多巴胺和L-精氨酸制备超轻氮掺杂石墨烯气凝胶吸油性能的研究（英文）

采用水热法制备了超轻氮掺杂石墨烯气凝胶。分析表征结果表明,多巴胺不仅为还原剂而且提供氮源,石墨烯溶液前躯体的pH值对水热法制备超轻氮掺杂石墨烯气凝胶很大的影响,通过调节多巴胺和L-精氨酸在石墨烯溶液前躯体的浓度,可制备密度为2.54 mg/cm~3超轻氮掺杂石墨烯气凝胶,由于氮掺杂、低密度和大的比表面积,超轻氮掺杂石墨烯气凝胶对各种油品都有良好的吸附性能。     

一种高效的多孔氮掺杂碳基气凝胶催化剂及其催化乙苯氧化性能

通过水热合成和高温煅烧的方法制备了多孔氮掺杂碳基复合气凝胶,其可作为一种高效的催化剂.该方法是以蒲绒和石墨烯气凝胶作为碳源和模板,尿素作为氮源.分别采用XRD,FT-IR,Raman和TEM对这些催化剂进行表征分析.以叔丁基过氧化氢为氧化剂,探究该复合气凝胶在乙苯选择性氧化生成苯乙酮的反应体系中的催化性能,实验结果表明,该复合气凝胶在该体系中具有优异的催化活性,苯乙酮的选择性可达92%以上.这是由于复合气凝胶中的多孔结构,氮元素的掺杂以及蒲绒和石墨烯气凝胶之间的相互作用.将生物质蒲绒转化为高催化活性碳材料,这种新颖的方法为寻找高性能催化氧化乙苯的催化剂提供了新的设计前景.     

石墨烯基气凝胶催化还原特性及其应用

石墨烯基气凝胶(GA)是一种内部连通的三维石墨烯宏观体,其在继承了石墨烯良好的化学稳定性和优良催化性能的同时拥有更高的比表面积和导电性。GA由于其优越的性能和独特的结构在催化、能量存储、吸附等领域得到广泛的应用。本文主要从GA催化还原特性展开,综述了具有不同催化性能的石墨烯基气凝胶的制备方法,将其总结归纳分为GA、掺杂型GA、复合型GA以及掺杂复合型GA四种类型,并详细介绍了制备方法对石墨烯基气凝胶催化性能的影响。石墨烯基气凝胶因具有优良的电化学活性和催化特性,在燃料电池、染料敏化太阳能电池、微生物电解池和电化学传感器等领域具有广泛的应用前景。最后对石墨烯基气凝胶在催化领域的应用前景进行分析和展望。     

硫/石墨烯气凝胶的绿色可控制备及锂硫电池性能

以氧化石墨烯(GO)为碳前驱体,H_2O_2作为绿色氧化剂,H_2S为还原剂和硫源,水热法制备了硫含量可控的硫/石墨烯气凝胶。通过调控加入到GO溶液中H_2O_2的用量使复合物中硫的质量分数在64%～84%间变动。将硫/石墨烯气凝胶用于锂硫电池正极材料,硫质量分数为70%的复合物表现了较好的锂硫电池性能,在0.1 A/g的电流密度下,其放电比容量可达1290 mA·h/g,在1.0 A/g的电流密度下循环100次,其比容量从385 mA·h/g逐渐降低到275 mA·h/g,保持率为71.4%,表现了较好的循环稳定性。该方法将有毒的H_2S用H_2O_2氧化成单质硫,同时H_2O_2被还原成H_2O,此过程中没有产生任何污染物,实现了硫/石墨烯气凝胶的绿色制备。     

氮掺杂还原氧化石墨烯/四氧化三钴双功能催化剂的制备及表征

采用尿素作为氮源,通过热退火法制备氮掺杂还原氧化石墨烯,然后以乙酰丙酮钴作为钴源通过水热法制备氮掺杂还原氧化石墨烯/四氧化三钴杂化纳米片作为催化氧还原和氧析出反应的双功能催化剂。利用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线电子能谱仪(XPS)等对其进行形貌结构表征,通过旋转圆盘电极等电化学测试对其电催化性能进行分析,可以看出该催化剂具有良好的氧还原和氧析出催化性能。     

石墨烯掺杂碳气凝胶粉体的制备及电磁干扰性能

采用溶胶-凝胶、 超临界干燥及高温裂解技术制备了不同石墨烯掺杂量的碳气凝胶(G-CA)粉体材料, 通过控制材料的组成和微观结构, 制备了密度仅为0.0093 g/cm³的低密度高导电性气凝胶粉体. 将G-CA粉体布撒在空气中, 测试其对毫米波、 可见光和红外光的衰减性能. 结果表明, 相对于纯碳气凝胶和纯石墨烯气凝胶, G-CA粉体对3种波段的电磁波的衰减性能大幅度提高. 其中石墨烯/掺杂量为7%的碳气凝胶(7%G-CA)在布撒初期和布撒20 min后, 对红外光和可见光均具有97%和94%以上的遮蔽率; 对于毫米波, 在布撒初期和布撒10 min以后, 分别具有75%和65%以上的遮蔽率. G-CA粉体具有良好的分等级微纳米结构及高导电性和超低密度, 该微观结构与组成的协同作用使其呈现出优异的多波段、 长时有效的电磁干扰性能, 有望扩展和延伸传统烟幕材料的应用范围.     

勃姆石纤维增强二氧化硅气凝胶的制备及性能

以六水合氯化铝为铝源, 通过水热法制备勃姆石纤维; 以甲基三甲氧基硅烷和正硅酸乙酯为硅源共前驱体, 采用溶胶-凝胶法进而常压干燥制备了勃姆石纤维掺杂的二氧化硅复合气凝胶; 探究了勃姆石纤维的掺杂量对复合气凝胶性能的影响. 当勃姆石纤维的掺杂量(质量分数)为1%时, 气凝胶的机械性能最好, 能够承受17.1%的压缩应变, 最大压缩强度为1.12 MPa, 压缩模量高达2.57 MPa, 复合气凝胶在150 ℃仍然具有较低的导热系数(0.0670 W·m^?1·K^?1). 勃姆石纤维能够一定程度地抑制二氧化硅颗粒在高温下的烧结和相转变, 对二氧化硅气凝胶的耐高温性能有显著的提升作用, 复合气凝胶在1100 ℃高温热处理后, 仍能保持良好的隔热性能和较高的机械强度.     

氮掺杂石墨烯量子点用于定量分析牛血清白蛋白的含量

合成了氮掺杂石墨烯量子点,并基于茜素红-氮掺杂石墨烯量子点之间的相互作用形成氢键复合物,茜素红可以对所合成的氮掺杂石墨烯量子点产生明显的荧光猝灭作用(荧光关),氮掺杂石墨烯量子点荧光强度的变化(F0/F)与茜素红浓度(2.78~23.59 nmol/L)具有良好的线性关系,检出限为1.24 nmol/L;继续向该溶液中加入牛血清白蛋白,会使原已发生荧光猝灭的氮掺杂石墨烯量子点溶液的荧光发射强度得以恢复(荧光开),且荧光发射强度的恢复与牛血清白蛋白浓度(0.1~0.375 g/L)之间具有良好的线性关系,检出限为0.011 g/L。此外,该"关-开"荧光检测体系被用来定量分析人尿液中的牛血清白蛋白含量,方法已用于实际尿液样品的定量分析。     

氮掺杂石墨烯的生长机理及其在乙苯选择性氧化中的应用

以热解氧化石墨烯材料为碳基底,分别使用有机氮源和无机氮源对其进行氮掺杂处理,制备了一系列氮掺杂石墨烯材料.采用透射电子显微镜、扫描电子显微镜、拉曼光谱和X射线光电子能谱等表征方法考察了氮掺杂石墨烯的生长机理.结果表明,随着制备过程中退火温度的改变,氮掺杂石墨烯中不同氮物种的含量有显著差别.这种差异是由不同氮物种化学环境的差异所导致的.所制备的含氮石墨烯材料对乙苯选择性氧化制苯乙酮反应均表现出优良的催化活性.其中,石墨氮的含量对于提高苯乙酮收率起到至关重要的作用.此外,通过氧化剂控制活化的方法可以消除过多的结构缺陷和过量氮掺杂对催化反应的不利影响,有效提升氮掺杂石墨烯的催化活性.     

纳米Cu_2O/氮掺杂石墨烯复合修饰电极对多巴胺的电化学分析研究

本文通过化学还原法制备纳米Cu_2O/氮掺杂石墨烯(NG)复合材料,用于构建一种新型的多巴胺(DA)电化学传感器。采用X射线衍射法和扫描电镜对纳米Cu_2O/氮掺杂石墨烯复合材料进行表征。在pH为7.0的磷酸盐缓冲液中,采用循环伏安法和计时电流法分别研究了DA在纳米Cu_2O/氮掺杂石墨烯复合修饰电极上的电化学行为。结果表明,该修饰电极对DA表现出显著的电催化活性,且DA在修饰电极上的反应受吸附控制。在最佳实验条件下,催化电流与DA的浓度在0.5~700μmol/L之间呈线性关系(r=0.9943),检测限达0.17μmol/L。该修饰电极的选择性高、重复性和再现性好。方法用于实际样品中DA的检测,获得结果较好。     

A non‐covalent functionalization of copper tetraphenylporphyrin/chemically reduced graphene oxide nanocomposite for the selective determination of dopamine

A non‐covalent functionalization based on a copper tetraphenylporphyrin/chemically reduced graphene oxide (Cu‐TPP/CRGO) nanocomposite is demonstrated for selective determination of dopamine (DA) in pharmaceutical and biological samples. A homogeneous electron‐rich environment can be created on the graphene surface by Cu‐TPP due to the π–π non‐covalent stacking interaction. The synthesized Cu‐TPP/CRGO nanocomposite was characterized using scanning electron microscopy NMR, ultraviolet–visible and electrochemical impedance spectroscopies. The electrocatalytic activity of DA was evaluated using cyclic voltammetry and differential pulse voltammetry. The oxidation peak current (I_pa) of DA increased linearly with increasing concentration of DA in the range 2–200 μM. The detection limit was calculated as 0.76 μM with a high sensitivity of 2.46 μA μM^?1 cm ^{? 2}. The practicality of the proposed DA sensor was evaluated in DA hydrochloride injection, human urine and saliva, and showed satisfactory recovery results for the detection of DA. In addition, the Cu‐TPP/CRGO nanocomposite‐modified electrode showed excellent stability, repeatability and reproducibility towards the detection of DA. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis of polydopamine‐coated graphene–polymer nanocomposites via RAFT polymerization

Graphene‐polymer nanocomposites have significant potential in many applications such as photovoltaic devices, fuel cells, and sensors. Functionalization of graphene is an essential step in the synthesis of uniformly distributed graphene‐polymer nanocomposites, but often results in structural defects in the graphitic sp² carbon framework. To address this issue, we synthesized graphene oxide (GO) by oxidative exfoliation of graphite and then reduced it into graphene via self‐polymerization of dopamine (DA). The simultaneous reduction of GO into graphene, and polymerization and coating of polydopamine (PDA) on the reduced graphene oxide (RGO) surface were confirmed with XRD, UV–Vis, XPS, Raman, TGA, and FTIR. The degree of reduction of GO increased with increasing DA/GO ratio from 1/4 to 4/1 and/or with increasing temperature from room temperature to 60 °C. A RAFT agent, 2‐(dodecylthiocarbonothioylthio)?2‐methylpropionic acid, was linked onto the surface of the PDA/RGO, with a higher equivalence of RAFT agent in the reaction leading to a higher concentration of RAFT sites on the surface. Graphene‐poly(methyl methacrylate), graphene‐poly(tert‐butyl acrylate), and graphene‐poly(N‐isopropylacrylamide) nanocomposites were synthesized via RAFT polymerization, showing their characteristic solubility in several different solvents. This novel synthetic route was found facile and can be readily used for the rational design of graphene‐polymer nanocomposites, promoting their applications. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3941–3949     

Selective Detection of Dopamine in the Presence of Uric Acid Using NiO Nanoparticles Decorated on Graphene Nanosheets Modified Screen‐printed Electrodes

A convenient, low cost, and sensitive electrochemical method, based on a disposable graphene nanosheets (GR) and NiO nanoparticles modified carbon screen printed electrode (NiO/GR/SPE), is described for the simultaneous determination of dopamine (DA) and uric acid (UA). The modified electrode exhibited good electrocatalytic properties toward the oxidation of DA and UA. A peak potential difference of 150 mV between DA and UA was large enough to determine DA and UA individually and simultaneously. The anodic peak currents of DA were found to be linear in the concentration range of 1.0–500.0 μM with the detection limit of 3.14×10^?7 M.     

Atomistic Simulations of Dopamine Diffusion Dynamics on a Pristine Graphene Surface**

Carbon microelectrodes enable in vivo detection of neurotransmitters, and new electrodes aim to optimize the carbon surface. However, atomistic detail on the diffusion and orientation of neurotransmitters near these surfaces is lacking. Here, we employ molecular dynamics simulations to investigate the surface diffusion of dopamine (DA), its oxidation product dopamine-o-quinone (DOQ), and their protonated forms on the pristine basal plane of flat graphene. We find that all DA species rapidly adsorb to the surface and remain adsorbed, even without a holding potential or graphene surface defects. We also find that the diffusivities of the adsorbed and the fully solvated DA are similar and that the protonated species diffuse more slowly on the surface than their corresponding neutral forms, while the oxidized species diffuse more rapidly. Structurally, we find that the underlying graphene lattice has little influence over the molecular adsorbate's lateral position, and the vertical placement of the amine group on dopamine is highly dependent upon its charge. Finally, we find that solvation has a large effect on surface diffusivities. These first results from molecular dynamics simulations of dopamine at the aqueous-graphene interface show that dopamine diffuses rapidly on the surface, even without an applied potential, and provide a basis for future simulations of neurotransmitter structure and dynamics on advanced carbon materials electrodes.     

(4-Ferrocenylethyne) phenylamine on Graphene as the Signal Amplificator to Determinate Dopamine and Acetaminophen Simultaneously

A novel (4‐ferrocenylethyne) phenylamine functionalized graphene sheets (FEPA‐GR), coupling with chitosan (CS) were used as a signal amplification platform for simultaneous and sensitive determination of dopamine (DA) and acetaminophen (AC). In this work, FEPA used as electron transfer mediator can be immobilized on GR surface via strong π‐π stacking interaction between the conjugate chain of FEPA and GR, which effectively prevents FEPA electron mediator leaking from the electrode surface and amplified the signal. Transmission electron microscopy, FT‐IR spectroscopy, UV‐vis spectroscopy and electrochemical experiments results are all demonstrated the strong π‐π stacking interaction between FEPA and GR. The resulted biosensor exhibited a fast response, remarkable electrocatalytic activity, perfect anti‐interference ability and good stability for simultaneous detection of DA and AC. Under the optimum conditions, the oxidation peak currents of DA and AC were linearly correlated to their concentrations in the range of 2.0–135.0 µmol·L^?1 and 0.3–80.0 µmol·L^?1, respectively. The lower detection limits for DA and AC were 0.30 and 0.05 µmol·L^?1, respectively. The feasibility of the proposed method was validated by successfully applied to the simultaneous determination of DA and AC in serum samples with the standard addition method.     

Facile synthesis of nitrogen-doped graphene aerogels for electrochemical detection of dopamine

Nitrogen-doped graphene aerogels with three-dimensional network structures are fabricated using hydrothermal method which includes the reduction of graphene oxide by organic amine and self-assembly of reduced graphene oxide. The effect of amine-containing compounds including aniline, 2-aminoethanol, ethylenediamine, melamine and chitosan on the assembly of nitrogen-doped graphene aerogel is investigated. The microstructure and chemical composition of nitrogen-doped graphene aerogels are characterized. The results reveal that nitrogen-doped graphene aerogel prepared using aniline as nitrogen source possesses a large specific surface area, high nitrogen content, good mechanical strength and excellent electrical conductivity. Based on these features, the as-prepared nitrogen-doped graphene aerogel shows high performance in electrochemical detection of dopamine in the presence of uric acid and ascorbic acid. Given the facile and scalable processability of aerogels, the proposed nitrogen-doped graphene aerogels are expected to have potential applications in sensors and other related devices.     

A Selective Voltammetric Method for Detecting Dopamine at Quercetin Modified Electrode Incorporating Graphene

The development of a quercetin‐graphene composite‐modified glassy carbon electrode (Qu/GH/GCE) for the selective and sensitive detection of dopamine (DA) is described in this paper. To fabricate the Qu/GH/GCE, graphene (GH) was first coated onto the surface of a glassy carbon electrode (GCE) and then quercetin (Qu) was electrodeposited on the GH matrix. Transmission electron microscopy (TEM) was used to characterize the morphology of the obtained GH and Qu/GH, and the electrochemical properties of the modified electrode were studied using electrochemical techniques. The as‐prepared Qu/GH/GCE occupied a synthetic property between GH and Qu. The common overlapped electrochemical oxidation peaks of DA and AA were completely separated and a remarkable increasing electron‐oxidation current of DA occurred on the Qu/GH/GCE, which enabled the sensitive and selective electrochemical detection of DA in the presence of ascorbic acid (AA) with peak difference of ca. 452 mV between DA and AA. The peak current obtained at 0.174 V (vs. saturated calomel electrode, SCE) from differential pulse voltammetry (DPV) is linearly dependent on the DA concentration in the range from 3.0×10^?8 to 4.0×10^?4 mol/L with a detection limit of 1.0×10^?8 mol/L. Furthermore, the Qu/GH/GCE exhibits good reproducibility and stability, and has been used for the determination of DA in samples of rat’s striatum tissue with satisfactory results.     

Graphene Paper Decorated with a 2D Array of Dendritic Platinum Nanoparticles for Ultrasensitive Electrochemical Detection of Dopamine Secreted by Live Cells

To circumvent the bottlenecks of non‐flexibility, low sensitivity, and narrow workable detection range of conventional biosensors for biological molecule detection (e.g., dopamine (DA) secreted by living cells), a new hybrid flexible electrochemical biosensor has been created by decorating closely packed dendritic Pt nanoparticles (NPs) on freestanding graphene paper. This innovative structural integration of ultrathin graphene paper and uniform 2D arrays of dendritic NPs by tailored wet chemical synthesis has been achieved by a modular strategy through a facile and delicately controlled oil–water interfacial assembly method, whereby the uniform distribution of catalytic dendritic NPs on the graphene paper is maximized. In this way, the performance is improved by several orders of magnitude. The developed hybrid electrode shows a high sensitivity of 2 μA cm^?2 μm ^?1, up to about 33 times higher than those of conventional sensors, a low detection limit of 5 nm, and a wide linear range of 87 nm to 100 μm . These combined features enable the ultrasensitive detection of DA released from pheochromocytoma (PC 12) cells. The unique features of this flexible sensor can be attributed to the well‐tailored uniform 2D array of dendritic Pt NPs and the modular electrode assembly at the oil–water interface. Its excellent performance holds much promise for the future development of optimized flexible electrochemical sensors for a diverse range of electroactive molecules to better serve society.     

A Promising Electrochemical Platform for Dopamine and Uric Acid Detection Based on a Polyaniline/Iron Oxide-Tin Oxide/Reduced Graphene Oxide Ternary Composite

A ternary polyaniline/Fe₂O₃-SnO₂/reduced graphene oxide (PFSG) nanocomposite was prepared using a simple two-step hydrothermal treatment. The composite was applied as a glassy carbon electrode modifier (GCE) to enhance dopamine (DA) and uric acid (UA) detection. The ternary PFSG composite was compared with its binary precursor Fe₂O₃-SnO₂/reduced graphene oxide (FSG). The influence of the modified GCE electrodes on their performance as a sensing platform was determined. GCE/PFSG showed better sensing parameters than GCE/FSG due to the introduction of polyaniline (PANI), increasing the electrocatalytic properties of the electrode towards the detected analytes. GCE/PFSG enabled the detection of low concentrations of DA (0.076 µM) and UA (1.6 µM). The peak potential separation between DA and UA was very good (180 mV). Moreover, the DA oxidation peak was unaffected even if the concentration of UA was ten times higher. The fabricated sensor showed excellent performance in the simultaneous detection with DA and UA limits of detection: LOD_DA = 0.15 µM and LOD_UA = 6.4 µM, and outstanding long-term stability towards DA and UA, holding 100% and 90% of their initial signals respectively, after one month of use.     

Reduced Graphene Oxide Non‐covalent Functionalized with Zinc Tetra Phenyl Porphyrin Nanocomposite for Electrochemical Detection of Dopamine in Human Serum and Rat Brain Samples

We described the use of a nanocomposite consisting of reduced graphene oxide and zinc tetraphenylporphyrin (RGO/Zn‐TPP) for electrochemical sensing of dopamine (DA). The surface of RGO was homogeneously functionalized with Zn‐TPP via non‐covalent π‐π interaction. The nanocomposite was characterized by scanning electron microscopy, UV‐Vis spectrometry, nuclear magnetic resonance spectroscopy and electrochemical impedance spectroscopy. The electroanalysis behavior of the nanocomposite was studied by cyclic voltammetry and amperometry. The excellent electrocatalytic activity is found for oxidation of DA, best at working voltage of 0.214 V (vs. Ag/AgCl) and linear response range of 0.04–238.8 μM. The sensitivity and detection limit were of 0.665 μA µM^?1 cm^?2 and 3 nM, respectrively. The electrode is well reproducible, stable, and represents a viable platform for the analysis of DA in DA injection, human serum and rat brain sample.