液体弹珠：制备策略、物理性质及应用探索

Liquid marbles (LMs) are liquid droplets coated with a layer of lyophobic particles at the air-liquid interface. Since the pioneering work by Aussillous et al. in 2001, LMs have attracted significant attention owing to their facile fabrication, flexibility in the choice of the constituent particles and liquids, intriguing properties such as non-wetting and non-adhesive nature, satisfactory elasticity and stability, as well as promising applications in microfluidics, sensors, controlled release, and microreactors. The classical strategy for the preparation of LMs involves rolling a small volume of a droplet on a lyophobic powder bed for complete encapsulation of the liquid by the particles. In addition, various innovative methods, including electrostatic and coalescent approaches, have been developed for preparing special LMs with a complicated structure or morphology. Diverse materials such as water, surfactant solutions, liquid metals, reagents, blood, and even viscous adhesives have been employed as the internal liquid for the fabrication of LMs. Theoretically, any particulates such as lycopodium, polytetrafluoroethylene, Fe₃O₄, SiO₂, and graphite grains can be employed as the outer coating, but they are usually required to be lyophobic with sizes of less than hundreds of microns. The unique structure of the particle-covered droplet and the dual solid-liquid characteristics endow LMs with some unique and interesting properties, especially the non-wetting and non-adhesive nature. As the lyophobic coating particles restrain the internal liquid from contacting the substrate, LMs can move easily across either solid or liquid surfaces, neither wetting the substrate nor contaminating the internal liquid. An equally fascinating property of LMs is their satisfactory stability, which is necessary for most of their applications. The high stability of LMs stems from the protection of the coating powders and is embodied in both good mechanical stability (remaining intact after being released from a certain height or under a certain compression) and long lifetime (greatly suppressing the evaporation of the internal liquid). These extraordinary properties make LMs promising candidates for use in multitudinous fields, especially droplet microfluidics and microreactors. The potential application of LMs in microfluidics is ascribed to their non-wetting, non-adhesive nature and other features such as an ability to float on a liquid surface, coalescence, split, a small force of rolling friction, and response to external forces. Notably, LMs hold great promise for applications in microreactions, because they can create a confined reaction microenvironment, minimize reagent usage, facilitate unhindered gas exchange between the internal liquid medium and the surrounding environment, and allow the entry/exit of the reactants/products. We herein review the recent advances in LMs, such as manufacturing techniques, formation mechanisms, physical properties, and emerging applications. In particular, much attention is paid to the factors affecting the stability of LMs and the potential strategies to increase their stability. Moreover, this review discusses the challenges in the future development of LMs, suggests several possible ways of addressing these challenges, and forecasts the future development directions. We believe that this review can help researchers gain a better understanding of LMs and promote their further advances.     

超疏水性材料表面的制备、应用和相关理论研究的新进展

文章总结了Wenzel方程、Cassie方程及一种具有极高精确度的,可方便测出固体表面上液滴前进角和后退角的测试方法等超疏水表面的最新理论研究成果;回顾了溶胶凝胶法、化学修饰法、喷涂法、液相法、化学蚀刻法、水热法、微相分离法、原位聚合法、静电纺丝法、阳极氧化法等近几年出现的超疏水表面的制备方法;介绍了在微物质能量、生物医学、光学、燃料以及电池应用等领域超疏水表面的最新功能性的应用。最后,客观地展望了超疏水表面制备及理论研究的发展方向。     

结构化液体的设计、构筑与应用

结构化液体是近年来基于二元流体体系,利用固体粒子液/液界面自组装和堵塞相变构筑的一类非平衡态软物质材料,兼具固体的结构稳定性和液体的流动性.然而,受限于组装基元和成型方法,制备具有精准结构的智能结构化液体及衍生功能材料仍面临挑战.我们课题组在该领域开展了大量研究工作,在发展界面调控新机制,制备液体/固体新材料,以及实现材料器件新突破等方面取得了系列创新成果.本专论从固体粒子界面自组装机制出发,重点阐述了一种利用纳米粒子和聚合物液/液界面共组装制备纳米粒子表面活性剂,进而构筑结构化液体的普适策略;总结归纳了结构化液体在响应性调控、高效精准构筑以及功能材料制备等方面的研究进展;并对该领域面临的机遇和挑战做出展望.     

离子液体和聚离子液体固相微萃取涂层制备及应用进展

固相微萃取(Solid-phase microextraction,SPME)技术因其具有操作简单、萃取时间短、无需有机溶剂、易于自动化操作等优点,成为近年来发展起来的一种新型样品前处理技术。涂层是SPME技术的核心,决定了涂层萃取的选择性和容量。离子液体和聚离子液体因具有环境友好、蒸汽压低、热稳定性好、设计灵活、粘度大等特点,已作为一类新的涂层材料广泛应用于SPME,并对各种分析物均展现出良好的萃取效果和选择性。本文从制备技术、形貌、选择性、稳定性、寿命、应用等方面综述了近年来离子液体和聚离子液体基SPME涂层的研究进展,对它们的优缺点进行了对比讨论,并对其未来发展方向进行了展望。     

基于微纳结构液体灌注的超滑表面的制备与应用

超滑表面利用其基底上的微纳结构通过毛细作用将润滑油等液体锁定在孔隙中,孔隙中浸润的润滑油在基底形成一层动态油膜,油膜与不溶液体的液-液界面代替了固体与液体的固-液界面,从而大幅减少了滑动阻力。与传统具有类似低滚动角特性的超疏水和超疏油表面相比,孔隙中填充润滑油比空气具有更好的压力稳定性,而且润滑油的毛细流动性使得超滑表面具有良好的自修复能力。由于其明显的优势,近些年超滑表面已成为国际学术界研究热点,应用也拓展到防结冰、强化传热、减阻、抗生物黏附、微流控等领域。目前超滑表面研究仍存在重要挑战,例如如何避免润滑油的挥发带来的性能退化、如何针对各种材质和结构设计合适的加工工艺制备微纳结构等,这些问题限制了超滑表面的广泛应用。本文综述了超滑表面的制备工艺以及应用,分析了现存的问题,并且对超滑表面未来的发展趋势进行了展望。     

耐久型超疏水表面:理论模型、制备策略和评价方法

超疏水材料以其独特的润湿性在日常生活和工业领域都展示出广阔的应用前景,但其表面的微纳米结构和低表面能物质易受到机械摩擦或化学侵蚀而失去超疏水性。当前诸多报道都采用微纳结构设计和表面优化来延长超疏水材料的耐久性,以期提升其商业价值。本文先从表面浸润模型出发,包括经典理论、亚稳态理论和接触线理论,梳理了超疏水理论模型的发展脉络,阐明这些理论在超疏水耐久性设计上发挥的关键指导作用。接着对微纳米结构设计、胶黏+涂装、铠装防护、自修复和气膜修补等延长超疏水耐久性的制备策略进行了总结,并对不同制备策略各自的优势和局限性进行简要评述。本综述还从机械稳定性和化学稳定性两方面汇总了超疏水耐久性的快速评价手段,讨论了提升超疏水表面耐久性所遇到的问题,并展望了超疏水材料的发展前景,以期助力长效超疏水材料的研发和应用。     

烧结型NdFeB永磁体表面有机纳米复合膜的制备及性能

采用自组装分子膜技术在烧结型NdFeB永磁体表面制备了三嗪硫醇三乙基硅烷(TES)自组装分子膜(TES-SAMs), 在TES-SAMs的基础上利用自主开发的有机镀膜技术制备了具有含氟官能团的三嗪硫醇(ATP)有机纳米复合薄膜(TES-ATP). 通过X射线光电子能谱仪(XPS)、傅里叶变换红外(FTIR)光谱仪、椭圆偏振光谱仪、原子力显微镜(AFM)和接触角测量仪对薄膜的表面状况进行评价, 使用UMT-2型摩擦磨损试验机研究TES-SAMs和TES-ATP的微摩擦学性能. 研究结果表明: TES-SAMs和TES-ATP的膜厚分别是5.08和29.78nm; 表面自由能从基体的73.13 mJ·m^-2下降到TES-SAMs的63.69 mJ·m^-2和TES-ATP复合膜的10.19 mJ·m^-2, 且TES-ATP复合膜对蒸馏水的接触角为123.5°, 成功实现了NdFeB表面由亲水到疏水的转换.TES-SAMs和TES-ATP均能有效降低摩擦系数, TES-SAMs的摩擦系数为0.22, TES-ATP的摩擦系数为0.12, 而基体的摩擦系数为0.71; 同时, TES-ATP还表现出良好的抗磨性能. TES-ATP复合膜为微机电系统中的摩擦磨损问题的解决提供了一种新思路.     

基于离子液体的炭材料制备、改性及应用

离子液体因其熔点低、液态温域宽、蒸气压低、热稳定性高、电导率高、电化学窗口宽、结构可设计及对许多化合物的亲和性等系列性能而引起人们广泛关注。离子液体在炭材料制备、改性领域展示出了良好的前景及巨大的应用潜力,可直接作为碳源,经过高温炭化实现杂原子掺杂制备多孔炭材料;离子液体也可充当反应介质和致孔剂,将生物质转化为多孔炭材料;此外,由于离子液体与炭材料相容性较好,可以用于多孔炭材料改性制备炭复合材料。基于离子液体的炭材料在电催化、超级电容器、吸附分离及生物医学等领域具有潜在的应用价值。本文总结了基于离子液体炭材料的制备、改性及应用最新研究进展,并着重介绍了其在能源和环境相关领域的应用。     

室温离子液体:合成、性质及应用

室温离子液体是一类熔点在室温附近的熔融盐 ,以其熔点低、蒸气压小、电化学窗口大、酸性可调及良好的溶解度、粘度、密度等特点已经或正在电化学、有机合成、催化、分离等领域被广泛应用 ,并因其对环境友好吸引了工业上的兴趣     

酸性离子液体中铂纳米粒子的制备、表征及应用

基于功能化离子液体的特性,开发出不使用聚合物保护剂制备铂纳米粒子并同时获得具有金属和酸活性中心双功能催化剂的新方法。首先,设计并合成出了一种新型季铵型质子(Br?nsted)酸性离子液体(N, N, N-三甲基-N-磺丁基硫酸氢铵([HSO₃-b-N(CH₃)₃]HSO₄)),然后,利用化学还原方法在该离子液体中制备了金属铂纳米粒子,并采用紫外光谱、傅立叶红外光谱、X-光电子能谱、透射电子显微镜和X射线衍射等方法对所制备的金属铂纳米粒子进行了结构表征。结果表明,所制备的铂纳米粒子具有面心立方结构,离子液体作为修饰剂修饰在铂纳米粒子的表面,有效地阻止了铂纳米粒子的团聚;将该含有铂纳米粒子的酸性离子液体作为双功能催化剂,直接用于硝基苯加氢合成对氨基苯酚反应,发现其具有良好的催化性能,在85 ℃、4 h、0.4 MPa条件下,硝基苯转化率为98.6%,对氨基苯酚收率为75.8%,回收的酸性离子液体纳米铂双功能催化体系中铂纳米粒子依然具有很好的分散性和稳定性。     

液体弹珠及其研究进展

润湿性是固体表面的重要性质之一,主要由表面的化学组成和微观几何结构共同决定。不粘连表面是指具有特殊的表面形貌及性能,使得诸如尘土、水、冰以及污染物较难黏附的特殊表面。液体弹珠是被高疏水性颗粒包裹形成的不润湿的液滴,可以稳定地静置于固体及液体表面。本文介绍了液体弹珠的结构和制备方法,综述了液体弹珠的静态力学性能及其在磁场电场下的响应性能,探讨了这种新型不粘连体系用于移动和控制微量液滴的独特优势,展望了其发展趋势以及应用前景。     

Plasmonic Liquid Marbles: A Miniature Substrate‐less SERS Platform for Quantitative and Multiplex Ultratrace Molecular Detection

Inspired by aphids, liquid marbles have been studied extensively and have found application as isolated microreactors, as micropumps, and in sensing. However, current liquid‐marble‐based sensing methodologies are limited to qualitative colorimetry‐based detection. Herein we describe the fabrication of a plasmonic liquid marble as a substrate‐less analytical platform which, when coupled with ultrasensitive SERS, enables simultaneous multiplex quantification and the identification of ultratrace analytes across separate phases. Our plasmonic liquid marble demonstrates excellent mechanical stability and is suitable for the quantitative examination of ultratrace analytes, with detection limits as low as 0.3 fmol, which corresponds to an analytical enhancement factor of 5×10⁸. The results of our simultaneous detection scheme based on plasmonic liquid marbles and an aqueous–solid–organic interface quantitatively tally with those found for the individual detection of methylene blue and coumarin.     

Nonaqueous Lyotropic Ionic Liquid Crystals: Preparation,Characterization, and Application in Extraction

A class of new ionic liquid (IL)‐based nonaqueous lyotropic liquid crystals (LLCs) and the development of an efficient IL extraction process based on LC chemistry are reported. The nonaqueous LLCs feature extraordinarily high extraction capacity, excellent separation selectivity, easy recovery, and biocompatibility. This work also demonstrates that the introduction of self‐assembled anisotropic nanostructures into an IL system is an efficient way to overcome the intrinsically strong polarity of ILs and enhances the molecular recognition ability of ILs. The distribution coefficients of IL‐based LLCs for organic compounds with H‐bond donors reached unprecedented values of 50–60 at very high feed concentrations (>100 mg mL^?1), which are 800–1000 times greater than those of common ILs as well as traditional organic and polymer extractants. The IL‐based nonaqueous LLCs combining the unique properties of ILs and LCs open a new avenue for the development of high‐performance extraction methods.     

超亲水表面制备方法及其应用

特殊浸润性表面由于其独特的浸润行为在液体输送、涂料、防水、建筑和医用材料等领域都有着重要的应用。作为一种典型的特殊浸润性表面,超亲水表面（与水的接触角接近于0°）具有防雾和自清洁的功能,在工业生产和实际生活中具有广泛的应用。本文总结了近年来超亲水表面的制备方法以及与超亲水性密切相关的其他特殊浸润性表面的研究进展,包括超...     

手性液晶聚硅氧烷毛细管柱的制备及应用

合成了一种手性液晶侧链的聚硅氧烷固定液，并涂制成毛细管柱，此柱适合于分离各种取代基的酚类异构体。对柱效和选择性进行了评价。     

功能离子液体杂化固相纳米材料的制备及催化应用

离子液体是一种新颖的软功能材料,它既可以作为催化反应的绿色介质,也可以作为催化反应的活性组分,还可以作为一种客体的催化功能分子来修饰一些固相纳米材料。本文主要立足于多相催化材料的设计合成和应用的角度,结合近几年来一些新颖的固相纳米材料,系统地综述了功能离子液体对这些固相材料的杂化方法及其在催化应用中表现出的一些独特的催化性能。最后,对功能离子液体杂化固相纳米材料的研究现状进行了总结,并对将来可能的发展方向进行了展望。     

1-乙基-3-丁基苯并咪唑六氟化磷离子液体液相微萃取剂的制备与应用

合成了1-乙基苯并咪唑（eBim）、1-乙基-3-丁基苯并咪唑溴(C4eBimBr)中间体和1-乙基-3-丁基苯并咪唑六氟化磷(C4eBimPF6)离子液体。 通过红外光谱和核磁共振波谱表征了各步反应产物的结构。 基于离子液体分散液相微萃取-高效液相色谱法分析了水中邻苯二甲酸辛酯(DOP)和邻苯二甲酸壬酯(DNP)。 考察了萃取温度、萃取时间和离子液体用量对DOP和DNP萃取效果的影响。 在1.0～10 μg/L范围内,DOP和DNP的色谱峰高与质量浓度分别呈线性关系,相关系数（r2）分别为0.984 7和0.987 2。 DOP和DNP的最低检出限分别为0.018和0.052 μg/L,加标回收率分别为94.3%~102%和93.5%~103%。