Aqueous ammonium ion batteries (AIBs) have emerged as a promising next‐generation rechargeable battery due to their safety, sustainability, abundant resources, and superior electrochemical performance. However, organic anode materials, particularly polyimide anode materials, suffer from low specific capacity caused by limited active sites. Herein, the study has developed a micro‐granular‐structured π‐conjugated enhanced polyimide (PTPD) as the anode material for AIBs. The large π‐conjugated enhanced structure enables long‐range electron delocalization, decreased bandgap, and reduced spatial steric hindrance, resulting in increased active sites capable of storing NH4+ ions. PTPD exhibits reversible oxidation and reduction reaction in (NH4)2SO4 solution, delivering a high specific capacity of 206.67 mAh g−1 at a current density of 0.5 A g−1, exceptional rate capability, and excellent cycling stability with a capacity retention of 74.28% after 2500 cycles at a current density of 10 A g−1. Furthermore, theoretical simulations and materials analysis demonstrate that PTPD undergoes enol‐keto transformation of carbonyl groups, effectively capturing NH4+ to store charges. This study provides an effective strategy for designing polymer‐based AIBs anodes with high specific capacity and cycling stability.
水铵离子电池（AIBs）因其安全性、可持续性、丰富的资源和优异的电化学性能，已成为一种前景广阔的下一代充电电池。然而，有机负极材料，尤其是聚酰亚胺负极材料，因活性位点有限而导致比容量较低。本研究开发了一种微颗粒结构的π共轭增强聚酰亚胺（PTPD）作为 AIB 的阳极材料。大型π-共轭增强结构可实现长程电子析出、降低带隙并减少空间立体阻碍，从而增加了能够存储 NH4+ 离子的活性位点。PTPD 在 (NH4)2SO4 溶液中表现出可逆的氧化和还原反应，在 0.5 A g-1 的电流密度下可提供 206.67 mAh g-1 的高比容量、卓越的速率能力和出色的循环稳定性，在 10 A g-1 的电流密度下循环 2500 次后容量保持率为 74.28%。此外，理论模拟和材料分析表明，PTPD 会发生羰基的烯醇-酮基转化，从而有效捕获 NH4+ 以存储电荷。这项研究为设计具有高比容量和循环稳定性的聚合物基 AIBs 阳极提供了一种有效的策略。
{"title":"Conjugated Enhanced Polyimide Enables High‐Capacity Ammonium Ion Storage","authors":"Fuyao Huang, Wenkai Zhao, Yujia Guo, Yongqi Mi, Sehrish Gull, Guankui Long, Pengcheng Du","doi":"10.1002/adfm.202407313","DOIUrl":"https://doi.org/10.1002/adfm.202407313","url":null,"abstract":"Aqueous ammonium ion batteries (AIBs) have emerged as a promising next‐generation rechargeable battery due to their safety, sustainability, abundant resources, and superior electrochemical performance. However, organic anode materials, particularly polyimide anode materials, suffer from low specific capacity caused by limited active sites. Herein, the study has developed a micro‐granular‐structured π‐conjugated enhanced polyimide (PTPD) as the anode material for AIBs. The large π‐conjugated enhanced structure enables long‐range electron delocalization, decreased bandgap, and reduced spatial steric hindrance, resulting in increased active sites capable of storing NH<jats:sub>4</jats:sub><jats:sup>+</jats:sup> ions. PTPD exhibits reversible oxidation and reduction reaction in (NH<jats:sub>4</jats:sub>)<jats:sub>2</jats:sub>SO<jats:sub>4</jats:sub> solution, delivering a high specific capacity of 206.67 mAh g<jats:sup>−1</jats:sup> at a current density of 0.5 A g<jats:sup>−1</jats:sup>, exceptional rate capability, and excellent cycling stability with a capacity retention of 74.28% after 2500 cycles at a current density of 10 A g<jats:sup>−1</jats:sup>. Furthermore, theoretical simulations and materials analysis demonstrate that PTPD undergoes enol‐keto transformation of carbonyl groups, effectively capturing NH<jats:sub>4</jats:sub><jats:sup>+</jats:sup> to store charges. This study provides an effective strategy for designing polymer‐based AIBs anodes with high specific capacity and cycling stability.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":null,"pages":null},"PeriodicalIF":19.0,"publicationDate":"2024-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141774763","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}
Tolga Zorlu, I. Brian Becerril‐Castro, Ana Sousa‐Castillo, Begoña Puértolas, Lucas V. Besteiro, Zhiming Wang, Alexander Govorov, Miguel A. Correa‐Duarte, Ramon A. Alvarez‐Puebla
Plasmonic metal–organic frameworks (plasmonic‐MOFs) ingeniously meld the homogeneous and vast porosity of MOFs with the distinctive plasmonic characteristics of metallic nanoparticles (NPs), creating a powerful synergy. This innovative combination is leveraged for enhanced plasmon‐induced hot‐electron photocatalysis, particularly within polystyrene beads adorned with silver nanoparticles (AgNPs) and encapsulated by zeolitic imidazolate framework‐8 (ZIF‐8). The strategic incorporation of AgNPs into this composite material generates hot carriers, significantly enhancing the catalytic performance of ZIF‐8. This approach not only exemplifies the potential for advanced photocatalytic processes of MOFs, but also paves the way for groundbreaking applications in environmental remediation and sustainable chemistry.
{"title":"Metal–Organic Frameworks Photocatalyst Through Plasmon‐Induced Hot‐Electrons","authors":"Tolga Zorlu, I. Brian Becerril‐Castro, Ana Sousa‐Castillo, Begoña Puértolas, Lucas V. Besteiro, Zhiming Wang, Alexander Govorov, Miguel A. Correa‐Duarte, Ramon A. Alvarez‐Puebla","doi":"10.1002/adfm.202410352","DOIUrl":"https://doi.org/10.1002/adfm.202410352","url":null,"abstract":"Plasmonic metal–organic frameworks (plasmonic‐MOFs) ingeniously meld the homogeneous and vast porosity of MOFs with the distinctive plasmonic characteristics of metallic nanoparticles (NPs), creating a powerful synergy. This innovative combination is leveraged for enhanced plasmon‐induced hot‐electron photocatalysis, particularly within polystyrene beads adorned with silver nanoparticles (AgNPs) and encapsulated by zeolitic imidazolate framework‐8 (ZIF‐8). The strategic incorporation of AgNPs into this composite material generates hot carriers, significantly enhancing the catalytic performance of ZIF‐8. This approach not only exemplifies the potential for advanced photocatalytic processes of MOFs, but also paves the way for groundbreaking applications in environmental remediation and sustainable chemistry.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":null,"pages":null},"PeriodicalIF":19.0,"publicationDate":"2024-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141774893","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}
Xiuwen Zheng, Xiangfu Zhou, Yaolong Yang, Wenjie Xiong, Shuling Ye, Yiting Xu, Birong Zeng, Conghui Yuan, Lizong Dai
Organogels are less explored toward on‐sink flexible and stretchable electronics compared to hydrogels, due to the challenges in simultaneously achieving biocompability, satisfactory mechanical properties, environmental‐adaptive adhesion capability, and fast stimuli‐response. Herein, it is shown that a boronate ester polymer organogel with dynamic covalent and hydrogen bonds formed between the polymer networks and organic solvents meets all the above requirements. This is achieved through the gelation of a polymer bearing with boronic acid, imidazolium salt, and amide groups (named QBAM) in ethylene glycol (EG). The strong interactions between the polymer chains and the EG not only improve the toughness of QBAMs, but also inhibit the volatilization of EG, leading to a wide temperature (−10 to 190 °C) adaptability. Due to the abundant hydrogen bonds and electrostatic interaction, QBAM organogels are highly adhesive to a variety of substrates. The presence of imidazolium salt endows QBAM organogels with promising ionic conductivity. Strain sensors fabricated with QBAM organogels fit well on human skin and exhibit the advantages of high strain sensitivity (GF = 9.049), fast response (≈60.4 ms), good cyclic stability, and broaden temperature adaptability. This work opens up a new avenue for the design of multifunctional and biocompatible organogels for on‐skin devices.
{"title":"Anchoring Solvent Molecules onto Polymer Chains Through Dynamic Interactions for a Wide Temperature Range Adaptable and Ultra‐Fast Responsive Adhesive Organogels","authors":"Xiuwen Zheng, Xiangfu Zhou, Yaolong Yang, Wenjie Xiong, Shuling Ye, Yiting Xu, Birong Zeng, Conghui Yuan, Lizong Dai","doi":"10.1002/adfm.202408351","DOIUrl":"https://doi.org/10.1002/adfm.202408351","url":null,"abstract":"Organogels are less explored toward on‐sink flexible and stretchable electronics compared to hydrogels, due to the challenges in simultaneously achieving biocompability, satisfactory mechanical properties, environmental‐adaptive adhesion capability, and fast stimuli‐response. Herein, it is shown that a boronate ester polymer organogel with dynamic covalent and hydrogen bonds formed between the polymer networks and organic solvents meets all the above requirements. This is achieved through the gelation of a polymer bearing with boronic acid, imidazolium salt, and amide groups (named QBAM) in ethylene glycol (EG). The strong interactions between the polymer chains and the EG not only improve the toughness of QBAMs, but also inhibit the volatilization of EG, leading to a wide temperature (−10 to 190 °C) adaptability. Due to the abundant hydrogen bonds and electrostatic interaction, QBAM organogels are highly adhesive to a variety of substrates. The presence of imidazolium salt endows QBAM organogels with promising ionic conductivity. Strain sensors fabricated with QBAM organogels fit well on human skin and exhibit the advantages of high strain sensitivity (GF = 9.049), fast response (≈60.4 ms), good cyclic stability, and broaden temperature adaptability. This work opens up a new avenue for the design of multifunctional and biocompatible organogels for on‐skin devices.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":null,"pages":null},"PeriodicalIF":19.0,"publicationDate":"2024-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141774762","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}
Sluggish ion diffusion of large sodium ions is one of the main drawbacks challenging the development of metal selenides‐based anode materials for sodium‐ion batteries (SIBs). A spin‐state regulating strategy is first proposed in this work to lift the p‐band center (ɛp) of Se for a fast Na+ transfer kinetic in (Co,Cu)Se2. By utilizing the electron transfer from Cu to Co, the π‐symmetry t2g of Co is fully occupied to decrease the spin polarization. The resultant electron repulsion between Co and Se weakens Co–Se bond to lift the ɛp of Se. The enhanced sodium adsorption energy effectively accelerates the ion transfer at the active material–electrolyte interface. As a result, the (Co,Cu)Se2/NC electrode exhibits an superior sodium storage performance with a capacity of 445 mAh g−1 at 0.2 A g−1, 312 mAh g−1 at 50 A g−1, and 363 mAh g−1 after 10 000 cycles at 10.0 A g−1. The insight into the working mechanism of regulating spin‐state of metals to lift the p‐band center of Se can provide guidelines for the development of both metal selenides‐based anode material and high‐performance SIBs.
大钠离子扩散缓慢是钠离子电池 (SIB) 金属硒化物阳极材料开发过程中面临的主要挑战之一。本研究首次提出了一种自旋态调节策略，以提升 Se 的 p 波段中心（ɛp），从而在（Co,Cu）Se2 中实现快速的 Na+ 转移动力学。通过利用从 Cu 到 Co 的电子转移，Co 的 π 对称 t2g 被完全占据，从而降低了自旋极化。Co 和 Se 之间由此产生的电子排斥削弱了 Co-Se 键，从而提高了 Se 的ɛp。钠吸附能的增强有效地加速了活性材料-电解质界面上的离子转移。因此，(Co,Cu)Se2/NC 电极显示出卓越的钠存储性能，在 0.2 A g-1 时容量为 445 mAh g-1，在 50 A g-1 时容量为 312 mAh g-1，在 10.0 A g-1 时循环 10,000 次后容量为 363 mAh g-1。对调节金属自旋态以提升硒的 p 带中心的工作机制的深入了解，可为开发基于金属硒化物的正极材料和高性能 SIB 提供指导。
{"title":"Engineering Metal Electron Spin Polarization to Regulate p‐Band Center of Se for Enhanced Sodium‐Ion Storage","authors":"Dandan Wang, Yunfeng Chao, Kaiyang Guo, Zhuosen Wang, Mingxing Yang, Jianhua Zhu, Xinwei Cui, Qun Xu","doi":"10.1002/adfm.202405642","DOIUrl":"https://doi.org/10.1002/adfm.202405642","url":null,"abstract":"Sluggish ion diffusion of large sodium ions is one of the main drawbacks challenging the development of metal selenides‐based anode materials for sodium‐ion batteries (SIBs). A spin‐state regulating strategy is first proposed in this work to lift the p‐band center (ɛ<jats:sub>p</jats:sub>) of Se for a fast Na<jats:sup>+</jats:sup> transfer kinetic in (Co,Cu)Se<jats:sub>2</jats:sub>. By utilizing the electron transfer from Cu to Co, the π‐symmetry t<jats:sub>2g</jats:sub> of Co is fully occupied to decrease the spin polarization. The resultant electron repulsion between Co and Se weakens Co–Se bond to lift the ɛ<jats:sub>p</jats:sub> of Se. The enhanced sodium adsorption energy effectively accelerates the ion transfer at the active material–electrolyte interface. As a result, the (Co,Cu)Se<jats:sub>2</jats:sub>/NC electrode exhibits an superior sodium storage performance with a capacity of 445 mAh g<jats:sup>−1</jats:sup> at 0.2 A g<jats:sup>−1</jats:sup>, 312 mAh g<jats:sup>−1</jats:sup> at 50 A g<jats:sup>−1</jats:sup>, and 363 mAh g<jats:sup>−1</jats:sup> after 10 000 cycles at 10.0 A g<jats:sup>−1</jats:sup>. The insight into the working mechanism of regulating spin‐state of metals to lift the p‐band center of Se can provide guidelines for the development of both metal selenides‐based anode material and high‐performance SIBs.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":null,"pages":null},"PeriodicalIF":19.0,"publicationDate":"2024-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141774889","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}
Yunting Zhu, Tian Ye, Hailang Wen, Rongbin Xu, Yi Zhong, Guangyang Lin, Dongxue Liang, Weiwei Cai, Daquan Yu, Weiyi Lin
Nanomaterial phonon transport is crucial for miniaturized devices and superior thermophysical properties in condensed matter physics. Diamond nanosheets, applicable in nanoelectronics/optoelectronics, offer availability to explore dimensionality's impact on phonon transport. Raman spectroscopy is used to study the thermal conductivity (κ) of diamond nanosheets with a thickness below 100 nm. Results show a law above 140 K, highlighting Umklapp phonon scattering. Despite the reduced thickness, κ (1100‐2000 W/mK) remains higher than metals and most semiconductors, showcasing diamonds' remarkable in‐plane heat transfer. Intriguingly, the research uncovers unique length‐dependent behavior , consistent with graphene, the two‐dimensional (2D) allotrope. This research offers insights into thermal transport in quasi‐2D nanosheets, with significant implications for nanoscale heat management and highly efficient thermal devices.
在凝聚态物理学中，纳米材料的声子传输对于微型设备和优异的热物理性能至关重要。适用于纳米电子学/光电子学的金刚石纳米片可用于探索尺寸对声子传输的影响。拉曼光谱用于研究厚度低于 100 纳米的金刚石纳米片的热导率 (κ)。结果表明，在 140 K 以上有一个规律，突出显示了 Umklapp 声子散射。尽管厚度减小了，但κ（1100-2000 W/mK）仍然高于金属和大多数半导体，显示了金刚石卓越的面内传热性。有趣的是，这项研究发现了独特的长度依赖行为，与二维（2D）同素异形体石墨烯一致。这项研究深入揭示了准二维纳米片中的热传输，对纳米级热管理和高效热设备具有重要意义。
{"title":"Quasi‐2D Phonon Transport in Diamond Nanosheet","authors":"Yunting Zhu, Tian Ye, Hailang Wen, Rongbin Xu, Yi Zhong, Guangyang Lin, Dongxue Liang, Weiwei Cai, Daquan Yu, Weiyi Lin","doi":"10.1002/adfm.202407333","DOIUrl":"https://doi.org/10.1002/adfm.202407333","url":null,"abstract":"Nanomaterial phonon transport is crucial for miniaturized devices and superior thermophysical properties in condensed matter physics. Diamond nanosheets, applicable in nanoelectronics/optoelectronics, offer availability to explore dimensionality's impact on phonon transport. Raman spectroscopy is used to study the thermal conductivity (κ) of diamond nanosheets with a thickness below 100 nm. Results show a law above 140 K, highlighting Umklapp phonon scattering. Despite the reduced thickness, κ (1100‐2000 W/mK) remains higher than metals and most semiconductors, showcasing diamonds' remarkable in‐plane heat transfer. Intriguingly, the research uncovers unique length‐dependent behavior , consistent with graphene, the two‐dimensional (2D) allotrope. This research offers insights into thermal transport in quasi‐2D nanosheets, with significant implications for nanoscale heat management and highly efficient thermal devices.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":null,"pages":null},"PeriodicalIF":19.0,"publicationDate":"2024-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141774887","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}
Sougata Mallick, Peng Ye, Willem Boutu, David Gauthier, Hamed Merdji, Manuel Bibes, Michel Viret, Karim Bouzehouane, Vincent Cros
Owing to their high mobility and immunity to topological deflection, skyrmions in antiferromagnetic (AFM) systems are gaining attention as a potential solution for next‐generation magnetic data storage. Synthetic antiferromagnets (SAFs) offer a promising avenue to tune the properties of the individual magnetic layers, facilitating the conditions necessary for skyrmions to be used in practical devices. Despite recent advancements achieving fast skyrmion mobility, the nucleation of small and rigid circular skyrmions without an external field remains challenging in SAFs. Theoretical predictions suggest that optical vortex (OAM) beams can stabilize skyrmionic spin textures by transferring their spin and orbital angular momentum to the magnetic material. Here, this intriguing proposal is delved into and the creation of sub‐50 nm compact skyrmions in SAFs using OAM beams is successfully demonstrated, eliminating the need for external magnetic fields. Additionally, the results underscore the importance of beam energy and the number of pulses, as both factors play critical roles in the stabilization of these AFM skyrmionic textures. This breakthrough is significant as it paves the way for stabilizing true zero‐field skyrmions in AFM systems, where magnetization is minimally affected by external magnetic fields. This work will open a potential avenue for stabilizing small, compact skyrmions in antiferroic systems, facilitating their implementation in logic and memory devices.
由于反铁磁（AFM）系统中的天离子具有高流动性和抗拓扑偏转性，因此作为下一代磁性数据存储的潜在解决方案正日益受到关注。合成反铁磁体（SAFs）为调整单个磁层的特性提供了一条大有可为的途径，从而为在实际设备中使用天融子提供了必要条件。尽管最近在实现快速天融子迁移率方面取得了进展，但在 SAF 中，在没有外部磁场的情况下核聚小而坚硬的圆形天融子仍然具有挑战性。理论预测表明，光漩涡（OAM）束可以通过将自旋和轨道角动量传递给磁性材料来稳定天离子自旋纹理。在这里，我们深入探讨了这一引人入胜的建议，并成功演示了利用 OAM 光束在 SAF 中创建 50 纳米以下的紧凑型天空离子，从而消除了对外部磁场的需求。此外，研究结果还强调了光束能量和脉冲数的重要性，因为这两个因素在稳定这些 AFM 天幕纹理方面起着至关重要的作用。这一突破意义重大，因为它为在原子力显微镜系统中稳定真正的零场天电离铺平了道路，在这种系统中，磁化受外部磁场的影响最小。这项工作将为稳定反铁氧体系统中的小型、紧凑的天电离子开辟一条潜在的途径，从而促进它们在逻辑和存储器件中的应用。
{"title":"OAM Driven Nucleation of Sub‐50 nm Compact Antiferromagnetic Skyrmions","authors":"Sougata Mallick, Peng Ye, Willem Boutu, David Gauthier, Hamed Merdji, Manuel Bibes, Michel Viret, Karim Bouzehouane, Vincent Cros","doi":"10.1002/adfm.202409528","DOIUrl":"https://doi.org/10.1002/adfm.202409528","url":null,"abstract":"Owing to their high mobility and immunity to topological deflection, skyrmions in antiferromagnetic (AFM) systems are gaining attention as a potential solution for next‐generation magnetic data storage. Synthetic antiferromagnets (SAFs) offer a promising avenue to tune the properties of the individual magnetic layers, facilitating the conditions necessary for skyrmions to be used in practical devices. Despite recent advancements achieving fast skyrmion mobility, the nucleation of small and rigid circular skyrmions without an external field remains challenging in SAFs. Theoretical predictions suggest that optical vortex (OAM) beams can stabilize skyrmionic spin textures by transferring their spin and orbital angular momentum to the magnetic material. Here, this intriguing proposal is delved into and the creation of sub‐50 nm compact skyrmions in SAFs using OAM beams is successfully demonstrated, eliminating the need for external magnetic fields. Additionally, the results underscore the importance of beam energy and the number of pulses, as both factors play critical roles in the stabilization of these AFM skyrmionic textures. This breakthrough is significant as it paves the way for stabilizing true zero‐field skyrmions in AFM systems, where magnetization is minimally affected by external magnetic fields. This work will open a potential avenue for stabilizing small, compact skyrmions in antiferroic systems, facilitating their implementation in logic and memory devices.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":null,"pages":null},"PeriodicalIF":19.0,"publicationDate":"2024-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141774895","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 directional and dynamic hydrogen bonds are of vital importance for both nucleic acids and proteins, but they naturally apply strong multiple hydrogen bonds in pendant groups and weak single hydrogen bond in the backbone. The hierarchy and orthogonality of multiple and single hydrogen bonds in biological systems inspire to elegantly tailor the supramolecular polymeric materials for robust mechanical properties. Herein, this work has fabricated dynamic ultrastrong and tough supramolecular materials through bioinspired rational design of strong multiple hydrogen bonds in pendant groups and weak single hydrogen bond in the backbone. Based on quadruple hydrogen bonds of ureidopyrimidinone and single hydrogen bond of amide, the supramolecular polymer with optimized hierarchical hydrogen bonds possesses high tensile strength and strong toughness of 30.6 MPa and 74.0 MJ m−3, respectively. Meanwhile, the dynamic dissociation and reformation of the hierarchical hydrogen bonds endow the supramolecular polymer with efficient crack resistance, self‐healing, recyclability, and high energy dissipation. Flexible and self‐healing conductors can be prepared by blending the supramolecular polymer with liquid metal in a simple manner. Therefore, this work expects that the plenty of hydrogen bonding pairs in the supramolecular toolkit provide many opportunities to produce robust and tough supramolecular polymeric materials without covalent crosslinking.
{"title":"Hierarchical Hydrogen Bonds Endow Supramolecular Polymers with High Strength, Toughness, and Self‐Healing Properties","authors":"Jiang Wu, Fanxuan Zeng, Ziyang Fan, Shouhu Xuan, Zan Hua, Guangming Liu","doi":"10.1002/adfm.202410518","DOIUrl":"https://doi.org/10.1002/adfm.202410518","url":null,"abstract":"The directional and dynamic hydrogen bonds are of vital importance for both nucleic acids and proteins, but they naturally apply strong multiple hydrogen bonds in pendant groups and weak single hydrogen bond in the backbone. The hierarchy and orthogonality of multiple and single hydrogen bonds in biological systems inspire to elegantly tailor the supramolecular polymeric materials for robust mechanical properties. Herein, this work has fabricated dynamic ultrastrong and tough supramolecular materials through bioinspired rational design of strong multiple hydrogen bonds in pendant groups and weak single hydrogen bond in the backbone. Based on quadruple hydrogen bonds of ureidopyrimidinone and single hydrogen bond of amide, the supramolecular polymer with optimized hierarchical hydrogen bonds possesses high tensile strength and strong toughness of 30.6 MPa and 74.0 MJ m<jats:sup>−3</jats:sup>, respectively. Meanwhile, the dynamic dissociation and reformation of the hierarchical hydrogen bonds endow the supramolecular polymer with efficient crack resistance, self‐healing, recyclability, and high energy dissipation. Flexible and self‐healing conductors can be prepared by blending the supramolecular polymer with liquid metal in a simple manner. Therefore, this work expects that the plenty of hydrogen bonding pairs in the supramolecular toolkit provide many opportunities to produce robust and tough supramolecular polymeric materials without covalent crosslinking.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":null,"pages":null},"PeriodicalIF":19.0,"publicationDate":"2024-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141774767","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}
Ruxia Fan, Katarina Knuuttila, Benjamin Schmuck, Gabriele Greco, Anna Rising, Markus B. Linder, A. Sesilja Aranko
Despite impressive progress in the field, there are still several major bottlenecks in producing fibers from recombinantly produced spider‐silk‐like proteins to replicate the extraordinary mechanical properties of spider major ampullate silk. The conventional artificial fiber spinning processes rely primarily on organic solvents to coagulate proteins into fibers and require complex post‐treatments to obtain fibers with valuable properties. This is due to challenges in obtaining soluble silk proteins, but also because the native silk spinning process leading to the hierarchical organization of the silk proteins is not fully understood and is hard to replicate in a manner applicable to industrial settings. Here, recombinant spider‐silk fusion proteins are efficiently produced and processed into as‐spun fibers with a toughness modulus of 120 MJ m−3 and extensibility of 255% using solely aqueous solutions. The spider‐silk fusion proteins assemble in a manner similar to that reported for native spider silk: they phase separate induced by salting out, followed by alignment and a secondary structure transition triggered by shear forces and dehydration. Finally, the design of the fusion silk proteins enables straightforward functionalization of the fibers under mild all‐aqueous conditions via a simple biomolecular click reaction both pre‐ and post‐spinning.
{"title":"Sustainable Spinning of Artificial Spider Silk Fibers with Excellent Toughness and Inherent Potential for Functionalization","authors":"Ruxia Fan, Katarina Knuuttila, Benjamin Schmuck, Gabriele Greco, Anna Rising, Markus B. Linder, A. Sesilja Aranko","doi":"10.1002/adfm.202410415","DOIUrl":"https://doi.org/10.1002/adfm.202410415","url":null,"abstract":"Despite impressive progress in the field, there are still several major bottlenecks in producing fibers from recombinantly produced spider‐silk‐like proteins to replicate the extraordinary mechanical properties of spider major ampullate silk. The conventional artificial fiber spinning processes rely primarily on organic solvents to coagulate proteins into fibers and require complex post‐treatments to obtain fibers with valuable properties. This is due to challenges in obtaining soluble silk proteins, but also because the native silk spinning process leading to the hierarchical organization of the silk proteins is not fully understood and is hard to replicate in a manner applicable to industrial settings. Here, recombinant spider‐silk fusion proteins are efficiently produced and processed into as‐spun fibers with a toughness modulus of 120 MJ m<jats:sup>−3</jats:sup> and extensibility of 255% using solely aqueous solutions. The spider‐silk fusion proteins assemble in a manner similar to that reported for native spider silk: they phase separate induced by salting out, followed by alignment and a secondary structure transition triggered by shear forces and dehydration. Finally, the design of the fusion silk proteins enables straightforward functionalization of the fibers under mild all‐aqueous conditions via a simple biomolecular click reaction both pre‐ and post‐spinning.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":null,"pages":null},"PeriodicalIF":19.0,"publicationDate":"2024-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141774890","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}
Alina A. Manshina, Ilya I. Tumkin, Evgeniia M. Khairullina, Mizue Mizoshiri, Andreas Ostendorf, Sergei A. Kulinich, Sergey Makarov, Aleksandr A. Kuchmizhak, Evgeny L. Gurevich
The use of photons to directly or indirectly drive chemical reactions has revolutionized the field of nanomaterial synthesis resulting in appearance of new sustainable laser chemistry methods for manufacturing of micro‐ and nanostructures. The incident laser radiation triggers a complex interplay between the chemical and physical processes at the interface between the solid surface and the liquid or gas environment. In such a multi‐parameter system, the precise control over the resulting nanostructures is not possible without deep understanding of both environment‐affected chemical and physical processes. The present review intends to provide detailed systematization of these processes surveying both well‐established and emerging laser technologies for production of advanced nanostructures and nanomaterials. Both gases and liquids are considered as potential reacting environments affecting the fabrication process, while subtractive and additive manufacturing methods are analyzed. Finally, the prospects and emerging applications of such technologies are discussed.
{"title":"The Second Laser Revolution in Chemistry: Emerging Laser Technologies for Precise Fabrication of Multifunctional Nanomaterials and Nanostructures","authors":"Alina A. Manshina, Ilya I. Tumkin, Evgeniia M. Khairullina, Mizue Mizoshiri, Andreas Ostendorf, Sergei A. Kulinich, Sergey Makarov, Aleksandr A. Kuchmizhak, Evgeny L. Gurevich","doi":"10.1002/adfm.202405457","DOIUrl":"https://doi.org/10.1002/adfm.202405457","url":null,"abstract":"The use of photons to directly or indirectly drive chemical reactions has revolutionized the field of nanomaterial synthesis resulting in appearance of new sustainable laser chemistry methods for manufacturing of micro‐ and nanostructures. The incident laser radiation triggers a complex interplay between the chemical and physical processes at the interface between the solid surface and the liquid or gas environment. In such a multi‐parameter system, the precise control over the resulting nanostructures is not possible without deep understanding of both environment‐affected chemical and physical processes. The present review intends to provide detailed systematization of these processes surveying both well‐established and emerging laser technologies for production of advanced nanostructures and nanomaterials. Both gases and liquids are considered as potential reacting environments affecting the fabrication process, while subtractive and additive manufacturing methods are analyzed. Finally, the prospects and emerging applications of such technologies are discussed.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":null,"pages":null},"PeriodicalIF":19.0,"publicationDate":"2024-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141774888","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}
Haoran Shi, Huanxin Huo, Hongxing Yang, Hongshan Li, Jingjie Shen, Jianyong Wan, Guanben Du, Long Yang
Cellulose consists of a natural, rigid polymer that is widely used to improve the mechanical and water‐holding properties of hydrogels. However, its abundant hydroxyl groups make it highly absorbent to free water, leading to swelling behavior. This increased free water content will also decrease mechanical and adhesive performance. In this study, cellulose is successfully hydrophobically modified to reduce its absorption of free water. Gelatin is then cross‐linked with cellulose through a Schiff‐base reaction, resulting in increased bound water content. This significantly enhances resistance to swelling and permeability, and improves the freeze–thaw stability of the hydrogel. Due to its internal hydrophobicity, water molecules can quickly penetrate into the interior, reducing their residence time on the hydrogel surface. This allows the hydrogel to maintain high adhesion in natural environments, achieving an adhesion strength of up to 3.0 MPa on wood and bamboo‐based materials. The hydrogel can retain its adhesive properties even after prolonged exposure to a humid environment. Additionally, Na+ ions enhance the electrical conductivity and sensitivity of the hydrogel (gauge factor (GF) = 1.51), demonstrating its potential applications in flexible sensing.
{"title":"Cellulose‐Based Dual‐Network Conductive Hydrogel with Exceptional Adhesion","authors":"Haoran Shi, Huanxin Huo, Hongxing Yang, Hongshan Li, Jingjie Shen, Jianyong Wan, Guanben Du, Long Yang","doi":"10.1002/adfm.202408560","DOIUrl":"https://doi.org/10.1002/adfm.202408560","url":null,"abstract":"Cellulose consists of a natural, rigid polymer that is widely used to improve the mechanical and water‐holding properties of hydrogels. However, its abundant hydroxyl groups make it highly absorbent to free water, leading to swelling behavior. This increased free water content will also decrease mechanical and adhesive performance. In this study, cellulose is successfully hydrophobically modified to reduce its absorption of free water. Gelatin is then cross‐linked with cellulose through a Schiff‐base reaction, resulting in increased bound water content. This significantly enhances resistance to swelling and permeability, and improves the freeze–thaw stability of the hydrogel. Due to its internal hydrophobicity, water molecules can quickly penetrate into the interior, reducing their residence time on the hydrogel surface. This allows the hydrogel to maintain high adhesion in natural environments, achieving an adhesion strength of up to 3.0 MPa on wood and bamboo‐based materials. The hydrogel can retain its adhesive properties even after prolonged exposure to a humid environment. Additionally, Na<jats:sup>+</jats:sup> ions enhance the electrical conductivity and sensitivity of the hydrogel (gauge factor (GF) = 1.51), demonstrating its potential applications in flexible sensing.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":null,"pages":null},"PeriodicalIF":19.0,"publicationDate":"2024-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141774891","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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