有序中孔炭的电化学储氢性能

将蔗糖、聚环氧乙烯-聚环氧丙烯-聚环氧乙烯三嵌段共聚物和硅源构成的复合物进行预炭化、炭化和除硅处理合成出有序中孔炭, 采用XRD、TEM、HRTEM和N2吸脱附等手段对其进行表征, 并将有序中孔炭制成电极开展恒流充放电储氢性能研究. 结果显示, 具有较高比表面积(720 m2·g-1)和孔容(0.86 cm3·g-1)的有序中孔炭材料的电化学储氢容量为70.1 mAh·g-1, 高于具有相对较低比表面积(610 m2·g-1)和孔容(0.66 cm3·g-1)的有序中孔炭储氢容量(64.1 mAh·g-1). 通过与单壁碳纳米管电极(25.9 mAh·g-1)的对比, 表明有序中孔炭具有良好的电化学储氢性能和更高的电化学活性.     

有序中孔炭/四氧化三铁复合材料的制备及其用于血红蛋白的电化学研究

采用微湿含浸法制备了有序中孔炭/四氧化三铁磁性材料.采用透射电镜和X射线衍射对复合材料进行了表征.将血红蛋白(Hb)固定于材料表面,对其直接电化学行为进行了研究,结果表明Hb在该材料内仍保持了其生物活性,在pH=7.0的PBS缓冲液中,血红蛋白表现出一对峰形良好的准可逆氧化还原峰,为Hb的Fe(Ⅲ)/Fe(Ⅱ)电对的特征峰,求出式电位E0’为-0.306 V,电子转移数为n=1.226,电荷传递系数为α=0.51,表观异相电子转移速率常数为KS=0.0144s-1.在3.00×10-6到1.50×10-4mol/L浓度范围内,血红蛋白的浓度与其响应电流呈良好的线性关系,线性相关系数为R=0.9924,最低检测限为0.270×10-6mol/L.     

含噻吩的共聚物有序薄膜的制备及电性能测试

通过自组装技术(SAM)在ITO基底表面化学吸附一层规整有序单分子膜,然后在催化剂存在下,通过表面引发Suzuki缩聚反应制备得到有序的聚合物薄膜,并研究了聚合条件对聚合物薄膜性能的影响。从SEM和AFM对聚合物薄膜的形貌表征结果可知,聚合物薄膜已经顺利制备于ITO玻璃表面,并且以化学键与ITO表面垂直相连。通过对不同聚合条件下聚合物薄膜的XRD测试,结果表明随着聚合时间的延长及聚合单体浓度的增加,聚合物薄膜的有序性增加。除此之外,还对聚合物薄膜进行了光电性能测试,循环伏安的测试结果表明,随着聚合时间的延长及聚合单体浓度的增加,所得聚合物薄膜的能隙也在不断增加。电流-电压(I-V)测试结果表明,聚合物薄膜的电流随着电压的增大而增大,呈线性趋势,表明聚合物薄膜与ITO是欧姆接触,有利于电荷在电极的收集。     

三维有序大孔炭的设计构筑、性能及应用研究

多孔炭材料具有高的比表面积、发达的孔结构、耐热、耐腐蚀、无毒无害、价廉、易操作等特点,以其为研究核心,在学术界和工业界均具有广阔的应用前景。通过胶晶模板法合成孔径在亚微米范围内的三维有序大孔炭,其高度规整的孔道结构,在吸附分离、催化和电极等领域已展现出巨大的应用潜能。利用双模板法将介孔结构融汇于三维有序大孔炭的孔壁中,设计构筑出三维有序大孔-介孔炭,势必会显著增强其应用价值。本文主要阐述了以胶晶为主体模板制备三维有序大孔炭的各种路径;采用双模板法将介孔引入大孔通道内获取三维有序大孔-介孔炭;探索影响孔结构参数的主要因素,并与各种功能材料复合增强其性能;着重对三维有序大孔炭及大孔-介孔炭在环境净化和新型能源转化与储备领域的应用进行概述。     

孔径渐变的有序介孔炭的合成及电化学应用

以SBA-15为模板,硼酸为孔道扩张剂,蔗糖为碳源制备了一系列孔径渐变的有序硼杂介孔炭材料,并研究了其电化学电容性能。氮气静态吸附测试表明,当硼酸物质的量分数从0%增大到75%时,介孔炭的孔径从3.3nm增大至8.1nm,并保持有序的介孔结构。电化学测试表明,在KOH电解液中,硼杂介孔炭比电容明显高于未掺杂硼有序介孔炭,孔道有序性和孔径大小共同影响了炭材料的电容性能。当硼酸物质的量分数为50%时,炭材料的比电容性能最优。     

蟹壳基氮/氧共掺杂多孔炭的原位制备及其超级电容器性能

采用废弃蟹壳为碳源,KOH为活化剂原位制备了氮/氧共掺杂多孔炭,并研究其作为电极材料在超级电容器中的应用。 固定蟹壳与KOH的质量比为5:3,考察了煅烧温度对所得炭材料产率、孔结构和氮氧含量的影响。 结果表明,蟹壳基炭材料的孔结构和氮/氧含量可通过改变煅烧温度调变。 随着煅烧温度从500 ℃上升至700 ℃,多孔炭的比表面积和孔体积逐渐增大,而氮/氧含量随温度升高则降低。 采用循环伏安和恒流充放电对所得材料的电化学性能进行测试。 结果表明,所得多孔炭的电化学性能取决于其孔结构与氮/氧表面性质的协同作用,其中煅烧温度为600 ℃所得的多孔炭比表面积为612 m²/g,氮和氧含量分别为3.53%和32.8%,在50 mA/g的电流密度下比电容达到310 F/g,循环1000次比电容仍然保持95%以上,展现出良好的电化学性能。     

有序介孔碳负载NiCo2O4电极的制备及其超电容性能

以有序介孔碳(OMC)为载体,采用共沉淀法制备了OMC/NiCo2O4复合物.用X射线衍射(XRD)、傅里叶变换红外(FT-IR)光谱和透射电镜(TEM)研究其结构与形貌,发现NiCo2O4纳米颗粒均匀地负载在有序介孔碳上.循环伏安和恒流充放电测试表明,NiCo2O4质量分数为40%时,在1A·g-1的电流密度下,复合物电极的比电容可以达到577.0F·g-1,电流密度为8A·g-1时,比电容可以达到470.8F·g-1,并具有良好的循环稳定性.在2A·g-1的电流密度下,经过2000次循环后,比电容还可达到508.4F·g-1,电容保持率为92.7%.     

纤维素纳米晶模板法制备多级孔炭材料及其电化学性能

以纤维素纳米晶(CNC)为模板,酚醛树脂为碳源,KOH为活化剂,通过高温碳化制备了多级孔炭材料.采用透射电子显微镜(TEM)、扫描电子显微镜(SEM)和X射线光电子能谱仪(XPS)等手段对合成的一系列炭材料进行了表征.结果表明,前驱体中CNC的降解会形成与CNC直径相当的介孔,KOH活化则会导致炭材料产生大量的微孔和大孔,以及部分4 nm左右较小尺度的介孔,所制备炭材料呈现明显的多级孔特性,其比表面积达554.7 m²/g,总孔体积为0.323 cm³/g.以CNC为模板,KOH活化的炭材料作为电极材料时,在1.0 A/g电流密度下其比电容达202.8 F/g,当电流密度升高至40.0 A/g时,其电容保持率仍达69%,表明该炭材料具有优异的倍率性能;由该电极材料组装的超级电容器在10000次充放电循环后,电容保持率达95%以上,具有良好的循环稳定性.     

一维有序聚苯胺纳米阵列的制备及电化学储能性能

以导电玻璃FTO为基底电极, 在硫酸溶液中, 分别研究了苯胺单体浓度和恒定电流大小对聚苯胺(PANI)形貌的影响; 同时恒定苯胺单体的浓度和工作电流, 探究了不同类型的质子酸对PANI阵列形貌的影响. 结果表明, 采用恒电流方法可以制备出一维有序PANI纳米线阵列, 而且当苯胺的浓度为0.1 mol/L, 恒电流法的工作电流密度为0.03 mA/cm²时, 所制备的PANI纳米线阵列形貌最佳; 当用HCl, HNO₃和对甲苯磺酸(p-TSA)作为合成PANI的支持液时, 得到树桩状的PANI 纳米结构, 不能得到均一的纳米线阵列结构. 电化学性能测试结果表明, 制备的最佳形貌PANI纳米线阵列的比电容值可达560 F/g; 循环1000周后电容损失率为11%.     

以原位形成的磷酸铝骨架为模板制备纳米孔炭(英文)

以不同有机物(邻苯二酚、间苯二酚、对苯二酚、乙二醇、环己胺)为辅助炭源,通过直接炭化含柠檬酸及磷酸铝的复合物制备了一系列纳米孔炭材料(NC),采用多种表征手段研究了辅助炭源对最终炭材料性质的影响.结果表明,NC材料的结构和表面官能团性质随辅助炭源的变化而改变,其中以间苯二酚、对苯二酚、环己胺为辅助炭源制备的炭材料在空气氧化苯甲醇反应中表现有较高的催化活性.     

基于介孔碳的电化学酪氨酸酶生物传感器法测定水体中的苯酚及高效液相色谱法评价

采用新型的介孔碳材料作为固载酪氨酸酶的检测平台构建生物传感器,应用于水体环境中苯酚污染物的检测,并通过高效液相色谱法对电化学酪氨酸酶生物传感器法的准确性进行了评价。研究表明,介孔碳的"空间限制效应"能够防止酪氨酸酶(三维尺寸为6.5 nm×9.8 nm×5.5 nm)体外去折叠失活。基于介孔碳材料构建的电化学酪氨酸酶生物传感器在苯酚污染物检测方面显示了优良的性能,其重现性、灵敏度、稳定性、选择性以及检出限均比较令人满意。基于介孔碳的电化学酪氨酸酶生物传感器对苯酚污染物的检出限达到20 nmol/L,线性范围为0.1~10 μmol/L。采用基于介孔碳的电化学酪氨酸酶生物传感器和高效液相色谱法对实际水样品进行测定结果比对,结果表明该生物传感器方法检测结果准确、有效,适合于苯酚污染物突发污染事件的应急检测。     

Synthesis and characterisation of Ag-nanoparticles immobilised on ordered mesoporous carbon as an efficient sensing platform: application to electrocatalytic determination of hydrazine

In this study, a new strategy for the preparation of a modified glassy carbon electrode (GCE) based on a novel nano-sensing layer for the electrocatalytic oxidation of hydrazine was suggested. The suggested nano-sensing layer was prepared with the immobilisation of silver nanoparticles (AgNPs) on ordered mesoporous carbon. The morphology and properties of the prepared nanocomposite on the surface of GCE were characterised by scanning electron microscopy, transmission electron microscopy, N₂ adsorption-desorption, X-ray powder diffraction and electrochemical impedance spectroscopy. The electrochemical response characteristics of the modified electrode towards the target analyte were investigated by cyclic voltammetry. Under optimal experimental conditions, the suggested modified GCE showed excellent catalytic activity towards the electro-oxidation of hydrazine (pH = 7.5) with a significant increase in anodic peak currents in comparison with the unmodified GCE. By differential pulse voltammetry and amperometric methods, the suggested sensor demonstrated wide dynamic concentration ranges of 0.08–33.8 µM and 0.01–128 µM with the detection limit (S/N = 3) of 0.027 and 0.003 µM for hydrazine, respectively. The suggested hydrazine sensor was successfully applied for the highly sensitive determination of hydrazine in different real samples with satisfactory results.     

有序介孔碳CMK-3负载金纳米微粒复合材料的制备和表征

分别采用等体积浸渍-甲醛还原、等体积浸渍-氢气还原及溶胶负载法在介孔碳CMK-3上负载金纳米微粒;利用透射电镜和粉末X射线衍射仪对比分析了采用3种方法得到的复合材料的微结构和相组成;并测定了采用溶胶负载法得到的不同金含量的复合材料的热稳定性.结果表明,所制备的金纳米微粒的尺寸因制备方法不同而呈现明显差异;负载于复合材料中的金纳米微粒具有很好的热稳定性.     

阿拉伯糖基有序介孔碳修饰电极检测盐酸奈福泮的研究

以阿拉伯糖为碳源,介孔硅(SBA-15)为模板剂,用硬模板法制备有序介孔碳材料,采用场发射扫描电镜(Scanning Electron Microscopy,SEM)、透射电子显微镜(Transmission Electron Microscope,TEM)、全自动比表面及孔隙度分析仪(Brunner Emmet Te...     

含氮前驱体对氮杂有序介孔炭材料及其氧还原电催化性能的影响

燃料电池中贵金属铂的大量使用是阻碍其发展的关键因素,亟需探索高效廉价的替代型电催化剂.在目前的替代型非贵金属催化剂研究中,氮杂炭材料是一类氧还原反应催化活性最好、成本最低廉的催化剂,被认为是最有可能取代Pt催化剂而获得实际应用的催化剂.氮杂有序介孔炭材料因具有极高的比表面积和规整的孔道结构,可实现活性位点的密集组装与反应物料的快速传输,受到研究者的广泛关注.本文分别以苯胺、吡咯和邻菲罗啉为含氮前驱体,介孔分子筛SBA-15为硬模板,采用纳米浇铸法成功制备了具有高比表面积的氮杂有序介孔炭材料,系统研究了不同含氮前驱体对氮杂有序介孔炭材料的影响.采用氮气吸附-脱附等温线、透射电子显微镜(TEM)、X射线衍射(XRD)和X射线光电子能谱(XPS)等方法研究了氮杂有序介孔炭的组成与结构,采用循环伏安法(CV)以及线性扫描伏安法(LSV)等手段考察了其电化学行为与氧还原反应极化性能.氮气吸附-脱附等温线结果表明,采用三种不同含氮前驱体制备的氮杂炭材料都对应Ⅳ型吸脱附等温线以及H4型滞后环,表明所制备的氮杂炭材料具有介孔结构.由TEM可以清楚地观察到氮杂炭材料已经成功地反转了SBA-15模板的孔道结构.同时发现,含氮前驱体对氮杂炭材料的比表面积和孔结构产生较大影响:以吡咯和邻菲罗啉为前驱体制备的炭材料C-PY-900和C-Phen-900的比表面积较高,分别为765和746 m2/g,而以苯胺为前驱体制备的炭材料C-PA-900比表面积较小(569 m2/g);三种炭材料平均孔径大小顺序为C-Phen-900 (3.7 nm)＜ C-PY-900 (5.0 nm)＜ C-PA-900 (5.9 nm),这是由于不同含氮前驱体在高温焙烧过程中热分解行为不同所致.XRD结果发现,含氮前驱体对氮杂炭材料的晶型基本没有影响,均为无定形碳.XPS结果表明,采用苯胺、吡咯以及林菲啰啉为前驱体制备的氮杂炭材料中氮含量基本相同,分别为3.13 at％,3.32 at％和3.33 at％,说明在相同热解条件下材料中的氮含量基本不受前驱体的影响,但不同配位环境的氮含量以及氮活化碳原子的含量却有较大差异,其氮活化碳原子的相对含量分别为15.60％,19.87％和23.04％.电化学测试结果表明,三种氮杂介孔炭材料的氧还原反应电催化活性顺序为C-PA-900＜C-PY-900＜C-Phen-900,其H2O2产率低于30％,说明氧还原反应经历4电子转移路径.在碱性条件下,所制氮杂有序介孔炭材料C-PY-900和C-Phen-900表现出较商品Pt/C催化剂更加优异的氧还原反应电催化性能.综上可见,通过改变含氮前驱体的类型可以有效调变氮杂炭材料的比表面积、孔道结构以及N 1s与C 1s化学态,从而调控氧还原反应活性,本文不仅制备出高活性的非贵金属氧还原电催化剂,同时也为高活性炭基电催化剂的可控制备提供了思路.     

Arsenic sorption and redox transformation on iron‐impregnated ordered mesoporous carbon

Ordered mesoporous carbon has been actively investigated for its potential applications as catalyst supports, electrochemical materials and gas separation media. In this study, we tested an iron‐modified ordered mesoporous carbon (FeOMC) for its ability to adsorb arsenic from the aqueous phase. The FeOMC synthesis involved the preparation of an ordered silica template SBA‐15, in situ polymerization of acrylic acid in the template, carbonization and template removal to obtain the ordered mesoporous carbon, and iron impregnation. Batch experiments showed that the pH level of the solution had a major impact on arsenic sorption. Further, we found that the presence of anions (i.e. PO₄^3? and SiO₃^2?) could significantly decrease the sorption of both arsenate and arsenite. Arsenite oxidation to arsenate was observed in alkaline solutions, with or without anions being present. The oxidation of arsenite was attributed to both direct and catalytic reactions with the surface functional groups on the ordered mesoporous carbon. Adsorption of arsenic on FeOMC could be well explained by the surface complexation model. Copyright © 2007 John Wiley & Sons, Ltd.     

Highly crystalline and conductive nitrogen-doped mesoporous carbon with graphitic walls and its electrochemical performance

We present a rational and simple methodology to fabricate highly conductive nitrogen-doped ordered mesoporous carbon with a graphitic wall structure by the simple adjustment of the carbonization temperature of mesoporous carbon nitride without the addition of any external nitrogen sources. By simply controlling the heat-treatment temperature, the structural order and intrinsic properties such as surface area, conductivity, and pore volume, and the nitrogen content of ordered graphitic mesoporous carbon can be controlled. Among the materials studied, the sample heat-treated at 1000 °C shows the highest conductivity, which is 32 times higher than that for the samples treated at 800 °C and retains the well-ordered mesoporous structure of the parent mesoporous carbon nitride and a reasonable amount of nitrogen in the graphitic framework. Since these materials exhibit high conductivity with the nitrogen atoms in the graphitic framework, we further demonstrate their use as a support for nanoparticle fabrication without the addition of any external stabilizing or size-controlling agent, as well as the anode electrode catalysts. Highly dispersed platinum nanoparticles with a size similar to that of the pore diameter of the support can be fabricated since the nitrogen atoms and the well-ordered porous structure in the mesoporous graphitic carbon framework act as a stabilizing and size-controlling agent, respectively. Furthermore the Pt-loaded, nitrogen-doped mesoporous graphitic carbon sample with a high conductivity shows much higher anodic electrocatalytic activity than the other materials used in the study.     

Catalytic properties of Ru nanoparticles embedded on ordered mesoporous carbon with different pore size in Fischer-Tropsch synthesis

A series of 3 wt% Ru embedded on ordered mesoporous carbon (OMC) catalysts with different pore sizes were prepared by autoreduction between ruthenium precursors and carbon sources at 1123 K. Ru nanoparticles were embedded on the carbon walls of OMC. Characterization technologies including power X-ray diffraction (XRD), nitrogen adsorption-desorption, transmission electron microscopy (TEM), and hydrogen temperature-programmed reduction (H₂-TPR) were used to scrutinize the catalysts. The catalyst activity for Fischer-Tropsch synthesis (FTS) was measured in a fixed bed reactor. It was revealed that 3 wt% Ru-OMC catalysts exhibited highly ordered mesoporous structure and large surface area. Compared with the catalysts with smaller pores, the catalysts with larger pores were inclined to form larger Ru particles. These 3 wt% Ru-OMC catalysts with different pore sizes were more stable than 3 wt% Ru/AC catalyst during the FTS reactions because Ru particles were embedded on the carbon walls, suppressing particles aggregation, movement and oxidation. The catalytic activity and C₅₊ selectivity were found to increase with the increasing pore size, however, CH₄ selectivity showed the opposite trend. These changes may be explained in terms of the special environment of the active Ru sites and the diffusion of products in the pores of the catalysts, suggesting that the activity and hydrocarbon selectivity are more dependent on the pore size of OMC than on the Ru particle size.     

超级电容器用中孔炭复合电极材料研究进展

超级电容器是一类利用电化学双电层或电极材料在电极/溶液界面发生的氧化还原反应来存储能量的装置,除兼有常规电容器功率密度大和二次电池能量密度高的特点外,还具有可逆性好和循环寿命长等优点.本文重点介绍了近几年国内外对中孔炭材料、表面官能团修饰中孔炭材料、中孔炭-金属氧化物、中孔炭-导电聚合物等几类电极材料的研究现状;并且展望了超级电容器用中孔炭及其复合电极材料的当前研究热点和发展前景.