
{"title":"In-situ hydrothermal fabrication of Bi25FeO40/BiFeO3 heterojunction with trinary synergy of piezo-photocatalysis and peroxymonosulfate activation for efficient tetracycline degradation","authors":"Xiaoye Fan, Haiou Liang, Xingwei Sun, Man Zhang, Tong Xu, Jie Bai","doi":"10.1016/j.apsusc.2025.165575","DOIUrl":"https://doi.org/10.1016/j.apsusc.2025.165575","url":null,"abstract":"","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"165 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145732264","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 recent synthesis of penta‐PdTe 2 sheet highlights the growing interest in pentagonal topologies for developing new 2D materials. Distinct from previously synthesized 2D pentagonal materials, penta‐PdTe 2 possesses the heaviest elemental composition to date, rendering its phonon transport properties particularly intriguing. In this study, the universal machine‐learning potential, NEP89, is fine‐tuned using high‐accuracy first‐principles data spanning monolayer, bilayer, and twisted configurations of penta‐PdTe 2 and achieving an energy prediction error within 2.3 meV atom −1 . Leveraging the homogeneous non‐equilibrium molecular dynamics simulations with the fine‐tuned machine‐learning potential and Wigner transport theory, the phonon transport behavior and lattice thermal conductivity is systematically investigated. These results reveal that interlayer stacking reduces the bilayer thermal conductivity to 28.00% of the monolayer value, while interlayer twisting induces a further reduction to 76.19%, leading to an ultralow thermal conductivity of (0.30 ± 0.059) W m −1 K −1 . These findings demonstrate that the interplay of pentagonal topology, strategic elemental composition, and twist engineering provides an effective route for tuning phonon transport in 2D materials.
{"title":"Twisting‐Induced Phonon Localization and Ultralow Thermal Conductivity in Penta‐PdTe 2 Bilayer Revealed by a Universal Machine‐Learning Potential","authors":"Chenxin Zhang, Qian Wang, Puru Jena","doi":"10.1002/smll.202509794","DOIUrl":"https://doi.org/10.1002/smll.202509794","url":null,"abstract":"The recent synthesis of penta‐PdTe <jats:sub>2</jats:sub> sheet highlights the growing interest in pentagonal topologies for developing new 2D materials. Distinct from previously synthesized 2D pentagonal materials, penta‐PdTe <jats:sub>2</jats:sub> possesses the heaviest elemental composition to date, rendering its phonon transport properties particularly intriguing. In this study, the universal machine‐learning potential, NEP89, is fine‐tuned using high‐accuracy first‐principles data spanning monolayer, bilayer, and twisted configurations of penta‐PdTe <jats:sub>2</jats:sub> and achieving an energy prediction error within 2.3 meV atom <jats:sup>−1</jats:sup> . Leveraging the homogeneous non‐equilibrium molecular dynamics simulations with the fine‐tuned machine‐learning potential and Wigner transport theory, the phonon transport behavior and lattice thermal conductivity is systematically investigated. These results reveal that interlayer stacking reduces the bilayer thermal conductivity to 28.00% of the monolayer value, while interlayer twisting induces a further reduction to 76.19%, leading to an ultralow thermal conductivity of (0.30 ± 0.059) W m <jats:sup>−1</jats:sup> K <jats:sup>−1</jats:sup> . These findings demonstrate that the interplay of pentagonal topology, strategic elemental composition, and twist engineering provides an effective route for tuning phonon transport in 2D materials.","PeriodicalId":228,"journal":{"name":"Small","volume":"15 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145731571","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 spatial arrangement between metal and acid sites critically influences the hydroisomerization efficiency of metal/zeolite catalysts in n ‐alkane conversion. Nevertheless, achieving precise control on metal‐acid intimacy remains a significant challenge at the nanoscale. Herein, Pt nanoparticles are strategically tailored on TiO 2 ‐modified ZSM‐5 carriers via atomic layer deposition, leveraging the TiO 2 spacer thickness as a tunable parameter to modulate interfacial distances. In the hydroisomerization of n ‐hexane, the catalytic performance of the Pt‐Ti/ZSM‐5 with different TiO 2 thickness displayed a volcano‐shaped trend with respect to the metal‐acid distances, peaking at 67.5% iso ‐C6 yield under optimized proximity. This enhanced performance arose from the metal‐acid distance‐mediated diffusion confinement, resulting in the kinetically favorable reaction pathways. The established structure‐property relationship provides a blueprint for rationally designing spatially optimized metal/zeolite catalysts, while advancing the fundamental understanding of bifunctional catalysis.
{"title":"Tailoring the Proximity of Metal‐Acid in Metal/zeolite Bifunctional Catalysts for Enhanced n ‐Hexane Hydroisomerization","authors":"Junjie Li, Yu Wang, Nan Zhang, Jing Ai, Haoshang Wang, Zhizheng Sheng, Jian Zhou, Chuang Liu, Chuanming Wang, Shengli Zhao, Tiezhu Zhang, Fanshun Lin, Zhendong Wang, Yongfeng Hu, Weimin Yang","doi":"10.1002/smll.202509411","DOIUrl":"https://doi.org/10.1002/smll.202509411","url":null,"abstract":"The spatial arrangement between metal and acid sites critically influences the hydroisomerization efficiency of metal/zeolite catalysts in <jats:italic>n</jats:italic> ‐alkane conversion. Nevertheless, achieving precise control on metal‐acid intimacy remains a significant challenge at the nanoscale. Herein, Pt nanoparticles are strategically tailored on TiO <jats:sub>2</jats:sub> ‐modified ZSM‐5 carriers via atomic layer deposition, leveraging the TiO <jats:sub>2</jats:sub> spacer thickness as a tunable parameter to modulate interfacial distances. In the hydroisomerization of <jats:italic>n</jats:italic> ‐hexane, the catalytic performance of the Pt‐Ti/ZSM‐5 with different TiO <jats:sub>2</jats:sub> thickness displayed a volcano‐shaped trend with respect to the metal‐acid distances, peaking at 67.5% <jats:italic>iso</jats:italic> ‐C6 yield under optimized proximity. This enhanced performance arose from the metal‐acid distance‐mediated diffusion confinement, resulting in the kinetically favorable reaction pathways. The established structure‐property relationship provides a blueprint for rationally designing spatially optimized metal/zeolite catalysts, while advancing the fundamental understanding of bifunctional catalysis.","PeriodicalId":228,"journal":{"name":"Small","volume":"9 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145731573","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}
Guangshuai Zhang, Rui Zhang, Ziang Zeng, Beiwen Liu, Yongzhao Hou, Bo Zhong, Long Xia, Guangwu Wen, Dong Wang, Xiaoxiao Huang
High‐entropy oxides (HEOs) hold great potential as electromagnetic absorption (EMA) materials due to their fascinating “cocktail” effect. However, its intrinsic poor dielectric loss hinders EMA capability, while the ingredient design can facilitate dielectric loss regulation, which is critically lacking. Herein, an electronic delocalization engineering that is motivated by metal elements modulation, is implemented on 2D spinel‐type HEOs, which enhances the dielectric loss. In the HEOs with coexisting Cu and Mn (CuMn‐HEOs), the electronic delocalization triggers the restructuring of transition metal valence states and generates abundant oxygen vacancies, which effectively adjust the dielectric loss. Due to the electronic delocalization and unique nanosheet structure, the CuMn‐HEOs exhibit markedly superior absorption performance to other HEOs without Cu and Mn coexisting. Among them, the (CrMnFeNiCu) 3 O 4 achieves a remarkable minimum reflection loss (RL min ) of −50.7 dB (1.94 mm) and a maximum effective absorption bandwidth (EAB max ) of 4.7 GHz. Moreover, through radar scattering cross‐section simulation and assembling HEOs with polyvinyl alcohol into a soft membrane, the practical application potential of CuMn‐HEOs has been proven. This work demonstrates the great potential of electronic delocalization engineering on improving the intrinsic electromagnetic loss capability of metal oxides and paves new insights for developing advanced EMA materials.
{"title":"Electron Delocalization Engineering on 2D High‐Entropy Metal Oxides for Boosting Electromagnetic Wave Absorption","authors":"Guangshuai Zhang, Rui Zhang, Ziang Zeng, Beiwen Liu, Yongzhao Hou, Bo Zhong, Long Xia, Guangwu Wen, Dong Wang, Xiaoxiao Huang","doi":"10.1002/adfm.202527135","DOIUrl":"https://doi.org/10.1002/adfm.202527135","url":null,"abstract":"High‐entropy oxides (HEOs) hold great potential as electromagnetic absorption (EMA) materials due to their fascinating “cocktail” effect. However, its intrinsic poor dielectric loss hinders EMA capability, while the ingredient design can facilitate dielectric loss regulation, which is critically lacking. Herein, an electronic delocalization engineering that is motivated by metal elements modulation, is implemented on 2D spinel‐type HEOs, which enhances the dielectric loss. In the HEOs with coexisting Cu and Mn (CuMn‐HEOs), the electronic delocalization triggers the restructuring of transition metal valence states and generates abundant oxygen vacancies, which effectively adjust the dielectric loss. Due to the electronic delocalization and unique nanosheet structure, the CuMn‐HEOs exhibit markedly superior absorption performance to other HEOs without Cu and Mn coexisting. Among them, the (CrMnFeNiCu) <jats:sub>3</jats:sub> O <jats:sub>4</jats:sub> achieves a remarkable minimum reflection loss (RL <jats:sub>min</jats:sub> ) of −50.7 dB (1.94 mm) and a maximum effective absorption bandwidth (EAB <jats:sub>max</jats:sub> ) of 4.7 GHz. Moreover, through radar scattering cross‐section simulation and assembling HEOs with polyvinyl alcohol into a soft membrane, the practical application potential of CuMn‐HEOs has been proven. This work demonstrates the great potential of electronic delocalization engineering on improving the intrinsic electromagnetic loss capability of metal oxides and paves new insights for developing advanced EMA materials.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"146 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145731609","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Leveraging the property of moisture‐sensitive foods that generate freely mobile ions during hygroscopic deliquescence, an edible electronic device is proposed in which ion migration enables both self‐powering and antimicrobial preservation. When applied as a fruit coating, this edible electronic device generates directed mobile ions through moisture absorption, exhibiting a peak power density of 0.45 mW cm −3 and enabling direct energy supply for environmental sensors. Simultaneously, the numerous migrating ions interact electrostatically with the negatively charged bacterial membrane, disrupting the charge balance of the membrane, thereby maintaining effective antimicrobial preservation. This self‐powered, fully edible, water‐soluble coating extends the shelf life of fruit by 2.5 to 3.4 times, enabling the development of an intelligent food logistics system for fruit preservation and real‐time monitoring. Furthermore, only 1.5 g of low‐cost food‐based materials, when assembled into an edible circuit, can output up to 81.5 V of direct current or a peak current of 6.1 mA in air. This self‐powered edible electronic concept offers a completely green solution to energy challenges in fields such as food safety monitoring and ingestible medical devices.
利用水分敏感食品在吸湿潮解过程中产生自由移动离子的特性，提出了一种可食用的电子设备，其中离子迁移可以实现自供电和抗菌保存。当应用于水果涂层时，这种可食用电子设备通过吸湿产生定向移动离子，显示出0.45 mW cm - 3的峰值功率密度，并为环境传感器提供直接能量。同时，大量的迁移离子与带负电荷的细菌膜发生静电相互作用，破坏膜的电荷平衡，从而保持有效的抗菌保存。这种自供电、完全可食用的水溶性涂层可将水果的保质期延长2.5至3.4倍，从而开发出用于水果保存和实时监控的智能食品物流系统。此外，只需1.5克低成本的食品基材料，当组装成可食用电路时，就可以在空气中输出高达81.5 V的直流电或6.1 mA的峰值电流。这种自供电的可食用电子概念为食品安全监测和可食用医疗设备等领域的能源挑战提供了完全绿色的解决方案。
{"title":"Edible Electronics for Energy Harvesting and Antibacterial Preservation via Moisture‐Induced Ion Migration","authors":"Yunhao Hu, Xianrong Zeng, Weifeng Yang, Wei Wei, Yuji Ma, Bo Wu, Kerui Li, Yaogang Li, Qinghong Zhang, Ru Xiao, Chengyi Hou, Minwei Zhang, Hongzhi Wang, Hui Wang","doi":"10.1002/adfm.202528942","DOIUrl":"https://doi.org/10.1002/adfm.202528942","url":null,"abstract":"Leveraging the property of moisture‐sensitive foods that generate freely mobile ions during hygroscopic deliquescence, an edible electronic device is proposed in which ion migration enables both self‐powering and antimicrobial preservation. When applied as a fruit coating, this edible electronic device generates directed mobile ions through moisture absorption, exhibiting a peak power density of 0.45 mW cm <jats:sup>−3</jats:sup> and enabling direct energy supply for environmental sensors. Simultaneously, the numerous migrating ions interact electrostatically with the negatively charged bacterial membrane, disrupting the charge balance of the membrane, thereby maintaining effective antimicrobial preservation. This self‐powered, fully edible, water‐soluble coating extends the shelf life of fruit by 2.5 to 3.4 times, enabling the development of an intelligent food logistics system for fruit preservation and real‐time monitoring. Furthermore, only 1.5 g of low‐cost food‐based materials, when assembled into an edible circuit, can output up to 81.5 V of direct current or a peak current of 6.1 mA in air. This self‐powered edible electronic concept offers a completely green solution to energy challenges in fields such as food safety monitoring and ingestible medical devices.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"39 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145731613","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Binrong Huang, Dasol Kim, Yuan Yu, Jinxuan Zhong, Jianbo Zhu, Yaoling Shen, Yu Guo, Moran Wang, Jiawei Huang, Tu Lyu, Nan Lin, Yongsheng Zhang, Matthias Wuttig, Lipeng Hu
Tailoring chemical bonds offers an innovative way to design materials for a wide range of applications. Metavalent bonding is conducive to excellent thermoelectric performance in p‐bonded chalcogenides with octahedral coordination. However, the requirement to form a bond through only a single p‐electron between adjacent atoms (half of an electron pair), such as in PbTe and Bi 2 Te 3 , limits the number of possible materials. Here, it is shown that the essence of metavalent bonding is a half‐filled single‐electron σ‐bond, which can also be formed with a significant s‐orbital contribution. This is illustrated for AgBiSe 2 , which crystallizes in three different phases: hexagonal, rhombohedral, and cubic. Quantum chemical calculations and bond‐breaking behavior reveal that all three octahedrally coordinated AgBiSe 2 phases utilize metavalent bonding. In addition, PbTe alloying is used to tune the chemical bonding and Br doping to optimize the carrier concentration. With these modifications, a record‐high zTmax value of 1.1 is achieved in n‐type cubic (AgBiSe 2 ) 0.75 (PbTe) 0.25 −0.01BiBr 3 at 798 K. The understanding and tailoring of chemical bonds achieved in AgBiSe 2 can be easily extended to other AgVVI 2 compounds.
{"title":"s‐Orbital Mediated Metavalent Bonding Enables State‐Of‐The‐Art n‐Type AgBiSe 2 Thermoelectrics","authors":"Binrong Huang, Dasol Kim, Yuan Yu, Jinxuan Zhong, Jianbo Zhu, Yaoling Shen, Yu Guo, Moran Wang, Jiawei Huang, Tu Lyu, Nan Lin, Yongsheng Zhang, Matthias Wuttig, Lipeng Hu","doi":"10.1002/adfm.202530091","DOIUrl":"https://doi.org/10.1002/adfm.202530091","url":null,"abstract":"Tailoring chemical bonds offers an innovative way to design materials for a wide range of applications. Metavalent bonding is conducive to excellent thermoelectric performance in p‐bonded chalcogenides with octahedral coordination. However, the requirement to form a bond through only a single p‐electron between adjacent atoms (half of an electron pair), such as in PbTe and Bi <jats:sub>2</jats:sub> Te <jats:sub>3</jats:sub> , limits the number of possible materials. Here, it is shown that the essence of metavalent bonding is a half‐filled single‐electron σ‐bond, which can also be formed with a significant s‐orbital contribution. This is illustrated for AgBiSe <jats:sub>2</jats:sub> , which crystallizes in three different phases: hexagonal, rhombohedral, and cubic. Quantum chemical calculations and bond‐breaking behavior reveal that all three octahedrally coordinated AgBiSe <jats:sub>2</jats:sub> phases utilize metavalent bonding. In addition, PbTe alloying is used to tune the chemical bonding and Br doping to optimize the carrier concentration. With these modifications, a record‐high <jats:italic>zT</jats:italic> <jats:sub>max</jats:sub> value of 1.1 is achieved in n‐type cubic (AgBiSe <jats:sub>2</jats:sub> ) <jats:sub>0.75</jats:sub> (PbTe) <jats:sub>0.25</jats:sub> −0.01BiBr <jats:sub>3</jats:sub> at 798 K. The understanding and tailoring of chemical bonds achieved in AgBiSe <jats:sub>2</jats:sub> can be easily extended to other AgVVI <jats:sub>2</jats:sub> compounds.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"1 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145731620","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Marco Piazzoni, Ilaria Borghi, Francesca Cadamuro, Sophia Dalfino, Riccardo Campanile, Sofia Nizzolo, Valeria Cassina, Francesca Tallia, Julian R. Jones, Francesco Mantegazza, Sabrina Bertini, Lorenzo Moroni, Francesco Nicotra, Laura Russo
The successful clinical translation of large‐scale tissue‐engineered constructs is significantly hindered by the lack of functional vascularization, which is crucial for delivering oxygen and nutrients to cells. Current in vitro angiogenesis models often rely on murine tumor‐derived extracellular matrix (ECM) materials, which suffer from non‐defined composition and batch‐to‐batch variability, and on the delivery of growth factors at non‐physiological concentrations. Hydrogels offer a superior alternative for the rational design of biomimetic ECM environments, because of their versatility in tuning biochemical and mechanical properties. This study presents a novel growth factor‐free hydrogel composed of gelatin, chondroitin sulfate, and laminin, designed to promote endothelial cell (EC) angiogenesis in vitro. The hydrogel's mechanical properties are precisely controlled by varying its crosslinking degree, attesting that a softer substrate (Young's modulus ≈80 Pa) significantly boosts ECs tube formation. Furthermore, the angiogenic process is enhanced by several hours with ions released by bioactive glass 58S (BG58S), specifically calcium and silicon. Finally, the expression of angiogenesis‐related genes and the production of matrix remodeling enzymes is augmented in the presence of BG58S‐conditioned medium. It is believed that this bioinstructive sulfate GAG based hydrogel represents a promising solution for vascularizing 3D cellular constructs, marking a significant step toward the clinical application of tissue engineering products.
{"title":"Endothelial Cells Angiogenesis in Sulfated Glycosaminoglycan (GAG) Hydrogels Enhanced by Bioactive Glass‐Released Ions","authors":"Marco Piazzoni, Ilaria Borghi, Francesca Cadamuro, Sophia Dalfino, Riccardo Campanile, Sofia Nizzolo, Valeria Cassina, Francesca Tallia, Julian R. Jones, Francesco Mantegazza, Sabrina Bertini, Lorenzo Moroni, Francesco Nicotra, Laura Russo","doi":"10.1002/adfm.202519933","DOIUrl":"https://doi.org/10.1002/adfm.202519933","url":null,"abstract":"The successful clinical translation of large‐scale tissue‐engineered constructs is significantly hindered by the lack of functional vascularization, which is crucial for delivering oxygen and nutrients to cells. Current in vitro angiogenesis models often rely on murine tumor‐derived extracellular matrix (ECM) materials, which suffer from non‐defined composition and batch‐to‐batch variability, and on the delivery of growth factors at non‐physiological concentrations. Hydrogels offer a superior alternative for the rational design of biomimetic ECM environments, because of their versatility in tuning biochemical and mechanical properties. This study presents a novel growth factor‐free hydrogel composed of gelatin, chondroitin sulfate, and laminin, designed to promote endothelial cell (EC) angiogenesis in vitro. The hydrogel's mechanical properties are precisely controlled by varying its crosslinking degree, attesting that a softer substrate (Young's modulus ≈80 Pa) significantly boosts ECs tube formation. Furthermore, the angiogenic process is enhanced by several hours with ions released by bioactive glass 58S (BG58S), specifically calcium and silicon. Finally, the expression of angiogenesis‐related genes and the production of matrix remodeling enzymes is augmented in the presence of BG58S‐conditioned medium. It is believed that this bioinstructive sulfate GAG based hydrogel represents a promising solution for vascularizing 3D cellular constructs, marking a significant step toward the clinical application of tissue engineering products.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"147 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145731724","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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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