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Cation-π Interactions Based Conductive Hydrogels with Slide-Ring Structure Toward Super Long-Time in-air/Underwater Linear Sensing and Communication. 基于阳离子-π相互作用的具有滑环结构的导电水凝胶,实现超长时间的空气/水下线性传感和通信。
IF 13 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-04 DOI: 10.1002/smll.202406902
Yang Bai, Yuxin Shi, Xuchao Li, Yucong Zhang, Yaqi Wang

Conductive hydrogels (CHs) are attracted more attention in the flexible wearable sensors field, however, how to stably apply CHs underwater is still a big challenge. In order to achieve the usage of CHs in aquatic environments, the integrated properties such as water retention ability, resistance to swelling, toughness, adhesiveness, linear GF sensing, and long-term usage are necessary to consider, but rarely reported in the previous reports. This paper proposes CHs prepared using cationic and aromatic monomers along with polyrotaxanes-based crosslinkers. Due to the intermolecular cation-π interactions and topological slide-ring-based polyrotaxanes, the CHs exhibit good mechanical performance, adhesive nature, and anti-swelling properties. The presence of slide-ring-based topological architecture effectively mitigates stress concentration. Additionally, the encapsulation of PA allows CHs to maintain functionality even after 240 days of direct placement at room temperature. Notably, the designed CHs exhibit linear sensitivity in detecting land/underwater human motions, and serve as Morse code signal transmitters for information transmission. Thus, the designed CHs may have broad applications in the underwater wearable sensors field.

导电水凝胶(CHs)在柔性可穿戴传感器领域受到越来越多的关注,然而,如何在水下稳定地应用 CHs 仍然是一个巨大的挑战。为了实现 CHs 在水下环境中的应用,需要考虑其保水能力、抗膨胀性、韧性、粘附性、线性 GF 传感和长期使用等综合特性,但以往的报道很少。本文提出使用阳离子和芳香族单体以及聚异氰脲类交联剂制备 CHs。由于分子间的阳离子-π相互作用和基于拓扑滑环的聚拉克森,CHs 表现出良好的机械性能、粘合性和抗膨胀性。基于滑环的拓扑结构可有效缓解应力集中。此外,PA 的封装使 CHs 在室温下直接放置 240 天后仍能保持功能。值得注意的是,所设计的 CHs 在检测陆地/水下人体运动时表现出线性灵敏度,并可作为摩尔斯电码信号发射器进行信息传输。因此,所设计的 CH 在水下可穿戴传感器领域具有广泛的应用前景。
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引用次数: 0
High-Energy-Density All-V2O5 Battery. 高能量密度 All-V2O5 电池。
IF 13 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-04 DOI: 10.1002/smll.202407159
Guolong Wang, Jingqi Wang, Jiale Song, Yuxi Tai, Junwen Ren, Jiamei Liu, Xiaowei Shi, Zehua Zhao, Lei Li

Symmetrical batteries hold great promise as cost-effective and safe candidates for future battery technology. However, they realistically suffer low energy density due to the challenge in integrating high specific capacity with high voltage plateau from the limited choice of bipolar electrodes. Herein, a high-voltage all-V2O5 symmetrical battery with clear voltage plateau is conceptualized by decoupling the cathodic/anodic redox reactions based upon the episteme of V2O5 intercalation chemistry. As the proof-of-concept, a hierarchical V2O5-carboncomposite (VO-C) bipolar electrode with boosted electron/ion transport kinetics is fabricated, which shows high performance as both cathode and anode in their precisely clamped working potential windows. Accordingly, the symmetrical full-battery exhibits a high capacity of 174 mAh g-1 along with peak voltage output of above 2.9 V at 0.5C, remarkable capacity retention of 81% from 0.5C to 10C, and good cycling stability of 70% capacity retention after 300 cycles at 5C. Notably, its energy density reaches 429 Wh kg-1 at 0.5C estimated by the cathode mass, which outperforms most of the existing Li/Na/K-based symmetrical batteries. This study leaps forward the performance of symmetrical battery and provides guidance to extend the scope of future battery designs.

对称电池是未来电池技术中极具成本效益和安全性的候选产品。然而,由于双极性电极的选择有限,高比容量与高电压平台的整合面临挑战,因此它们的能量密度较低。在此,基于 V2O5 插层化学的认识,通过解耦阴极/阳极氧化还原反应,构思了一种具有明显电压高原的高电压全 V2O5 对称电池。作为概念验证,制备了具有增强电子/离子传输动力学的分层 V2O5 碳复合材料(VO-C)双极电极,该电极在精确箝位的工作电位窗口中作为阴极和阳极均表现出高性能。因此,对称全电池的容量高达 174 mAh g-1,在 0.5C 时的峰值电压输出超过 2.9 V,从 0.5C 到 10C 的显著容量保持率为 81%,在 5C 下循环 300 次后的容量保持率为 70%,具有良好的循环稳定性。值得注意的是,根据正极质量估算,其能量密度在 0.5C 时达到 429 Wh kg-1,优于大多数现有的锂/镍/钾基对称电池。这项研究跃进了对称电池的性能,为扩展未来电池设计的范围提供了指导。
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引用次数: 0
High-Performance Pure Polymer Electrolytes with Enhanced Ionic Conductivity for Room-Temperature Applications. 用于室温应用的具有增强离子传导性的高性能纯聚合物电解质。
IF 13 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-04 DOI: 10.1002/smll.202405565
Yongquan Zhang, Zengxu Chen, Jingshun Wang, Shuo Fan, Tiandong Zhang, Changhai Zhang, Yue Zhang, Qingguo Chi

All-solid-state lithium metal batteries (ASSLMBs) are renowned for their high energy density and safety, positioning them as leading candidates for next-generation energy storage solutions. In this study, pure polymer solid-state electrolytes are developed using the solution casting method, optimized for room temperature operation. The base material, poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), is enhanced with succinonitrile (SN) and polyacrylonitrile (PAN) to improve its electrochemical performance at room temperature. The optimized electrolyte, PSP-0.05, demonstrated superior characteristics, including an ionic conductivity (σ) of 3.2 × 10-4 S cm-1 and a wide voltage window of up to 5 V. When integrated into full batteries, PSP-0.05 exhibited exceptional performance in multiplicative cycling tests at room temperature, achieving discharge specific capacities of 132 and 113 mAh g-1 at 3 and 5 C rates, respectively. Additionally, long-term cycling at 1 C rate resulted in an initial discharge-specific capacity of 145.2 mAh g-1 with over 94.9% capacity retention after 1000 cycles. Given the simplicity of the preparation process and its impressive electrochemical properties, the PSP-0.05 electrolyte holds significant potential for practical applications in safer ASSLMBs.

全固态锂金属电池(ASSLMB)以其高能量密度和安全性而著称,是下一代能源存储解决方案的主要候选材料。本研究采用溶液浇铸法开发了纯聚合物固态电解质,并针对室温操作进行了优化。基础材料聚偏氟乙烯-六氟丙烯(PVDF-HFP)用琥珀腈(SN)和聚丙烯腈(PAN)进行了增强,以改善其室温下的电化学性能。优化后的电解质 PSP-0.05 显示出卓越的特性,包括 3.2 × 10-4 S cm-1 的离子电导率 (σ)和高达 5 V 的宽电压窗口。当 PSP-0.05 集成到完整电池中时,在室温下的倍率循环测试中表现出卓越的性能,在 3 C 和 5 C 速率下的放电比容量分别达到 132 mAh g-1 和 113 mAh g-1。此外,在 1 C 速率下进行长期循环时,初始放电比容量为 145.2 mAh g-1,1000 次循环后容量保持率超过 94.9%。考虑到制备过程的简便性及其令人印象深刻的电化学特性,PSP-0.05 电解质在更安全的 ASSLMB 的实际应用中具有巨大的潜力。
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引用次数: 0
Recent Achievements in Heterogeneous Bimetallic Atomically Dispersed Catalysts for Zn-Air Batteries: A Minireview. 用于锌-空气电池的异质双金属原子分散催化剂的最新研究成果:小视角。
IF 13 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-04 DOI: 10.1002/smll.202406776
Sanshuang Gao, Kang Lian, Xinzhong Wang, Xijun Liu, Abdukader Abdukayum, Qingquan Kong, Guangzhi Hu

Rechargeable Zn-air batteries (ZABs) hold promise as the next-generation energy-storage devices owing to their affordability, environmental friendliness, and safety. However, cathodic catalysts are easily inactivated in prolonged redox potential environments, resulting in inadequate energy efficiency and poor cycle stability. To address these challenges, anodic active sites require multiple-atom combinations, that is, ensembles of metals. Heterogeneous bimetallic atomically dispersed catalysts (HBADCs), consisting of heterogeneous isolated single atoms and atomic pairs, are expected to synergistically boost the cyclic oxygen reduction and evolution reactions of ZABs owing to their tuneable microenvironments. This minireview revisits recent achievements in HBADCs for ZABs. Coordination environment engineering and catalytic substrate structure optimization strategies are summarized to predict the innovation direction for HBADCs in ZAB performance enhancement. These HBADCs are divided into ferrous and nonferrous dual sites with unique microenvironments, including synergistic effects, ion modulation, electronic coupling, and catalytic activity. Finally, conclusions and perspectives relating to future challenges and potential opportunities are provided to optimise the performance of ZABs.

可充电锌空气电池(ZAB)因其经济实惠、环保和安全而有望成为下一代储能设备。然而,阴极催化剂在长时间的氧化还原电位环境中很容易失活,导致能量效率不足和循环稳定性差。为了应对这些挑战,阳极活性位点需要多原子组合,即金属组合。异质双金属原子分散催化剂(HBADCs)由异质孤立的单原子和原子对组成,由于其微观环境可调,有望协同促进 ZABs 的循环氧还原和进化反应。这篇微型综述回顾了用于 ZABs 的 HBADC 最近取得的成就。总结了配位环境工程和催化底物结构优化策略,预测了 HBADCs 在提高 ZAB 性能方面的创新方向。这些 HBADC 分为具有独特微环境的铁性和非铁性双位点,包括协同效应、离子调制、电子耦合和催化活性。最后,还提供了与未来挑战和潜在机遇有关的结论和展望,以优化 ZAB 的性能。
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引用次数: 0
Single-Atom Catalysts with Isolated Cu1-N4 Sites for Atopic Dermatitis Cascade Catalytic Therapy via Activating PPAR Signaling. 具有隔离 Cu1-N4 位点的单原子催化剂可通过激活 PPAR 信号,对特应性皮炎进行级联催化治疗。
IF 13 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-04 DOI: 10.1002/smll.202407365
Le Kuai, Fang Huang, Lijie Mao, Yi Ru, Jingsi Jiang, Jiankun Song, Si Chen, Ke Li, Yongyong Li, Haiqing Dong, Xiangyu Lu, Bin Li, Jianlin Shi

Atopic dermatitis (AD) is one of the most common allergic skin disorders affecting over 230 million people worldwide, while safe and efficient therapeutic options for AD are currently rarely available. Reactive oxygen species (ROS) accumulation plays a key role in AD's disease progression. Therefore, a novel single-atom catalyst is designed with isolated Cu1-N4 sites anchored on carbon support (Cu1-N4 ISAC), featuring triple antioxidant enzyme-mimicking activities, for efficient AD cascade catalytic therapy (CCT). The excellent superoxide dismutase (SOD)-, glutathione peroxidase (GPx)-, and ascorbate peroxidase (APx)-like activities of Cu1-N4 ISACs enable the sequential conversion of O2- to H2O2 and then to harmless H2O, thereby protecting keratinocytes from oxidative stress damage. Notably, two novel experimental methods are developed to directly prove the SOD-GPx and SOD-APx cascade catalytic activities for the first time. In vivo experiments show that Cu1-N4 ISACs are more potent than a recommended typical medicine (halcinonide solution). Additionally, RNA sequencing and bioinformatic analysis reveal that Cu1-N4 ISACs reduce inflammation and inhibit ROS production by activating PPAR signaling, which is aberrantly reduced in AD. Therefore, the synthesized catalytic medicine offers an alternative to alleviate AD and has the potential to serve as PPAR agonists for treating similar diseases.

特应性皮炎(AD)是最常见的过敏性皮肤病之一,影响着全球超过 2.3 亿人,但目前很少有安全有效的 AD 治疗方案。活性氧(ROS)的积累在过敏性皮炎的发病过程中起着关键作用。因此,我们设计了一种新型单原子催化剂,它在碳载体上锚定了孤立的 Cu1-N4 位点(Cu1-N4 ISAC),具有三重抗氧化酶模拟活性,可用于高效的 AD 级联催化治疗(CCT)。Cu1-N4 ISACs具有出色的超氧化物歧化酶(SOD)、谷胱甘肽过氧化物酶(GPx)和抗坏血酸过氧化物酶(APx)模拟活性,能将O2依次转化为H2O2,再转化为无害的H2O,从而保护角质细胞免受氧化应激损伤。值得注意的是,研究人员开发了两种新的实验方法,首次直接证明了 SOD-GPx 和 SOD-APx 级联催化活性。体内实验表明,Cu1-N4 ISACs 比推荐的典型药物(卤西尼特溶液)更有效。此外,RNA 测序和生物信息学分析表明,Cu1-N4 ISACs 可通过激活 PPAR 信号减少炎症反应和抑制 ROS 的产生,而 PPAR 信号在 AD 中异常减少。因此,合成的催化药物为缓解阿德氏病提供了一种替代方法,并有可能成为治疗类似疾病的 PPAR 激动剂。
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引用次数: 0
Self-Oxidated Hybrid Conductive Network Enables Efficient Electrochemical Lithium Extraction Under High-Altitude Environment. 自氧化混合导电网络实现了高海拔环境下的高效电化学锂提取。
IF 13 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-04 DOI: 10.1002/smll.202406607
Zhixin Wan, Ziqi Liu, Yiyang Xiao, Qinqin Ruan, Qian Wang, Haitao Zhang, Meng Yao, Yun Zhang

The electrochemical deintercalation method has been considered as an effective way to address the demand for lithium resources due to its environmental friendliness, high selectivity, and high efficiency. However, the performance of electrochemical lithium extraction is closely dependent on the electrode material and needs to be compatible under plateau environments with high-altitude and low-temperature. Herein, an in situ self-oxidation method is conducted to construct a hybrid conductive network on the surface of LiFePO4 (LFP-HN). The introduction of a hybrid conductive network enhanced the interfacial electron/lithium-ion transfer. In addition, structural stability is strengthened through suppressing the intercalation of impurity cations. Consequently, the LFP-HN delivered extremely high lithium extraction capacity (27.42 mg g-1), low energy consumption (4.91 Wh mol-1), and superior purity (91.05%) in Baqiancuo real brine (4788 m, -10 °C). What's more, LFP-HN-based large-scale prototypes are constructed and operated at Baqiancuo, which is calculated to extract 25 kg Lithium Carbonate Equivalent per cycle (4.55 h, 100 pairs of plates). Based on the excellent performance, the modification strategy developed in this work can be a promising solution for industrial lithium extraction under high-altitude environment.

电化学脱闰法因其环保、高选择性和高效率而被认为是解决锂资源需求的有效方法。然而,电化学提锂的性能与电极材料密切相关,需要与高海拔、低温的高原环境相适应。本文采用原位自氧化法在磷酸铁锂(LFP-HN)表面构建了混合导电网络。混合导电网络的引入增强了界面电子/锂离子转移。此外,通过抑制杂质阳离子的插层,还增强了结构的稳定性。因此,LFP-HN 在巴前厝盐水(4788 米,-10 °C)中具有极高的锂萃取能力(27.42 mg g-1)、低能耗(4.91 Wh mol-1)和卓越的纯度(91.05%)。此外,基于 LFP-HN 的大型原型已在巴谦错建成并运行,经计算,每个循环(4.55 小时,100 对板)可提取 25 千克碳酸锂当量。基于其优异的性能,本文所开发的改性策略有望成为高海拔环境下工业提锂的一种解决方案。
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引用次数: 0
Reconfigurable All-Oil Microfluidic Devices by 3D Printing (Small 40/2024) 通过三维打印实现可重构的全油微流体设备(40/2024 小尺寸)
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-03 DOI: 10.1002/smll.202470298
Weixiao Feng, Yunhui Wen, Shuyi Sun, Peifan Li, Shaowei Shi
Microfluidic Devices
微流体设备
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引用次数: 0
High-Valence Mn MOF Inspired by Laccase Mediators Enables Versatile Nature-Mimicking Catalysis. 受乳酶介质启发的高价锰 MOF 可实现多功能仿自然催化。
IF 13 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-03 DOI: 10.1002/smll.202405293
Lili Xu, Jianli Nan, Songxue Han, Zhixuan Yu, Shuangli Wu, Youxing Fang, Shaojun Dong

In nature, active Mn3+ -ligand complexes produced by laccase catalyzed oxidation can act as the low-molecular mass, diffusible redox mediators to oxidize the phenolic substrates overcoming the limitations of natural enzymes. Learning from the metal-ligand coordination of natural functional units, high-valence Mn metal-organic framework (Mn MOF) is constructed to simulate the catalysis in natural mediator system. Benefiting from the characteristics of nanoscale size, rich metal coordination unsaturated sites, and mixed valence state dominated by Mn(III), Nano Mn(III)-TP exhibits superior laccase-mimicking activity, whose Vmax (maximal reaction rate) is much higher than that of natural laccase. Referring to natural systems, relevant free radical experiments prove that the material induces the production of active oxygen species with the assistance of carboxylic acid, and active oxygen species further oxidize phenolic substrates. Based on its robust performances, the primary oxidative degradation of an emerging pollutant triclosan (TCS) is creatively applied, an important antiasthmatic medicine terbutaline sulfate (TBT) detection, and the synthesis of non-toxic and black near-natural dyes for dyeing. By simulating the essential mediators of natural enzymatic catalysis, an Mn MOF-based material that demonstrates multiple novel applications is successfully developed, which introduces a new reliable strategy for achieving versatile nature-mimicking catalysis.

在自然界中,漆酶催化氧化产生的活性 Mn3+ 配体可以作为低分子质量、可扩散的氧化还原介质来氧化酚类底物,克服了天然酶的局限性。借鉴天然功能单元的金属配位,构建了高价锰金属有机框架(Mn MOF)来模拟天然介质系统的催化作用。得益于纳米级尺寸、丰富的金属配位不饱和位点以及以锰(III)为主的混合价态等特点,纳米锰(III)-TP 表现出卓越的漆酶模拟活性,其 Vmax(最大反应速率)远高于天然漆酶。参照自然体系,相关的自由基实验证明,该材料在羧酸的帮助下诱导活性氧的产生,活性氧进一步氧化酚类底物。基于其强大的性能,该材料被创造性地应用于新兴污染物三氯生(TCS)的一级氧化降解、重要抗哮喘药物硫酸特布他林(TBT)的检测以及无毒黑色近天然染料的合成。通过模拟天然酶催化的基本介质,成功开发了一种基于 Mn MOF 的材料,它展示了多种新颖的应用,为实现多功能仿自然催化引入了一种新的可靠策略。
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引用次数: 0
Accelerating the Hydrogen Evolution Kinetics with a Pulsed Laser–Synthesized Platinum Nanocluster–Decorated Nitrogen-Doped Carbon Electrocatalyst for Alkaline Seawater Electrolysis (Small 40/2024) 利用脉冲激光合成的铂纳米簇装饰掺氮碳电催化剂加速碱性海水电解中的氢演化动力学(40/2024 号小论文)
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-03 DOI: 10.1002/smll.202470297
Velusamy Maheskumar, Ahreum Min, Anuj Kumar, Raja Arumugam Senthil, Cheol Joo Moon, Myong Yong Choi
Seawater Electrolysis
海水电解
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引用次数: 0
Reconfigurable Resistive Switching Memory for Telegraph Code Sensing and Recognizing Reservoir Computing Systems (Small 40/2024) 用于电报编码感应和识别水库计算系统的可重构电阻式开关存储器(小型 40/2024)
IF 13.3 2区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-03 DOI: 10.1002/smll.202470296
Dohyung Kim, Phuoc Loc Truong, Cheong Beom Lee, Hyeonsu Bang, Jia Choi, Seokhyun Ham, Jong Hwan Ko, Kyeounghak Kim, Daeho Lee, Hui Joon Park
Reservoir Computing Systems
储层计算系统
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引用次数: 0
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