Donghan Li, Shurui Ning, Lu Yu, Fan Jiang, Dawei Zhao, Shixin Zhang, Mingyi Liao, Qingshi Meng, Qinghong Fang, Hailan Kang, Long Li
To address the challenges associated with the difficult recycling of fluorinated specialty materials and the subpar performance of recycled products, a molecular reconstruction strategy of oxidative degradation, fluorination addition is reported, and end-group transformation, which upcycled waste fluororubber into high-performance, chemically awakenable amino-terminated low-molecular-weight fluoropolymer (ATLF-Boc). Leveraging the chemical properties of the vinylidene fluoride structure in the waste fluororubber, carboxyl-terminated low-molecular-weight fluoropolymer (CTLF) with controlled molecular weight and end-group content are synthesized. Further, the whole chain is structurally strengthened at the molecular scale to achieve higher fluorine content and thermal stability, and saturated carboxyl-terminated low-molecular-weight fluoropolymer (SCTLF) is synthesized. Subsequently, to balance high reactivity and stable storage, high-performance ATLF-Boc is synthesized, realizing the upcycling of waste fluororubber. After upcycling, the awakened ATLF exhibits a high fluorine content (66.95%), and the cured ATLF shows the regulation of surface hydrophilicity and hydrophobicity (between 43° and 114°), a high tensile strength of 13.3 MPa, an excellent thermal stability (T10% = 359 °C). In this study, a novel solution for the upcycling of waste fluororubbers for fabricating functional materials is offered, which is of great significance in the field of fluorinated specialty materials.
{"title":"Molecular Reconstruction for the High-Performance Recycled Fluororubbers","authors":"Donghan Li, Shurui Ning, Lu Yu, Fan Jiang, Dawei Zhao, Shixin Zhang, Mingyi Liao, Qingshi Meng, Qinghong Fang, Hailan Kang, Long Li","doi":"10.1002/adma.202501622","DOIUrl":"https://doi.org/10.1002/adma.202501622","url":null,"abstract":"To address the challenges associated with the difficult recycling of fluorinated specialty materials and the subpar performance of recycled products, a molecular reconstruction strategy of oxidative degradation, fluorination addition is reported, and end-group transformation, which upcycled waste fluororubber into high-performance, chemically awakenable amino-terminated low-molecular-weight fluoropolymer (ATLF-Boc). Leveraging the chemical properties of the vinylidene fluoride structure in the waste fluororubber, carboxyl-terminated low-molecular-weight fluoropolymer (CTLF) with controlled molecular weight and end-group content are synthesized. Further, the whole chain is structurally strengthened at the molecular scale to achieve higher fluorine content and thermal stability, and saturated carboxyl-terminated low-molecular-weight fluoropolymer (SCTLF) is synthesized. Subsequently, to balance high reactivity and stable storage, high-performance ATLF-Boc is synthesized, realizing the upcycling of waste fluororubber. After upcycling, the awakened ATLF exhibits a high fluorine content (66.95%), and the cured ATLF shows the regulation of surface hydrophilicity and hydrophobicity (between 43° and 114°), a high tensile strength of 13.3 MPa, an excellent thermal stability (T<sub>10%</sub> = 359 °C). In this study, a novel solution for the upcycling of waste fluororubbers for fabricating functional materials is offered, which is of great significance in the field of fluorinated specialty materials.","PeriodicalId":114,"journal":{"name":"Advanced Materials","volume":"16 1","pages":""},"PeriodicalIF":29.4,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143805989","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}
Thermoelectric (TE) materials can interconvert electricity into heat, rendering them versatile for refrigeration and power generation. GeTe as a distinguished TE material has attracted considerable focus owing to its excellent TE performance. Herein, the milestones of research progress on GeTe are reviewed. The intrinsic potentials of GeTe are elaborated, mainly focusing on crystal structure, band structure and microstructures. The path of GeTe-based thermoelectrics from performance optimization to the devices is attempted to chart, referring to its shortcomings and characteristics. Primarily, optimization of the synthesis process is implemented to inhibit the generation of Ge precipitates and phonon migration. Furthermore, the thermoelectric performance of GeTe is enhanced through its features, including phase transition, multiple valence bands, and various microstructures via doping and alloying. Subsequently, the advancements of GeTe thermoelectric devices are presented from the aspect of device integration. Eventually, the prospect and challenges for the future direction of GeTe-based materials are proposed, offering a roadmap to inject vitality into further developments.
{"title":"Advanced GeTe-Based Thermoelectrics: Charting the Path from Performance Optimization to Devices","authors":"Yang Jin, Yuting Qiu, Caofeng Pan, Li-Dong Zhao","doi":"10.1002/adma.202500802","DOIUrl":"https://doi.org/10.1002/adma.202500802","url":null,"abstract":"Thermoelectric (TE) materials can interconvert electricity into heat, rendering them versatile for refrigeration and power generation. GeTe as a distinguished TE material has attracted considerable focus owing to its excellent TE performance. Herein, the milestones of research progress on GeTe are reviewed. The intrinsic potentials of GeTe are elaborated, mainly focusing on crystal structure, band structure and microstructures. The path of GeTe-based thermoelectrics from performance optimization to the devices is attempted to chart, referring to its shortcomings and characteristics. Primarily, optimization of the synthesis process is implemented to inhibit the generation of Ge precipitates and phonon migration. Furthermore, the thermoelectric performance of GeTe is enhanced through its features, including phase transition, multiple valence bands, and various microstructures via doping and alloying. Subsequently, the advancements of GeTe thermoelectric devices are presented from the aspect of device integration. Eventually, the prospect and challenges for the future direction of GeTe-based materials are proposed, offering a roadmap to inject vitality into further developments.","PeriodicalId":114,"journal":{"name":"Advanced Materials","volume":"21 1","pages":""},"PeriodicalIF":29.4,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143805985","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}
Inspired by biological systems, neuromorphic computing can process extensive data and complex tasks more efficiently than traditional architectures. Artificial synaptic devices, serving as fundamental components in neuromorphic computing, needto closely mimic synaptic characteristics and construct neural network computing systems. However, most existing multifunctional synapse devices are structurally complex and lack tunability, making them unsuitable for building smarter computing systems. In this work, a flexible tunable-plasticity synaptic transistor (TST) is realized with memory modulation and neuromorphic computing capabilities by using indium gallium zinc oxide as channel and a hybrid layer of polyimide and Al2O3 as dielectric. The TST exhibits a novel transition from short-term plasticity to long-term one by adjusting stimulus amplitude, mirroring dynamic human memory and forgetting behaviors across various scenarios. A neural network system with low non-linearity and a wide range of conductance variations is constructed, and it demonstrates a 94.1% recognition rate on classical datasets. A reservoir computing system for 4-bit coding is also developed, which significantly reduces computational complexity and network size without sacrificing recognition accuracy. The devices and the system work as the foundation of more intelligent and more efficient computing systems.
{"title":"Flexible Tunable-Plasticity Synaptic Transistors for Mimicking Dynamic Cognition and Reservoir Computing","authors":"Sixin Zhang, Jiahao Zhu, Rui Qiu, Dexing Liu, Qinqi Ren, Min Zhang","doi":"10.1002/adma.202418418","DOIUrl":"https://doi.org/10.1002/adma.202418418","url":null,"abstract":"Inspired by biological systems, neuromorphic computing can process extensive data and complex tasks more efficiently than traditional architectures. Artificial synaptic devices, serving as fundamental components in neuromorphic computing, needto closely mimic synaptic characteristics and construct neural network computing systems. However, most existing multifunctional synapse devices are structurally complex and lack tunability, making them unsuitable for building smarter computing systems. In this work, a flexible tunable-plasticity synaptic transistor (TST) is realized with memory modulation and neuromorphic computing capabilities by using indium gallium zinc oxide as channel and a hybrid layer of polyimide and Al<sub>2</sub>O<sub>3</sub> as dielectric. The TST exhibits a novel transition from short-term plasticity to long-term one by adjusting stimulus amplitude, mirroring dynamic human memory and forgetting behaviors across various scenarios. A neural network system with low non-linearity and a wide range of conductance variations is constructed, and it demonstrates a 94.1% recognition rate on classical datasets. A reservoir computing system for 4-bit coding is also developed, which significantly reduces computational complexity and network size without sacrificing recognition accuracy. The devices and the system work as the foundation of more intelligent and more efficient computing systems.","PeriodicalId":114,"journal":{"name":"Advanced Materials","volume":"38 1","pages":""},"PeriodicalIF":29.4,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143805988","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}
Despite the rapid development of perovskite solar cells (PSCs) in the past decade, the open-circuit voltage (VOC) of PSCs still lags behind the theoretical Shockley–Queisser limit. Energy-level mismatch and unwanted nonradiative recombination at key interfaces are the main factors detrimental to VOC. Herein, a perovskite crystallization-driven template is constructed at the SnO2/perovskite buried interface through a self-assembled amphiphilic phosphonate derivative. The highly oriented supramolecular template grows from an evolutionary selection growth via solid–solid phase transition. This strategy induces perovskite crystallization into a highly preferred (100) orientation toward out-of-plane direction and facilitated carrier extraction and transfer due to the elimination of energy barrier. This self-assembly process positively passivates the intrinsic surface defects at the SnO2/perovskite interface through the functionalized moieties, a marked contrast to the passive effect achieved via incidental contacts in conventional passivation methods. As a result, PSCs with buried interface modification exhibit a promising PCE of 25.34%, with a maximum VOC of 1.23 V, corresponding to a mere 0.306 V deficit (for perovskite bandgap of 1.536 eV), reaching 97.2% of the theoretical VOC limit. This strategy spontaneously improves the long-term operational stability of PSCs under thermal and moisture stress (ISOS-L-3: MPP, 65 °C, 50% RH, T92 lifetime exceeding 1200 h).
{"title":"Buried Interface Regulation with a Supramolecular Assembled Template Enables High-Performance Perovskite Solar Cells for Minimizing the VOC Deficit","authors":"Zhenrong Wang, Qiong Liang, Mingliang Li, Guohao Sun, Shiang Li, Tao Zhu, Yu Han, Hao Xia, Zhiwei Ren, Bingcheng Yu, Jiyao Zhang, Ruijie Ma, Thachoth Chandran Hrisheekesh, Lei Cheng, Liren Zhang, Dongyang Li, Shuyan Chen, Xinhui Lu, Chang Yan, Randi Azmi, Kuan Liu, Jinyao Tang, Gang Li","doi":"10.1002/adma.202418011","DOIUrl":"https://doi.org/10.1002/adma.202418011","url":null,"abstract":"Despite the rapid development of perovskite solar cells (PSCs) in the past decade, the open-circuit voltage (<i>V</i><sub>OC</sub>) of PSCs still lags behind the theoretical Shockley–Queisser limit. Energy-level mismatch and unwanted nonradiative recombination at key interfaces are the main factors detrimental to <i>V</i><sub>OC</sub>. Herein, a perovskite crystallization-driven template is constructed at the SnO<sub>2</sub>/perovskite buried interface through a self-assembled amphiphilic phosphonate derivative. The highly oriented supramolecular template grows from an evolutionary selection growth via solid–solid phase transition. This strategy induces perovskite crystallization into a highly preferred (100) orientation toward out-of-plane direction and facilitated carrier extraction and transfer due to the elimination of energy barrier. This self-assembly process positively passivates the intrinsic surface defects at the SnO<sub>2</sub>/perovskite interface through the functionalized moieties, a marked contrast to the passive effect achieved via incidental contacts in conventional passivation methods. As a result, PSCs with buried interface modification exhibit a promising PCE of 25.34%, with a maximum <i>V</i><sub>OC</sub> of 1.23 V, corresponding to a mere 0.306 V deficit (for perovskite bandgap of 1.536 eV), reaching 97.2% of the theoretical <i>V</i><sub>OC</sub> limit. This strategy spontaneously improves the long-term operational stability of PSCs under thermal and moisture stress (ISOS-L-3: MPP, 65 °C, 50% RH, T<sub>92</sub> lifetime exceeding 1200 h).","PeriodicalId":114,"journal":{"name":"Advanced Materials","volume":"125 1","pages":""},"PeriodicalIF":29.4,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143805990","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}
Huimin Lu, Lei Zhang, Jingyan Jiang, Jian Song, Zhongchao Zhou, Wujian Wu, Ziqian Cheng, Tengfei Yan, Hong Hu, Tingting Zhao, Zhen Xu, Siyi Luo, Hui Li, Jianhua Zhang, Charles H. Lawrie
Conjugated polymers (CPs) show great potential for pressure detection due to the amorphous polymer packing, but a lack of clarity regarding sensing mechanisms hampers the development of further applications. Herein, a sacrificial template‐full solution method with both rough surface and high conductivity is described that can be applied to sandwich‐structured resistive pressure sensors. Transient absorption measurements demonstrate the significant increase of carrier lifetime (from 1.44 to 2.54 ns) induced by pressure, which directly evidenced the superior sensing mechanism of sidechain doped conjugated polymer. This sensor displayed low‐pressure detection limit of 0.7 Pa as well as a rapid response time of 18.8 ms, enabling multi‐mode motion analysis including wrist pulse, swallowing, finger bending, grabbing, and typing. Additionally, an intelligent vocal recognition system with convolutional neural networks is used which can achieve >96% classification accuracy across diverse vocal profiles. This general approach is anticipated and enables a new direction for the development of pressure sensors.
{"title":"Pressure Induced Molecular‐Arrangement and Charge‐Density Perturbance in Doped Polymer for Intelligent Motion and Vocal Recognitions","authors":"Huimin Lu, Lei Zhang, Jingyan Jiang, Jian Song, Zhongchao Zhou, Wujian Wu, Ziqian Cheng, Tengfei Yan, Hong Hu, Tingting Zhao, Zhen Xu, Siyi Luo, Hui Li, Jianhua Zhang, Charles H. Lawrie","doi":"10.1002/adma.202500077","DOIUrl":"https://doi.org/10.1002/adma.202500077","url":null,"abstract":"Conjugated polymers (CPs) show great potential for pressure detection due to the amorphous polymer packing, but a lack of clarity regarding sensing mechanisms hampers the development of further applications. Herein, a sacrificial template‐full solution method with both rough surface and high conductivity is described that can be applied to sandwich‐structured resistive pressure sensors. Transient absorption measurements demonstrate the significant increase of carrier lifetime (from 1.44 to 2.54 ns) induced by pressure, which directly evidenced the superior sensing mechanism of sidechain doped conjugated polymer. This sensor displayed low‐pressure detection limit of 0.7 Pa as well as a rapid response time of 18.8 ms, enabling multi‐mode motion analysis including wrist pulse, swallowing, finger bending, grabbing, and typing. Additionally, an intelligent vocal recognition system with convolutional neural networks is used which can achieve >96% classification accuracy across diverse vocal profiles. This general approach is anticipated and enables a new direction for the development of pressure sensors.","PeriodicalId":114,"journal":{"name":"Advanced Materials","volume":"29 1","pages":""},"PeriodicalIF":29.4,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143805920","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}
Living tubular organs can spatiotemporally and cyclically deform their muscular walls to implement adaptable and sustainable peristaltic pumping applicable to broad matter, achieved via asymmetric and non-equilibrium self-oscillating deformations of muscular walls. However, man-made tubular soft actuators have been limited to pumping a few simple matters, because of their reciprocal and monotonic wall motions that cannot break time-reversal symmetry and system equilibrium to gain adaptable and sustainable pumping. Here, a phototunable Rayleigh 3D soft self-oscillator (PR3DSSO) capable of multimodal, nonreciprocal, self-sustainable wall deformations is presented. PR3DSSO's design leverages two direction-and-dimension-phototunable tubular instabilities: snapping and postbuckling. The post-buckling instability can generate local-wall origami which cannot only fold local walls into multimodal shape-mode waves, but also break wall-motion symmetry; snapping instabilities help break equilibrium in wall motions to initiate autonomous wall motions. These phototunable-instabilities-driven wall deformations unprecedentedly create Rayleigh-like 3D wall motions, which allow for versatile biomimetic tubular peristaltic pumping adapt to broad matter. Our PR3DSSO would spur creative life-like active-material designs and novel pumping functions.
{"title":"Phototunable Rayleigh 3D Soft Self-Oscillator Enabling Versatile Biomimetic Tubular Peristaltic Pumping","authors":"Tonghui Zhao, Jiu-an Lv","doi":"10.1002/adma.202502434","DOIUrl":"https://doi.org/10.1002/adma.202502434","url":null,"abstract":"Living tubular organs can spatiotemporally and cyclically deform their muscular walls to implement adaptable and sustainable peristaltic pumping applicable to broad matter, achieved via asymmetric and non-equilibrium self-oscillating deformations of muscular walls. However, man-made tubular soft actuators have been limited to pumping a few simple matters, because of their reciprocal and monotonic wall motions that cannot break time-reversal symmetry and system equilibrium to gain adaptable and sustainable pumping. Here, a phototunable Rayleigh 3D soft self-oscillator (PR3DSSO) capable of multimodal, nonreciprocal, self-sustainable wall deformations is presented. PR3DSSO's design leverages two direction-and-dimension-phototunable tubular instabilities: snapping and postbuckling. The post-buckling instability can generate local-wall origami which cannot only fold local walls into multimodal shape-mode waves, but also break wall-motion symmetry; snapping instabilities help break equilibrium in wall motions to initiate autonomous wall motions. These phototunable-instabilities-driven wall deformations unprecedentedly create Rayleigh-like 3D wall motions, which allow for versatile biomimetic tubular peristaltic pumping adapt to broad matter. Our PR3DSSO would spur creative life-like active-material designs and novel pumping functions.","PeriodicalId":114,"journal":{"name":"Advanced Materials","volume":"91 1","pages":""},"PeriodicalIF":29.4,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143805986","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}
Yang Liu, Chunling Wang, Pengfei Wei, Chengzhi Yang, Xiaoyu Cheng, Yinlong Zhang, Guangjun Nie
The severe bleeding complications of long-term antiplatelet therapy limit its broader application in the treatment or prevention of thrombosis-associated diseases. This risk is particularly serious when facing emergency surgeries where rapid restoration of normal platelet function is required. Timely reversal of the effects of antiplatelet agents becomes crucial in such scenarios. Despite the widespread use of clopidogrel and prasugrel for their potent antiplatelet activity, the absence of specific and effective reversal agents remains a notable challenge. The pharmacological activity of clopidogrel and prasugrel is mediated by sulfhydryl-containing active metabolites, which form disulfide bonds with P2Y12 receptors on the surface of platelets to inhibit their aggregation. Taking advantage of this action mechanism of these “irreversible” antiplatelet drugs, click chemistry-functionalized mesoporous silica (SiO2-Mal) nanotraps are fabricated to capture the antiplatelet drugs' active metabolites and restore hemostasis. Subsequently, a comprehensive assessment of the effectiveness and safety of the SiO2-Mal nanotraps is conducted using mouse, rabbit, and pig animal models, highlighting their potential application as a functional reversal agent for clinically relevant thienopyridine antiplatelet drugs, believed until now to be irreversible in their inhibition of platelet activity.
{"title":"Mesoporous Silica Nanotraps for Mitigating Bleeding Risk From ‘Irreversible’ Antiplatelet Drugs","authors":"Yang Liu, Chunling Wang, Pengfei Wei, Chengzhi Yang, Xiaoyu Cheng, Yinlong Zhang, Guangjun Nie","doi":"10.1002/adma.202501576","DOIUrl":"https://doi.org/10.1002/adma.202501576","url":null,"abstract":"The severe bleeding complications of long-term antiplatelet therapy limit its broader application in the treatment or prevention of thrombosis-associated diseases. This risk is particularly serious when facing emergency surgeries where rapid restoration of normal platelet function is required. Timely reversal of the effects of antiplatelet agents becomes crucial in such scenarios. Despite the widespread use of clopidogrel and prasugrel for their potent antiplatelet activity, the absence of specific and effective reversal agents remains a notable challenge. The pharmacological activity of clopidogrel and prasugrel is mediated by sulfhydryl-containing active metabolites, which form disulfide bonds with P2Y<sub>12</sub> receptors on the surface of platelets to inhibit their aggregation. Taking advantage of this action mechanism of these “irreversible” antiplatelet drugs, click chemistry-functionalized mesoporous silica (SiO<sub>2</sub>-Mal) nanotraps are fabricated to capture the antiplatelet drugs' active metabolites and restore hemostasis. Subsequently, a comprehensive assessment of the effectiveness and safety of the SiO<sub>2</sub>-Mal nanotraps is conducted using mouse, rabbit, and pig animal models, highlighting their potential application as a functional reversal agent for clinically relevant thienopyridine antiplatelet drugs, believed until now to be irreversible in their inhibition of platelet activity.","PeriodicalId":114,"journal":{"name":"Advanced Materials","volume":"31 1","pages":""},"PeriodicalIF":29.4,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143798424","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}
Dilong Liu, Zhaoting Zhu, An Cao, Yue Li, Yadong Yin
Emulsions are versatile and robust platforms for colloidal self-assembly, but their ability to create complex and functional superstructures is hindered by the inherent symmetry of droplets. Here the creation of an aerosol of nested transient emulsion droplets with inherent asymmetry is reported, achieved by converging beams of water and 1-butanol mists. Self-assembly of nanoparticles occurs within such emulsion droplets as driven by the rapid two-phase interface diffusion, producing anisotropic superstructures. A unique hollowing process is observed due to the asymmetric diffusion of solvents, akin to the Kirkendall effect. This novel assembly platform offers several advantages, including asymmetric self-assembly in air, surfactant-free operation, and tunable droplet size. It enables the creation of clean, functional nanoparticle superstructures that can be easily disassembled when needed. These advancements pave the way for exploring intricate, anisotropic superstructures with diverse applications that are unavailable in conventional superstructures of spherical symmetry.
{"title":"Asymmetric Self-Assembly of Colloidal Superstructures in Nested Transient Emulsion Aerosols","authors":"Dilong Liu, Zhaoting Zhu, An Cao, Yue Li, Yadong Yin","doi":"10.1002/adma.202420269","DOIUrl":"https://doi.org/10.1002/adma.202420269","url":null,"abstract":"Emulsions are versatile and robust platforms for colloidal self-assembly, but their ability to create complex and functional superstructures is hindered by the inherent symmetry of droplets. Here the creation of an aerosol of nested transient emulsion droplets with inherent asymmetry is reported, achieved by converging beams of water and 1-butanol mists. Self-assembly of nanoparticles occurs within such emulsion droplets as driven by the rapid two-phase interface diffusion, producing anisotropic superstructures. A unique hollowing process is observed due to the asymmetric diffusion of solvents, akin to the Kirkendall effect. This novel assembly platform offers several advantages, including asymmetric self-assembly in air, surfactant-free operation, and tunable droplet size. It enables the creation of clean, functional nanoparticle superstructures that can be easily disassembled when needed. These advancements pave the way for exploring intricate, anisotropic superstructures with diverse applications that are unavailable in conventional superstructures of spherical symmetry.","PeriodicalId":114,"journal":{"name":"Advanced Materials","volume":"30 1","pages":""},"PeriodicalIF":29.4,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143798460","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 selective CO2 electroreduction (CO2R) toward specific C2 products represents a critical challenge for practical applicability, requiring precise control over *CO intermediates. Herein, a “polymer-halogen” pocketed Cu catalyst is proposed, wherein the adjustable concentration of Iodide ion (I−) within the pocket enables continuous modulation of *CO adsorption configurations on the Cu, thereby enabling tailored CO2R toward ethylene or ethanol production. A perfluorosulfonic acid (PFSA)-modified CuI catalyst is constructed, where I− is in situ leaching from CuI and subsequently confined by PFSA as an anion shielding layer to form polymer-halogen pockets. By tuning the thickness of PFSA shell, the amount of I− in the pocket can be controlled. The surface-enhanced in situ Raman spectroscopy demonstrates that the coverage of *CO intermediates on Cu surface increases and tends to adsorb at low coordination Cu sites in catalyst granule for dimerization reaction as the I− concentration in the pocket increases. Furthermore, the coordination environment exhibits distinct product selectivity. *CO at medium-coordinated sites favor ethanol production, while those at low-coordinated sites are conducive to ethylene formation. This strategy enables wide modulation of ethylene-to-ethanol ratios from 0.65 to 3.96, achieving peak Faradaic efficiencies (FE) of 60.3 ± 2.1% for ethylene and 48.3 ± 1.3% for ethanol.
{"title":"Polymer-Halogen Pockets Steering *CO Adsorption Configurations for Highly Selective CO2 Electroreduction","authors":"Mao Wu, Ruoou Yang, Junyuan Duan, Shicheng Zhu, Bowen Chen, Zhaoyang Shi, Youwen Liu, Huiqiao Li, Bao Yu Xia, Tianyou Zhai","doi":"10.1002/adma.202504292","DOIUrl":"https://doi.org/10.1002/adma.202504292","url":null,"abstract":"The selective CO<sub>2</sub> electroreduction (CO<sub>2</sub>R) toward specific C<sub>2</sub> products represents a critical challenge for practical applicability, requiring precise control over <sup>*</sup>CO intermediates. Herein, a “polymer-halogen” pocketed Cu catalyst is proposed, wherein the adjustable concentration of Iodide ion (I<sup>−</sup>) within the pocket enables continuous modulation of <sup>*</sup>CO adsorption configurations on the Cu, thereby enabling tailored CO<sub>2</sub>R toward ethylene or ethanol production. A perfluorosulfonic acid (PFSA)-modified CuI catalyst is constructed, where I<sup>−</sup> is in situ leaching from CuI and subsequently confined by PFSA as an anion shielding layer to form polymer-halogen pockets. By tuning the thickness of PFSA shell, the amount of I<sup>−</sup> in the pocket can be controlled. The surface-enhanced in situ Raman spectroscopy demonstrates that the coverage of <sup>*</sup>CO intermediates on Cu surface increases and tends to adsorb at low coordination Cu sites in catalyst granule for dimerization reaction as the I<sup>−</sup> concentration in the pocket increases. Furthermore, the coordination environment exhibits distinct product selectivity. <sup>*</sup>CO at medium-coordinated sites favor ethanol production, while those at low-coordinated sites are conducive to ethylene formation. This strategy enables wide modulation of ethylene-to-ethanol ratios from 0.65 to 3.96, achieving peak Faradaic efficiencies (FE) of 60.3 ± 2.1% for ethylene and 48.3 ± 1.3% for ethanol.","PeriodicalId":114,"journal":{"name":"Advanced Materials","volume":"2 1","pages":""},"PeriodicalIF":29.4,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143805992","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 soft hydrogel power source is an interesting example of generating electricity from clean energy. However, ion-selective hydrogel membranes in the systems are often limited by low ion selectivity, high membrane resistance, insufficient mass transfer, and ion concentration polarization, resulting in a generally low power output. Inspired by the unique structure of the electric ray's electric organ, a vertically stacked hydrogel artificial electric organ is proposed, aiming to increase the output current to a greater extent. By constructing the charge gradient in ultrathin ion-selective hydrogel membranes, ion transport is accelerated while mitigating the ion concentration polarization. A single hydrogel artificial electric organ achieves high outputs of ≈290 mV and ≈1.46 mA cm−2 with rechargeability, surpassing similar devices. Density functional theory further reveals that the energy barrier of ion transport in charge-gradient membranes is lower than that in nongradient membranes. More impressively, the device can still be applied as a linear self-powered pressure sensor for monitoring human activities after the ion gradient is completely dissipated. This study elucidates the key role of the structure and design of ion-selective membranes in the artificial gel power generation system, providing new insights into the further development and multifunctional application of flexible gel power source.
{"title":"Mechanically Enhanced, Environmentally Stable, and Bioinspired Charge-Gradient Hydrogel Membranes for Efficient Ion Gradient Power Generation and Linear Self-Powered Sensing","authors":"Jianyu Yin, Peixue Jia, Ziqi Ren, Qixiang Zhang, Wenzhong Lu, Qianqian Yao, Mingfang Deng, Xubin Zhou, Yihua Gao, Nishuang Liu","doi":"10.1002/adma.202417944","DOIUrl":"https://doi.org/10.1002/adma.202417944","url":null,"abstract":"The soft hydrogel power source is an interesting example of generating electricity from clean energy. However, ion-selective hydrogel membranes in the systems are often limited by low ion selectivity, high membrane resistance, insufficient mass transfer, and ion concentration polarization, resulting in a generally low power output. Inspired by the unique structure of the electric ray's electric organ, a vertically stacked hydrogel artificial electric organ is proposed, aiming to increase the output current to a greater extent. By constructing the charge gradient in ultrathin ion-selective hydrogel membranes, ion transport is accelerated while mitigating the ion concentration polarization. A single hydrogel artificial electric organ achieves high outputs of ≈290 mV and ≈1.46 mA cm<sup>−2</sup> with rechargeability, surpassing similar devices. Density functional theory further reveals that the energy barrier of ion transport in charge-gradient membranes is lower than that in nongradient membranes. More impressively, the device can still be applied as a linear self-powered pressure sensor for monitoring human activities after the ion gradient is completely dissipated. This study elucidates the key role of the structure and design of ion-selective membranes in the artificial gel power generation system, providing new insights into the further development and multifunctional application of flexible gel power source.","PeriodicalId":114,"journal":{"name":"Advanced Materials","volume":"25 1","pages":""},"PeriodicalIF":29.4,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143805995","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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