纤维素基气凝胶型吸油材料的研究进展

近年来,开发绿色、可回收的高效吸油材料吸引了国内外学者的广泛关注.纤维素基气凝胶兼具多孔气凝胶型材料比表面积大、孔隙率高的特点以及纤维素材料天然、可再生的优势,对其进行表面疏水化处理后,是一种极具发展潜力的环保型吸油材料.本文分别系统综述了再生纤维素基气凝胶型、天然纤维素基气凝胶型及细菌纤维素基气凝胶型吸油材料的研究进展,并对它们的制备方法和吸油性能进行了归纳总结,最后讨论了当前纤维素基气凝胶型吸油材料研究中存在的问题和今后的研究方向.     

利用离子液体制备纤维素基气凝胶

纤维素基气凝胶材料的研究在近年来吸引了人们极大的关注,这是因为这类新型材料具有通常无机气凝胶的典型结构特点,如超轻、高孔率、高比表面积等,同时具有天然生物质材料的原料丰富、可再生、可生物降解的优点。本文首先简要介绍了纤维素基气凝胶材料及其发展概况,进而主要介绍了以离子液体为溶剂制备再生纤维素基气凝胶的研究进展,包括纤维素基气凝胶的制备方法、结构及其功能性。最后对离子液体法制备的纤维素基气凝胶材料的前景进行了简要的展望。     

以纤维素/AmimCl溶液制备纤维素气凝胶

利用离子液体AmimCl溶解结合超临界CO2干燥的方法制备了纤维素气凝胶材料.研究了不同初始浓度的纤维素溶液及其在不同凝固浴中制备的纤维素凝胶的流变行为,进一步考察了纤维素溶液浓度和凝固浴种类对纤维素气凝胶材料结构的影响.结果表明,随着初始纤维素溶液浓度的增大,气凝胶的孔结构逐渐致密,比表面积随之减小;凝固浴的组成对纤维素气凝胶的结构也有较大影响.采用适当的制备条件,可以制备出高比表面积的纤维素气凝胶材料.对纤维素气凝胶的热性能进行了表征,结果表明所得到的气凝胶材料具有较好的热稳定性和较高的炭残余含量.     

高力学强度细菌纤维素气凝胶纤维的连续化制备

气凝胶纤维因其高外表面积和高柔韧性在能量管理系统中具有潜在应用而引起了广泛关注.但是,目前制备的气凝胶纤维力学强度较低,限制了其实际应用.为提高气凝胶纤维力学性能,在始终保持细菌纤维素(BC)纳米纤维处于湿态下,利用NaOH/尿素/硫脲复合溶剂直接低温溶解原生BC,获得透明的BC纺丝原液;通过湿法纺丝制备了BC水凝胶纤维,经过水洗和冷冻干燥后处理,制得BC气凝胶纤维.采用偏光显微镜(POM)、13C核磁共振(13C-NMR)和高级旋转流变仪研究BC在复合溶剂中的溶解过程与状态;利用全反射傅里叶变换红外吸收光谱(ATR-FTIR)、X射线衍射(XRD)和热失重(TG)研究BC溶解前后结构与性能变化;利用场发射扫描电镜(FESEM)、全自动比表面积和孔径分布分析仪、单丝强力仪对获得的BC气凝胶纤维结构与性能进行表征.结果表明,复合溶剂在?15℃条件下可以直接溶解原生湿态BC,最高溶解浓度为3 wt%;采用湿法纺丝制得高度多孔的连续BC气凝胶纤维,比表面积高达192 m^2/g且具有优异的力学性能,断裂强度和杨氏模量高达(9.36±1.68)MPa和(176±17.55)MPa,如0.4 mg BC气凝胶纤维可以支撑高于其本身质量5×10^4倍的重物.     

气凝胶

气凝胶是由胶体粒子或高聚物分子相互聚结构成纳米多孔网络结构，并在孔隙中充满气态分散介质的一种高分散固态材料。近来来气凝胶研究得到了很大的发展，本文对气凝胶的制备方法、结构与特性、应用前景等方面的研究进展作一简要的评述。     

气凝胶微球的制备及应用

气凝胶由于其优异的理化性能和广阔的应用前景,近年来的发展十分迅速。然而传统的气凝胶多为块体材料,一定程度上忽略了特殊应用场景下对尺寸和形状的特定需求。将气凝胶材料制备成微球,一方面能够拓宽气凝胶材料的应用领域,另一方面也丰富了多孔微球材料的内涵。本文从几类主要的气凝胶体系(氧化硅气凝胶、纤维素气凝胶、间苯二酚-甲醛(RF)/碳气凝胶和石墨烯气凝胶)出发,综述了这些气凝胶微球的制备方法及其应用实例,并对气凝胶微球的研究现状及发展趋势做了简要评述。     

纳米纤维素基多层级孔道结构碳气凝胶的制备及在锂电池中的应用

采用纳米精磨法对商品桉木浆进行纳米纤丝化处理,得到了高长径比、尺寸均一的纳米纤丝化纤维素(NFC),平均直径为230.10 nm,长度达数十微米.将其组装、干燥后制得具有大量介孔的纳米纤丝化纤维素气凝胶(NFCA).将NFCA在氮气氛围下高温碳化制得碳气凝胶(CNFA),或在氢氧化钾条件下辅助碳化制得具有多层级孔道结构的碳气凝胶(CNFA-A),在保留的碳气凝胶骨架结构上进行孔洞构建.通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)表征及Nanomeasure统计分析,发现NFC的平均直径经碳化后减小到53.16 nm.利用X射线衍射(XRD)、BET比表面积测试和拉曼光谱揭示了碳化处理对纳米纤维素结构、比表面积、石墨化程度和缺陷的影响.结果表明,KOH辅助碳化处理后的碳气凝胶不仅保留了纤维素气凝胶前驱体的网络结构,还在其骨架上二次构建了更多的微孔和介孔,其比表面积高达488.92 m2/g,总孔容为0.404 cm3/g,所得的碳骨架被部分石墨化,具有良好的导电性.这类源于生物质的高比表面积碳气凝胶在被用作锂离子电池(LIB)负极材料时表现出优异的电化学性能,在电流密度1 A/g下连续充放电1000次后比容量达到409 m A·h/g,在电流密度高达20 A/g下,比容量还能维持在219 m A·h/g.     

以细菌纤维素为前驱体简便制备氮掺杂碳纤维气凝胶作为高效氧还原催化剂

数十年来,碳气凝胶因其在催化剂载体、电容器和锂电池电极材料以及吸附剂等领域的潜在应用而备受关注.然而,传统碳气凝胶的制备往往使用昂贵且有毒的前驱体,其方法也较为复杂,不利于大规模生产及应用.本文介绍了一种以细菌纤维素为前驱体制备氮掺杂碳纤维气凝胶的方法.该方法廉价高效,简单易行且对环境无害.所制气凝胶具有密度低、孔隙度高、比表面积大以及导电性良好等优点.它继承了细菌纤维素生物质优异的三维交联多孔结构的特点,可直接用作氧还原催化剂,表现出优异的催化性能,预示着其广泛的应用前景.这在该领域的应用报道尚属首次.     

碳气凝胶的制备研究

气凝胶是由纳米量级超细粒子或高聚物分子聚结构成的多孔性轻质固态材料 ,它在声学、光学、电学、动力学和低温热学等方面具有独特性质 ,因此受到多方面研究者的重视 [1～ 4 ] .碳气凝胶最先是由 Pekala等 [5] 在 80年代末研制成功的 ,其突出特点是网络连续 ,电导率高 ,孔洞微小且相互贯通 ,比表面大 ,密度变化范围大 ,是制造高性能电容器和电池的新一代理想材料[6 ,7] .这种材料的低温电导率随温度连续单调变化 ,在一定温区范围内 ( <1 0 0 K)其电阻温度敏感度远大于传统的掺碳玻璃、锗以及其它金属电阻温度计材料 ,可望成为一种理想的低…     

石墨烯气凝胶的可控组装

石墨烯气凝胶一般是由石墨烯片层经过湿法化学组装或气相化学生长获得的一种具有连通多孔网络结构的石墨烯三维宏观体材料,表现出极高的比表面积、良好的导电性以及优异的机械性能等,在电化学储能、吸附、催化以及传感等领域有着极为重要的应用。本文从石墨烯气凝胶的结构设计与组装策略出发,综述了近年来石墨烯纳米结构单元在石墨烯气凝胶材料（氧化石墨烯、还原氧化石墨烯、化学气相沉积（CVD）石墨烯、以及复合气凝胶等）中的组装行为,并对石墨烯气凝胶目前的现状及今后发展方向做了简要评述。     

Green Preparation of Durian Rind-Based Cellulose Nanofiber and Its Application in Aerogel

In this study, a green, highly efficient and low energy consumption preparation method of cellulose nanofiber (CNF) was developed by using agricultural and forestry waste durian rinds as raw materials. The power of ultrasonic treatment was successfully reduced to only 360 W with low molecular weight liquid DMSO. The obtained durian rind-based CNF had a diameter of 8–20 nm and a length of several micrometers. It had good dispersion and stability in water, and could spontaneously cross-link to form hydrogel at room temperature when the concentration was more than 0.5%. The microscopic morphology and compressive properties of CNF aerogels and composite cellulose aerogels prepared from durian rind-based CNF were evaluated. It was found that CNF could effectively prevent the volume shrinkage of aerogel, and the concentration of CNF had a significant effect on the microstructure and mechanical properties of aerogel. The CNF aerogel with 1% CNF exhibited a sheet structure braced by fibers, which had the strongest compression performance. The porosity of CNF aerogels was high to 99%. The compressive strength of the composite cellulose aerogel with durian rind-based CNF was effectively enhanced.     

HTO/Cellulose Aerogel for Rapid and Highly Selective Li+ Recovery from Seawater

To achieve rapid and highly efficient recovery of Li⁺ from seawater, a series of H₂TiO₃/cellulose aerogels (HTO/CA) with a porous network were prepared by a simple and effective method. The as-prepared HTO/CA were characterized and their Li⁺ adsorption performance was evaluated. The obtained results revealed that the maximum capacity of HTO/CA to adsorb Li⁺ was 28.58 ± 0.71 mg g⁻¹. The dynamic k₂ value indicated that the Li⁺ adsorption rate of HTO/CA was nearly five times that of HTO powder. Furthermore, the aerogel retained extremely high Li⁺ selectivity compared with Mg²⁺, Ca²⁺, K⁺, and Na⁺. After regeneration for five cycles, the HTO/CA retained a Li⁺ adsorption capacity of 22.95 mg g⁻¹. Moreover, the HTO/CA showed an excellent adsorption efficiency of 69.93% ± 0.04% and high selectivity to Li⁺ in actual seawater. These findings confirm its potential as an adsorbent for recovering Li⁺ from seawater.     

纤维素的均相化学反应

本文回顾了近10多年来的纤维素均相反应发展过程,研究了PF/DMSO、LiCl/DMAc、N₂O₄/DMF、苯/DMSO、LiCl/DMI和水等溶剂体系的纤维素均相反应条件(如酯化反应、交联反应、醚化反应、接枝共聚等),并总结了纤维素均相衍生化的分析方法,讨论了各种方法的优缺点以及发展前景.     

Shape-Memory and Anisotropic Carbon Aerogel from Biomass and Graphene Oxide

Biomass, as the most abundant and sustainable resource on the earth, has been regarded as an ideal carbon source to prepare various carbon materials. However, manufacturing shape-memory carbon aerogels with excellent compressibility and elasticity from biomass remains an open challenge. Herein, a cellulose-derived carbon aerogel with an anisotropic architecture is fabricated with the assistance of graphene oxide (GO) through a directional freeze-drying process and carbonization. The carbon aerogel displays excellent shape-memory performances, with high stress and height retentions of 93.6% and 95.5% after 1000 compression cycles, respectively. Moreover, the carbon aerogel can identify large ranges of compression strain (10–80%), and demonstrates excellent current stability during cyclic compression. The carbon aerogel can precisely capture a variety of biological signals in the human body, and thus can be used in wearable electronic devices.     

3D打印MXene气凝胶基微型超级电容器技术与材料研究进展

微型超级电容器(Micro-supercapacitors,MSCs)作为便携、可穿戴、可植入的微型能量存储单元,因高功率密度、瞬间充放电及长循环寿命的优势,在柔性微型电化学储能技术中取得了快速发展。MXene基气凝胶材料因其三维多孔网状结构、优越导电性、亲水性等优势,能够缩短离子传输路径与提高电荷转移效率,在构建柔性MSCs中发挥重要作用,如活性电极材料、柔性导电集流体、油墨印刷等。然而,开发低价、高效、高性能的柔性MSCs器件仍面临诸多挑战。三维(3D)打印能够构建几何形状复杂的3D结构,制造不同尺寸和形状的微型储能器件。为了优化其电化学性能,分别对3D打印技术分类及其最新进展、可打印MXenes材料的设计原理研究进行了综述,总结了它们在与可穿戴电子设备集成MSCs设备中的应用。并对MXenes材料在解决3D打印MSCs的挑战性问题与发展前景做出展望。     

Adaptive Structured Pickering Emulsions and Porous Materials Based on Cellulose Nanocrystal Surfactants

Taking advantage of the formation and assembly of cellulose nanocrystal surfactants (CNCSs) at the water–oil interface, where polar cellulose nanocrystals (CNCs) and end‐functionalized polymer chains interact, the preparation and stability of emulsions prepared with CNCSs were investigated. The packing density of CNCSs at the interface can be adjusted by tuning parameters such as pH, ionic strength, and concentration/molecular weight of the end‐functionalized polymer ligands. Stable non‐spherical emulsions are obtained during homogenization, as a result of the interfacial jamming of CNCSs, with pH‐triggered reconfigurability. Porous materials are prepared by freeze‐drying creamed, CNCS‐stabilized emulsions. The cells of the porous materials have a controlled pore size and shape that are commensurate with the droplets in the emulsion and are responsive to pH. The behavior of the adaptive, reconfigurable supracolloidal system is coupled to its internal and surrounding environment.     

新型力学性能增强二氧化硅气凝胶块体隔热材料

作为一种轻质和超高孔隙率的三维纳米多孔材料,二氧化硅气凝胶具有极低的常温导热系数,成为理想的纳米多孔超级隔热材料。然而,二氧化硅气凝胶的力学性能很差,且常压干燥制备的气凝胶整体性较差,这些都极大地限制了二氧化硅气凝胶的实际应用。近年来,通过复合或交联的方法制备得到的新型二氧化硅气凝胶,在一定程度上提高了其整体性、强度和柔韧性,使得二氧化硅气凝胶作为单独的块体材料应用成为可能。本文简要介绍二氧化硅气凝胶的多孔结构、基本性质和隔热原理,并对纤维增强、聚合物交联和其他复合二氧化硅气凝胶作为块体隔热材料的研究现状进行重点综述。最后,总结了该领域存在的关键问题,并提出未来的研究方向。     

Hybrid Plasmonic–Aerogel Materials as Optical Superheaters with Engineered Resonances

Solar radiation is a versatile source of energy, convertible to different forms of power. A direct path to exploit it is the generation of heat, for applications including passive building heating, but it can also drive secondary energy‐conversion steps. We present a novel concept for a hybrid material which is both strongly photo‐absorbing and with superior characteristics for the insulation of heat. The combination of that two properties is rather unique, and make this material an optical superheater. To realize such a material, we are combining plasmonic nanoheaters with alumina aerogel. The aerogel has the double function of providing structural support for plasmonic nanocrystals, which serve as nanoheaters, and reducing the diffusion rate of the heat generated by them, resulting in large local temperature increases under a relatively low radiation intensity. This work includes theoretical discussion on the physical mechanisms impacting the system's balanced thermal equilibrium.