高结构稳定性、低泄漏率三维铜@石墨烯复合相变材料的制备

由于能源消费需求的持续增长和传统化学燃料的日益枯竭,对可再生能源的需求日益迫切。以地热能、太阳能为代表的可再生能源脱颖而出。然而,这些能源的应用易受到天气、季节、地点和时间的影响,具有不稳定性、随机性、波动性和间歇性。储能技术是解决上述问题的有效途径,它可以在需要的时候储存或释放能量。在各种储能技术可选材料中,相变材料(PCMs)是智能热能管理和便携式热能领域的有力候选者。大多数相变材料都存在导热系数低、环境污染、熔点泄漏等问题,因此有必要将相变材料封装到支撑骨架材料中。事实上,支撑材料在应用中仍面临着一些重大挑战。首先,骨架材料应能抵抗相变材料在相变过程中的体积变化,即具有良好的结构稳定性。其次,还应具有较高的导热系数和较低的泄漏率。石墨烯气凝胶(GA)已被证明是提高相变材料形状稳定性的有效支撑骨架,但相变引起的泄漏和网络结构的脆性是制约其应用的关键问题。在此,我们提出了一种双脉冲电镀的强化策略,用于制备铜@石墨烯气凝胶(Cu@GA)作为相变储能骨架材料。这一结构设计中,石墨烯气凝胶上的石墨烯片层上均匀地镀上了铜层,且不同片之间被铜镀层所连接。这种铜增强石墨烯气凝胶网络结构赋予复合材料良好的导热性和坚固的骨架稳定性,有利于增强相变换热和抑制相变过程中的泄漏。此外,通过真空浸渍法将十八胺(ODA)封装在Cu@GA骨架中,获得了结构稳定性高、泄漏率低的复合相变材料(Cu@GA/ODA),保证了ODA在Cu@GA骨架材料中的均匀分散和填充。通过比较复合相变材料的重量变化,研究了不同骨架对复合相变材料泄漏率的影响。优化后的复合相变材料(CPCM)Cu@GA/ODA经20次储热、放热循环后,泄漏率降低至19.82% (w,质量分数),而GA/ODA和GOA/ODA为骨架的复合相变材料的泄漏率分别为80.31% (w)和72.99% (w)。为了探讨这种影响的原因,用扫描电子显微镜(SEM)观察了循环后骨架的形貌。铜/石墨烯气凝胶(Cu@GA)骨架材料没有明显的收缩或坍塌,仍可以保持完整的三维网络结构,而氧化石墨烯气凝胶(GOA)和石墨烯气凝胶(GA)的骨架材料三维结构不复存在,且在氧化石墨烯/石墨烯片能够观察到明显的裂隙。铜涂层可以提高骨架的微观结构稳定性,有利于提高结构稳定性,降低复合材料的泄漏率。同时,该研究为构建理想的金属增强石墨烯气凝胶复合骨架材料铺平了新的道路,该复合材料具有优异的综合性能,可用于未来的相变储能、多孔微波吸收和储能应用。     

气凝胶材料的研究进展及其在航空航天领域的应用

气凝胶材料是由聚合物分子链或纳米粒子组成的一种三维纳米骨架结构的多孔材料,它具有低密度、高孔体积、高孔隙率和大比表面积等结构特点,表现出优异的光、热、声、电和力学等特性.气凝胶这种轻质材料能够很好地代替金属材料,在隔热保温、电磁屏蔽、能量储存和基体骨架等航空航天领域具有广泛的应用前景.本文介绍了气凝胶最新研究进展及其在...     

石蜡/膨胀石墨/石墨烯复合相变储热材料的制备及性能

以石蜡(PA)作为相变储热材料、 膨胀石墨(EG)作为主导热材料和支撑材料, 石墨烯气凝胶(GA)作为导热增强材料和辅支撑材料制备了PA/EG/GA复合相变材料, 研究了GA添加量对复合相变材料相变温度、 相变潜热、 导热性能以及循环稳定性的影响. 结果表明, 所制备的80%PA-17%EG-3%GA复合相变材料导热性能良好, 循环稳定性出色. 与80%PA-20%EG复合材料相比, 该材料的相变温度、 相变潜热以及循环稳定性无明显变化, 但导热系数由4.089 W/(m·K)提升到了5.336 W/(m·K), 显示出良好的应用前景.     

基于Hofmeister效应制备高强韧壳聚糖气凝胶

气凝胶在绝热保温、催化、吸附分离等领域有着广泛的应用,通常需要对气凝胶的微观结构和力学性能进行调控以满足特定需求.然而,开发绿色技术制备高强韧天然高分子气凝胶仍然面临巨大的挑战.本文报道了在壳聚糖新溶剂中基于Hofmeister效应调控壳聚糖分子链的侧向聚集和重结晶,影响壳聚糖水凝胶和气凝胶的微观形貌、孔隙结构和力学性能等物理性质,构建出高强韧壳聚糖气凝胶.通过改变盐的种类,可以有效调控壳聚糖水凝胶和气凝胶的力学性能,并显示出遵循Hofmeister序列的规律.壳聚糖气凝胶的拉伸强度、杨氏模量和断裂功最高可达(23.1±0.4) MPa、(198.0±43.8) MPa和(9.6±0.9) MJ/m³,比表面积最高可达410 m²/g.这种简单策略有助于制备高强韧壳聚糖气凝胶,在柔性电子器件、组织工程材料、药物/蛋白载体和催化等领域有潜在应用前景.     

二氧化硅气凝胶在保温隔热领域中的应用

二氧化硅(SiO_2)气凝胶是通过使用气体来置换湿溶胶中的液体,从而得到一种结构可控的新型轻质纳米多孔固态材料.SiO_2气凝胶材料与其他保温隔热材料相比,具有较低的导热系数(≈0.013 W/(m·K))和较高的透明性,在保温隔热领域中开发潜力巨大,有望替代传统的保温隔热材料.尽管气凝胶目前的成本高于传统的隔热材料,但是我们相信通过科学家和工程学家的不断努力,气凝胶的生产成本会被不断的降低,最终遍及世界各地.本文作者综述了SiO_2气凝胶材料在隔热领域的多种应用形式,介绍了目前国内外气凝胶公司研发产品情况以及实际应用案例.     

气凝胶的阻燃改性研究进展

气凝胶由于其密度极低、孔隙率极高、导热系数极低等特点而在保温、隔热、吸附、催化等领域得到快速发展.近年来,研究者开始研究气凝胶的阻燃性能.本文综述了近年来国内外硅系气凝胶、高分子气凝胶以及碳系气凝胶的阻燃改性的研究进展,包括这三类气凝胶各自的特点、用作阻燃材料时相关的阻燃改性技术以及其对材料阻燃性能的影响.最后指出了气凝胶在阻燃领域应用的不足、需要解决的关键问题以及发展前景.     

无柔性间隔基侧链型液晶高分子复合定形相变材料的制备与性能研究

设计合成了一系列具有不同烷氧基尾链长度的单体4′-烷氧基-4-联苯酚甲基丙烯酸酯Mbi Cm(m=1,2,4,6,8,10,12,14,16,18),通过自由基聚合方法合成了相应的具有不同烷氧基尾链长度的无柔性间隔基侧链型液晶高分子PMbi Cm,将所得的侧链型液晶高分子和相变材料石蜡按一定质量比混合,通过"加热-冷却法"成功制备了定形相变材料.通过凝胶测试发现当尾链长度为m=12,14,16,18时,高分子对固体石蜡具有良好的凝胶定形效果,且随着烷氧基尾链的增长,聚合物和石蜡的相容性增加,最低凝胶浓度降低,得到定形相变材料的凝胶解缔温度也相应下降.通过示差扫描量热法(DSC)、热重分析法(TG)、流变(Rheology)等测试考察了定形相变材料的相变储能性能、热稳定性和流变性能,实验结果表明该定形相变材料具有相变焓值高、热稳定性好、凝胶强度高等优点.通过红外光谱(FTIR)、偏光显微镜(POM)和扫描电镜(SEM)等测试发现PMbi Cm通过非共价键作用力自聚集形成三维凝胶网络结构,对石蜡起固定支撑作用.     

气凝胶维度结构设计与功能化应用的研究进展

气凝胶是一类兼具重要科学研究意义和巨大工程化应用价值的纳米多孔材料, 其制备过程涉及溶胶-凝胶化学转变、结构调控、界面张力消除等基础科学问题, 在理化性能方面同时具有超低密度和超低热导率特性, 是一类理想的轻量化超级隔热保温材料, 在航空航天、交通运输等对重量要求严苛的应用领域极具吸引力. 此外, 得益于气凝胶的高比表面积、高孔隙率、连续开孔等结构特征, 其在吸附、催化、药物载体、能源和环境修复等领域也具有重要应用潜力. 因此, 近年来气凝胶及其应用获得国内外学术和产业界的极大研究兴趣. 本综述调研了自气凝胶首次报道以来相关文献与知识产权的概况, 而后以制备方法、气凝胶种类、维度结构设计、新型应用为轴, 系统概括了气凝胶的制备方法, 新型气凝胶的种类, 以维度为特色的气凝胶材料, 以及气凝胶的独特应用. 如近五年来涌现的新型超分子气凝胶、智能响应气凝胶、气凝胶纤维、气凝胶的增材制造等, 都在一定程度上颠覆了传统材料、突破了传统制备方法的局限. 最后对气凝胶近年来的发展做了简要总结和展望.     

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.     

相变材料在建筑节能中的应用

相变材料可以通过相态的转变以潜热的形式对环境温度进行调控,在诸多领域具有广阔的应用前景,因而成为材料科学领域的研究热点。近年来,为降低建筑能耗,相变材料已经在建筑节能领域实现了示范性的应用,这一新技术的应用能够有效降低建筑能耗并提高舒适度。本课题组在前期工作的基础上,综述了相变材料最新应用技术及相变材料在建筑节能领域的应用,并展望了相变材料在建筑节能领域的发展趋势。     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.     

Synthesis of N-substituted carbazolones from α-iodo enaminones via Pd(0)-catalyzed intramolecular coupling under microwave irradiation

A variety of N-aryl and N-alkyl carbazolones were conveniently achieved in good to high yields via Pd₂(dba)₃-mediated intramolecular coupling of N-substituted α-iodo enaminones under microwave irradiation. The Pd(0)-catalyzed cyclization was found to proceed favorably with the more electron-deficient phenyl ring during the reactions involving unsymmetrical N,N-diaryl α-iodo enaminones. This unique property enables the construction of carbazolone skeleton containing nitro substituted benzenoid ring.     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles by intramolecular nitrilimine cycloaddition

Both substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles have been synthesized by the 3+2 intramolecular dipolar cycloaddition of nitrilimines to alkynes. This cyclization has been extended to more versatile 3-bromo derivatives by the use of alkynylbromides as dipolarophiles.