镉在羧基化石墨烯电极上的电化学研究

本实验制备了羧基化的氧化石墨烯,并将其修饰在玻碳电极(GCE)表面制备了羧基化石墨烯/玻碳电极(GO-COOH/GCE),以此为工作电极研究了镉在GO-COOH/GCE上的电化学行为及测定方法。与裸玻碳电极(GCE)相比,GO-COOH膜修饰玻碳电极能显著加强镉的氧化还原峰电流。在pH=4.5的NaAc-HAc缓冲溶液中,镉在GO-COOH/GCE电极上出现1组氧化还原峰,Epa=-0.81 V,Epc=-0.93 V,△E=0.12 V;ipa=8.04μA,ipc=8.54μA,ipa/ipc=0.94。氧化峰电流与Cd2+浓度在5.5×10-7～7.5×10-6g.L-1(r=0.9969)范围内呈良好的线性关系,检出限为2.0×10-7g.L-1。实际样品测定的RSD为1.2%(n=5),平均回收率为101.3%。GO-COOH膜对镉的电化学氧化有明显的催化作用,本法是一种可靠、快捷、灵敏的检测方法,可以用于保健品螺旋藻药片中镉含量的测定。     

一种基于乙炔黑/壳聚糖膜修饰电极的对氨基酚传感研究

制备了一种乙炔黑/壳聚糖薄膜修饰的玻碳电极,用循环伏安法详细研究了对氨基酚在该修饰电极上的电化学行为.结果表明: 对氨基酚在此膜修饰电极上呈现出一对可逆的氧化还原峰.相对于裸玻碳电极,该氧化还原峰的峰电流明显提高,峰电位差减小,可逆性变好,表明乙炔黑/壳聚糖薄膜电极对对氨基酚的电化学氧化具有良好的催化作用.对氨基酚的氧化峰电流与其浓度在1.0×10-7～2.0×10-6 mol/L和2 0×10-6～5.0×10-4 mol/L范围内均呈良好的线性关系; 检出限为5.0×10-8 mol/L(S/N=3).应用此修饰电极测定实际水样,结果较满意.     

邻苯二胺在L-酪氨酸功能化的玻碳电极上的聚合及其性能

首先在非水介质中通过电化学氧化将L-酪氨酸以C-N键共价键合在玻碳电极表面,形成L-酪氨酸接枝单层膜.再在L-酪氨酸功能化的玻碳电极上对邻苯二胺进行电化学聚合,从而制备了聚邻苯二胺/L-酪氨酸复合膜修饰玻碳电极(聚-o-PD-Tyr/GCE).研究发现聚-o-PD-Tyr/GCE在pH 6.8的磷酸缓冲溶液(PBS)中对抗坏血酸的电化学氧化具有催化作用,其氧化电位为0.35 V,比在裸玻碳电极上(0.58 V)降低了0.23 V,峰电流也明显升高.抗坏血酸在修饰电极上响应电流与其浓度在2.5×10-4～1.5×10-3mol·L-1范围内呈线性关系,检出限(3s/k)为43.64μmol·L-1.经修饰的电极保存在0.1 mol·L-1PBS中,可至少稳定5d.对5×10-4mol·L-1抗坏血酸溶液连续测定10次,测得此电极的相对标准偏差为3.2%.     

L-色氨酸在聚甲基红膜修饰电极上的电化学行为及其分析研究

用循环伏安法制备了聚甲基红膜修饰玻碳电极(PMRE/GCE)。研究了L-色氨酸(L-Trp)在该修饰电极上的电化学行为,探讨了不同缓冲溶液、pH以及扫描速率等的影响。实验表明:在pH=5.5的HAc-NaAc支持电解质中,L-Trp在PMRE/GCE上的电化学氧化反应是一不可逆过程,于0.783V(vs.SCE)处产生一灵敏的氧化峰,峰电流大大增加。氧化峰电流与L-Trp的浓度在2.0×10-6~1.0×10-3mol/L范围内呈良好的线性关系,检出限为8.0×10-7mol/L,样品检测平均回收率为100.16%。     

碳纳米管修饰电极上沙丁胺醇电催化氧化研究

将多壁碳纳米管(MWNT)分散在疏水性表面活性剂双十六烷基磷酸(DHP)溶液中形成稳定、均相的分散液,然后制备多壁碳纳米管-DHP复合膜修饰玻碳电极(MWNT-DHP/GCE).应用方波伏安法研究了沙丁胺醇在修饰电极上的电化学行为,结果表明,碳纳米管复合膜修饰电极对沙丁胺醇的氧化有良好的电催化活性,其氧化反应为一电子一质子过程,氧化电位比裸玻碳电极负移40 mV,峰电流增加了4.5倍.在最佳测试条件下,氧化峰电流与沙丁胺醇浓度在8.3×10-7~3.3×10-6mol/L范围内呈良好线性关系,开路富集2min,检出限达1.8×10-7mol/L.该修饰电极具有良好的重现性、稳定性.     

对乙酰氨基酚在纳米金/十二烷基苯磺酸钠修饰电极上的电化学行为研究

基于电化学沉积法制备了纳米金/十二烷基苯磺酸钠修饰玻碳电极(Nano-Au/SDBS/GCE),并采用扫描电子显微镜、X-射线光电子能谱和电化学方法进行表征。研究了对乙酰氨基酚在Nano-Au/SDBS/GCE上的伏安行为,结果表明,对乙酰氨基酚由在裸玻碳电极上的不可逆氧化过程变为准可逆过程,氧化峰峰电位由0.60 V负移至0.50 V,且在0.42 V处产生一个新的还原峰,表明nano-Au/SDBS膜能催化对乙酰氨基酚的电化学反应。在优化条件下,氧化峰峰电流与对乙酰氨基酚浓度在1.0×10-6mol/L～9.0×10-6mol.L–1和1.0×10-5～1.0×10-4mol.L–1间有良好的线性关系,检出限为8.0×10-7mol.L–1(S/N=3)。     

纳米金/三聚氰胺修饰电极检测亚硝酸盐

采用电聚合方法制备三聚氰胺(MA)膜修饰玻碳电极(GCE),然后采用原位恒电位沉积法制备金纳米颗粒(Au),并将其修饰于膜电极表面,制得纳米金/三聚氰胺修饰玻碳电极(Au/MA/GCE)。用扫描电子显微镜(SEM)对修饰电极进行表面形貌和元素成分分析。用循环伏安法研究亚硝酸根(NO2-)在该修饰电极上的电化学行为发现,NO2-在0.85 V出现一灵敏的氧化峰。在优化的实验条件下,NO2-在1.0×10-5～1.0×10-3mol/L浓度范围内与其氧化峰电流成线性关系,检测下限为8.9×10-7mol/L。将修饰电极用于实际样品中NO2-的检测,效果良好。     

金纳米颗粒在玻碳电极表面的固载及其对抗坏血酸的电催化氧化

采用电化学方法先在玻碳电极(GCE)表面共价键合一末端带有巯基的2-氨基乙硫醇(AET)单层,通过硫-金相互作用将金纳米颗粒(GNP)固载在玻碳电极表面,制备了GNP修饰的GNP-AET/GCE电极.采用X射线光电子能谱和循环伏安法对固载纳米金的玻碳电极的结构和性能进行表征.研究发现:GNP-AET/GCE电极不仅对抗坏血酸具有良好的催化性能,使其氧化过电位由玻碳电极上的0.53V负移到0.33V,氧化峰电流明显增加,而且能将多巴胺和抗坏血酸在玻碳电极上重叠的氧化波分成两个独立的氧化峰,峰间电位差为0.29V,提出了用差分脉冲伏安法在多巴胺共存在测定抗坏血酸的选择性方法.峰电流与抗坏血酸浓度在8.5×10-6～1.0×10-4 mol·L-1之间呈线性关系,其检出限为4.7×10-6 mol·L-1.     

基于多壁碳纳米管/壳聚糖多层膜修饰玻碳电极邻苯二酚的测定

改进了碳纳米管在壳聚糖溶液中的分散方法,制备了多壁碳纳米管/壳聚糖多层膜修饰玻碳电极,对比了不同修饰层数膜电极的循环伏安和电化学阻抗行为,5层多壁碳纳米管/壳聚糖膜修饰玻碳电极的电化学性能优良.在最优实验条件下,该修饰玻碳电极对邻苯二酚(CAT)有灵敏的响应,CAT浓度在3.99×10-6～9.09×10-4mol/L范围内与氧化峰电流呈良好的线性关系,检出限为2.39×10-6mol/L(S/N=3).该修饰玻碳电极性能稳定,测定4×10-5mol/LCAT溶液,RSD(n=10)为2.1%;15周后,该电极的响应值仅降低1.9%.     

抗坏血酸在石墨烯微片修饰玻碳电极上的电化学行为及其测定

基于石墨烯微片修饰玻碳电极对抗坏血酸的电催化作用,建立了测定抗坏血酸的电化学分析方法。石墨烯微片修饰玻碳电极与裸玻碳电极相比,显著提高了抗坏血酸的氧化峰电流,降低了氧化峰电位,提高了测定的灵敏度。该电极测定抗坏血酸的线性范围为5.0×10-5～2.5×10-2mol/L,最低检测限为6.5×10-7mol/L(信噪比=3)。     

The Colloidal Stabilization of Carbon with Carbon: Carbon Nanobubbles as both Dispersant and Glue for Carbon Nanotubes

The superior physical properties of carbon nanotubes (CNTs) have led to their broad application. Intrinsically, CNTs tend to agglomerate from hydrophobic interactions, which is highly undesirable for solution processing and device fabrication. Commonly, a stabilizer consisting of organic surfactants or polymers is used to disperse CNTs. Recently, we synthesized nitrogen‐doped carbon hollow nanospheres (25–90 nm), termed carbon “nanobubbles”. They bear superior dispersability in water and distinctive graphitic order. Herein, we describe the nanobubble‐assisted dispersion of CNTs in aqueous solution upon sonication. This process relies on the π–π interaction between the two aromatic carbon nanostructures, which can process their carbon mixture in water into conductive filter membranes, ink, and discs. This stabilization can be extended to other aromatic carbons. In addition, the π–π interaction may create a new type of carbon p–n junction that can be used to improve charge separation.     

一维新型碳的同素异形体:碳链

碳链是一种完全一维的、具有电子轨道sp杂化结构的新型碳的同素异形体.正是由于碳链的独特的一维结构,使其拥有区别于富勒烯、石墨烯和碳纳米管的化学键,从而表现出更加优异的性能,如:理论预言碳链的机械强度是石墨烯的几倍;碳链的导热也类似于石墨烯和碳纳米管;碳链是具有直接带隙的半导体材料,且带隙的大小可以通过其长度来调控,其长...     

Adsorption of Carbon Dioxide on Activated Carbon

The adsorption of CO2 on a raw activated carbon A and three modified activated carbon samples B, C, and D at temperatures ranging from 303 to 333 K and the thermodynamics of adsorption have been investigated using a vacuum adsorption apparatus in order to obtain more information about the effect of CO2 on removal of organic sulfur-containing compounds in industrial gases. The active ingredients impregnated in the carbon samples show significant influence on the adsorption for CO2 and its volumes adsorbed on modified carbon samples B, C, and D are all larger than that on the raw carbon sample A. On the other hand, the physical parameters such as surface area, pore volume, and micropore volume of carbon samples show no influence on the adsorbed amount of CO2. The Dubinin-Radushkevich (D-R) equation was the best model for fitting the adsorption data on carbon samples A and B, while the Preundlich equation was the best fit for the adsorption on carbon samples C and D. The isosteric heats of adsorption on carbon samples A, B, C, and D derived from the adsorption isotherms using the Clapeyron equation decreased slightly increasing surface loading. The heat of adsorption lay between 10.5 and 28.4 kJ/mol, with the carbon sample D having the highest value at all surface coverages that were studied. The observed entropy change associated with the adsorption for the carbon samples A, B, and C (above the surface coverage of 7 ml/g) was lower than the theoretical value for mobile adsorption. However, it was higher than the theoretical value for mobile adsorption but lower than the theoretical value for localized adsorption for carbon sample D.     

Growth of Single-walled Carbon Nanotubes on Substrates Using Carbon Monoxide as Carbon Source

The growth of single-walled carbon nanotubes(SWCNTs) on substrates has attracted great interests because of the potential applications in various fields. Carbon monoxide(CO) was used as the carbon source for the growth of SWCNTs on silicon substrates. Random or oriented SWCNTs can be produced by varying the CO flow rate. When the flow rate of CO was as low as 20 sccm(sccm:standard cubic centimeter per minute), dense SWCNT networks with clean surface were produced. When the flow rate was above 50 sccm, vertically aligned SWCNT(VA-SWCNT) arrays were grown. Well-aligned VA-SWCNT arrays were obtained in the temperature range of 650-800℃ and the content of large-diameter(above 1.7 nm) tubes in the array increased with the temperature. The height of the array was affected by the growth temperature, the CO flow rate, and the growth time. These findings indicate CO can be used as an efficient carbon source for the growth of SWCNTs on substrates under low flow rates.     

埃洛石纳米管模板法一步法制备一维碳纳米管/碳纳米棒混合纳米碳材料

利用埃洛石纳米管(HNTs)特有的中空纳米结构,以及丰富的界面化学性质,以聚乙烯醇(PVA)为碳源,采用浸渍填充纳米孔方法实现了一步制备一维碳纳米管(CNTs)/碳纳米棒(CNRs)混合纳米碳材料。考察模板剂(HNTs)和碳源(PVA)之间的比例关系对混合纳米碳材料的结构影响,利用XRD、FTIR、Raman、N2吸附-脱附测试、TEM、SEM以及电阻率和分散性等表征手段分析混合纳米碳材料的结构变化。结果发现,PVA填充含量的增加将导致产物中CNRs的质量分数增加;当PVA和HNTs质量之比为1∶1时,所制备的CNTs/CNRs的孔体积达到最大值2.142 cm~3·g-1,比表面积达到583 m~2·g-1,并且表现出较好的电导率和分散性,表明低的PVA填充比例制备的混合碳材料中CNTs含量较高。     

二氧化碳与低碳经济发展

由于二氧化碳无色无味,又存在于大气中,因此它在植物生长中的重要性被人类忽略了。其实二氧化碳是光合作用的反应物,是植物生长的重要原料;又是一种新型绿色肥料。人类应该着力开发以二氧化碳为原料的新型肥料发展低碳经济。     

Ni/γ-Al2O3催化剂上CH4-CO2重整体系中积碳-消碳的研究

用动态热重技术和色谱技术联用以及XRD和TEM等表征手段,研究了Ni/γ-Al     

Carbon clusters

Some of the most significant discoveries and achievements concerning the mass spectra and gas phase ion chemistry of carbon clusters are reviewed. These include (1) nanosecond and femtosecond laser ionizations; (2) ion structures through ion/molecule reactions, ion chromatography, and computational methods; (3) carbon cluster cooling through radiative decay, dissociative decay, and thermionic emission; (4) mechanisms and energetics of fragmentation reactions; (5) endohedral fullerenes including recent data on ion beam implantation, and (6) ion chemistry as a function of the fullerene charge state.     

Palladium-Catalyzed Addition of Carbon Monoxide and Carbon Tetrachloride to 1-Octene in Supercritical Carbon Dioxide

The Pd-catalyzed addition of carbon monoxide and carbon tetrachloride to 1-octene gave coadduct [alkyl 2-( 2, 2, 2-trichloroethyl)octanoate] as the major product in supercritical carbon dioxide by using pyridine as the base. It was found that the selectivity and the yield of coadduct were greatly affected by the pressure of carbon dioxide, the reaction temperature and the amounts of alcohol and base used.     

碳纳米管含量对炭炭复合材料组织及力学性能的影响

炭纤维上原位合成了均匀生长且具有伸张形貌的碳纳米管,借助化学气相渗透制备了碳纳米管增强的炭炭复合材料,研究了不同含量的碳纳米管对炭炭复合材料组织和力学性能的影响。结果表明：炭纤维上生长碳纳米管改变了热解炭的沉积行为,诱导了各向同性热解炭的生成,且随着碳纳米管含量的增加,各向同性热解炭的厚度增加,但是复合材料的d002值却明显降低。微量的碳纳米管即可显著提高复合材料的力学强度,随着其含量的增加,复合材料的力学强度和模量迅速提高,但材料的断裂行为却急剧恶化,断裂模式由最初的假塑性断裂转变为脆性断裂。