intercalation

插层
  • 文章类型: Journal Article
    二维极限中的铁磁性已成为探索新物理现象和潜在应用的有趣话题。为了在二维材料中诱导铁磁性,插层被认为是一种有效的策略,这可能会在材料中引入晶格畸变和不成对自旋,以调节磁晶各向异性和磁交换相互作用。加强对二维材料磁性起源的认识,在这项工作中,通过化学插层将Cu引入到2DWO3中(2DCu/WO3)。与Cu和WO3的抗磁性相反,2DCu/WO3具有室温铁磁性。实验和理论结果将铁磁性归因于2DCu/WO3中的束缚磁极化子,该磁极化子由来自W5/W4的不成对自旋和来自氧空位的局部载流子组成。总的来说,这项工作提供了一种将铁磁性引入到反磁性WO3中的新方法,该方法可应用于更广泛的2D材料。
    Ferromagnetism in the two-dimensional limit has become an intriguing topic for exploring new physical phenomena and potential applications. To induce ferromagnetism in 2D materials, intercalation has been proposed to be an effective strategy, which could introduce lattice distortion and unpaired spin into the material to modulate the magnetocrystalline anisotropy and magnetic exchange interactions. To strengthen the understanding of the magnetic origin of 2D material, Cu was introduced into a 2D WO3 through chemical intercalation in this work (2D Cu/WO3). In contrast to the diamagnetic nature of the Cu and the WO3, room-temperature ferromagnetism was characterized for 2D Cu/WO3. Experimental and theoretical results attribute the ferromagnetism to the bound magnetic polaron in 2D Cu/WO3, which is consist of unpaired spins from W5+/W4+ with localized carriers from oxygen vacancies. Overall, this work provides a novel approach to introduce ferromagnetism into diamagnetic WO3, which could be applied for a wider scope of 2D materials.
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  • 文章类型: Journal Article
    DNA纳米结构已用于研究生物机械过程并构建人造纳米系统。许多应用场景需要能够稳健地产生大的单分子力的纳米器件。然而,大多数现有的动态DNA纳米结构是由空间分离的DNA链之间的概率杂交反应触发的,仅非确定性地产生相对较小的压缩力(≈0.4皮牛顿(pN))。这里,开发了嵌入剂触发的动态DNA折纸纳米结构,其中嵌入剂和纳米结构之间的大量局部结合反应共同导致相对较大的压缩力(≈11.2pN)的强大产生。具有不同刚度的生物分子负载,3、4和6螺旋DNA束被压缩力有效地弯曲。这项工作提供了一个强大而强大的力生成工具,用于在合成纳米系统中构建高度化学机械耦合的分子机器。
    DNA nanostructures have been utilized to study biological mechanical processes and construct artificial nanosystems. Many application scenarios necessitate nanodevices able to robustly generate large single molecular forces. However, most existing dynamic DNA nanostructures are triggered by probabilistic hybridization reactions between spatially separated DNA strands, which only non-deterministically generate relatively small compression forces (≈0.4 piconewtons (pN)). Here, an intercalator-triggered dynamic DNA origami nanostructure is developed, where large amounts of local binding reactions between intercalators and the nanostructure collectively lead to the robust generation of relatively large compression forces (≈11.2 pN). Biomolecular loads with different stiffnesses, 3, 4, and 6-helix DNA bundles are efficiently bent by the compression forces. This work provides a robust and powerful force-generation tool for building highly chemo-mechanically coupled molecular machines in synthetic nanosystems.
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  • 文章类型: Journal Article
    如今,MXene内部固有的重堆叠性质和弱的d-p杂化轨道相互作用仍然是电催化水分解领域的重大挑战,导致不令人满意的电催化活性和循环稳定性。在这里,这项工作旨在解决这些挑战,提高电催化性能,利用钴纳米粒子插层和增强π-捐赠效应。具体来说,钴纳米粒子被整合到V2CMXene纳米片中以减轻重新堆叠问题。同时,从钴到钒的显着电荷重新分布提高了轨道水平,减少π*-反键轨道占用,减轻Jahn-Teller失真。碲掺杂会引起由于电子云密度变化而引起的局部电场重排。因此,Co-V2CMXene-Te在80.8mV和287.7mV的超电势下获得了理想的析氢反应和析氧反应活性,分别,在-10mAcm-2和10mAcm-2的电流密度下。整个水分解装置实现了令人印象深刻的1.51V的低电池电压要求,以获得10mAcm-2。总的来说,当面对MXene的重新堆叠问题和弱的d-p杂化轨道相互作用时,这项工作可以提供一个有希望的解决方案,提供具有良好电催化活性和循环稳定性的高性能电催化剂。
    Nowadays, the inherent re-stacking nature and weak d-p hybridization orbital interactions within MXene remains significant challenges in the field of electrocatalytic water splitting, leading to unsatisfactory electrocatalytic activity and cycling stability. Herein, this work aims to address these challenges and improve electrocatalytic performance by utilizing cobalt nanoparticles intercalation coupled with enhanced π-donation effect. Specifically, cobalt nanoparticles are integrated into V2C MXene nanosheets to mitigate the re-stacking issue. Meanwhile, a notable charge redistribution from cobalt to vanadium elevates orbital levels, reduces π*-antibonding orbital occupancy and alleviates Jahn-Teller distortion. Doping with tellurium induces localized electric field rearrangement resulting from the changes in electron cloud density. As a result, Co-V2C MXene-Te acquires desirable activity for hydrogen evolution reaction and oxygen evolution reaction with the overpotential of 80.8 mV and 287.7 mV, respectively, at the current density of -10 mA cm-2 and 10 mA cm-2. The overall water splitting device achieves an impressive low cell voltage requirement of 1.51 V to obtain 10 mA cm-2. Overall, this work could offer a promising solution when facing the re-stacking issue and weak d-p hybridization orbital interactions of MXene, furnishing a high-performance electrocatalyst with favorable electrocatalytic activity and cycling stability.
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  • 文章类型: Journal Article
    具有可控几何形状的DNA纳米管具有广泛的跨学科应用。当制备不同宽度或不同手性的DNA纳米管时,现有的方法需要反复设计和合成特定的DNA序列,这可能是昂贵和费力的。这里,我们提出了一种嵌入剂辅助的DNA瓦片组装方法,该方法可以使用相同的DNA链生产不同宽度和手性的DNA纳米管。通过在组装过程中调节嵌入剂的浓度,可以调节DNA瓦片的扭曲方向和程度,导致形成具有可控宽度和手性的DNA纳米管。此外,通过引入额外的嵌入剂和二次退火,右旋纳米管可以重新配置成不同的左旋纳米管。我们期望这种方法可以普遍应用于调节各种DNA瓦片和其他手性材料的自组装途径,推进DNA瓷砖组装的景观。
    DNA nanotubes with controllable geometries hold a wide range of interdisciplinary applications. When preparing DNA nanotubes of varying widths or distinct chirality, existing methods require repeatedly designing and synthesizing specific DNA sequences, which can be costly and laborious. Here, we proposed an intercalator-assisted DNA tile assembly method which enables the production of DNA nanotubes of diverse widths and chirality using identical DNA strands. Through adjusting the concentration of intercalators during assembly, the twisting direction and extent of DNA tiles could be modulated, leading to the formation of DNA nanotubes featuring controllable widths and chirality. Moreover, through introducing additional intercalators and secondary annealing, right-handed nanotubes could be reconfigured into distinct left-handed nanotubes. We expect that this method could be universally applied to modulating the self-assembly pathways of various DNA tiles and other chiral materials, advancing the landscape of DNA tile assembly.
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  • 文章类型: Journal Article
    提出了一种新型的微波辅助插层(MAI)策略,用于快速有效地嵌入层状MXene,以制备大尺寸的单层MXene。在对Ti3AlC2进行LiF-HCl蚀刻后,将制备的多层Ti3C2Tx(M-T)与作为嵌入剂的Li3AlF6和作为溶剂的乙二醇(EG)在微波辐射下嵌入5分钟。此外,分散的高质量大尺寸单层Ti3C2Tx(S-T)纳米片的厚度为1.66nm,横向尺寸超过20μm,在进一步超声分层后,其产量超过60%静电沉淀,酸洗,和煅烧。此外,Pd/S-T复合催化剂,它是由Pd纳米颗粒负载在制备的S-T纳米片上构成的,在温和条件下用H2快速有效地选择性氢化硝基芳烃具有优异的性能。在室温下,在0.5MPa的H2压力下,在Pd/S-T催化剂上在20分钟内实现了硝基苯的完全转化和100%的苯胺选择性。这项工作提供了一种新的方法,快,和大规模制备单层MXene,并开发了一种构建高效纳米催化体系的新方法。
    A novel microwave-assisted intercalation (MAI) strategy is proposed for fast and efficient intercalation of layered MXene to prepare large-size single-layer MXene. After LiF-HCl etching of Ti3AlC2, the as-prepared multi-layer Ti3C2Tx (M-T) are intercalated with Li3AlF6 as an intercalator and ethylene glycol (EG) as a solvent under microwave irradiation for 5 min. Furthermore, the dispersed high-quality large-sized single-layer Ti3C2Tx (S-T) nanosheets with a thickness of 1.66 nm and a large lateral size over 20 µm are achieved with a yield of over 60% after a further ultrasonic delamination followed by electrostatic precipitation, acid washing, and calcination. In addition, Pd/S-T composite catalyst, which is constructed with Pd nanoparticles supported on the as-prepared S-T nanosheets, exhibits an excellent performance for rapid and efficient selective hydrogenation of nitroarenes with H2 under a mild condition. At room temperature, full conversion of nitrobenzene and 100% aniline selectivity are achieved over Pd/S-T catalyst in 20 min with 0.5 MPa of H2 pressure. This work provides a novel method for facile, fast, and large-scale preparation of single-layer MXene and develops a new approach for constructing efficient nanocatalytic systems.
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  • 文章类型: Journal Article
    钙离子电池(CIBs)由于Ca金属的低氧化还原电位和Ca元素的丰富储量而成为一种有前途的储能装置。然而,Ca2的大半径和二价性质导致其离子扩散动力学缓慢,并且缺乏适合Ca存储的电极材料。这里,提出了Na2Ti3O7(NTO)的层状结构作为非水ClBs的阳极材料。该NTO阳极在100mAg-1时显示出165mAhg-1的高放电容量和80%的显着容量保持率,即使在500mAg-1下进行2000次循环后,也超过了所有报道的用于CIBs的插层型阳极材料的性能。在第一次放电过程中,NTO转移到层状CaVINaIXTi3O7(CNTO),并嵌入Ca2并提取Na。然后,CNTO在随后的循环中经历Ca2+的可逆插入/提取。此外,密度泛函理论计算表明,NTO具有快速的二维Ca2扩散途径。此外,基于NTO作为阳极的fullCIBs进一步强调了其对CIBs的潜力。这项工作为CIBs提供了有前途的阳极材料,提供促进高性能数据库发展的机会。
    Calcium ion batteries (CIBs) are a promising energy storage device due to the low redox potential of the Ca metal and the abundant reserves of the Ca element. However, the large radius and divalent nature of Ca2+ lead to its slow ion diffusion kinetics and the lack of suitable electrode materials for Ca storage. Here, a layered structure of Na2Ti3O7 (NTO) is presented as an anode material for nonaqueous CIBs. This NTO anode demonstrates a high discharge capacity of 165 mA h g-1 at 100 mA g-1 and a remarkable capacity retention rate of 80%, even after 2000 cycles at 500 mA g-1, surpassing the performance of all reported intercalation-type anode materials for CIBs. The NTO transfers to layered CaVIINaIXTi3O7 (CNTO) with intercalation of Ca2+ and extraction of Na+ during the first discharge process. Then, the CNTO undergoes the reversible insertion/extraction of Ca2+ during subsequent cycling. Additionally, density functional theory calculations reveal that NTO possesses a rapid two-dimensional diffusion pathway for Ca2+. Moreover, the full CIBs based on NTO as the anode further underscore its potential for CIBs. This work presents promising anode materials for CIBs, offering opportunities to promote the development of high-performance CIBs.
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  • 文章类型: Journal Article
    在这里,我们提出了具有色散校正(DFT-D)计算的密度泛函理论,该计算的重点是将离子液体(IL)电解质嵌入二维(2D)Ti3C2TxMXenes中。这些IL包括阳离子1-乙基-3-甲基咪唑(Emim),伴随着三个不同的阴离子:双(三氟甲基磺酰基)酰亚胺(TFSA-),(氟磺酰基)酰亚胺(FSA-)和氟磺酰基(三氟甲磺酰基)酰亚胺(FTFA-)。通过改变表面终止元件,我们探索了中性白细胞插入的复杂几何形状,负,和正孔隙系统。通过五种群体分析模型实现电荷转移的准确估计,比如Hirshfeld,Hirshfeld-I,DDEC6(密度衍生静电和化学),Bader,和VDD(Voronoi变形密度)电荷。在这项工作中,我们推荐DDEC6和Hirshfeld-I充电型号,因为它们提供适度的价值并表现出合理的趋势。调查,旨在可视化非共价相互作用,阐明了阳离子-MXene和阴离子-MXene相互作用在控制MXenes内离子液体的嵌入现象中的作用。这种作用的大小取决于两个因素:阳离子的特定排列,以及参与该过程的阴离子物种的性质。
    Herein, we present a density functional theory with dispersion correction (DFT-D) calculations that focus on the intercalation of ionic liquids (ILs) electrolytes into the two-dimensional (2D) Ti3C2Tx MXenes. These ILs include the cation 1-ethyl-3-methylimidazolium (Emim+), accompanied by three distinct anions: bis(trifluoromethylsulfonyl)imide (TFSA-), (fluorosulfonyl)imide (FSA-) and fluorosulfonyl(trifluoromethanesulfonyl)imide (FTFSA-). By altering the surface termination elements, we explore the intricate geometries of IL intercalation in neutral, negative, and positive pore systems. Accurate estimation of charge transfer is achieved through five population analysis models, such as Hirshfeld, Hirshfeld-I, DDEC6 (density derived electrostatic and chemical), Bader, and VDD (voronoi deformation density) charges. In this work, we recommend the DDEC6 and Hirshfeld-I charge models, as they offer moderate values and exhibit reasonable trends. The investigation, aimed at visualizing non-covalent interactions, elucidates the role of cation-MXene and anion-MXene interactions in governing the intercalation phenomenon of ionic liquids within MXenes. The magnitude of this role depends on two factors: the specific arrangement of the cation, and the nature of the anionic species involved in the process.
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  • 文章类型: Journal Article
    在这项研究中,引入了一种新颖的方法来解决与含水锌离子电池中δ-MnO2的结构不稳定性和缓慢反应动力学相关的挑战。通过利用两性离子甜菜碱(Bet)进行插层,与传统的阳离子插层方法不同,合成了Bet插层MnO2(MnO2-Bet)。Bet中带正电荷的季铵基团与δ-MnO2层中带负电荷的氧原子形成强烈的静电相互作用,增强结构稳定性,防止层坍塌。同时,Bet中带负电荷的羧酸盐基团通过它们的相互作用促进H+/Zn2+离子的快速扩散,从而改善反应动力学。所得的MnO2-Bet阴极显示出高的比容量,优异的倍率能力,快速反应动力学,和延长循环寿命。这种双功能嵌入策略显着优化了δ-MnO2的电化学性能,使其成为高级水性锌离子电池的有前途的正极材料。
    In this study, a novel approach is introduced to address the challenges associated with structural instability and sluggish reaction kinetics of δ-MnO2 in aqueous zinc ion batteries. By leveraging zwitterionic betaine (Bet) for intercalation, a departure from traditional cation intercalation methods, Bet-intercalated MnO2 (MnO2-Bet) is synthesized. The positively charged quaternary ammonium groups in Bet form strong electrostatic interactions with the negatively charged oxygen atoms in the δ-MnO2 layers, enhancing structural stability and preventing layer collapse. Concurrently, the negatively charged carboxylate groups in Bet facilitate the rapid diffusion of H+/Zn2+ ions through their interactions, thus improving reaction kinetics. The resulting MnO2-Bet cathode demonstrates high specific capacity, excellent rate capability, fast reaction kinetics, and extended cycle life. This dual-function intercalation strategy significantly optimizes the electrochemical performance of δ-MnO2, establishing it as a promising cathode material for advanced aqueous zinc ion batteries.
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  • 文章类型: Journal Article
    层状材料的插层提供了一种灵活的方法来调整其结构并产生意想不到的性能。在这次审查中,我们提供了层状材料化学插层的观点,包括石墨/石墨烯,过渡金属二硫属化物,MXenes,和一些特殊的材料。讨论了不同插层方法的特点及其化学机理。讨论了插层对基质材料结构变化的影响以及结构变化如何影响插层化合物的固有性质。此外,我们提供了插层化合物在能量转换和存储等领域的应用前景,催化作用,智能设备,生物医学应用,和环境修复。最后,我们提供了对层状材料化学插层的挑战和未来机遇的简要见解。本文受版权保护。保留所有权利。
    The intercalation of layered materials offers a flexible approach for tailoring their structures and generating unexpected properties. This review provides perspectives on the chemical intercalation of layered materials, including graphite/graphene, transition metal dichalcogenides, MXenes, and some particular materials. The characteristics of the different intercalation methods and their chemical mechanisms are discussed. The influence of intercalation on the structural changes of the host materials and the structural change how to affect the intrinsic properties of the intercalation compounds are discussed. Furthermore, a perspective on the applications of intercalation compounds in fields such as energy conversion and storage, catalysis, smart devices, biomedical applications, and environmental remediation is provided. Finally, brief insights into the challenges and future opportunities for the chemical intercalation of layered materials are provided.
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  • 文章类型: Journal Article
    由于超高的表面积和独特的表面应变,具有原子厚度的金属烯材料在电催化中受到越来越多的关注。然而,金属烯的连续菌株调节仍然是一个巨大的挑战。在这里,利用Cu2+在双轴应变上的自催化还原,碳插层Ir金属烯,我们实现了对碳提取动力学的控制,能够精细调节碳嵌入浓度,并在前所未有的宽范围内连续调节(111)平面内(-2.0%-2.6%)和平面间(3.5%-8.8%)菌株。电催化测量揭示了对析氢反应(HER)的应变依赖性活性,其中晶格常数最小的弱应变Ir金属烯(w-Ir金属烯)在-0.02V相对于可逆氢电极(RHE)时表现出最高的质量活性为2.89Amg-1Ir。理论计算验证了晶格压缩在通过下移d带中心优化H在碳插层Ir金属烯表面上的结合中的关键作用,进一步强调了菌株工程对增强电催化的重要性。
    Metallene materials with atomic thicknesses are receiving increasing attention in electrocatalysis due to ultrahigh surface areas and distinctive surface strain. However, the continuous strain regulation of metallene remains a grand challenge. Herein, taking advantage of autocatalytic reduction of Cu2+ on biaxially strained, carbon-intercalated Ir metallene, we achieve control over the carbon extraction kinetics, enabling fine regulation of carbon intercalation concentration and continuous tuning of (111) in-plane (-2.0%-2.6%) and interplanar (3.5%-8.8%) strains over unprecedentedly wide ranges. Electrocatalysis measurements reveal the strain-dependent activity toward hydrogen evolution reaction (HER), where weakly strained Ir metallene (w-Ir metallene) with the smallest lattice constant presents the highest mass activity of 2.89 A mg-1Ir at -0.02 V vs reversible hydrogen electrode (RHE). Theoretical calculations validated the pivotal role of lattice compression in optimizing H binding on carbon-intercalated Ir metallene surfaces by downshifting the d-band center, further highlighting the significance of strain engineering for boosted electrocatalysis.
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