Advanced hepatocellular carcinoma (HCC) presents a strongly immunosuppressive tumor microenvironment, which enables tumor cells to evade immune cell attacks and hinder effective drug killing, thereby hindering the achievement of the desired therapeutic effect. In response, a novel nanoplatform- AuHNR@γ-Fe2O3@Lenvatinib@β-Glucan (AFLG) with surface modified β-1,3-glucan is developed, which exhibits potent immunostimulatory effect and the capability of repolarizing macrophages, to counteract the immunosuppressive conditions present in the tumor microenvironment. Leveraging the hollow structure of gold nanorods, Lenvatinib is efficiently loaded, a first-line targeted drug for HCC, which effectively inhibits tumor angiogenesis. Additionally, through atomic layer deposition, γ-Fe2O3 is generated on the hollow gold nanorod surface, endowing it with chemodynamic therapy and magnetic resonance T2-weighted imaging capabilities while excellently maintaining the gold nanorod's superior photothermal therapy and photoacoustic imaging properties under 1064 nm excitation. These AFLG NPs feature dual-modal imaging and quadruple-modal synergistic therapy capabilities, along with their powerful potential in remodeling the immunosuppressive tumor microenvironment, offering an encouraging novel approach for the treatment of hepatocellular carcinoma.
{"title":"A Nanoplatform of Reversing Tumor Immunosuppressive Microenvironment Based on the NIR-II Gold Hollow Nanorod for the Treatment of Hepatocellular Carcinoma","authors":"Xinyuan Cui, Cheng Cao, Wanting Hao, Xinni Pan, Yu Cao, Yanfei Fu, Huifang Hao, Yingao Jiao, Shujing Lin, Shengsheng Cui, Ruokun Li, Yanlei Liu, Fuhua Yan","doi":"10.1002/smll.202500144","DOIUrl":"https://doi.org/10.1002/smll.202500144","url":null,"abstract":"Advanced hepatocellular carcinoma (HCC) presents a strongly immunosuppressive tumor microenvironment, which enables tumor cells to evade immune cell attacks and hinder effective drug killing, thereby hindering the achievement of the desired therapeutic effect. In response, a novel nanoplatform- AuHNR@γ-Fe<sub>2</sub>O<sub>3</sub>@Lenvatinib@β-Glucan (AFLG) with surface modified β-1,3-glucan is developed, which exhibits potent immunostimulatory effect and the capability of repolarizing macrophages, to counteract the immunosuppressive conditions present in the tumor microenvironment. Leveraging the hollow structure of gold nanorods, Lenvatinib is efficiently loaded, a first-line targeted drug for HCC, which effectively inhibits tumor angiogenesis. Additionally, through atomic layer deposition, γ-Fe<sub>2</sub>O<sub>3</sub> is generated on the hollow gold nanorod surface, endowing it with chemodynamic therapy and magnetic resonance T<sub>2</sub>-weighted imaging capabilities while excellently maintaining the gold nanorod's superior photothermal therapy and photoacoustic imaging properties under 1064 nm excitation. These AFLG NPs feature dual-modal imaging and quadruple-modal synergistic therapy capabilities, along with their powerful potential in remodeling the immunosuppressive tumor microenvironment, offering an encouraging novel approach for the treatment of hepatocellular carcinoma.","PeriodicalId":228,"journal":{"name":"Small","volume":"88 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695846","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}
Aiguo Rao, Shiyu Zhang, Mingqing Yang, Lei Wang, Chunhui Niu, Ming Fu
Recently, various types of resonant cavities are widely fused with inorganic electrochromic material WO3 to compensate for its monotonous color modulation range. However, combining stabilized flexibility and vivid color performance in electrochromic devices is limited by the inherent brittleness and constrained transparency of commonly used top transparent electrodes, such as indium tin oxide (ITO). Herein, a novel top electrode-free structure of Cr/WO3/Au metal-dielectric-metal (MDM) resonant cavity type flexible multicolor electrochromic device based on inner-layer porous Nylon 66 substrate is reported. By implementing a UV-cured gel electrolyte and PET thermoplastic sealing process, the electrochromic device exhibits ultra-flexibility, retaining 92.9% of its initial performance after 900 bending cycles at a radius of 4 mm, a wide color gamut spanning hues from violet to red, 40.59% maximum reflectance, and fast response times (tcolored/tbleached = 4.5 s/4.8 s). The porous MDM cavity generates a sharper scattered multi-beam interference resonance and provides a multi-path transport channel for ions, while the bottom porous Au reflection layer serves as the conductive electrode thus replacing the top transparent electrodes in traditional sandwich-like electrochromic device structure. Moreover, a large-area multipixel electrochromic array is further proposed to display different patterns, which demonstrates potential applications in future wearable electronic labels and smart camouflage.
{"title":"Top Electrode-Free Electrochromic Device with Ultra-Flexibility and Wide Color Gamut Based on Porous Resonant Cavity","authors":"Aiguo Rao, Shiyu Zhang, Mingqing Yang, Lei Wang, Chunhui Niu, Ming Fu","doi":"10.1002/smll.202412644","DOIUrl":"https://doi.org/10.1002/smll.202412644","url":null,"abstract":"Recently, various types of resonant cavities are widely fused with inorganic electrochromic material WO<sub>3</sub> to compensate for its monotonous color modulation range. However, combining stabilized flexibility and vivid color performance in electrochromic devices is limited by the inherent brittleness and constrained transparency of commonly used top transparent electrodes, such as indium tin oxide (ITO). Herein, a novel top electrode-free structure of Cr/WO<sub>3</sub>/Au metal-dielectric-metal (MDM) resonant cavity type flexible multicolor electrochromic device based on inner-layer porous Nylon 66 substrate is reported. By implementing a UV-cured gel electrolyte and PET thermoplastic sealing process, the electrochromic device exhibits ultra-flexibility, retaining 92.9% of its initial performance after 900 bending cycles at a radius of 4 mm, a wide color gamut spanning hues from violet to red, 40.59% maximum reflectance, and fast response times (<i>t<sub>colored</sub></i>/<i>t<sub>bleached</sub></i> = 4.5 s/4.8 s). The porous MDM cavity generates a sharper scattered multi-beam interference resonance and provides a multi-path transport channel for ions, while the bottom porous Au reflection layer serves as the conductive electrode thus replacing the top transparent electrodes in traditional sandwich-like electrochromic device structure. Moreover, a large-area multipixel electrochromic array is further proposed to display different patterns, which demonstrates potential applications in future wearable electronic labels and smart camouflage.","PeriodicalId":228,"journal":{"name":"Small","volume":"69 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695657","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}
Seonghun Shin, Owen D. Land, Warren D. Seider, Jinkee Lee, Daeyeon Lee
Double emulsions with core-shell structures are versatile materials used in applications such as cell culture, drug delivery, and materials synthesis. A droplet library with precisely controlled dimensions and properties would streamline screening and optimization for specific applications. While microfluidic droplet generation offers high precision, it is typically labor-intensive and sensitive to disturbances, requiring continuous operator intervention. To address these limitations, we present an artificial intelligence (AI)-empowered automated double emulsion droplet library generator. This system integrates a convolutional neural network (CNN)-based object detection model, decision-making, and feedback control algorithms to automate droplet generation and collection. The system monitors droplet generation every 171 ms—faster than a Formula 1 driver's reaction time—ensuring rapid response to disturbances and consistent production of single-core double emulsions. It autonomously generates libraries of 25 distinct monodisperse droplets with user-defined properties. This automation reduces labor and waste, enhances precision, and supports rapid and reliable droplet library generation. We anticipate that this platform will accelerate discovery and optimization in biomedical, biological, and materials research.
{"title":"Artificial Intelligence-Empowered Automated Double Emulsion Droplet Library Generation","authors":"Seonghun Shin, Owen D. Land, Warren D. Seider, Jinkee Lee, Daeyeon Lee","doi":"10.1002/smll.202412099","DOIUrl":"https://doi.org/10.1002/smll.202412099","url":null,"abstract":"Double emulsions with core-shell structures are versatile materials used in applications such as cell culture, drug delivery, and materials synthesis. A droplet library with precisely controlled dimensions and properties would streamline screening and optimization for specific applications. While microfluidic droplet generation offers high precision, it is typically labor-intensive and sensitive to disturbances, requiring continuous operator intervention. To address these limitations, we present an artificial intelligence (AI)-empowered automated double emulsion droplet library generator. This system integrates a convolutional neural network (CNN)-based object detection model, decision-making, and feedback control algorithms to automate droplet generation and collection. The system monitors droplet generation every 171 ms—faster than a Formula 1 driver's reaction time—ensuring rapid response to disturbances and consistent production of single-core double emulsions. It autonomously generates libraries of 25 distinct monodisperse droplets with user-defined properties. This automation reduces labor and waste, enhances precision, and supports rapid and reliable droplet library generation. We anticipate that this platform will accelerate discovery and optimization in biomedical, biological, and materials research.","PeriodicalId":228,"journal":{"name":"Small","volume":"10 2 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695840","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}
Min Zhu, Ting Zhang, Jinlong Wu, Xiuli Wang, Jin Zhang, Feng Li, Jing Li
Lattice strain is widely recognized as an effective strategy for tuning transition metal catalytic activity, yet its direct impact on electrochemical CO₂ reduction (ECO₂RR) remains not fully understood. In this work, a strategy of Cu-doped Ag is employed to construct a series of AgCu nanosheet structures (NS) with varying lattice compression rates (from −1.90% to −2.75%). Density Functional Theory (DFT) calculations, along with in situ infrared spectroscopic analysis, demonstrate that Cu incorporation efficiently modulates the electronic structure of Ag, promoting enhanced charge transfer. Especially, the changed lattice compression rates can alter the charge density at adsorption sites, thereby ameliorating the surface coverage of CO and adsorption energy of the reaction intermediates (*COOH and *CO). As a result, the AgCu5% catalyst exhibits a maximum Faradaic efficiency (FE) of 95.5% for CO production in an H-cell and 98% in a flow cell at −0.8 VRHE, respectively. Simultaneously, the AgCu5% catalyst achieves FECO of above 86% in the ultrawide current range of 33–215 mA cm−2. The work affords an effective way to use a strain compression strategy to improve the CO2 reduction performance.
{"title":"Efficient Electrochemical CO2 Conversion to CO via Cu-Doped Induced Lattice Compression in Ag Nanosheets","authors":"Min Zhu, Ting Zhang, Jinlong Wu, Xiuli Wang, Jin Zhang, Feng Li, Jing Li","doi":"10.1002/smll.202412550","DOIUrl":"https://doi.org/10.1002/smll.202412550","url":null,"abstract":"Lattice strain is widely recognized as an effective strategy for tuning transition metal catalytic activity, yet its direct impact on electrochemical CO₂ reduction (ECO₂RR) remains not fully understood. In this work, a strategy of Cu-doped Ag is employed to construct a series of AgCu nanosheet structures (NS) with varying lattice compression rates (from −1.90% to −2.75%). Density Functional Theory (DFT) calculations, along with in situ infrared spectroscopic analysis, demonstrate that Cu incorporation efficiently modulates the electronic structure of Ag, promoting enhanced charge transfer. Especially, the changed lattice compression rates can alter the charge density at adsorption sites, thereby ameliorating the surface coverage of CO and adsorption energy of the reaction intermediates (<sup>*</sup>COOH and <sup>*</sup>CO). As a result, the AgCu<sub>5%</sub> catalyst exhibits a maximum Faradaic efficiency (FE) of 95.5% for CO production in an H-cell and 98% in a flow cell at −0.8 V<sub>RHE</sub>, respectively. Simultaneously, the AgCu<sub>5%</sub> catalyst achieves FE<sub>CO</sub> of above 86% in the ultrawide current range of 33–215 mA cm<sup>−2</sup>. The work affords an effective way to use a strain compression strategy to improve the CO<sub>2</sub> reduction performance.","PeriodicalId":228,"journal":{"name":"Small","volume":"29 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695839","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}
Ke Shi, Yaze Chen, Haijiao Peng, Yuhao Liu, Chao Lu
Stimulus-responsive covalent organic frameworks (COFs) own color-switching characteristics when exposed to external stimuli. However, the investigations on the multiple solvent-responsive COFs remain a challenge due to the synthetic difficulties and uncontrollable charge transfer process toward various solvents. In this contribution, two novel isomeric COFs with a regulated intramolecular charge transfer (ICT) process by modulating the distance between the donor/acceptor and the linkage are synthesized. The as-prepared two isomeric COFs exhibited significantly distinct solvatochromic behaviors in water, acid, and halogenated solvents, respectively. These multiple solvent-responsive functions are attributed to the various enhancement degrees of the ICT process by the hydrogen bond interactions, protonation interactions, and halogen/π interactions, respectively. In addition, the two isomeric COFs are employed as stimulation-responsive powder or ink, displaying excellent image and data encryption performances. The work can not only offer a novel viewpoint for the creation of multiple solvent-responsive COFs but also expand the COFs' potential applications in information encryption and anti-counterfeiting.
{"title":"Intramolecular Charge Transfer-Regulated Isomeric Covalent Organic Frameworks for Multiple Solvent-Response","authors":"Ke Shi, Yaze Chen, Haijiao Peng, Yuhao Liu, Chao Lu","doi":"10.1002/smll.202501139","DOIUrl":"https://doi.org/10.1002/smll.202501139","url":null,"abstract":"Stimulus-responsive covalent organic frameworks (COFs) own color-switching characteristics when exposed to external stimuli. However, the investigations on the multiple solvent-responsive COFs remain a challenge due to the synthetic difficulties and uncontrollable charge transfer process toward various solvents. In this contribution, two novel isomeric COFs with a regulated intramolecular charge transfer (ICT) process by modulating the distance between the donor/acceptor and the linkage are synthesized. The as-prepared two isomeric COFs exhibited significantly distinct solvatochromic behaviors in water, acid, and halogenated solvents, respectively. These multiple solvent-responsive functions are attributed to the various enhancement degrees of the ICT process by the hydrogen bond interactions, protonation interactions, and halogen/π interactions, respectively. In addition, the two isomeric COFs are employed as stimulation-responsive powder or ink, displaying excellent image and data encryption performances. The work can not only offer a novel viewpoint for the creation of multiple solvent-responsive COFs but also expand the COFs' potential applications in information encryption and anti-counterfeiting.","PeriodicalId":228,"journal":{"name":"Small","volume":"183 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695849","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}
Tawsif Ibne Alam, Sumaiya Umme Hani, Zongliang Guo, Safayet Ahmed, Ahmed Mortuza Saleque, Md. Nahian Al Subri Ivan, Shuvra Saha, Yuen Hong Tsang
Van der Waals (vdW) heterojunctions represent a significant frontier in post-Moore era optoelectronics, especially in optimizing photosensor performance through multivariate approaches. Here synergistic engineering of GaS–WSe2 all-vdW photodiodes is investigated, which exhibit broadband detection (275–1064 nm), multispectral unity approaching linearity, alongside a substantial linear dynamic range (LDR) of 106.78 dB. Additionally, the photodiodes achieve a remarkable on/off ratio of 105 and rapid response edges of 545/471 µs under a 405 nm pulsed source, exhibiting ultralow light detection capabilities (dark currents ∼fA), culminating in a peak responsivity of 376.78 mA W−1 and a detectivity of 4.12 × 10¹¹ Jones under 450 nm illumination, complemented by an external quantum efficiency (EQE) of 30% and a fill factor of ≈0.33. Based on the analysis of multiple all-vdW devices, the importance of Fermi-level pinning free metal–2D interface engineering that enables effective modulation of the Schottky barrier height via vdW metal contacts is highlighted and meticulous thickness-engineered layers in developing a robust depletion region within the type-II GaS–WSe2 heterojunction are employed, ultimately achieving a favorable balance among photocarrier generation recombination, separation, transport, and extraction. This comprehensive investigation sets the stage for future developments in critically engineered next-generation vdW optoelectronic devices.
{"title":"Synergistically Engineered All Van der Waals GaS–WSe2 Photodiodes: Approaching Near-Unity Polychromatic Linearity for Multifunctional Optoelectronics","authors":"Tawsif Ibne Alam, Sumaiya Umme Hani, Zongliang Guo, Safayet Ahmed, Ahmed Mortuza Saleque, Md. Nahian Al Subri Ivan, Shuvra Saha, Yuen Hong Tsang","doi":"10.1002/smll.202410841","DOIUrl":"https://doi.org/10.1002/smll.202410841","url":null,"abstract":"Van der Waals (vdW) heterojunctions represent a significant frontier in post-Moore era optoelectronics, especially in optimizing photosensor performance through multivariate approaches. Here synergistic engineering of GaS–WSe<sub>2</sub> all-vdW photodiodes is investigated, which exhibit broadband detection (275–1064 nm), multispectral unity approaching linearity, alongside a substantial linear dynamic range (LDR) of 106.78 dB. Additionally, the photodiodes achieve a remarkable on/off ratio of 10<sup>5</sup> and rapid response edges of 545/471 µs under a 405 nm pulsed source, exhibiting ultralow light detection capabilities (dark currents ∼fA), culminating in a peak responsivity of 376.78 mA W<sup>−1</sup> and a detectivity of 4.12 × 10¹¹ Jones under 450 nm illumination, complemented by an external quantum efficiency (EQE) of 30% and a fill factor of ≈0.33. Based on the analysis of multiple all-vdW devices, the importance of Fermi-level pinning free metal–2D interface engineering that enables effective modulation of the Schottky barrier height via vdW metal contacts is highlighted and meticulous thickness-engineered layers in developing a robust depletion region within the type-II GaS–WSe<sub>2</sub> heterojunction are employed, ultimately achieving a favorable balance among photocarrier generation recombination, separation, transport, and extraction. This comprehensive investigation sets the stage for future developments in critically engineered next-generation vdW optoelectronic devices.","PeriodicalId":228,"journal":{"name":"Small","volume":"37 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143678320","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}
Ridwan A. Ahmed, Rohith Srinivaas Mohanakrishnan, Jingyang Wang, Krishna P. Koirala, Qian Zhao, Yanbao Fu, Ying Chen, Justin C. Rastinejad, Tianyu Li, Lirong Zhong, Mateusz Zuba, Carrie Siu, Ozgenur Kahvecioglu, Raphaële J. Clément, Bryan D. McCloskey, Vincent S. Battaglia, Kristin Persson, Chongmin Wang, Wu Xu
Lithium (Li)-excess transition metal oxide materials which crystallize in the cation-disordered rock salt (DRX) structure are promising cathodes for realizing low-cost, high-energy-density Li batteries. However, the state-of-the-art electrolytes for Li-ion batteries cannot meet the high-voltage stability requirement for high-voltage DRX cathodes, thus new electrolytes are urgently demanded. It has been reported that the solvation structures and properties of the electrolytes critically influence the performance and stability of the batteries. In this study, the structure–property relationships of various electrolytes with different solvent-to-diluent ratios are systematically investigated through a combination of theoretical calculations and experimental tests and analyses. This approach guides the development of electrolytes with unique solvation structures and characteristics, exhibiting high voltage stability, and enhancing the formation of stable electrode/electrolyte interphases. These electrolytes enable the realization of Li||Li1.094Mn0.676Ti0.228O2 (LMTO) DRX cells with improved performance compared to the conventional electrolyte. Specifically, Li||LMTO cells with the optimized advanced controlled-solvation electrolyte deliver higher specific capacity and longer cycle life compared to cells with the conventional electrolyte. Additionally, the investigation into the structure–property relationship provides a foundational basis for designing advanced electrolytes, which are crucial for the stable cycling of emerging high-voltage cathodes.
{"title":"Designing Advanced Electrolytes for High-Voltage High-Capacity Disordered Rocksalt Cathodes","authors":"Ridwan A. Ahmed, Rohith Srinivaas Mohanakrishnan, Jingyang Wang, Krishna P. Koirala, Qian Zhao, Yanbao Fu, Ying Chen, Justin C. Rastinejad, Tianyu Li, Lirong Zhong, Mateusz Zuba, Carrie Siu, Ozgenur Kahvecioglu, Raphaële J. Clément, Bryan D. McCloskey, Vincent S. Battaglia, Kristin Persson, Chongmin Wang, Wu Xu","doi":"10.1002/smll.202501600","DOIUrl":"https://doi.org/10.1002/smll.202501600","url":null,"abstract":"Lithium (Li)-excess transition metal oxide materials which crystallize in the cation-disordered rock salt (DRX) structure are promising cathodes for realizing low-cost, high-energy-density Li batteries. However, the state-of-the-art electrolytes for Li-ion batteries cannot meet the high-voltage stability requirement for high-voltage DRX cathodes, thus new electrolytes are urgently demanded. It has been reported that the solvation structures and properties of the electrolytes critically influence the performance and stability of the batteries. In this study, the structure–property relationships of various electrolytes with different solvent-to-diluent ratios are systematically investigated through a combination of theoretical calculations and experimental tests and analyses. This approach guides the development of electrolytes with unique solvation structures and characteristics, exhibiting high voltage stability, and enhancing the formation of stable electrode/electrolyte interphases. These electrolytes enable the realization of Li||Li<sub>1.094</sub>Mn<sub>0.676</sub>Ti<sub>0.228</sub>O<sub>2</sub> (LMTO) DRX cells with improved performance compared to the conventional electrolyte. Specifically, Li||LMTO cells with the optimized advanced controlled-solvation electrolyte deliver higher specific capacity and longer cycle life compared to cells with the conventional electrolyte. Additionally, the investigation into the structure–property relationship provides a foundational basis for designing advanced electrolytes, which are crucial for the stable cycling of emerging high-voltage cathodes.","PeriodicalId":228,"journal":{"name":"Small","volume":"71 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143678321","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}
Lijun Xu, Junlin Li, Zhangtong Han, Huang Ye, Qianwen Guan, Hang Li, Chengshu Zhang, Junhua Luo
2D Ruddlesden-Popper (RP) hybrid perovskite ferroelectrics have emerged as a promising class of direct X-ray detection materials. However, their intrinsic van der Waals gaps result in weak interlayer interactions that destabilize the layered motifs impacting the stability of the X-ray detector. Thus, it is crucial but remains toughly challenge to enhance interlayer interactions exploring stable RP perovskite ferroelectric X-ray detectors. Here, halogen bond is proposed to enhance the interlayer interactions of RP perovskite ferroelectrics obtaining a 2D trilayered ferroelectric, (BrPA)2(EA)2Pb3Br10 (BEPB, BrPA = 3-bromopropylaminium; EA = ethylammonium). Strikingly, the strong Br···Br halogen bonds lock cations to the inorganic skeletons, and C─H···Br hydrogen bonds bridge adjacent spacing sheets, which effectively improves structural stability and suppresses ion migration. The typical P-E hysteresis loops reveal its concrete ferroelectric behaviors, giving a large polarization of ≈7.3 µC cm−2. Consequently, the BEPB-based X-ray detector results in a high sensitivity of 562.6 µC Gy−1 cm−2 at 0 V bias, and most importantly, it exhibits low baseline drift and exceptional environmental stability. As far as is known, halogen bond strengthening 2D multilayered ferroelectric to achieve stable and efficient X-ray detection is unprecedented, which sheds light on the future design of stable optoelectronic devices toward practical applications.
{"title":"2D Multilayered Perovskite Ferroelectric with Halogen Bond Induced Interlayer Locking Structure toward Efficient Self-Powered X-Ray Detection","authors":"Lijun Xu, Junlin Li, Zhangtong Han, Huang Ye, Qianwen Guan, Hang Li, Chengshu Zhang, Junhua Luo","doi":"10.1002/smll.202412284","DOIUrl":"https://doi.org/10.1002/smll.202412284","url":null,"abstract":"2D Ruddlesden-Popper (RP) hybrid perovskite ferroelectrics have emerged as a promising class of direct X-ray detection materials. However, their intrinsic van der Waals gaps result in weak interlayer interactions that destabilize the layered motifs impacting the stability of the X-ray detector. Thus, it is crucial but remains toughly challenge to enhance interlayer interactions exploring stable RP perovskite ferroelectric X-ray detectors. Here, halogen bond is proposed to enhance the interlayer interactions of RP perovskite ferroelectrics obtaining a 2D trilayered ferroelectric, (BrPA)<sub>2</sub>(EA)<sub>2</sub>Pb<sub>3</sub>Br<sub>10</sub> (<b>BEPB</b>, BrPA = 3-bromopropylaminium; EA = ethylammonium). Strikingly, the strong Br···Br halogen bonds lock cations to the inorganic skeletons, and C─H···Br hydrogen bonds bridge adjacent spacing sheets, which effectively improves structural stability and suppresses ion migration. The typical <i>P-E</i> hysteresis loops reveal its concrete ferroelectric behaviors, giving a large polarization of ≈7.3 µC cm<sup>−2</sup>. Consequently, the <b>BEPB</b>-based X-ray detector results in a high sensitivity of 562.6 µC Gy<sup>−1</sup> cm<sup>−2</sup> at 0 V bias, and most importantly, it exhibits low baseline drift and exceptional environmental stability. As far as is known, halogen bond strengthening 2D multilayered ferroelectric to achieve stable and efficient X-ray detection is unprecedented, which sheds light on the future design of stable optoelectronic devices toward practical applications.","PeriodicalId":228,"journal":{"name":"Small","volume":"33 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143678325","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}
Yumin Lee, Youngji Kim, Minji Kim, In Soo Kim, Cheon Woo Moon, Jerome Kartham Hyun
Nature typically creates white and black structural coloration through disordered, dense assemblies of scatterers and absorbers that scatter and absorb light uniformly across the visible range, respectively. However, this approach conflicts with structural coloration designs for vibrant hues, which use ordered and uniform nanostructures. This structural discrepancy presents a challenge when trying to incorporate white and black alongside other colors in dynamic structural colors. Herein, a dynamic reflective coloration strategy is demonstrated, capable of switching between white, black, and other hues from ordered nanostructures. This is accomplished by exploiting reversible Cu electrodeposition within the slits of a nanograting and observing its cross‐polarized reflection, resolving colors from the grating birefringence. By electrochemically modulating the Cu thickness, birefringence is selectively activated, mixed, and eliminated from photonic (Rayleigh‐Wood) and near‐plasmonic resonances, producing blue, orange, white, and black colors. These results offer a pathway to dynamic white and black structural coloration compatible with ordered nanostructures.
{"title":"Overcoming the Structural Incompatibility Between White, Black, and Vibrant Hues in Dynamic Structural Colors","authors":"Yumin Lee, Youngji Kim, Minji Kim, In Soo Kim, Cheon Woo Moon, Jerome Kartham Hyun","doi":"10.1002/smll.202502181","DOIUrl":"https://doi.org/10.1002/smll.202502181","url":null,"abstract":"Nature typically creates white and black structural coloration through disordered, dense assemblies of scatterers and absorbers that scatter and absorb light uniformly across the visible range, respectively. However, this approach conflicts with structural coloration designs for vibrant hues, which use ordered and uniform nanostructures. This structural discrepancy presents a challenge when trying to incorporate white and black alongside other colors in dynamic structural colors. Herein, a dynamic reflective coloration strategy is demonstrated, capable of switching between white, black, and other hues from ordered nanostructures. This is accomplished by exploiting reversible Cu electrodeposition within the slits of a nanograting and observing its cross‐polarized reflection, resolving colors from the grating birefringence. By electrochemically modulating the Cu thickness, birefringence is selectively activated, mixed, and eliminated from photonic (Rayleigh‐Wood) and near‐plasmonic resonances, producing blue, orange, white, and black colors. These results offer a pathway to dynamic white and black structural coloration compatible with ordered nanostructures.","PeriodicalId":228,"journal":{"name":"Small","volume":"88 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143677872","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}
Yaoyu Gu, Yu Zhang, Mengdong Wei, Hang Ye, Yang Wang, Shaojie Qu, Kuan Hu, Xiaorui Li, Juanjuan Zhang, Ruoyu Wu, Chunsheng Liu, Dianzeng Jia, He Lin
This study investigates the impact of Ca2+ and phytic acid (PA) pre-insertion on the performance of vanadium oxide (V6O13) as a cathode material for aqueous zinc-ion batteries. Ab initio molecular dynamics (AIMD) simulations reveal that the diffusion coefficient of Ca2⁺ is higher than that of Zn2+, leading to the preferential extraction of Ca2⁺. The extracted Ca2⁺ readily forms a dense cathode-electrolyte interphase (CEI) with SO₄2− on the electrode surface, effectively mitigating electrode dissolution. Furthermore, density functional theory (DFT) calculations indicate that the incorporation of Ca2⁺ lowers the diffusion energy barrier for Zn2⁺, facilitating its diffusion. Additionally, PA insertion stabilizes the interlayer spacing of V6O13, and its strong chelating ability stabilizes the structure by preventing collapse during cycling. Experimental validation through a one-step solvothermal method confirms these theoretical predictions. The CaVO-PA composite exhibits excellent cycling stability, with a capacity retention rate increasing from 60% to 102% after 3000 cycles at 10 A g−¹. Even at 20 A g−¹, it delivers a specific capacity of 170.2 mAh g−¹ with stable Coulombic efficiency. After 10 000 cycles, the capacity shows no significant degradation, demonstrating superior cycling stability and high current tolerance, thereby confirming the effectiveness of the CEI and PA in enhancing electrochemical performance.
{"title":"Superior Cycling Stability in Zinc-Ion Batteries with Ca2+-Induced Cathode-Electrolyte Interface and Phytic Acid: Experimental Validation of Theoretical Predictions","authors":"Yaoyu Gu, Yu Zhang, Mengdong Wei, Hang Ye, Yang Wang, Shaojie Qu, Kuan Hu, Xiaorui Li, Juanjuan Zhang, Ruoyu Wu, Chunsheng Liu, Dianzeng Jia, He Lin","doi":"10.1002/smll.202501294","DOIUrl":"https://doi.org/10.1002/smll.202501294","url":null,"abstract":"This study investigates the impact of Ca<sup>2+</sup> and phytic acid (PA) pre-insertion on the performance of vanadium oxide (V<sub>6</sub>O<sub>13</sub>) as a cathode material for aqueous zinc-ion batteries. Ab initio molecular dynamics (AIMD) simulations reveal that the diffusion coefficient of Ca<sup>2</sup>⁺ is higher than that of Zn<sup>2+</sup>, leading to the preferential extraction of Ca<sup>2</sup>⁺. The extracted Ca<sup>2</sup>⁺ readily forms a dense cathode-electrolyte interphase (CEI) with SO₄<sup>2</sup><sup>−</sup> on the electrode surface, effectively mitigating electrode dissolution. Furthermore, density functional theory (DFT) calculations indicate that the incorporation of Ca<sup>2</sup>⁺ lowers the diffusion energy barrier for Zn<sup>2</sup>⁺, facilitating its diffusion. Additionally, PA insertion stabilizes the interlayer spacing of V<sub>6</sub>O<sub>13</sub>, and its strong chelating ability stabilizes the structure by preventing collapse during cycling. Experimental validation through a one-step solvothermal method confirms these theoretical predictions. The CaVO-PA composite exhibits excellent cycling stability, with a capacity retention rate increasing from 60% to 102% after 3000 cycles at 10 A g<sup>−</sup>¹. Even at 20 A g<sup>−</sup>¹, it delivers a specific capacity of 170.2 mAh g<sup>−</sup>¹ with stable Coulombic efficiency. After 10 000 cycles, the capacity shows no significant degradation, demonstrating superior cycling stability and high current tolerance, thereby confirming the effectiveness of the CEI and PA in enhancing electrochemical performance.","PeriodicalId":228,"journal":{"name":"Small","volume":"183 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143678318","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：