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Fluorous and Organic Extraction Systems: A Comparison from the Perspectives of Coordination Structures, Interfaces, and Bulk Extraction Phases. 氟萃取系统与有机萃取系统:从配位结构、界面和块状萃取相的角度进行比较。
IF 3.7 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-07 DOI: 10.1021/acs.langmuir.4c02268
Yuki Ueda, Cyril Micheau, Kazuhiro Akutsu-Suyama, Kohei Tokunaga, Masako Yamada, Norifumi L Yamada, Damien Bourgeois, Ryuhei Motokawa

Microscopic structures in liquid-liquid extraction, such as structuration between extractants or extracted complexes in bulk organic phases and at interfaces, can influence macroscopic phenomena, such as the distribution behavior of solutes, including extraction efficiency and selectivity. In this study, we correlated the macroscopic behavior of the Zr(IV) extraction from nitric acid solutions with microscopic structural information to understand at the molecular level the key factors contributing to the higher metal ion extraction performance in the fluorous extraction system as compared to the analogous organic extraction system. The fluorous and organic extraction systems consist of tris(4,4,5,5,6,6,7,7,7-nonafluoroheptyl) phosphate (TFP) in perfluorohexane and tri-n-heptyl phosphate (THP) in n-hexane, respectively. Extended X-ray absorption fine structure, neutron reflectometry (NR), and small-angle neutron scattering revealed the structural information around the central metal ion of the complex, at the interface, and in the bulk extraction phase, respectively. NR results showed that extractant molecules did not accumulate much at the interface in both extraction system. In the fluorous extraction system, extractant aggregates with a 1.46 nm radius of gyration (Rg) were formed after contact with nitric acid, and remained even after Zr(IV) extraction through the form of a 1:3 (Zr(IV):TFP) complex. In contrast, in the organic extraction system, only extractant dimers with Rg of 0.70 nm were formed and Zr(IV) is extracted through the form of a 1:2 (Zr(IV):THP) complex. We speculate that differences in the local coordination structure around the Zr(IV) ion and the structuration of the extractant molecules in the bulk extraction phase contribute to the high Zr(IV) extraction performance in the fluorous extraction system. In particular, the size of the aggregates hardly changed with increasing Zr(IV) concentration in the fluorous phase, which may be closely related to the absence of phase splitting in the fluorous extraction system.

液液萃取过程中的微观结构,如萃取剂之间的结构或萃取复合物在有机相中和界面上的结构,会影响宏观现象,如溶质的分布行为,包括萃取效率和选择性。在本研究中,我们将硝酸溶液中萃取 Zr(IV)的宏观行为与微观结构信息联系起来,从分子水平上了解了导致流态萃取体系与类似有机萃取体系相比具有更高的金属离子萃取性能的关键因素。氟萃取系统和有机萃取系统分别由全氟己烷中的磷酸三(4,4,5,5,6,6,7,7,7-二氟庚基)酯(TFP)和正己烷中的磷酸三正庚基酯(THP)组成。扩展 X 射线吸收精细结构、中子反射仪(NR)和小角中子散射分别揭示了络合物中心金属离子周围、界面和萃取相中的结构信息。NR结果表明,在两种萃取体系中,萃取剂分子在界面上的聚集都不大。在氟萃取体系中,萃取剂在与硝酸接触后形成了回转半径为1.46 nm(Rg)的聚集体,并通过1:3(Zr(IV):TFP)络合物的形式在萃取Zr(IV)后仍然存在。相反,在有机萃取体系中,只形成了 Rg 为 0.70 nm 的萃取剂二聚体,并通过 1:2 (Zr(IV):THP)复合物的形式萃取出 Zr(IV)。我们推测,Zr(IV)离子周围的局部配位结构和萃取剂分子在大块萃取相中的结构差异,是氟萃取体系中Zr(IV)萃取性能高的原因。特别是,随着萃取相中 Zr(IV)浓度的增加,聚集体的大小几乎没有变化,这可能与萃取体系中不存在相分裂密切相关。
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引用次数: 0
Graphene Oxide-Enhanced Nucleation and Growth of Calcium-Silicate-Hydrate Gel at Nanoscale: A Molecular Dynamics Study 氧化石墨烯在纳米尺度上增强了硅酸钙-水合物凝胶的成核和生长:分子动力学研究
IF 3.9 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-07 DOI: 10.1021/acs.langmuir.4c02686
Luyao Duan, Junfei Zhang, Guowei Ma, Zhu Pan
Graphene oxide (GO) enhances the performance of cement-based materials by optimizing the microstructure of calcium-silicate-hydrate (C–S–H). However, the influence of GO on the nucleation and growth of C–S–H gel at nanoscale is unexplored. This study investigates this mechanism by molecular dynamics simulation at nano scale. Results show that GO can reduce the activation energy during the polymerization reaction of silicon oxide tetrahedra during the reaction process, and can increase the content of polymer Q3 and Q4. The influence of GO with epoxy (–O−), hydroxyl (−OH) and carboxyl (−COOH) groups on the radial distribution function (RDF), mean square displacement (MSD), and atomic spatial distribution of monomers are studied. Results show that GO–OH exhibits excellent performance, with the highest number of bridging oxygen atoms (about 0.6), the lowest Q0 monomer content (just 26.8%), the highest RDF (27.18), and the highest MSD (calcium and silicon content around 20,000 Å2). This paper elucidates the nucleation and growth mechanism of C–S–H influenced by GO to develop high performance cement.
氧化石墨烯(GO)通过优化水合硅酸钙(C-S-H)的微观结构来提高水泥基材料的性能。然而,GO 在纳米尺度上对 C-S-H 凝胶的成核和生长的影响尚未得到研究。本研究通过纳米尺度的分子动力学模拟研究了这一机制。结果表明,在反应过程中,GO 能降低氧化硅四面体聚合反应过程中的活化能,并能增加聚合物 Q3 和 Q4 的含量。研究了带有环氧基(-O-)、羟基(-OH)和羧基(-COOH)的 GO 对单体的径向分布函数(RDF)、均方位移(MSD)和原子空间分布的影响。结果表明,GO-OH 表现出优异的性能,桥接氧原子数最多(约 0.6),Q0 单体含量最低(仅 26.8%),RDF 最高(27.18),MSD 最高(钙和硅含量约为 20,000 Å2)。本文阐明了受 GO 影响的 C-S-H 成核和生长机制,从而开发出高性能水泥。
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引用次数: 0
Deciphering the Influence of Zwitterionic Surfactants on Pluronic Co-assemblies: A Synergistic Odyssey through Spectroscopic, Microscopic, and Scattering Techniques 解密聚羧酸共聚物表面活性剂的影响:光谱、显微镜和散射技术的协同奥德赛
IF 3.9 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-07 DOI: 10.1021/acs.langmuir.4c02978
Sapana Sinha, Sagar Srivastava, Vinod K. Aswal, Debabrata Seth
Fundamental investigations into the photophysical properties and microenvironmental features of pluronic–zwitterionic surfactant mixed assemblies are essential for advancing our understanding of molecular interactions at the nanoscale, setting the stage for innovative solutions in drug delivery, diagnostics, and other applications of pluronic–zwitterionic surfactant assemblies. This investigation explores the intricate photophysics of pluronic–zwitterionic surfactant mixed assemblies, utilizing the twisted intramolecular charge transfer state forming styryl dye trans-2-[(4-dimethylamino) styryl] benzothiazole as a probe. By comparing the behaviors of two distinct poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) block copolymers with block composition of (PEO)132-(PPO)50-(PEO)132 [F108] and (PEO)100-(PPO)65-(PEO)100 [F127] at concentrations of 5 and 10 wt %, this study systematically examines the impact of the addition of zwitterionic surfactants. Through a comprehensive set of analytical techniques, including UV–visible absorption, steady-state emission, and time-resolved fluorescence emission studies, significant alterations in the emission spectra and quantum yields were observed upon the addition of zwitterionic surfactants. These modifications suggest a dynamic equilibrium for the transitioning of dye molecules between various microenvironments within the assemblies. Additionally, dynamic light scattering, zeta potential (ζ), nuclear Overhauser effect spectroscopy, small-angle neutron scattering, cryogenic transmission electron microscopy, field emission scanning electron microscopy, and fluorescence lifetime imaging microscopy analyses have shed light on the substantial impact of surfactant incorporation on the structural properties of assemblies.
有关pluronic-zwitterionic 表面活性剂混合组装体的光物理特性和微环境特征的基础研究,对于加深我们对纳米尺度分子相互作用的理解至关重要,从而为pluronic-zwitterionic 表面活性剂组装体在药物输送、诊断和其他应用领域的创新解决方案奠定基础。这项研究以形成苯乙烯染料反式-2-[(4-二甲基氨基)苯乙烯基]苯并噻唑的分子内电荷转移态扭曲为探针,探索了pluronic-齐聚物表面活性剂混合组装体错综复杂的光物理。通过比较嵌段组成为(PEO)132-(PPO)50-(PEO)132 [F108]和(PEO)100-(PPO)65-(PEO)100 [F127]的两种不同聚(环氧乙烷)-嵌段-聚(环氧丙烷)-嵌段-聚(环氧乙烷)嵌段共聚物在 5 和 10 wt % 浓度下的行为,本研究系统地考察了添加齐聚物表面活性剂的影响。通过一套全面的分析技术,包括紫外可见吸收、稳态发射和时间分辨荧光发射研究,观察到添加齐聚物表面活性剂后发射光谱和量子产率的显著变化。这些变化表明,染料分子在组装体内部各种微环境之间的转换达到了动态平衡。此外,动态光散射、ZETA 电位(ζ)、核奥弗霍塞尔效应光谱、小角中子散射、低温透射电子显微镜、场发射扫描电子显微镜和荧光寿命成像显微镜分析都揭示了表面活性剂的加入对组装体结构特性的重大影响。
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引用次数: 0
Wood Surface-Embedding of Functional Monodisperse SiO2 Microspheres for Achieving Robust, Durable, Nature-Inspired, Programmable Superrepellent Interfaces. 木质表面嵌入功能性单分散二氧化硅微球,以实现坚固、耐用、受自然启发、可编程的超级排斥界面。
IF 3.7 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-06 DOI: 10.1021/acs.langmuir.4c03178
Huajie Shen, Kangkang Zhang, Donghai Huang, Yuan Miao, Caipin Lian, Xinzhen Zhuo

Nature-inspired, robust, durable, liquid-repellent interfaces have attracted considerable interest in the field of wood biomimetic intelligence science and technology application. However, realizing green environmental protection and low maintenance and replacement cost wood surfaces constructed with micro/nanoarchitectures is not an easy task. Aiming at the problem of poor waterproof performance of wood, a silicon dioxide/polydimethylsiloxane (SiO2/PDMS) self-cleaning programmable superhydrophobic coating was biomimetically constructed on the wood substrate by surface-embedded dual-dipping design based on the "substrates + nanoparticles" hybrid principle of the lotus leaf effect. This robust, durable, nature-inspired, self-cleaning, programmable superhydrophobic coating was found to have no observable impact on the original color and texture of the natural wood. The SiO2/PDMS/wood prepared exhibited exceptional liquid repellency and a high static water contact angle (WCA) of 158.5° and a low slide angle (SA) of 10°, including everyday general-purpose droplets, indicating that the introduction of the monodisperse SiO2 microspheres can effectively enhance the superhydrophobic properties of the hydrophilic wood. We applied this strategy to a variety of substrates, including wood-cellulose aerogel and wood-cellulose paper, and demonstrated that the liquid-repellent nature of the self-cleaning superhydrophobic coating remained unchanged. Moreover, the superhydrophobic surface of SiO2/PDMS/wood was preserved even after harsh abrasion conditions, including mechanical damage (sandpaper, sharp steel blade, and tapes), thermal damage (UV irradiation and low/high-temperature exposure such as steaming and freezing), chemical damage, and solvent corrosion (immersion in acid, alkali), demonstrating robust stability of the superhydrophobic coating. Furthermore, the SiO2/PDMS programmable superhydrophobic coating exhibits exceptional exciting self-cleaning and stain-resistant properties, making it offer greater possibilities in terms of scientific challenges and real-world problem-solving at biomimetic smart superhydrophobic interfaces in wood.

在木材仿生智能科学与技术应用领域,受大自然启发而产生的坚固、耐用、憎液界面引起了人们的极大兴趣。然而,实现绿色环保、低维护和更换成本的微/纳米结构木材表面并非易事。针对木材防水性能差的问题,根据荷叶效应的 "基底+纳米颗粒 "混合原理,通过表面嵌入式双浸渍设计,在木材基底上仿生构建了二氧化硅/聚二甲基硅氧烷(SiO2/PDMS)自清洁可编程超疏水涂层。研究发现,这种坚固耐用、源于自然、自清洁、可编程的超疏水涂层对天然木材原有的颜色和纹理没有明显影响。制备的二氧化硅/PDMS/木材具有优异的憎液性能,静态水接触角(WCA)高达 158.5°,滑动角(SA)低达 10°,包括日常通用液滴,这表明单分散二氧化硅微球的引入可有效增强亲水性木材的超疏水特性。我们将这一策略应用于多种基材,包括木纤维素气凝胶和木纤维素纸,结果表明自清洁超疏水涂层的憎液特性保持不变。此外,SiO2/PDMS/木材的超疏水表面即使在恶劣的磨损条件下也能保持不变,包括机械损伤(砂纸、锋利的钢刀和胶带)、热损伤(紫外线照射和低/高温暴露,如蒸煮和冷冻)、化学损伤和溶剂腐蚀(浸泡在酸、碱中),这表明超疏水涂层具有很强的稳定性。此外,SiO2/PDMS 可编程超疏水性涂层还表现出令人兴奋的自清洁和抗污性能,这使它在木材仿生智能超疏水性界面的科学挑战和实际问题解决方面提供了更大的可能性。
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引用次数: 0
Enabling Efficient Oxygen Evolution via Anchoring Carbon-Layer-Confined RuOx on a Well-Matched Substrate 通过在匹配良好的基底上锚定碳层限制的 RuOx,实现高效氧气进化
IF 3.9 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-06 DOI: 10.1021/acs.langmuir.4c03507
Liming Zeng, Bang Yuan, Qing Zhou
Oxygen evolution reaction (OER) is a multistep proton-coupled four-electron process with sluggish kinetics, which seriously limits the hydrogen production efficiency, thus it is of great importance to develop an efficient and stable OER catalyst. In this study, a two-step differential pyrolysis strategy is employed to design a three-dimensional porous microstructured material consisting of RuOx nanoparticles coated by a thin-layer carbon, where the active particles were isolated in separate chambers and the RuOx nanoparticles mainly existed in the form of a heterogeneous interface between RuO2 and partial metallic Ru. The preparation parameters of the catalysts are optimized via combining transient and steady-state polarization properties, and the target catalyst Cat-500–1.5t shows the best OER catalytic performance after ca. 60 h of a chronopotentiometry test in an acidic medium with a much smaller performance change than other samples. The unique design of adopting a carbon layer to form separate reaction chambers largely mitigates the excessive oxidation loss of the active components under strong oxidation potential. The suitability of the catalyst with the loaded substrate and test media is explored, and in an acidic medium, the carbon paper is much better than the titanium fiber, while in an alkaline medium, the titanium fiber is obviously superior to the carbon paper. On both carbon paper and titanium fiber, the performance in an alkaline medium outperforms that in an acidic medium, and the possible reasons for the performance difference are analyzed. Herein, to obtain the actual electrocatalytic performance, the optimal design of the catalyst structure and matching suitable conductive substrate in a specific medium are quite necessary, which provides a feasible strategy for the acquisition of efficient and stable electrocatalysts and the desirable presentation of performance.
氧进化反应(OER)是一个多步骤质子耦合四电子过程,其动力学缓慢,严重限制了制氢效率,因此开发一种高效稳定的 OER 催化剂具有重要意义。本研究采用两步差热分解策略设计了一种由纳米 RuOx 粒子包覆薄层碳组成的三维多孔微结构材料,其中活性粒子被隔离在不同的腔室中,纳米 RuOx 粒子主要以 RuO2 和部分金属 Ru 的异质界面形式存在。通过结合瞬态和稳态极化特性,对催化剂的制备参数进行了优化,目标催化剂 Cat-500-1.5t 在经过约 60 h 的慢动作催化后显示出最佳的 OER 催化性能。目标催化剂 Cat-500-1.5t 在酸性介质中经过约 60 小时的计时电位测试后,显示出最佳的 OER 催化性能,其性能变化远远小于其他样品。采用碳层形成独立反应室的独特设计在很大程度上减轻了活性成分在强氧化电位下的过度氧化损失。在酸性介质中,碳纸的性能远优于钛纤维,而在碱性介质中,钛纤维则明显优于碳纸。碳纸和钛纤维在碱性介质中的性能均优于酸性介质,并分析了造成性能差异的可能原因。由此可见,要获得实际的电催化性能,催化剂结构的优化设计和在特定介质中匹配合适的导电基底是十分必要的,这为获得高效稳定的电催化剂和理想的性能表现提供了可行的策略。
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引用次数: 0
Competing Bifurcations Determine Symmetry Breaking During Droplet Snaps on Smooth Patterned Surfaces. 竞争性分岔决定了光滑图案表面水滴扣合过程中的对称性破坏。
IF 3.7 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-06 DOI: 10.1021/acs.langmuir.4c02908
Lucile Bisquert, Élfego Ruiz-Gutiérrez, Marc Pradas, Rodrigo Ledesma-Aguilar

The shape and stability of a droplet in contact with a solid surface is affected by the chemical composition and topography of the solid, and crucially, by the droplet's size. During a variation in size, most often observed during evaporation, droplets on smooth patterned surfaces can undergo sudden shape and position changes. Such changes, called snaps, are prompted by the surface pattern and arise from fold and pitchfork bifurcations which respectively cause symmetric and asymmetric motions. Yet, which type of snap is likely to be observed is an open fundamental question that has relevance in the rational design of surfaces for managing droplets. Here we show that the likelihood of observing symmetric or asymmetric snaps depends on the distance between fold and pitchfork bifurcation points and on how this distance varies for droplets that grow or shrink in size on surfaces patterned with a smooth topography. Our results can help develop strategies to control droplets by exploiting smooth surface patterns but also have broader relevance in situations where different types of bifurcations compete in determining the stability of a system, for instance in snap-through instabilities observed in elastic media.

与固体表面接触的液滴的形状和稳定性受固体的化学成分和地形的影响,最重要的是受液滴大小的影响。在蒸发过程中最常观察到的尺寸变化过程中,光滑图案表面上的液滴会发生形状和位置的突然变化。这种变化被称为 "突变"(snap),是由表面图案引起的,由分别引起对称和不对称运动的褶皱和杈状分叉产生。然而,哪种类型的卡扣有可能被观察到是一个未决的基本问题,它与管理液滴的表面的合理设计息息相关。在这里,我们展示了观察到对称或不对称卡扣的可能性取决于折叠点和叉形分叉点之间的距离,以及液滴在具有光滑地形图案的表面上增大或缩小时这一距离的变化情况。我们的研究结果不仅有助于开发利用光滑表面图案控制液滴的策略,而且在不同类型的分叉竞争决定系统稳定性的情况下,例如在弹性介质中观察到的卡突不稳定性中,也具有更广泛的意义。
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引用次数: 0
Fe-Doped Ni3S2 Induces Self-Reconstruction for Urea-Assisted Water Electrolysis Enhancement. 掺铁 Ni3S2 可诱导尿素辅助水电解增强的自重构。
IF 3.7 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-06 DOI: 10.1021/acs.langmuir.4c03343
Xinyu Yang, Yifeng Liu, Qianqiao Chen, Wanchin Yu, Qin Zhong

Urea oxidation reaction (UOR) is an attractive alternative anodic reaction to oxygen evolution reaction (OER) for its low thermodynamic potential (0.37 V vs RHE). A major challenge that prohibits its practical application is the six-electron transfer process during UOR, demanding enhancements in the catalytic activity. Herein, a Fe-doped Ni3S2 catalyst with a uniform flower-like structure is synthesized in situ on nickel foam via a simple one-step hydrothermal method. The electrochemical properties of Fe-Ni3S2 are significantly improved since a current density of 10 mA cm-2 only requires a 1.33 V potential and remains stable for 60 h. The structural characterization demonstrates a strong interaction between Fe and Ni3S2. After Fe doping, the active site increases, which promotes the formation of NiOOH on the catalyst surface, thus speeding up the UOR process. These changes are beneficial to charge transfer and optimize the adsorption energy of the intermediates. In situ EIS further confirms that Fe promotes electron transfer during the UOR process, reduces the interface resistance between the catalyst and the electrolyte, and lowers the driving voltage.

尿素氧化反应(UOR)的热力学电位较低(0.37 V 对 RHE),是氧进化反应(OER)的一种有吸引力的替代阳极反应。阻碍其实际应用的一个主要挑战是 UOR 反应过程中的六电子转移过程,这就要求提高催化活性。本文通过简单的一步水热法,在泡沫镍上原位合成了具有均匀花状结构的掺铁 Ni3S2 催化剂。由于 10 mA cm-2 的电流密度只需要 1.33 V 的电位,且能保持稳定 60 小时,Fe-Ni3S2 的电化学性能得到了显著改善。掺入 Fe 后,活性位点增加,促进了催化剂表面 NiOOH 的形成,从而加快了 UOR 过程。这些变化有利于电荷转移,并优化了中间产物的吸附能。原位 EIS 进一步证实,铁在 UOR 过程中促进了电子转移,降低了催化剂与电解质之间的界面电阻,并降低了驱动电压。
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引用次数: 0
Regulating the Performance of CO2 Adsorbents Based on the Pyrolysis Mechanism of Self-Sacrificial Templating Agents 根据自人工模板剂的热解机理调节二氧化碳吸附剂的性能
IF 3.9 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-06 DOI: 10.1021/acs.langmuir.4c03844
Su Dan Bao, Agula Bao
Previous research has proven that the pore shape and nitrogen group content of adsorbents play essential roles in determining their carbon dioxide (CO2) adsorption performance. In this article, a series of nitrogen-doped porous carbon materials were prepared for CO2 adsorption by varying the proportion of carbon nitride, the pyrolysis temperature, and the activation ratio of KOH, using chitosan as the carbon source, carbon nitride (g-C3N4 and g-C3N5) as self-sacrificing templating agents, and KOH as the activator. Among the prepared materials, T6-850-1 has the highest specific surface area (SBET) of 2336 m2/g, and T6-750-1 has the highest microporous area (Smicro) and CO2 adsorption capacity (1 bar, 298 K) of 1969 m2/g and 3.49 mmol/g, respectively. The thermal decomposition temperature and products of carbon nitride templates were characterized and tested by thermogravimetric infrared gas chromatography-mass spectrometry (TG-IR-GC-MS), and the thermal decomposition mechanisms of the two carbon nitride templates were investigated. We found that the thermal stability of the template directly affects the pore structure of the final sample as well as the type and quantity of nitrogen species.
以往的研究证明,吸附剂的孔隙形状和氮基团含量对其二氧化碳(CO2)吸附性能起着至关重要的作用。本文以壳聚糖为碳源,氮化碳(g-C3N4 和 g-C3N5)为自吸收模板剂,KOH 为活化剂,通过改变氮化碳的比例、热解温度和 KOH 的活化比,制备了一系列掺氮多孔碳材料,用于吸附二氧化碳。在制备的材料中,T6-850-1 的比表面积(SBET)最高,为 2336 m2/g;T6-750-1 的微孔面积(Smicro)和二氧化碳吸附容量(1 bar, 298 K)最高,分别为 1969 m2/g 和 3.49 mmol/g。通过热重红外气相色谱-质谱法(TG-IR-GC-MS)对氮化碳模板的热分解温度和产物进行了表征和测试,并研究了两种氮化碳模板的热分解机理。我们发现,模板的热稳定性直接影响最终样品的孔结构以及氮物种的类型和数量。
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引用次数: 0
Glycoside-Mediated Enhancement of Stability in Aluminum Oxyhydroxide Nanoadjuvants during Freeze-Drying 通过糖苷提高氧化铝纳米佐剂在冷冻干燥过程中的稳定性
IF 3.9 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-06 DOI: 10.1021/acs.langmuir.4c03474
Mudasira Bhurt, Xin Li, Nan Zhang, Wenqi Yang, Muzhe Xu, Yang Liu, Yejiong Yu, Bingbing Sun
Aluminum-based adjuvants have been indispensable to vaccine potency. However, their effectiveness is difficult to maintain after freeze-drying, which limits the storage and application of aluminum-adjuvanted vaccines. In this study, the impact of freeze-drying on aluminum oxyhydroxide nanorods (AlOOH NRs) was investigated. Freeze-drying led to aggregation and resulted in the loss of the surface hydroxyl content of aluminum adjuvants. To alleviate freeze-drying-induced damage, the potency of different alkyl glycosides as protectants was further evaluated. It was demonstrated that the structural balance of the head and tail of a glycoside was more conducive to protecting AlOOH NRs from aggregation and loss of surface hydroxyl groups. These results underline the proper selection of protectants to protect adjuvants against functional defects caused by freeze-drying, which is important for the stability and efficacy of vaccines and biopharmaceutical products.
铝基佐剂对疫苗的效力不可或缺。然而,铝佐剂在冷冻干燥后很难保持其有效性,这限制了铝佐剂疫苗的储存和应用。本研究调查了冻干对氧化铝纳米棒(AlOOH NRs)的影响。冷冻干燥会导致铝佐剂表面羟基的聚集和损失。为了减轻冻干引起的损伤,研究人员进一步评估了不同烷基糖苷作为保护剂的功效。结果表明,糖苷头部和尾部的结构平衡更有利于保护 AlOOH NR 免受聚集和表面羟基的损失。这些结果强调了正确选择保护剂以保护佐剂免受冷冻干燥造成的功能缺陷的影响,这对疫苗和生物制药产品的稳定性和功效非常重要。
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引用次数: 0
Effects of Thermal Energy on the Formation of Lattice Strain in VO2 Thin Films Grown on TiO2(001). 热能对在 TiO2(001) 上生长的 VO2 薄膜中形成晶格应变的影响。
IF 3.7 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-06 DOI: 10.1021/acs.langmuir.4c03004
Reki Nakamoto, Hiroyuki Okazaki, Takanori Wakita, Takayoshi Yokoya, Yuji Muraoka

Film thickness is a well-known experimental parameter for controlling lattice strain in oxide films. However, due to environmental and resource conservation considerations, films need to be as thin as possible, increasing the need to find alternative factors for strain management. Herein, we present the importance of thermal energy as a factor for the formation of lattice strain in the oxide films, specifically focusing on the effects of laser fluence during pulsed laser deposition (PLD) on the in-plane lattice strain of vanadium dioxide (VO2) thin films grown on titanium dioxide (TiO2) (001). VO2 thin films were deposited using a KrF excimer laser (λ = 248 nm) at laser fluences ranging from 0.88 to 1.70 J/cm2. The film thickness ranged from 10-15 nm, below the critical thickness. Films grown at higher laser fluences exhibited smooth surfaces and completely strained in-plane lattices. In contrast, films grown at lower laser fluences displayed numerous small islands and relaxed in-plane lattice strain. The metal-insulator transition (MIT) temperature was lower for films grown at higher laser fluencies compared to those grown at lower laser fluences. It was also revealed that Ti-V interdiffusion occurs, forming a solid solution (V1-xTixO2) near the interface. These observations suggest that the thermal energy of the particles, influenced by laser fluence, is a critical factor in the formation of lattice strain in metal oxide films and also that laser fluence in PLD is an effective experimental parameter for strain management in oxide films. Our findings enhance the understanding of lattice strain formation in metal oxides and offer insights for establishing effective methods for controlling lattice strain in metal oxide films.

薄膜厚度是众所周知的控制氧化物薄膜晶格应变的实验参数。然而,出于环境和资源保护的考虑,薄膜需要越薄越好,这就更需要找到应变管理的替代因素。在此,我们介绍了热能作为氧化物薄膜晶格应变形成的一个重要因素,特别是脉冲激光沉积(PLD)过程中激光通量对生长在二氧化钛(TiO2)(001)上的二氧化钒(VO2)薄膜面内晶格应变的影响。VO2 薄膜使用 KrF 准分子激光器(λ = 248 nm)在 0.88 至 1.70 J/cm2 的激光通量下沉积。薄膜厚度为 10-15 nm,低于临界厚度。在较高激光通量下生长的薄膜表面光滑,面内晶格完全紧张。与此相反,在较低激光通量下生长的薄膜则显示出许多小的孤岛和松弛的面内晶格应变。与低激光通量下生长的薄膜相比,高激光通量下生长的薄膜的金属-绝缘体转变(MIT)温度更低。研究还发现,Ti-V 发生了相互扩散,在界面附近形成了固溶体(V1-xTixO2)。这些观察结果表明,粒子的热能受激光通量的影响,是金属氧化物薄膜中形成晶格应变的关键因素,而且 PLD 中的激光通量是氧化物薄膜应变管理的有效实验参数。我们的发现加深了人们对金属氧化物晶格应变形成的理解,并为建立控制金属氧化物薄膜晶格应变的有效方法提供了启示。
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