Jiaming Zuo, Tianya Jin, Hongxiang Li, Junhang Li, Xinyu Liu, Xinhong Yu, Yang Han, Yanchun Han
The continuous conjugated polymer network structure in an elastomer matrix is significant for carrier transport. However, high-mobility conjugated polymers tend to form island-like phase separation. Here, a strategy is proposed to achieve a continuous conjugated polymer network structure via weakening the intermolecular interaction between the conjugated polymer chains and fast aggregation between conjugated polymer backbones during the film-forming process. This is enabled by hot spin-coating poly(2,5-bis(4-hexyldodecyl)-2,5-dihydro-3,6-di-2-thienyl-pyrrolo[3,4-c]pyrrole-1,4-dione-alt-thiophene) (PDPPT3) and polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene (SEBS) blend hot solution at 130 °C. In the solution state, PDPPT3 is observed to form small aggregates at 130 °C due to the decreased intermolecular interaction. In the film-forming process, these small aggregates grow rapidly and form a continuous network due to the enhanced polymer chain motion. In the meantime, the large-scale phase separation is suppressed by the short film formation time. Eventually, a sandwich-like vertical phase separation is generated, comprising a PDPPT3-enriched continuous network at both the top and bottom surfaces. Under strain, this small-scale phase separation PDPPT3 network can rotate freely and maintain sufficient connections for carrier transport. Finally, the optimized films exhibit 177% fracture strain and high average mobility of 0.99 cm2 V−1 s−1 over 500 stretch-release cycles. This study offers a valuable approach for controlling morphology in blend systems.
{"title":"Continuous Conjugated Polymer Network in Elastomer Matrix Arising from Solution-State Aggregation and Film-Forming Dynamics Favoring Mechanical and Electrical Properties","authors":"Jiaming Zuo, Tianya Jin, Hongxiang Li, Junhang Li, Xinyu Liu, Xinhong Yu, Yang Han, Yanchun Han","doi":"10.1002/adfm.202424785","DOIUrl":"https://doi.org/10.1002/adfm.202424785","url":null,"abstract":"The continuous conjugated polymer network structure in an elastomer matrix is significant for carrier transport. However, high-mobility conjugated polymers tend to form island-like phase separation. Here, a strategy is proposed to achieve a continuous conjugated polymer network structure via weakening the intermolecular interaction between the conjugated polymer chains and fast aggregation between conjugated polymer backbones during the film-forming process. This is enabled by hot spin-coating poly(2,5-bis(4-hexyldodecyl)-2,5-dihydro-3,6-di-2-thienyl-pyrrolo[3,4-c]pyrrole-1,4-dione-alt-thiophene) (PDPPT3) and polystyrene-<i>block</i>-poly(ethylene-ran-butylene)-<i>block</i>-polystyrene (SEBS) blend hot solution at 130 °C. In the solution state, PDPPT3 is observed to form small aggregates at 130 °C due to the decreased intermolecular interaction. In the film-forming process, these small aggregates grow rapidly and form a continuous network due to the enhanced polymer chain motion. In the meantime, the large-scale phase separation is suppressed by the short film formation time. Eventually, a sandwich-like vertical phase separation is generated, comprising a PDPPT3-enriched continuous network at both the top and bottom surfaces. Under strain, this small-scale phase separation PDPPT3 network can rotate freely and maintain sufficient connections for carrier transport. Finally, the optimized films exhibit 177% fracture strain and high average mobility of 0.99 cm<sup>2</sup> V<sup>−1</sup> s<sup>−1</sup> over 500 stretch-release cycles. This study offers a valuable approach for controlling morphology in blend systems.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"69 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435560","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}
The formation of a stable passivation layer and the strong electrostatic interactions impede the diffusion of magnesium ions (Mg2+) at the Mg anode surface. Construction of an artificial solid electrolyte interphase (SEI) layer presents a promising approach to overcome these limitations. This study develops a synergistic and structurally stable Mg@SnSb SEI through an in situ reaction between the anode and a Tin trifluoromethanesulfonate and antimony chloride (Sn(OTf)2-SbCl3-based) electrolyte, featuring a low LUMO (lowest unoccupied molecular orbital). The in situ formed multi-phase SEI effectively reduces the interfacial reaction barriers and facilitates Mg2+ diffusion during both the plating and the stripping processes. Additionally, the formation of nano-grained microstructure enhances the uniformity of Mg plating/stripping and suppresses the decomposition of the OTf anions and DME solvent molecules. The Mg anode incorporating the Mg@SnSb SEI exhibits an exceptionally low overpotential of less than 0.07 V and an ultra-long cycle life exceeding 1500 h. In full-cell tests using Mg@SnSb||Mo6S8, the system achieved exceptional electrochemical performance, maintaining over 94% of its initial capacity after more than 400 cycles.
{"title":"Bifunctional Synergistic Mg@SnSb SEI for Low Interfacial Reaction Energy Barriers and Stable Cycling of High-Performance Rechargeable Magnesium Batteries","authors":"Xianhao Peng, Yuan Yuan, Dachong Gu, Dajian Li, Liang Wu, Ligang Zhang, Guangsheng Huang, Jingfeng Wang, Fusheng Pan","doi":"10.1002/adfm.202422278","DOIUrl":"https://doi.org/10.1002/adfm.202422278","url":null,"abstract":"The formation of a stable passivation layer and the strong electrostatic interactions impede the diffusion of magnesium ions (Mg<sup>2+</sup>) at the Mg anode surface. Construction of an artificial solid electrolyte interphase (SEI) layer presents a promising approach to overcome these limitations. This study develops a synergistic and structurally stable Mg@SnSb SEI through an in situ reaction between the anode and a Tin trifluoromethanesulfonate and antimony chloride (Sn(OTf)<sub>2</sub>-SbCl<sub>3</sub>-based) electrolyte, featuring a low LUMO (lowest unoccupied molecular orbital). The in situ formed multi-phase SEI effectively reduces the interfacial reaction barriers and facilitates Mg<sup>2+</sup> diffusion during both the plating and the stripping processes. Additionally, the formation of nano-grained microstructure enhances the uniformity of Mg plating/stripping and suppresses the decomposition of the OTf anions and DME solvent molecules. The Mg anode incorporating the Mg@SnSb SEI exhibits an exceptionally low overpotential of less than 0.07 V and an ultra-long cycle life exceeding 1500 h. In full-cell tests using Mg@SnSb||Mo<sub>6</sub>S<sub>8</sub>, the system achieved exceptional electrochemical performance, maintaining over 94% of its initial capacity after more than 400 cycles.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"1 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435563","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}
Mingfeng Xu, Giovanni Gammaitoni, Michael Häfner, Eduardo Villalobos-Portillo, Carlo Marini, Matteo Bianchini
In the quest to improve cathode materials for Na-ion batteries, a family of Li-substituted P2 layered oxides with nominal stoichiometry Na5/6LiyNi5/12-3y/2Mn7/12+y/2O2 (y = 2/18, 3/18, 4/18, 5/18) is studied. The consequences of Li substitution and the challenge of elevating the Na content are explored. Structurally, honeycomb ordering is observed in all samples, while Li induces the loss of Na+/vacancy ordering. Electrochemically, the materials exhibit an increasing trend of polarized hysteresis in the 1st cycle. Semi-simultaneous operando x-ray absorption and diffraction are coupled to appreciate the structural evolution and redox behavior during this process. Li in the transition metal site eliminates phase transitions at high voltage and modifies the activation of O-redox. All samples show anionic redox: as confirmed computationally, in the Li-free sample this is rooted in Ni─O hybridized states, while in the Li-containing samples in O non-bonding states. Composition Na0.745(6)Li0.164(4)Ni0.238(1)Mn0.599(3)O2 proves to have the least O-redox among all, coupled with reduced phase transitions, disordered occupancy of Na sites, and small volume change during cycling, leading to the best balance of cycling stability (≈92% after 100 cycles), capacity (> 100 mAh g−1) and rate capability. This can pave the way for further development of P2 layered oxides with redox-inactive dopants.
{"title":"Understanding and Optimizing Li Substitution in P2-Type Sodium Layered Oxides for Sodium-Ion Batteries","authors":"Mingfeng Xu, Giovanni Gammaitoni, Michael Häfner, Eduardo Villalobos-Portillo, Carlo Marini, Matteo Bianchini","doi":"10.1002/adfm.202425499","DOIUrl":"https://doi.org/10.1002/adfm.202425499","url":null,"abstract":"In the quest to improve cathode materials for Na-ion batteries, a family of Li-substituted P2 layered oxides with nominal stoichiometry Na<sub>5/6</sub>Li<sub><i>y</i></sub>Ni<sub>5/12-3<i>y</i>/2</sub>Mn<sub>7/12+<i>y</i>/2</sub>O<sub>2</sub> (<i>y</i> = 2/18, 3/18, 4/18, 5/18) is studied. The consequences of Li substitution and the challenge of elevating the Na content are explored. Structurally, honeycomb ordering is observed in all samples, while Li induces the loss of Na<sup>+</sup>/vacancy ordering. Electrochemically, the materials exhibit an increasing trend of polarized hysteresis in the 1st cycle. Semi-simultaneous <i>operando</i> x-ray absorption and diffraction are coupled to appreciate the structural evolution and redox behavior during this process. Li in the transition metal site eliminates phase transitions at high voltage and modifies the activation of O-redox. All samples show anionic redox: as confirmed computationally, in the Li-free sample this is rooted in Ni─O hybridized states, while in the Li-containing samples in O non-bonding states. Composition Na<sub>0.745(6)</sub>Li<sub>0.164(4)</sub>Ni<sub>0.238(1)</sub>Mn<sub>0.599(3)</sub>O<sub>2</sub> proves to have the least O-redox among all, coupled with reduced phase transitions, disordered occupancy of Na sites, and small volume change during cycling, leading to the best balance of cycling stability (≈92% after 100 cycles), capacity (> 100 mAh g<sup>−1</sup>) and rate capability. This can pave the way for further development of P2 layered oxides with redox-inactive dopants.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"54 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418010","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}
Liu Yu, Wen Li, Jiahui Cao, Rourou Miao, Yiqiu Fu, Xinyi Wang, Juntao Xie, Wen Zhang, Zhuo Mao, Hanjie Zhang, Yushi Zhang, Meitong Ou, Lin Mei
The abnormal metabolism of tumor cells fulfills their high energy demands for rapid growth while simultaneously reshaping the tumor microenvironment (TME), which suppresses immune cell function and facilitates immune evasion. Herein, a peptide-based nanocomplex (DCK@siGLUT1) that synergizes with photodynamic therapy (PDT) to disrupt tumor cell energy metabolism is developed. DCK@siGLUT1, utilizing a mitochondria-targeting peptide (dKLA) selectively accumulates in mitochondria, where it impairs mitochondrial membrane integrity, disrupts energy metabolism, and induces apoptosis. Upon apoptosis, activated caspase-3 (Casp3) cleaves DCK@siGLUT1, releasing siGLUT1 to silence glucose transporter 1 (GLUT1) expression, which further inhibits glucose uptake and intensifies metabolic collapse, thereby amplifying apoptotic effects. Moreover, Ce6, conjugated to dKLA, is co-delivered to the mitochondria and, upon light activation, exacerbates mitochondrial damage and metabolic disruption. These combined mechanisms intensify oxidative stress and apoptosis, further activate Casp3, and promote DCK@siGLUT1 cleavage, thereby driving a self-amplifying tumoricidal cascade. Furthermore, DCK@siGLUT1 effectively induces immunogenic cell death (ICD), triggers antitumor immune responses, and inhibits both primary and distant tumor growth and metastasis. This strategy offers a novel approach for targeting tumor energy metabolism in antitumor immunotherapy.
{"title":"Remodeling Tumor Metabolism via Self-Amplifying Energy-Depleting Nanocomplexes for Effective Photodynamic-Immunotherapy","authors":"Liu Yu, Wen Li, Jiahui Cao, Rourou Miao, Yiqiu Fu, Xinyi Wang, Juntao Xie, Wen Zhang, Zhuo Mao, Hanjie Zhang, Yushi Zhang, Meitong Ou, Lin Mei","doi":"10.1002/adfm.202425831","DOIUrl":"https://doi.org/10.1002/adfm.202425831","url":null,"abstract":"The abnormal metabolism of tumor cells fulfills their high energy demands for rapid growth while simultaneously reshaping the tumor microenvironment (TME), which suppresses immune cell function and facilitates immune evasion. Herein, a peptide-based nanocomplex (DCK@siGLUT1) that synergizes with photodynamic therapy (PDT) to disrupt tumor cell energy metabolism is developed. DCK@siGLUT1, utilizing a mitochondria-targeting peptide (dKLA) selectively accumulates in mitochondria, where it impairs mitochondrial membrane integrity, disrupts energy metabolism, and induces apoptosis. Upon apoptosis, activated caspase-3 (Casp3) cleaves DCK@siGLUT1, releasing siGLUT1 to silence glucose transporter 1 (GLUT1) expression, which further inhibits glucose uptake and intensifies metabolic collapse, thereby amplifying apoptotic effects. Moreover, Ce6, conjugated to dKLA, is co-delivered to the mitochondria and, upon light activation, exacerbates mitochondrial damage and metabolic disruption. These combined mechanisms intensify oxidative stress and apoptosis, further activate Casp3, and promote DCK@siGLUT1 cleavage, thereby driving a self-amplifying tumoricidal cascade. Furthermore, DCK@siGLUT1 effectively induces immunogenic cell death (ICD), triggers antitumor immune responses, and inhibits both primary and distant tumor growth and metastasis. This strategy offers a novel approach for targeting tumor energy metabolism in antitumor immunotherapy.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"2 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418316","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}
Huifang Yang, Chaohui Zhao, Yanze Wang, Xinqi Xu, Gaoyu Chen, Denglin Zhao, Zengguang Zhang, Min Rao, Juntao Lu, Yatao Zou, Zhongbin Wu, Wenbo Hu, Ziwei Li, Meng Su, Qiushui Chen, Xiaowang Liu, Nicolas H Voelcker, Bo Peng, Weidong Xu
Real-time, high-precision X-ray imaging is of critical importance in a wide range of applications, from medical diagnostics to security screening. While lanthanide luminescent materials are among the most commonly used scintillators, achieving a combination of large-area scalability, rapid response, and optimal performance remains challenging. Herein, a perovskite-inspired cerium halide nanocrystal scintillator is presented with a remarkable photoluminescence quantum yield approaching unity and a fast radiative recombination rate of ≈29 ns. By leveraging these promising characteristics, large-area X-ray imaging is demonstrated with a spatial resolution of 12.21 lp mm−1 and an ultra-low detection limit of 11.2 nGy s−1, alongside applications in dynamic imaging. Based on these paternal nanocrystals, the versatile spectral tunability through halide alloying and cation doping is further explored, offering a promising platform for future chemical and structural design toward advanced scintillations and other down-conversion applications.
{"title":"Sensitive and Fast X-Ray Scintillation with Perovskite-Inspired Cerium Halide Nanocrystals","authors":"Huifang Yang, Chaohui Zhao, Yanze Wang, Xinqi Xu, Gaoyu Chen, Denglin Zhao, Zengguang Zhang, Min Rao, Juntao Lu, Yatao Zou, Zhongbin Wu, Wenbo Hu, Ziwei Li, Meng Su, Qiushui Chen, Xiaowang Liu, Nicolas H Voelcker, Bo Peng, Weidong Xu","doi":"10.1002/adfm.202422959","DOIUrl":"https://doi.org/10.1002/adfm.202422959","url":null,"abstract":"Real-time, high-precision X-ray imaging is of critical importance in a wide range of applications, from medical diagnostics to security screening. While lanthanide luminescent materials are among the most commonly used scintillators, achieving a combination of large-area scalability, rapid response, and optimal performance remains challenging. Herein, a perovskite-inspired cerium halide nanocrystal scintillator is presented with a remarkable photoluminescence quantum yield approaching unity and a fast radiative recombination rate of ≈29 ns. By leveraging these promising characteristics, large-area X-ray imaging is demonstrated with a spatial resolution of 12.21 lp mm<sup>−1</sup> and an ultra-low detection limit of 11.2 nGy s<sup>−1</sup>, alongside applications in dynamic imaging. Based on these paternal nanocrystals, the versatile spectral tunability through halide alloying and cation doping is further explored, offering a promising platform for future chemical and structural design toward advanced scintillations and other down-conversion applications.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"81 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418348","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}
Zanyang Wang, Lu Song, Xuchun Zhang, Xin Wang, Zuojia Wang, Hongsheng Chen, Min Li, Dashuang Liao
Radiation-stealth integration, merging radiation regulation and scattering suppression into a unified framework, is essential for advanced radar communications and stealth technology. However, current state-of-the-art solutions that simultaneously modulate radiation and stealth characteristics encounter two main challenges: limited scalability due to high energy demands from active components, and constrained stealth bandwidth stemming from the inherent incompatibility between radiation and scattering. Here, passive folded metasurfaces (PFM) that integrate radiation regulation with stealth capabilities, eliminating the necessity for active components while achieving both in- and off-band stealth, referred to as cross-band stealth, are proposed. The PFM employs a hybrid architecture, cascading a quad-focal asymmetric metasurface (QFAM) and a polarization-conversion meta-mirror (PCM) incorporated with patterned feed arrays. The QFAM leverages local quad-focal phases and polarization selectivity to regulate radiation modes generated by encoded-excited feeds, enabling efficient beamforming reconfiguration without active components. Furthermore, the synergy between the QFAM and PCM dissipates in-band impinging waves through internal reflections and absorptions, while off-band waves undergo destructive interference enabled by checkboard-patterned modulators atop the QFAM, achieving cross-band stealth. To validate the capabilities of the proposed PFM, a prototype is fabricated and its versatile radiation-stealth functionalities, including 1D narrow- and wide-beam scanning, 2D beamforming, and cross-band stealth, are experimentally demonstrated.
{"title":"Synergizing Radiation Regulation and Cross-Band Stealth with Passive Folded Metasurfaces","authors":"Zanyang Wang, Lu Song, Xuchun Zhang, Xin Wang, Zuojia Wang, Hongsheng Chen, Min Li, Dashuang Liao","doi":"10.1002/adfm.202421782","DOIUrl":"https://doi.org/10.1002/adfm.202421782","url":null,"abstract":"Radiation-stealth integration, merging radiation regulation and scattering suppression into a unified framework, is essential for advanced radar communications and stealth technology. However, current state-of-the-art solutions that simultaneously modulate radiation and stealth characteristics encounter two main challenges: limited scalability due to high energy demands from active components, and constrained stealth bandwidth stemming from the inherent incompatibility between radiation and scattering. Here, passive folded metasurfaces (PFM) that integrate radiation regulation with stealth capabilities, eliminating the necessity for active components while achieving both in- and off-band stealth, referred to as cross-band stealth, are proposed. The PFM employs a hybrid architecture, cascading a quad-focal asymmetric metasurface (QFAM) and a polarization-conversion meta-mirror (PCM) incorporated with patterned feed arrays. The QFAM leverages local quad-focal phases and polarization selectivity to regulate radiation modes generated by encoded-excited feeds, enabling efficient beamforming reconfiguration without active components. Furthermore, the synergy between the QFAM and PCM dissipates in-band impinging waves through internal reflections and absorptions, while off-band waves undergo destructive interference enabled by checkboard-patterned modulators atop the QFAM, achieving cross-band stealth. To validate the capabilities of the proposed PFM, a prototype is fabricated and its versatile radiation-stealth functionalities, including 1D narrow- and wide-beam scanning, 2D beamforming, and cross-band stealth, are experimentally demonstrated.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"28 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418320","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}
Jiaxing Du, Marcello Righetto, Manuel Kober-Czerny, Siyu Yan, Karim A. Elmestekawy, Henry J. Snaith, Michael B. Johnston, Laura M. Herz
2D lead halide perovskites (2DPs) offer chemical compatibility with 3D perovskites and enhanced stability, which are attractive for applications in photovoltaic and light-emitting devices. However, such lowered structural dimensionality causes increased excitonic effects and highly anisotropic charge-carrier transport. Determining the diffusivity of excitations, in particular for out-of-plane or inter-layer transport, is therefore crucial, yet challenging to achieve. Here, an effective method is demonstrated for monitoring inter-layer diffusion of photoexcitations in (PEA)2PbI4 thin films by tracking time-dependent changes in photoluminescence spectra induced by photon reabsorption effects. Selective photoexcitation from either substrate- or air-side of the films reveals differences in diffusion dynamics encountered through the film profile. Time-dependent diffusion coefficients are extracted from spectral dynamics through a 1D diffusion model coupled with an interference correction for refractive index variations arising from the strong excitonic resonance of 2DPs. Such analysis, together with structural probes, shows that minute misalignment of 2DPs planes occurs at distances far from the substrate, where efficient in-plane transport consequently overshadows the less efficient out-of-plane transport in the direction perpendicular to the substrate. Through detailed analysis, a low out-of-plane excitation diffusion coefficient of (0.26 ± 0.03) ×10−4 cm2 s−1 is determined, consistent with a diffusion anisotropy of ≈4 orders of magnitude.
{"title":"Inter-Layer Diffusion of Excitations in 2D Perovskites Revealed by Photoluminescence Reabsorption","authors":"Jiaxing Du, Marcello Righetto, Manuel Kober-Czerny, Siyu Yan, Karim A. Elmestekawy, Henry J. Snaith, Michael B. Johnston, Laura M. Herz","doi":"10.1002/adfm.202421817","DOIUrl":"https://doi.org/10.1002/adfm.202421817","url":null,"abstract":"2D lead halide perovskites (2DPs) offer chemical compatibility with 3D perovskites and enhanced stability, which are attractive for applications in photovoltaic and light-emitting devices. However, such lowered structural dimensionality causes increased excitonic effects and highly anisotropic charge-carrier transport. Determining the diffusivity of excitations, in particular for out-of-plane or inter-layer transport, is therefore crucial, yet challenging to achieve. Here, an effective method is demonstrated for monitoring inter-layer diffusion of photoexcitations in (PEA)<sub>2</sub>PbI<sub>4</sub> thin films by tracking time-dependent changes in photoluminescence spectra induced by photon reabsorption effects. Selective photoexcitation from either substrate- or air-side of the films reveals differences in diffusion dynamics encountered through the film profile. Time-dependent diffusion coefficients are extracted from spectral dynamics through a 1D diffusion model coupled with an interference correction for refractive index variations arising from the strong excitonic resonance of 2DPs. Such analysis, together with structural probes, shows that minute misalignment of 2DPs planes occurs at distances far from the substrate, where efficient in-plane transport consequently overshadows the less efficient out-of-plane transport in the direction perpendicular to the substrate. Through detailed analysis, a low out-of-plane excitation diffusion coefficient of (0.26 ± 0.03) ×10<sup>−4</sup> cm<sup>2</sup> s<sup>−1</sup> is determined, consistent with a diffusion anisotropy of ≈4 orders of magnitude.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"2 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418355","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}
Metal nitride electrocatalysts have been extensively developed for efficient alkaline water splitting, but it still remains a huge challenge in improving their stability especially at high current density of over 500 mA cm−2. Herein the Co4N/MoN electrocatalyst with hierarchical nanoparticle-assembled nanosheet arrays is fabricated by a facile electrodeposition-nitridation method for alkaline hydrogen evolution reaction (HER). Results show that it exhibits an impressively low overpotential of 238 mV and high durability at 1.0 A cm−2 for over 100 h, which is the best among the reported cobalt-based nitride electrocatalysts with both excellent HER activity and robust stability at ampere-level current density. The superior intrinsic HER activity is mainly ascribed to the synergistic effect of Co4N and MoN, which can effectively reduce the H2O dissociation energy barrier and accelerate the alkaline HER kinetics. Moreover, benefiting from the vertically arrayed nanosheet structure with a solid framework and excellent mechanical strength, robust water electrolysis even at ampere-level current density can be achieved. This work provides an alternative way to develop metal nitride electrocatalysts via fabricating hierarchical heterostructure for efficient and stable industrial water splitting.
{"title":"Vertically Arrayed Co4N/MoN Nanosheets for Robust Alkaline Electrocatalytic Hydrogen Evolution at Ampere-Level Current Density","authors":"Can Li, Ningning Wang, Shuo Wang, Chenyang Li, Wenjun Fan, Taifeng Liu, Shanshan Chen, Fuxiang Zhang","doi":"10.1002/adfm.202423856","DOIUrl":"https://doi.org/10.1002/adfm.202423856","url":null,"abstract":"Metal nitride electrocatalysts have been extensively developed for efficient alkaline water splitting, but it still remains a huge challenge in improving their stability especially at high current density of over 500 mA cm<sup>−2</sup>. Herein the Co<sub>4</sub>N/MoN electrocatalyst with hierarchical nanoparticle-assembled nanosheet arrays is fabricated by a facile electrodeposition-nitridation method for alkaline hydrogen evolution reaction (HER). Results show that it exhibits an impressively low overpotential of 238 mV and high durability at 1.0 A cm<sup>−2</sup> for over 100 h, which is the best among the reported cobalt-based nitride electrocatalysts with both excellent HER activity and robust stability at ampere-level current density. The superior intrinsic HER activity is mainly ascribed to the synergistic effect of Co<sub>4</sub>N and MoN, which can effectively reduce the H<sub>2</sub>O dissociation energy barrier and accelerate the alkaline HER kinetics. Moreover, benefiting from the vertically arrayed nanosheet structure with a solid framework and excellent mechanical strength, robust water electrolysis even at ampere-level current density can be achieved. This work provides an alternative way to develop metal nitride electrocatalysts via fabricating hierarchical heterostructure for efficient and stable industrial water splitting.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"129 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418242","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}
Bo Zhao, Lixian Song, Zhijuan Zou, Zhu Xiong, Yunfeng Zhang, Qin Yang, Zixiong Shi, Yaping Zhang, Yingze Song
Concurrent regulation of sulfur redox kinetics and lithium deposition homogeneity is a key prerequisite for achieving high-performance lithium–sulfur (Li–S) batteries. To this end, rational design of dual-functional interlayers is recognized as a feasible yet promising approach. Herein, few-layered Ti3C2 MXene flakes are uniformly decorated into the porous carbon nanofiber film via a straightforward electrostatic spinning technique, wherein the Ti3C2 MXene content is fine-tuned to maximum sulfur utilization and stabilize lithium anode. For one thing, it is revealed by synchrotron radiation X-ray three-dimensional nano-computed tomography that Ti3C2 MXene-decorated fiber can expedite polysulfide conversion and induce favorable Li2S nucleation. For another, small-angle neutron scattering evidence substantiates that abundant lithiophilic sites are conducive to homogenizing Li-ion flux and promoting lithium deposition during cycling procedure. As a consequence, Li–S batteries maintain a stable operation at 2.0 C over 1000 cycles with a low-capacity degeneration rate of 0.057% per cycle, accompanied by a superior areal capacity of 7.5 mAh cm−2 when the sulfur loading is increased to 9.5 mg cm−2. More encouragingly, the as-assembled multi-layer Li–S pouch cell deliver an impressive cell energy density of 342.3 Wh kg−1 with smooth cyclic operation.
{"title":"Electrospun Ti3C2 MXene Fiber-Decorated Interlayer for Synchronous Sulfur Activation and Lithium Stabilization","authors":"Bo Zhao, Lixian Song, Zhijuan Zou, Zhu Xiong, Yunfeng Zhang, Qin Yang, Zixiong Shi, Yaping Zhang, Yingze Song","doi":"10.1002/adfm.202500079","DOIUrl":"https://doi.org/10.1002/adfm.202500079","url":null,"abstract":"Concurrent regulation of sulfur redox kinetics and lithium deposition homogeneity is a key prerequisite for achieving high-performance lithium–sulfur (Li–S) batteries. To this end, rational design of dual-functional interlayers is recognized as a feasible yet promising approach. Herein, few-layered Ti<sub>3</sub>C<sub>2</sub> MXene flakes are uniformly decorated into the porous carbon nanofiber film via a straightforward electrostatic spinning technique, wherein the Ti<sub>3</sub>C<sub>2</sub> MXene content is fine-tuned to maximum sulfur utilization and stabilize lithium anode. For one thing, it is revealed by synchrotron radiation X-ray three-dimensional nano-computed tomography that Ti<sub>3</sub>C<sub>2</sub> MXene-decorated fiber can expedite polysulfide conversion and induce favorable Li<sub>2</sub>S nucleation. For another, small-angle neutron scattering evidence substantiates that abundant lithiophilic sites are conducive to homogenizing Li-ion flux and promoting lithium deposition during cycling procedure. As a consequence, Li–S batteries maintain a stable operation at 2.0 C over 1000 cycles with a low-capacity degeneration rate of 0.057% per cycle, accompanied by a superior areal capacity of 7.5 mAh cm<sup>−2</sup> when the sulfur loading is increased to 9.5 mg cm<sup>−2</sup>. More encouragingly, the as-assembled multi-layer Li–S pouch cell deliver an impressive cell energy density of 342.3 Wh kg<sup>−1</sup> with smooth cyclic operation.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"13 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418321","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}
Thin-film composite (TFC) membranes are considered as an effective architecture to achieve selective separation for various application scenarios. However, most polymeric separation layers are in physically contacted with an underlying porous substrate, where the physical exfoliation or over-swelling of the selective layer severely shortens the usage lifespan. In this work, a novel interlayer assembly design is proposed to realize a polydimethylsiloxane (PDMS)/polyvinylidene fluoride (PVDF) TFC membrane with ultra-interfacial adhesion via the UV-triggered covalent attachment. Especially, by overcoming the chemical inertness of PVDF, the synthetic methacrylate-functionalized PVDF substrate is rapidly copolymerized with the methacrylate-functionalized PDMS layer. It shows that the critical load for selective layer failure is 56.92 mN with applied nano-scratch, 59% higher than the pristine one and also being the highest interfacial strength among the reported state-of-the-art ones. The resulting membrane also shows an excellent pervaporation performance for phenol than the pristine one, and a stable running with an average separation factor of 7.3 and membrane flux of 3142 g m−2 h−1 under extreme conditions (e.g., high phenol concentration of 20 wt.% and high temperature of 80 °C). This interlayer chemically bonded design principle provides a scalable approach to develop ultra-stable and efficient-separation TFC membranes adaptable to various separation purposes.
{"title":"Interlayer Assembly of Thin-Film Composite Membranes With Ultra-Interfacial Adhesion","authors":"Chao Sang, Siyuan Zhang, Geng Li, Hanzhu Wu, Siyu Pang, Yan Zhuang, Lankun Wang, Shilong Dong, Songyuan Yao, Lu Lu, Zhihao Si, Peng-Fei Cao, Peiyong Qin","doi":"10.1002/adfm.202420130","DOIUrl":"https://doi.org/10.1002/adfm.202420130","url":null,"abstract":"Thin-film composite (TFC) membranes are considered as an effective architecture to achieve selective separation for various application scenarios. However, most polymeric separation layers are in physically contacted with an underlying porous substrate, where the physical exfoliation or over-swelling of the selective layer severely shortens the usage lifespan. In this work, a novel interlayer assembly design is proposed to realize a polydimethylsiloxane (PDMS)/polyvinylidene fluoride (PVDF) TFC membrane with ultra-interfacial adhesion via the UV-triggered covalent attachment. Especially, by overcoming the chemical inertness of PVDF, the synthetic methacrylate-functionalized PVDF substrate is rapidly copolymerized with the methacrylate-functionalized PDMS layer. It shows that the critical load for selective layer failure is 56.92 mN with applied nano-scratch, 59% higher than the pristine one and also being the highest interfacial strength among the reported state-of-the-art ones. The resulting membrane also shows an excellent pervaporation performance for phenol than the pristine one, and a stable running with an average separation factor of 7.3 and membrane flux of 3142 g m<sup>−2</sup> h<sup>−1</sup> under extreme conditions (e.g., high phenol concentration of 20 wt.% and high temperature of 80 °C). This interlayer chemically bonded design principle provides a scalable approach to develop ultra-stable and efficient-separation TFC membranes adaptable to various separation purposes.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"11 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418323","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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