RF炭气凝胶孔结构的控制及其电化学性能研究

考察了在以间苯二酚(R)和甲醛(F)为原料,碳酸钠(C)为碱性催化剂,通过溶胶.凝胶过程和常压干燥方法制备RF炭气凝胶过程中CO2活化对炭气凝胶孔结构的影响,并通过恒流充放电和循环伏安法测试其电化学性能.结果表明:CO2活化可明显提高炭气凝胶BET比表面积(SBET)和孔容(Vtotal).RF炭气凝胶在900℃下活化3h,SBET从未活化时的633m2/g提高到1271m2/g;相应的电化学测试结果表明,以1mA/cm2的电流充放电,其比电容可从未活化样的81F/g增加到172F/g;以30mA/cm2的电流进行充放电试验,活化样的比电容仍可达到131 F/g.     

Organic aerogels from the polycondensation of resorcinol with formaldehyde

The polycondensation of resorcinol with formaldehyde under alkaline conditions results in the formation of surface functionalized polymer clusters. The covalent crosslinking of these clusters produces gels which are processed under supercritical conditions to obtain low density, organic aerogels ( 0.1 g cm^–3). The aerogels are transparent, dark red in colour, and consist of interconnected colloidal-like particles with diameters of approximately 10 nm. The polymerization mechanism, structure and properties of the resorcinol-formaldehyde aerogels are similar to the sol-gel processing of silica.     

Synthesis of β-SiC nanostructures via the carbothermal reduction of resorcinol–formaldehyde/SiO2 hybrid aerogels

The novel resorcinol–formaldehyde/SiO₂ (RF/SiO₂) hybrid aerogels were chosen to synthesize the cubic silicon carbide (β-SiC) nanostructures via a carbothermal reduction route. In this process, the in situ polymerized RF/SiO₂ aerogels were used as both the silicon and carbon sources. The morphologies and structures of SiC nanostructures were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), and high-resolution transmission electron microscope (HRTEM) equipped with EDS. The effects of C/Si atomic ratios in RF/SiO₂ aerogels and heat treatment temperatures on the formation of SiC nanomaterials were investigated in detail. It was shown that β-SiC nanowhiskers with diameters of 50–150 nm and high crystallinity were obtained at the temperatures from 1400 to 1500 °C. The role of the interpenetrating network of RF/SiO₂ hybrid aerogels in the carbothermal reduction was discussed and a possible mechanism was proposed.     

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 %.     

碳纳米管修饰银改性铁酸镧甲醛气敏传感器的制备和性能

银改性铁酸镧(Ag-LaFeO3)具有优良的甲醛敏感性能,但尚存在工作温度偏高、灵敏度不够理想等不足。在前期研究的基础上,采用碳纳米管(CNTs)对其进一步修饰,用溶胶-凝胶法(sol-gel)结合微波化学法制备了CNTs-Ag-LaFeO3粉末,研究了其结构和气敏性能,结果表明,CNTs-Ag-LaFeO3粉末均为单一钙钛矿结构,0.75%CNTs-Ag-LaFeO3在86℃下,对1.0×10-6甲醛气体的灵敏度为13,响应恢复时间分别为110和60s,而且在58℃下对1.0×10-6的甲醛气体也有明显的响应。     

室温条件下乙腈为溶剂炭气凝胶的制备与机理分析

与传统炭气凝胶制备不同,在室温条件下以乙腈为溶剂,间苯二酚和甲醛为前驱体,盐酸为催化剂,采用溶胶-凝胶、超临界干燥结合高温炭化工艺制备炭气凝胶(密度低至约50 mg.cm-3)。红外光谱、比表面积和孔径分布、扫描电子显微镜(SEM)和X射线衍射等测试表明,所制炭气凝胶是一种类石墨结构的非晶态材料,具有纳米骨架网络结构,比表面积达1 300 m2.g-1。对比不同配比气凝胶的SEM发现,气凝胶的颗粒尺寸为40 nm～70 nm。分析溶胶-凝胶过程中的温度变化和乙腈在凝胶化中作用得知,由于盐酸的催化和反应放热共同作用,实现了室温下间苯二酚和甲醛的加成和缩聚反应,并最终形成凝胶;乙腈在反应中起着一种分散剂的作用。     

A comparison of mechanical and wear properties of plasma sprayed carbon nanotube reinforced aluminum composites at nano and macro scale

The macro- and nano-scale mechanical and wear properties of carbon nanotube (CNT) reinforced Al-Si composite coatings prepared by plasma spraying have been compared in this paper. The composite coatings show a two phase microstructure; one phase being the Al-Si matrix with well dispersed CNTs and the other being the CNT clusters. Nanoindentation testing on the matrix portion with dispersed CNTs indicated an increase in the elastic modulus by 19% and 39% and an increase in the yield strength by 17.5% and 27% by the addition of 5 wt.% and 10 wt.% CNTs respectively. Macro-scale compression tests indicated no improvement in the elastic modulus but an increases in the compressive yield strength by 27% and 77% respectively, by addition of 5 wt.% and 10 wt.% CNTs. Nanoscratch testing carried out on the Al-Si matrix with dispersed CNTs indicated a decrease in scratch volume by 34% and 71% by addition of 5 wt.% and 10 wt.% CNTs respectively. Macro-scale wear tests indicated a decrease in the wear volume by 68% in case of 5 wt.% CNT coatings but an increase in the wear volume by 15% for the 10 wt.% CNT coating. The differences in mechanical and wear properties at nano and macro scales are explained in terms of the bimodal CNT dispersion (well dispersed and clusters) in Al-Si matrix, CNT cluster size and fraction and carbide formation.     

Defluoridation chemistry of synthetic hydroxyapatite at nano scale: equilibrium and kinetic studies

This study describes the advantages of nano-hydroxyapatite (n-HAp), a cost effective sorbent for fluoride removal. n-HAp possesses a maximum defluoridation capacity [DC] of 1845 mg F⁻/kg which is comparable with that of activated alumina, a defluoridation agent commonly used in the indigenous defluoridation technology. A new mechanism of fluoride removal by n-HAp was proposed in which it is established that this material removes fluoride by both ion-exchange and adsorption process. The n-HAp and fluoride-sorbed n-HAp were characterized using XRD, FTIR and TEM studies. The fluoride sorption was reasonably explained with Langmuir, Freundlich and Redlich–Peterson isotherms. Thermodynamic parameters such as ΔG°, ΔH°, ΔS° and E_a were calculated in order to understand the nature of sorption process. The sorption process was found to be controlled by pseudo-second-order and pore diffusion models. Field studies were carried out with the fluoride containing water sample collected from a nearby fluoride endemic area in order to test the suitability of n-HAp material as a defluoridating agent at field condition.     

纳米碳形貌对纳米碳/聚乙烯导电复合材料性能的影响

分别以纺锤形碳酸钙表面改性的二维片状石墨烯微片（CGM）和多壁碳纳米管（MWCNTs）作为导电剂填充改性聚乙烯（PE）制备导电复合材料。重点研究了二维或一维纳米碳/PE复合材料形成导电网络时力学与电学性能。CGM/PE或MWCNTs/PE复合材料达到抗静电要求时CGM的质量分数为8wt%,而MWCNTs的质量分数为1wt%。填充8wt% CGM的复合材料表现出优异的综合性能,而填充0.5wt% MWCNTs的复合材料综合力学性能达到最大值还未能达到抗静电要求,达到抗静电要求时MWCNTs/PE复合材料的综合力学性能出现下降趋势。通过形貌及流变学分析了复合材料不同的力学与电学性能的微观作用因素。CGM/PE复合材料流变渗流阈值与导电渗流阈值存在比较好的相关性,MWCNTs/PE复合材料达到流变渗流阈值还不能形成导电网络。结果表明,与二维CGM相比,一维MWCNTs不易均匀分散于聚合物基体中,并降低MWCNTs/PE复合材料的力学性能。     

蜜胺-酚醛树脂-甲醛基有机气凝胶纳米孔在裂解过程中的稳定性研究

热固型酚醛树脂、蜜胺、间甲酚和甲醛水溶液在碳酸钠催化下,经溶液-溶胶-凝胶过程合成了有机水凝胶,有机水凝胶经溶剂置换和超临界干燥形成了有机气凝胶.研究了裂解条件、固形物浓度、蜜胺/酚醛树脂比和间甲酚/酚醛树脂比对有机气凝胶纳米孔在裂解过程中稳定性的影响.结果表明:在相同的反应物配比下,随裂解温度的升高和时间的延长,气凝胶纳米骨架烧结程度增加,炭气凝胶的中孔分布向小孔方向移动.在酚醛树脂浓度为7.5g/100mL时,有机气凝胶的纳米骨架稳定性好,耐烧结性能好.在蜜胺/酚醛树脂比大或间甲酚/酚醛树脂比小时,有机气凝胶的纳米骨架的稳定性和耐烧结性好.这是由于构成有机气凝胶中孔的纳米骨架稳定性与其连续性及分子间作用力有关.     

苯酚-间甲酚-糠醛基炭气凝胶的制备及微结构控制

以苯酚、间甲酚和糠醛为原料,在正丙醇溶剂中以盐酸为催化剂经溶胶-凝胶过程合成了醇凝胶,直接超临界正丙醇干燥得到有机气凝胶,在氮气保护下裂解制备出富含中孔的炭气凝胶.用IR、N2吸附、SEM、TEM等表征气凝胶的结构特征,考察了问甲酚苯酚摩尔比对凝胶结构的影响.结果发现:提高间甲酚的含量能够增强聚合物的交联密度,减小聚合物与溶剂的相溶性,缩短相分离时间,有利于得到较小的纳米颗粒和孔径的炭气凝胶.所制得的炭气凝胶平均中孔孔径随间甲酚含量的增加从47 nm逐渐减小至13 nm,BET比表面积和中孔孔容在m-C/P=0.33时达到最大值.     

Co-Mn掺杂碳气凝胶的制备与性能

为探究不同碳化温度对Co-Mn掺杂碳气凝胶（Co-Mn/CA）电催化析氢性能的影响,以资源丰富且可再生的木质纤维素为碳源、四水乙酸钴为钴源、四水乙酸锰为Mn源,通过水热法制备出Co-Mn/CA。研究发现,纤维素气凝胶碳化后表面形貌发生改变,由片层结构转变为多孔结构,使其活性位点数量增多,电催化析氢活性增加。通过XRD和N₂吸-脱附对其结构进行了表征处理分析,结果表明,经碳化处理后的CA产物以无定型碳为主,经900℃碳化处理后的CA（CA-900）比表面积和总孔隙体积均为最大,分别为958 m2g-1和0.33 cm3·g-1。电化学性能测试表明,Co-Mn/CA-900表现出最好的电催化析氢反应（HER）催化活性,在1 mol/L KOH电解液中、50 mA·cm-2的电流密度下,具有175 mV的过电势,经过10 h的计时电位测试,压降仅为7%,表现出较好的电催化析氢稳定性。      

酚醛-糠醛基炭气凝胶对NaCl溶液的电吸附行为

以酚醛-糠醛基炭气凝胶为电极,用恒电位仪提供直流电压,在静态电吸附装置进行了NaCl溶液电吸附试验。考察了NaCl溶液浓度、炭气凝胶电极厚度及施加的电位等因素对电吸附的影响。研究表明,随着NaCl溶液浓度的增加,电吸附量明显增加。在低浓度下,微孔的“电场交叠效应”非常显著。0.6V~2.0V范围的电吸附试验表明,电位在1.5V以下电吸附量随电位改变异常显著,1.5V以后变化趋缓。炭气凝胶电极厚度在0.5nm~1.5mm范围增加时,电吸附量呈现单调减少的趋势。在电压为1.2V厚度为0.5mm时,其电吸附量达到12.7mg/gCA。理想的电吸附电极应富含中孔并尽可能降低电极厚度。     

炭气凝胶在电化学能源材料中的应用研究进展

炭气凝胶是一种新型、轻质、多孔的非晶态纳米材料,具有在纳米尺度可控和剪裁的连续三维网络结构.简单介绍了炭气凝胶的制备工艺,详细综述了炭气凝胶在电化学超级电容器、燃料电池和锂离子电池等电化学能量储存与转换系统中的主要应用研究进展.     

纳米多孔材料炭气凝胶及其在电吸附领域的应用

炭气凝胶作为一种新型具有特殊无定型结构的功能材料引起了各国研究者的极大兴趣.随着电吸附理论的发展,炭气凝胶日益成为具有诱人发展前景的电吸附材料.阐述了炭气凝胶的发展、研究动态及应用前景,探讨了电吸附理论及其基本原理,着重就炭气凝胶在电吸附领域的工业应用进行论述.     

Porous methacrylate tissue engineering scaffolds: using carbon dioxide to control porosity and interconnectivity

Porous scaffold structures are used in tissue engineering to provide structural guidance for regenerating tissues. The use of carbon dioxide (CO₂) to create such scaffolds has received some attention in the past but many researchers believe that although CO₂ processing of polymers can lead to porous scaffolds there is limited interconnectivity between the pores. In this study, highly porous (greater than 85%) and well interconnected scaffolds were obtained in which the size, distribution and number of pores could be controlled. This control was achieved by altering the rate of venting from polymer discs saturated with CO₂ under modest temperature and pressure. The polymer used is a blend of poly (ethyl methacrylate) and tetrahydrofurfuryl methacrylate (PEMA/THFMA). This polymer system has shown promise for potential applications in cartilage repair.     

常压干燥制备炭气凝胶及其电化学行为的研究

以甲酚为原料，添加适量的间苯二酚，在氢氧化钠催化作用下与甲醛聚合，经溶胶凝胶、溶剂置换、常压干燥和900℃炭化过程可制备纳米多孔材料炭气凝胶。N2吸附测试表明所制备炭气凝胶BET比表面积高于500m^2／g，在8nm～20nm范围具有集中的孔径分布，适合于做双电层电容器的电极材料。采用电化学阻抗谱测试电极的电化学行为，结果显示炭气凝胶电极在1mol／L的H2SO4电解液中的体积比电容接近70F／cm^3，质量比电容最高达97F／g。