气凝胶在气体吸附净化中的应用研究进展

气凝胶(Aerogels)是一种以空气为介质的轻质多孔性凝聚态物质,由胶体粒子或高聚物分子相互聚集构成独特的纳米多孔三维网络结构。气凝胶的颗粒相和孔隙尺寸均为纳米量级,具有相当高的比表面积和孔隙率、可调控的开放孔隙结构、易于化学修饰的表面以及多样化的种类和形态,其气体吸附量可比同等条件下活性炭吸附量高两个数量级,因此在气体吸附净化领域逐渐受到人们的广泛关注。目前,气体吸附净化领域研究较多的气凝胶主要是SiO_2气凝胶和炭气凝胶。此外,近年来对金属氧化物气凝胶以及SiC气凝胶、石墨烯气凝胶、生物质基气凝胶等新型气凝胶的气体吸附应用也有相应的研究报道。吸附材料对目标气体需要同时具有较高的吸附容量和良好的选择性吸附能力。气凝胶的高比表面积和多孔性质提供了众多的吸附位点,但仅依靠自身物理吸附作用的吸附量有限,对目标气体的选择性不高,在实际吸附应用中,往往由于共存气体组分的竞争吸附影响对目标气体的吸附性能。因此,为了进一步提升气凝胶的吸附容量,提高对目标气体的选择性,研究人员围绕气凝胶修饰改性进行了大量的研究探索工作,并取得了一定的进展。目前,气凝胶吸附净化研究报道的目标气体主要是温室气体CO_2和大气中主要的污染物挥发性有机化合物(VOCs)。针对目标气体的不同可分别通过氨基功能化、氮掺杂等方法引入碱性位点或通过引入非极性官能团对气凝胶进行疏水改性,以提升气凝胶对CO_2或VOCs的吸附量和选择性。所采用的修饰改性方式主要有以下两种:一是在湿凝胶形成后或超临界干燥后通过嫁接、浸渍等手段对气凝胶表面进行功能化改性,通过引入特定的官能团或活性组分提升气凝胶对目标气体的吸附量和选择性;另一种是在溶胶-凝胶反应过程中引入功能化前驱体,在分子或纳米尺度上赋予气凝胶网络特定的性能,进而有效平衡活性组分稳定性和对目标气体的吸附性能。此外,对于炭气凝胶,还可通过活化进一步增大比表面积,改善孔隙结构和表面化学性质,从而实现对目标气体污染物吸附性能的优化。本文归纳了各类气凝胶在CO_2与VOCs吸附净化方面的研究进展,介绍了气凝胶的制备过程和结构特点,讨论并对比了不同气凝胶对目标气体的吸附性能与吸附机理,总结了当前气体吸附净化研究中对气凝胶进行修饰改性的主要方法,最后指出提高气凝胶的结构稳定性和吸附速率、设计可同时吸附多种目标气体的气凝胶、缩短制备周期并降低成本是未来研究工作的重点。     

间苯二酚-甲醛碳气凝胶粉末的性能研究

间苯二酚-甲醛有机气凝胶粉末经过高温碳化处理得到其碳气凝胶粉末.利用全自动吸附仪进行了液氮温度下有机气凝胶粉末和碳气凝胶粉末的N2吸附孔结构表征,主要研究了有机气凝胶碳化前后孔径分布的变化.并采用透射电镜(SEM)和X射线衍射(XRD)对粉末进行分析,结果表明,经碳化后其比表面积有较大的提高(＞500m2/g),粉末粒径减小(＜100nm).     

KOH活化碳气凝胶对水中亚甲基蓝的吸附性能研究

以间苯二酚和甲醛为原料水热制备有机气凝胶,在碳化过程中使用KOH作活化剂制备出孔结构丰富的碳气凝胶。采用扫描电镜(SEM)、X射线衍射(XRD)及N2吸脱附法等手段对材料的结构及形貌表征,考察了活化剂用量、染料初始浓度、接触时间等因素对亚甲基蓝在碳气凝胶上吸附的影响,并进行了吸附类型和吸附动力学研究。结果表明:活化剂的加入使碳气凝胶材料的孔结构更加丰富,当活化剂与有机气凝胶的质量比达到2∶1时,其吸附性能最佳。碳气凝胶去除亚甲基蓝的吸附行为符合二级动力学模型。吸附类型为Langmuir吸附模型。     

Strong, low density, hexylene- and phenylene-bridged polysilsesquioxane aerogel–polycyanoacrylate composites

Nanocomposite aerogels were prepared by chemical vapor deposition and polymerization of cyanoacrylate on the surface of bridged polysilsesquioxane aerogels. Phenylene- and hexylene-bridged aerogels were prepared by sol–gel polymerizations and supercritical carbon dioxide drying. Hydrophobic organic bridging groups in the polysilsesquioxane aerogels reduced the amount of adsorbed water available for initiating polymerizations and led to higher molecular weight polycyanoacrylate than was observed with silica aerogels. Densities increased as much as 65% due to the addition of the organic polymer, but the nanocomposite aerogels remained highly porous with surface areas between 440 and 750 m²/g. Polycyanoacrylate–phenylene-bridged aerogel composites were the strongest with flexural strengths up to 780 kPa or 16-fold stronger than the untreated phenylene-bridged aerogels and fivefold stronger than a silica aerogel of the same density. The strongest polycyanoacrylate–hexylene-bridged aerogel composites had flexural strength of 285 kPa or ninefold stronger than the untreated hexylene-bridged aerogels and twice as strong as a silica aerogel of comparable density. The greater strength of the new composites is, in part, due to the greater strength of the bridged aerogels. However, higher molecular weight polycyanoacrylate, due to less surface water on the hydrophobic bridged aerogels, also contributes to the greater nanocomposite strengths.     

生物质基碳气凝胶制备及应用研究

生物质材料成本低廉、碳源丰富,是碳气凝胶制备中最经济、环保和可持续性的原料。生物质基碳气凝胶展现出密度低、弹性高、比表面积大和导电性好等优异特性,有望广泛应用于电化学储能器件和吸附净化等领域。综述了生物质基碳气凝胶,如纤维素碳气凝胶、木质素基碳气凝胶、生物质衍生物基碳气凝胶以及碳气凝胶复合结构材料的制备工艺,总结了生物质基碳气凝胶在吸附和电化学等领域的应用研究。最后,分析了大规模制备结构均一和性能优良的生物质基碳气凝胶面临的机遇与挑战。     

炭气凝胶及其有机气凝胶前驱体的吸附性能

间苯二酚和糠醛的醇溶液在六次甲基四胺催化下经溶胶-凝胶过程合成醇凝胶,常压干燥后得到有机气凝胶,经炭化获得炭气凝胶.利用TEM和N2吸附表征了炭气凝胶及其有机气凝胶前驱体的结构,并通过有机蒸汽吸附实验研究了气凝胶的结构-吸附性能关系.实验结果表明：有机气凝胶和炭气凝胶对极性有机蒸汽的静态饱和吸附量高于对非极性有机蒸汽的静态饱和吸附量;提高热处理温度,有利于气凝胶对低浓度极性有机蒸汽和各种浓度非极性有机蒸汽的吸附,但不利于对高浓度极性有机蒸汽的吸附;随着有机蒸汽浓度的提高,气凝胶对极性有机蒸汽的吸附量明显增大,但对非极性有机蒸汽的吸附量影响不大,仅略微上升.此外,气凝胶的室温脱附率高达60 %～85 %.     

氨基功能化纳米纤维素气凝胶的制备及性能

选用3-（2-氨基乙氨基）丙基甲基二甲氧基硅烷（AEAPMDS）对球形纤维素纳米纤维（CNF）湿凝胶进行化学修饰,探讨了改性反应条件对氨基纳米纤维素中N含量的影响,选用叔丁醇溶液为置换溶剂,采用冷冻干燥制备了一种新型的生物质气凝胶。对所制备的3-（2-氨基乙氨基）丙基甲基二甲氧基硅烷-纤维素纳米纤维（AEAPMDS-CNF）气凝胶的微观形貌、结构特征、力学强度及CO₂的吸附等性能进行表征和分析。结果表明：反应时间为10 h、反应温度为90℃、AEAPMDS溶液的质量分数为12wt%时,是AEAPMDS-CNF气凝胶的最佳制备方案。改性后的纤维素气凝胶具有三维网络孔结构、质轻（ρ ≤ 0.0573 g·cm^-3）、高孔隙率（ε>90%）等特点,其压缩强度为0.46 MPa,CO₂吸附量高达1.54 mmol·g^-1,表现出优异的CO₂吸附性能,具有很大的应用前景。     

聚氨酯基气凝胶隔热材料研究进展

聚氨酯基气凝胶隔热材料是一类新型隔热材料。聚氨酯分子结构的可设计性和气凝胶独特纳米多孔三维网络结构的有机结合能使聚氨酯基气凝胶材料具有更好的隔热性能。本文介绍了聚氨酯气凝胶、聚脲气凝胶和聚氨酯增强无机物气凝胶材料的研究现状,重点介绍其在隔热性能方面的研究进展。     

耐高温氧化铝气凝胶隔热复合材料研究进展

氧化铝气凝胶是一种高孔隙率、低密度、高比表面积、耐高温和低热导的纳米多孔材料, 在高温隔热领域(如航天飞行器热防护系统、工业窑炉保温材料等)具有广阔的应用前景。但是, 纯氧化铝气凝胶因耐温性(1000 ℃以上)、力学性能和高温隔热性能相对较差难以直接应用, 需要引入增强相和遮光组分制备成气凝胶复合材料以进行改善。本文对耐高温氧化铝气凝胶的制备、氧化铝气凝胶隔热复合材料的制备及性能等方面的最新研究进展进行了综述。研究人员通过原位掺杂改性、沉积改性、有机链和炭涂层改性等方法提高了氧化铝气凝胶的热稳定性。在氧化铝气凝胶中引入晶须、颗粒、多孔骨架和纤维等增强相, 能够大幅提高其力学性能; 纤维和遮光剂的协同作用, 能够提高氧化铝气凝胶抑制红外辐射的能力, 显著降低高温热导率。本文还提出了后续的研究方向：对氧化铝气凝胶的密度、微观结构进行精细调控, 再引入合适的异质元素和遮光剂,以进一步提高气凝胶的热稳定性和复合材料的隔热性能;深入研究复合材料在高温下结构和性能的演化, 以及氧化铝气凝胶和增强相之间的相互作用。作为一种新型的隔热材料, 氧化铝气凝胶复合材料将在高温隔热领域发挥其优势并逐步实现广泛应用。     

纳米纤维素基气凝胶的制备及其吸附性能研究进展

在可持续发展已成为全球各国共识的今天,合理且高效地研发及利用可再生生物质能源成为国内外各大课题组研究的热点及方向。而纳米纤维素作为典型的生物质可再生材料,将其应用到环境治理领域成为再好不过的选择。同时,以纳米纤维素为基体制备的气凝胶作为第三代气凝胶材料,具有高孔隙率、高比表面积、低密度、低介电常数和较高的吸附性等性能,在染料吸附、油污吸附、重金属离子吸附、CO 2气体吸附等吸附领域有着广阔的应用前景。综述了纳米纤维素的制备方法、纳米纤维素基气凝胶的制备工艺及其在吸附领域的应用,探讨了纳米纤维素基气凝胶在研发中存在的问题,展望了纳米纤维素基气凝胶在吸附领域的未来发展方向。     

Intelligent Mesoporous Materials for Selective Adsorption and Mechanical Release of Organic Pollutants from Water

Despite recent advances in the porous materials for efficient removal of dissolved organic pollutants from water, the regeneration of porous characteristics for reuse with preventing secondary contamination remains a challenge. Here, novel supramolecular absorbents with hydrophobic pore are prepared by the self‐assembly of propeller‐shaped aromatic amphiphiles. The assembly of folded propeller provides a mesoporous environment within aromatic segments, which is suitable for the removal of organic pollutants from waste water. The removal efficiency is found to be 92% and 90% for ethinyl oestradiol (Eo) and bisphenol A (BPA). Notably, the folded architecture of propeller is observed to be flattened by the salt addition, which results in the strong π–π interaction driving the porous materials closed and forms solid fibers. It is found that most of the removed pollutants are spontaneously released by the dynamic porous assembly, and subsequent dialysis triggers the porous materials to be recovered.     

Supercritical impregnation of drugs and supercritical fluid deposition of metals into aerogels

The presented review covers the latest research on supercritical impregnation into organic and inorganic aerogels by investigating those factors that influence the impregnation. Supercritical impregnation is a promising method for incorporating drugs within porous carriers including for water insoluble drugs. An additional step (reduction from metallic precursor to metal) is required for the supercritical impregnation of metallic precursors. Hence, this expanded method is preferably termed as supercritical fluid deposition or adsorption. Supercritical impregnation of drugs, as well as metals, are mostly influenced by interactions between the compound and aerogel matrix, supercritical impregnation conditions, and the characteristics of a compound within a supercritical fluid.     

Wet-resilient graphene aerogel for thermal conductivity enhancement in polymer nanocomposites

Three-dimensional(3D)graphene-based aerogels have significant potential for adsorption,sensors,and thermal management applications.However,their practical applications are limited by their disorganized structure and ultra-low resilience after compression.Some methods can realize a well-aligned structure,however,they involve high costs and complex technology.Herein,a 3D graphene hybrid aerogel with an anisotropic open-cell and well-oriented structure is realized by unidirectional freeze casting,which com-bines the'soft'(e.g.graphene oxide,Tween-80)and'hard'(e.g.graphene assembly)components to realize full recovery after flattening.A graphene aerogel annealed at a moderate temperature(～200℃)can pos-sess superhydrophilicity and outstanding wet-resilience properties,including after being pressed under 40 MPa.Furthermore,the graphene aerogel annealed at a high temperature of～1500℃exhibits excellent thermal conductivity enhancement efficiency in polydimethylsiloxane(PDMS).The resultant nanocom-posites clearly demonstrate anisotropic thermal conductivity and promising applications as thermal interface materials.This strategy offers new insights into the design and fabrication of 3D multifunctional graphene aerogels.     

Characterization of La2Mo2O9 aerogels synthesized by the sol-gel chemistry and high-temperature supercritical drying

A lanthanum molybdate aerogel, La2Mo2O9, with a mean particle size in the range from 100 to 150 nm, was synthesized by the sol-gel method and high-temperature supercritical drying. In this communication it is shown that control over the crystallinity of product aerogels can be exercised by changing the amount of water used for hydrolysis and the temperature for subsequent heat treatment. Methoxy species are formed on the surface during synthesis. The new aerogel may prove useful as a catalyst for the oxidation of hydrocarbons to oxygenated organic compounds.     

Preparation and characterisation of CNF/MWCNT carbon aerogel as efficient adsorbents

In recent years, carbon aerogels have attracted much attention in basic research and as potential applications in many fields. Herein, the authors report a novel approach using bamboo powder as raw material to fabricate cellulose nanofibers (CNFs)/multi‐walled carbon nanotubes (MWCNTs) carbon aerogels by a simple dipping and carbonisation process. The developed material exhibits many exciting properties including low density (0.056 g cm⁻³), high porosity (95%), efficient capability for separation of oily droplets from water, and high adsorption capacity for a variety of oils and organic solvents by up to 110 times its own weight. Furthermore, the CNF/MWCNT carbon aerogels (CMCA) can be recycled many times by distillation and combustion, satisfying the requirements of practical oil‐water separation. Taken together with its economical, environmentally benign manufacturing process, sustainability of the precursor and versatility of material, the CMCA developed in this study will be a promising candidate for addressing the problems arising from the spills of oily compounds.Inspec keywords: aerogels, adsorption, nanofibres, filled polymers, nanocomposites, multi‐wall carbon nanotubes, porosity, drops, distillation, combustion, nanofabrication, polymer fibresOther keywords: CNF‐MWCNT carbon aerogel, adsorbents, bamboo powder, cellulose nanofibers, multiwalled carbon nanotubes, dipping, carbonisation, density, porosity, oily droplets, adsorption capacity, organic solvents, distillation, combustion, practical oil‐water separation, manufacturing process, sustainability, C     

Self-Winding Gelatin–Amyloid Wires for Soft Actuators and Sensors

The origin of self-winding mechanisms in plants’ tendrils has fascinated scientists for centuries and continues to inspire developments in material science and nanotechnology. Here, bioinspired water-responsive wires that replicate these mechanisms, including the formation of coils and chiral perversions, are presented. A right-handed gelatin matrix is loaded with rigid left-handed amyloid fibrils and roll–dry-spun into wires in which self-winding activation emerges from simultaneous bending and twisting deformations. Wire bending is a consequence of amyloid fibrils’ concentration and distribution within the wire, whereas twisting is controlled by amyloid fibrils’ orientation. The resultant wires can be functionalized by organic molecules and inorganic nanoparticles, and potential applications in magnetic actuators and sensors are demonstrated. The simple fabrication method and the remarkable spontaneous self-winding response of these gelatin–amyloid wires exemplify how biomaterials based on mixed proteins have striking potential to develop advanced and tunable properties that can serve robotics, soft machines, and engineering systems.     

不同氧化程度氧化石墨烯/聚乙烯醇气凝胶对亚甲基蓝的吸附

氧化石墨烯(GO)对水中染料有着优异的吸附性能,但其氧化程度对复合材料吸附性能和机制的影响还未被充分研究。采用Hummer法,制备3种不同氧化程度的氧化石墨烯,与聚乙烯醇(PVA)复合得到三种GO/PVA气凝胶。利用红外光谱(FTIR)、元素分析(EA)和热重分析(TG)分析了3种GO的氧化程度;以亚甲基蓝(MB)为模拟污染物,通过静态吸附实验考察了GO氧化程度对GO/PVA气凝胶在不同溶液pH、吸附时间、初始浓度下对MB吸附性能的影响。通过吸附动力学模型、吸附等温线模型和吸附热力学模型探究了GO氧化程度对GO/PVA气凝胶吸附机制的影响。研究结果表明:GO/PVA气凝胶对MB的吸附行为受pH影响较小;提高GO的氧化程度可以明显提升GO/PVA气凝胶的吸附容量和吸附速度,GO氧化程度的提高增加了气凝胶上的吸附位点,有利于吸附。此外,GO氧化程度对GO/PVA气凝胶的吸附机制无明显影响。      

温和条件可控制备三维还原氧化石墨烯凝胶及其性能

为了实现石墨烯类三维气凝胶在温和环境条件下的大面积可控制备和高性能化,本文应用水合肼作为还原剂,通过低温预冷冻结合室温自然干燥,实现了室温还原自组装法可控制备直径30 cm的大面积三维还原氧化石墨烯(3D-RGO)气凝胶。该方法制备条件温和,不需任何加热条件和特殊冷冻干燥设备。通过对气凝胶制备过程中还原时间、预冷冻时间、预冷冻温度和反应容器进行控制,可以有效调节气凝胶的形状、表面浸润性、体积收缩率等,实现3D-RGO气凝胶的可控制备。该气凝胶不会出现明显的体积收缩和结构破裂,为具有约500μm的稳定孔径和3.8 mg/cm³的低密度的蜂窝状结构,并能够从90%的压缩应变下快速地恢复到初始状态,其干燥过程体积收缩率<5%;同时该石墨烯气凝胶展现良好稳定的导电性,在压缩应变从0%增加到90%时,其导电率从17.3 S/m增加至115.2 S/m。这种方法经济高效且易于制备出大面积的3D-RGO。     

Sugarcane bagasse: a potential low-cost biosorbent for the removal of hazardous materials

The contamination of surface water sources by organic and inorganic pollutants is a major concern in rapidly industrializing countries, and the removal of these potentially hazardous contaminants from the aquatic environment using environmentally friendly technologies is therefore crucial. Biosorption, the passive binding of pollutants using dead biomass, can be achieved using various low-cost agro-industrial residues, which are a convenient substitute to the existing technologies for removing pollutants from aqueous solutions. This review deals with the implementation of sugarcane bagasse as a cost-effective natural biosorbent. We have extensively reviewed the status of research into sugarcane bagasse-based biosorbents in raw and modified forms and explore their efficacy in the removal of pollutants. For this purpose, we considered the bagasse modification processes, modifying agents, and the effects of different experimental variables (for example, biosorbent dosage, initial pollutant ion concentration, solution pH and temperature, contact time, and adsorbent particle size) on the adsorption process and potential. Moreover, we propose the following important goals for future research: (1) determine the adsorption potential of sugarcane bagasse at pilot and industrial scales, (2) demonstrate the efficacies of biosorption techniques for real effluents, and (3) conduct a molecular modeling study to elucidate sugarcane bagasse-associated adsorption mechanism(s).     

SiO2气凝胶改性瓦楞纸板性能研究

目的应用SiO₂气凝胶疏水隔热水性涂料对瓦楞纸板表面进行改性,探究其对瓦楞纸板力学性能、疏水性能、隔热性能的影响。方法通过机械共混和表面改性相结合的方式制备疏水隔热水性涂料,采用线棒涂布器涂布于瓦楞纸板表面,通过测试纸板表面的接触角检验疏水效果,并测试改性后纸板的边压强度、平压强度、戳穿强度和压痕强度;制备90 mm×90 mm×100 mm的隔热包装箱,通过融冰试验测试其隔热效果。结果经SiO₂气凝胶疏水隔热水性涂料改性后的纸板接触角为91.75°,提高了6.25°。改性后纸板的横向边压强度、平压强度、戳穿强度和纵向压痕强度分别提高了5.6%,0.6%,2.4%和2.7%。当SiO₂气凝胶的质量分数为2%时,改性后的纸板具有最优的隔热性能。当湿膜厚度为60μm时,与未涂布的原瓦楞纸板相比,温度可降低13.6℃结论该方法扩大了SiO₂气凝胶在包装行业的应用范围,能为未来保温包装材料提供参考。