活性炭上化学气相沉积法生长纳米碳纤维

利用流化床技术,以天然气为碳源,负载于活性炭上的纳米镍粒子为催化剂,在750 ℃下采用化学气相沉积法制备了气相生长纳米碳纤维(VGCNFs)/活性炭(AC)复合物。通过对样品进行XRD、激光拉曼光谱、扫描电镜和氮吸附检测,发现VGCNFs生长在活性炭的各个侧面上,以顶部生长模式为主,纤维的直径在40～120 nm之间,由于粗糙的纤维表面和石墨片层的翘曲而缺陷较多。VGCNFs/AC复合物与原料活性炭相比,BET比表面积从2 367 m²·g^-1降到了1 474     

不同晶面Co基催化剂上CO活化行为研究

本研究用溶剂热法合成了三种暴露不同晶面的Co基催化剂,排除载体、助剂、晶粒尺寸等参数的影响,通过程序升温脱附、原位拉曼光谱、原位漫反射红外光谱等表征手段和化学瞬变反应技术,对不同晶面Co催化剂在费托反应过程中CO活化行为进行了研究。结果表明,CO的活化在不同晶面的Co基催化剂上具有结构敏感性。Co（10-11）晶面上CO以直接解离的方式进行活化,且CO解离生成的碳物种部分形成积炭,其余碳物种加氢生成CH_x;Co（0001）晶面上CO以氢助解离的方式活化,大量解离为积炭,少量碳物种氢化为CH_x;Co（11-20）晶面上CO直接解离,该催化剂上CO弱解离得到微量的积炭,其余碳物种在氢的存在下生成微量的CH_x中间体。     

氢化碳纳米球的铁磁性分析

为了研究球形碳结构的铁磁性的起源问题,以单质钠(Na)为还原剂,以三氯甲烷为原料,通过溶剂热合成法,分别在80、120℃下制备出2种氢化碳纳米球(HCNSs)并进行了系统表征。SEM图像表明:80℃下合成的HCNSs,其平均粒径为150 nm;而在120℃下合成的HCNSs平均粒径为300 nm,且碳球的分散性更佳。TEM图像表明,2种氢化碳纳米球皆为洋葱状类石墨结构,石墨层以波浪状分布在碳球的曲面上。从X射线光电子能谱可以看出:80℃HCNSs的氢化程度更高,同元素分析的结果一致。红外光谱(IR)表明,2种碳纳米球的碳氢键含量较低。拉曼光谱表明HCNSs具有较高的无序度和较差的结晶性。室温条件下对HCNSs进行了磁性表征,结果表明2种HCNSs均具有铁磁性。高浓度缺陷与波浪状排布的石墨层所导致的负高斯曲率是HCNSs具有铁磁性的主要原因。     

氢化石墨纳米结构的合成及尺寸相关的荧光性质

在溶剂热反应条件下(180℃),利用还原剂金属钾对卤代苯(溴苯和二溴苯)中的C—Br键进行选择性裂解,而含氢的碳六元环仍稳定且之间可以发生聚合成键,成功合成了2种不同的氢化石墨纳米结构,获得的产物分别呈黄褐色和黑色.拉曼和红外光谱分析结果表明,黑色产物为尺寸约2 nm的氢化石墨纳米片,而黄褐色样品为尺寸更小的氢化碳纳米结构;X射线衍射分析结果表明,2种产物都具有菱方结构但结晶性较低.对合成的氢化石墨纳米结构的荧光性质分析发现,样品具有尺寸相关的荧光现象,同等激发条件下,尺寸较小的黄褐色样品的发光强度约为黑色样品的15倍.     

静电自组装方法合成的具有多孔三维网络结构的Fe3O4/石墨烯复合材料作为高性能锂离子电池负极材料

采用静电自组装方法,分两步合成Fe（OH）₃/GO前驱体（GO：氧化石墨烯）,再通过水热反应和600 ℃高纯氮气气氛下煅烧,获得了Fe₃O₄/石墨烯复合材料. 通过X射线衍射（XRD）、扫描电镜（SEM）、高分辨透射电镜（HRTEM）、拉曼（Raman）光谱等多种分析,发现该复合材料具有三维多孔石墨烯网络结构. 把合成的这种Fe₃O₄/石墨烯复合材料作为锂离子电池负极材料,电化学测试结果表明其具有优良的电化学性能：首次放电容量为1390 mAh·g^-1,50次循环后容量为819 mAh·g^-1. 通过对比实验表明,三维石墨烯网络结构的形成对复合材料的电化学循环稳定性起着关键作用.     

自支撑多孔碳/硒复合柔性电极的制备及其电化学性能

以二氧化硅（SiO₂）为模板,结合静电纺丝与溶胶-凝胶法制备了多孔碳纳米纤维膜（PCNFS）,再通过熔融扩散法负载硒,制备了一种柔性的碳/硒复合电极（Se@PCNFS）。结合X射线衍射（XRD）、扫描电子显微镜（SEM）和透射电子显微镜（TEM）对材料的微观结构和形貌进行表征,结果显示多孔碳纤维直径约300 nm,硒均匀地嵌入碳纤维膜的孔洞中。电化学测试结果表明,1Se@PCNFS电极在锂硒电池中表现出优异的循环性能和倍率性能。在0.5C倍率下,初始放电比容量达到569 mAh·g^-1,循环500次后比容量为340 mAh·g^-1;在2C倍率时,比容量为403 mAh·g^-1。     

黄曲霉素B2分子吸附在银团簇的表面增强拉曼散射机理

采用密度泛函理论（DFT）B3LYP方法,6-311G（d,p）（C,H,O）/LANL2DZ（Ag）基组,计算了黄曲霉素B₂（AFB₂）分子吸附在Ag₂团簇的表面增强拉曼散射（SERS）光谱和预共振拉曼光谱,并与实验结果比较. 结果显示：AFB₂分子在基态Ag₂团簇表面吸附时,增强因子最大达到10²,对应吡喃（pyrane）环C=O伸缩振动,主要是由AFB₂分子周围化学环境改变而引起的基态静极化率改变导致的化学增强. 不同激发波长下的AFB₂分子预共振拉曼光谱的增强强度不同：电荷转移态激发波长为1144 和544 nm时拉曼信号增强了10²倍,而选择电荷转移预共振波长432和410 nm作为入射光时,其拉曼信号增强了10⁴倍,增强机理为银团簇和黄曲霉素分子之间的电荷转移共振增强. 因此通过改变入射光波长,选择电荷转移共振激发波长,更有利于强致癌物AFB₂分子的痕量检测.     

碳纳米粒子：合成及可见光催化降解萘酚绿

以酒石酸和酪氨酸为起始反应物,乙二醇为溶剂,采用溶剂热法一步合成了高发光强度的碳纳米粒子。利用XRD、TEM、FTIR和荧光光谱对碳纳米粒子的物相、形貌和粒径、表面基团及发光性能进行了表征。结果表明,合成的碳纳米粒子为粒径分布集中的球形,粒径10~30nm,分散性好,表面富含-COOH、-OH等官能团,具有激发波长依赖的光致发光特性。考察了反应温度、酒石酸与酪氨酸质量比对碳纳米粒子发光性能的影响。研究了碳纳米粒子/H₂O₂催化体系对萘酚绿的降解性能,结果表明：130mg·L^-1的萘酚绿溶液,可见光照射3.5h降解率可以达到96%。荧光光谱法表征指明降解过程中有羟基自由基生成。     

氧化石墨的谱学表征及分析

采用改进的Hummers法,通过改变氧化剂用量获得不同氧化程度的氧化石墨,用X射线衍射(XRD)、红外光谱(FTIR)和拉曼光谱(Raman)对产物进行结构和谱学特性的表征,并结合数学分析软件对部分红外和拉曼数据进行分峰拟合。结果表明,石墨经氧化后形成了含有C-OH、-COOH和C-O-C等官能团的石墨层间化合物;氧化剂用量较少时,石墨片层插层氧化不完全,产物的结构中仍存在未被氧化的原石墨周期性结构;随着氧化剂用量的增加,氧化石墨产物的XRD图中原石墨(002)衍射峰逐渐消失,结构中含氧官能团的量逐渐增加,产物的亲水性也逐渐增强;通过对红外光谱的拟合发现,氧化石墨样品在3 198 cm^-1附近有一个红外吸收峰,应归属于C-OH中OH的伸缩振动;随着氧化剂用量的增加,所得氧化石墨产物的拉曼光谱中D峰与G峰的强度积分比R(I_D/I_G)逐渐增大,产物结构中sp²平面域的平均尺寸逐渐减小。     

CoFe2O4纳米晶与牛血清白蛋白和牛血红蛋白的相互作用：吸附、纳米晶的团聚及蛋白构象的变化

水热制备了约10nm的CoFe₂O₄纳米晶,通过Zeta电势、动态光散射（Dynamic Light Scattering,DLS）和傅立叶变换红外光谱（FTIR）技术研究了纳米晶与牛血清白蛋白（Bovine Serum Albumin,BSA）和牛血红蛋白（Hemoglobin）的相互作用。纳米晶对BSA和血红蛋白都有很强的吸附,其中对血红蛋白的吸附符合静电吸附的规律,而对BSA的吸附则不符合静电吸附的规律。在pH=5.5和7.0时纳米晶对BSA和血红蛋白的吸附容量分别达到237.9mg·g^-1和256.9mg·g^-1。DLS结果表明蛋白质能够导致纳米晶团聚。吸附BSA或血红蛋白后,纳米晶的DLS粒径由51nm分别增大到472nm和114nm。CoFe₂O₄纳米晶还导致了蛋白质FTIR谱发生明显变化。BSA和血红蛋白的酰胺I带由于纳米晶的作用分别减少了4cm^-1和6cm^-1。     

Electrochemical production, characterization, and application of MWCNTs

The subject of this study is production of carbon nanotubes (CNTs) using an original procedure of reduction of lithium molten salts onto graphite cathode; their structural characterization and application as support material for electrocatalysts aimed for hydrogen evolution. As-produced CNTs were characterized by means of scanning and transmission electron microscopy (SEM and TEM), Raman spectroscopy, and thermogravimetric and differential thermal analysis (DTA). SEM and TEM images have shown that nanotubes are mostly of curved shape with length of 1–20 μm and diameter of 20–40 nm. Raman peaks indicate that the crystallinity of produced nanotubes is rather low. The obtained results suggest that formed product contains up to 80 % multiwalled carbon nanotubes (MWCNTs), while the rest being non-reacted graphite and fullerenes. DTA curves show that combustion process of the nanotubes takes place in two stages, i.e., at 450 and 720 °C. At the lower temperature, combustion of MWCNTs occurs, while at higher one, fullerenes and non-reacted graphite particles burn. As-produced MWCNTs were used as electrocatalyst’s support materials and their performance was compared with that of traditional carbon support material Vulcan XC-72. MWNTs have shown almost twice higher real surface area, and electrocatalyst deposited on them showed better catalytic activity than corresponding one deposited on Vulcan XC-72.     

Platelet Graphite Nanofibers for Electrochemical Sensing and Biosensing: The Influence of Graphene Sheet Orientation

Here, we demonstrate that platelet graphite nanofibers (PGNFs) exhibit fast heterogeneous electron‐transfer rates for a wide variety of compounds such as FeCl₃, ferrocyanide, dopamine, uric acid, ascorbic acid, and the reduced form of β‐nicotinamide adenine dinucleotide. The electrochemical properties of PGNFs are superior to those of multiwalled carbon nanotubes (MWCNTs) or graphite microparticles (GMPs). Transmission electron microscopy and Raman spectroscopy reveal that this arises from the unique graphene sheet orientation of such platelet nanofibers, which accounts for their unparalleled high ratio of graphene edge planes versus basal planes.     

High dispersion and electrocatalytic properties of platinum nanoparticles on graphitic carbon nanofibers (GCNFs)

Highly dispersed platinum nanoparticles were electrodeposited on graphitic carbon nanofibers (GCNFs) by cyclic voltammetry (CV) in 7.7 mM H2PtCl6+0.5 M HCl aqueous solutions. The graphitic carbon nanofibers (GCNFs) used in this paper were grown directly on a graphite disk by chemical vapor deposition (CVD). The micrographs and element composition of Pt/GCNFs/graphite electrode were characterized by scanning electron microscopy (SEM) and electron diffraction spectroscopy (EDS). The electrocatalytic properties of Pt/GCNFs/graphite electrode for methanol oxidation have been investigated by CV and excellent electrocatalytic activity can be observed even at very low platinum loading (md=8.79 microg cm(-2)). The highest mass activity (MA) for methanol oxidation reaches 323 Ag(-1) when Pt/GCNFs/graphite electrode was cycled at a sweep rate of 50 mVs(-1) by CV in 2 M CH3OH+1 M H2SO4 aqueous solutions. This may be attributed to the small particle size and high dispersion of platinum particles coated on GCNFs and shows good potential application in direct methanol fuel cell (DMFC). Additionally, the long-term cycling stability of platinum catalysts was also investigated.     

Studying lithium intercalation into graphite particles via in situ Raman spectroscopy and confocal microscopy

The electrochemical intercalation of lithium into single graphite particles was studied in situ using Raman microscopy combined with confocal microscopy. The degree of intercalation during cycling was obtained from changes in the Raman bands of carbon. Confocal microscopy was used to image the graphite electrode in order to monitor the intercalation into single graphite particles. An industrial button cell was modified such that Raman spectra and microscopic images of the back side of the negative electrode could be taken through a window in the cup of the cell. The liquid electrolyte consisted of a 1:1 mixture of ethylenecarbonate/dimethylcarbonate (EC/DMC) with 1 M LiPF₆. The spectroscopy and microscopy showed that lithium does not intercalate into the graphite in a homogeneous manner. Inhomogeneous lithium intercalation was even observed in single graphite particles.     

酚醛树脂包覆氧化天然石墨作为锂离子电池负极材料

天然石墨经过浓硫酸氧化处理,酚醛树脂包覆并高温碳化后形成具有核壳结构的碳包覆氧化天然石墨复合材料.采用扫描电子显微镜(SEM),透射电子显微镜(TEM),X射线衍射(XRD),激光显微拉曼光谱(Raman)等检测技术对氧化处理以及酚醛树脂热解碳包覆前后天然石墨材料的结构与形貌进行分析与表征.结果表明,氧化处理与适量的酚醛树脂热解碳包覆有效修复了天然石墨表面的一些缺陷结构,使其表面更为光滑.电化学测试结果显示,经过氧化处理与酚醛树脂热解碳包覆后天然石墨材料电化学性能得到明显提高.酚醛树脂包覆量为9%时,复合材料表现出最好的电化学性能,其首次放电比容量为434.0mAh·g-1,40次循环后,放电比容量保持在361.6mAh·g-1,而未经处理的天然石墨放电比容量仅为332.3mAh·g-1.该改性方法有效提高了天然石墨材料的比容量,对其进一步应用具有重要意义.     

碳纤维表面原位SiC纳米纤维的合成与生长

基于化学气相反应法,以高纯Si和SiO₂为反应源材料,在碳纤维表面原位生长β-SiC纳米纤维。采用XRD、SEM和TEM 等分析测试手段对SiC纳米纤维进行了表征分析,研究了不同反应温度和时间对生成β-SiC纳米纤维微观形貌和结构的影响,并探讨了β-SiC纳米纤维的生长机制。研究结果表明：采取化学气相反应法能够制备高质量、高纯度的β-SiC纳米纤维,纳米纤维的直径约为100~300 nm。随着反应温度的提高和时间的延长,纳米纤维的产额增加,且微观组织形貌发生了变化。结合制备过程和纳米纤维微观结构的观察分析,表明气-固(VS)机制是SiC纳米纤维生长的主要机理。     

碳纤维表面原位SiC纳米纤维的合成与生长

基于化学气相反应法,以高纯Si和SiO₂为反应源材料,在碳纤维表面原位生长β-SiC纳米纤维。采用XRD、SEM和TEM 等分析测试手段对SiC纳米纤维进行了表征分析,研究了不同反应温度和时间对生成β-SiC纳米纤维微观形貌和结构的影响,并探讨了β-SiC纳米纤维的生长机制。研究结果表明：采取化学气相反应法能够制备高质量、高纯度的β-SiC纳米纤维,纳米纤维的直径约为100~300 nm。随着反应温度的提高和时间的延长,纳米纤维的产额增加,且微观组织形貌发生了变化。结合制备过程和纳米纤维微观结构的观察分析,表明气-固(VS)机制是SiC纳米纤维生长的主要机理。     

载气对注入CVD法制备碳纳米管和碳纳米纤维的影响

采用注入化学蒸气沉积法,在石英管壁上制备得到了定向的多壁纳米碳管和纳米碳纤维.在相同的反应体系中,采用不同的载气,得到的碳材料的形态有较大不同.经SEM, TEM及Raman等证实,采用氩气和氮气作为载气时,得到了内部填充铁的碳纳米纤维,而且具有较好的类石墨晶体结构;用氢气作为载气时得到了中空的碳纳米管.通过控制氢气和惰性气体的比例,改变了碳纳米管的直径分布.     

Fabrication of carbon fibers with nanoporous morphologies from electrospun polyacrylonitrile/poly(L‐lactide) blends

Porous carbon nanofibers were prepared through electrospinning a blend solution of polyacrylonitrile and poly(L ‐lactide), followed by carbonization at different temperatures and in different atmospheres. Structural features of these porous carbon nanofibers were characterized using scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis, X‐ray powder diffraction, and Raman spectroscopy. Surface area and pore structure were evaluated using the nitrogen adsorption technique. It was found that carbon fibers prepared by this scalable and relatively economical method exhibited a porous surface morphology with high specific surface area and large pore volume. The fiber diameter, surface area, pore volume, bulky crystalline structure, and surface crystalline structure of these carbon nanofibers showed a strong dependence on the polymer precursor composition and carbonization condition. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 493–503, 2009     

竹节状纳米碳纤维的制备及嵌锂性能研究

以泡沫镍为催化剂,在600和700℃下,以CVD法热解乙炔气体制备大量的纳米碳纤维.随着制备温度增加,纳米碳纤维直径变小,竹节状含量减少, d002值减小,微晶片层平面Lc和La值增大,碳材料的可逆容量则下降.分别用透射电镜、 X射线衍射和拉曼光谱观察和测定了纳米碳纤维的形貌、微结构,发现在不同条件下生长的纳米碳纤维有不同的形貌和结构.对纳米碳纤维的电化学嵌锂性能的研究表明,纳米碳纤维的结构对其电化学嵌锂容量和充放电循环寿命起重要影响,制备温度越低,纳米碳纤维的石墨化程度越差,可逆嵌锂容量相应要高一些.