纳米Fe3O4-还原氧化石墨烯复合修饰玻碳电极的制备及电化学检测多巴胺

通过电化学还原法制备纳米Fe₃O₄-还原氧化石墨烯复合修饰玻碳（Fe₃O₄-rGO/GCE）电极,用于多巴胺（DA）的检测。采用SEM、TEM和循环伏安对纳米Fe₃O₄-rGO复合材料进行表征。在pH为7.0的磷酸盐缓冲液（PBS）中,采用循环伏安法研究了DA在纳米Fe₃O₄-rGO/GC上的电化学行为。实验结果表明,较裸GC电极和rGO修饰（rGO/GC）电极,由于纳米Fe₃O₄与rGO的协同作用,纳米Fe₃O₄-rGO/GC显著增大了Fe₃O₄-rGO/GC复合材料电极电化学活性面积和氧化峰电流强度i_pa。DA的浓度在6.0×10^-8~2.0×10^-6 mol/L和2.0×10^-6~8.0×10^-5 mol/L范围内,与氧化峰电流强度i_pa呈良好的线性关系,检出限达4.0×10^-9 mol/L（信噪比S/N=3）。抗坏血酸和尿酸共存物几乎不干扰DA的测定,选择性高。Fe₃O₄-rGO/GC修饰电极用于盐酸DA注射液中的DA含量测定,获得结果较好,回收率为97.1%~103.9%。     

疏松多孔CoFe2O4-还原石墨烯电极复合材料的制备与性能

采用原位溶剂热法,以氧化石墨烯（GO）与Co2+、Fe3+为原料制备疏松多孔的纳米CoFe₂O₄-还原氧化石墨烯（CoFe₂O₄-rGO）复合材料。采用XRD、Raman、SEM和HRTEM测试表征了纳米CoFe₂O₄-rGO复合材料的结构与形貌。测试结果表明,纳米CoFe₂O₄-rGO复合材料具有三维结构。自组装的多孔CoFe₂O₄纳米球粒径约为200 nm,在rGO上均匀分散,解决了CoFe₂O₄易团聚的问题。电化学测试结果表明,纳米CoFe₂O₄-rGO复合材料具有较高的比容量及优异的循环和倍率性能,在100 mA·g-1的电流密度下其比容量为1 262 mAh·g-1,50次循环后比容量仍能保持在642 mAh·g-1;并在2 000 mA·g-1的大电流密度下仍具有221 mAh·g-1的比容量。纳米CoFe₂O₄-rGO复合材料拥有更优异的电化学性能的原因在于CoFe₂O₄纳米球在rGO上均匀分布。三维结构增加了Li+储存的活性位点,有效缓解了电极的体积收缩/膨胀效应,提高了纳米CoFe₂O₄-rGO复合材料的导电性。      

Fe3O4-碳纳米管/聚偏氟乙烯复合材料的制备与性能

通过在碳纳米管（CNTs）表面进行功能化修饰,改善CNTs与聚偏氟乙烯（Polyvinylidene Fluoride,PVDF）的分散性及界面结合程度,从而获得优异的力学性能和电学性能,提高其在传感器、致动器和储能方面的应用性能。采用原位水热合成法,在CNTs表面修饰磁性Fe₃O₄纳米粒子,然后将Fe₃O₄-CNTs加入PVDF中,采用流延工艺制备出Fe₃O₄-CNTs/PVDF复合薄膜。采用SEM、TEM、XRD和DSC研究了Fe₃O₄-CNTs/PVDF复合薄膜的结构和结晶行为,采用动态力学分析（DMA）、宽带介电谱测试系统和交流击穿场强测试系统研究了Fe₃O₄-CNTs对复合材料力学性能、介电性能及击穿场强的影响。结果表明：Fe₃O₄-CNTs的引入促使PVDF形成了β晶相,同时抑制了Fe₃O₄-CNTs/PVDF复合材料结晶度的下降;提高了弹性模量,抑制了阻尼特性下降;提高了介电常数和击穿场强,抑制了介电损耗升高。     

Fe3O4@离子印迹聚(St-HPMA-DVB)复合材料的合成及其对水中高氯酸盐选择性吸附

采用超声协助悬浮聚合法以高氯酸根（ClO₄-）为模板制备了Fe₃O₄@离子印迹聚（苯乙烯-3-（2-氨基三乙基四胺）-2-甲基丙烯酸羟丙酯-二乙烯苯）（Fe₃O₄@ⅡP（St-HPMA-DVB））磁性复合材料,通过TEM、振动样品磁强计（VSM）、TGA、XRD、元素分析（EA）、FTIR等对其进行表征,考察了交联剂DVB用量对材料结构与性能的影响。结果表明:合成的Fe₃O₄@ⅡP（St-HPMA-DVB）磁性复合材料平均粒径为500~2 000 nm,随DVB用量的增加而增大;磁化强度为9.77~12.78 emu/g,随DVB用量的增加而减小;DVB的加入有利于Fe₃O₄@ⅡP（St-HPMA-DVB）磁性复合材料的离子印迹空腔的形成和稳定。考察了不同溶液pH值、ClO₄-的初始浓度、吸附时间等条件下Fe₃O₄@ⅡP（St-HPMA-DVB）吸附水中ClO₄-的性能,发现溶液pH值能显著影响Fe₃O₄@ⅡP（St-HPMA-DVB）磁性复合材料对ClO₄-的吸附效果,pH为3.0时效果最佳;不同DVB用量Fe₃O₄@ⅡP（St-HPMA-DVB）磁性复合材料对ClO₄-的吸附量和选择性有影响,当DVB用量为0.5 g时,Fe₃O₄@ⅡP（St-HPMA-DVB）磁性复合材料的吸附量和选择性最佳;吸附机制以离子交换和静电引力为主。等温吸附线符合Langmuir模型,Fe₃O₄@ⅡP（St-HPMA-DVB）磁性复合材料的饱和吸附量（q_m,c=76.9~111.1 mg/g）高于非离子印迹材料Fe₃O₄@非离子印迹聚（NIP）（St-HPMA-DVB）磁性复合材料（q_m,c=62.5 mg/g）。吸附过程可在10 min内达到平衡,符合准二级动力学模型;Fe₃O₄@ⅡP（St-HPMA-DVB）磁性复合材料能高选择性地有效吸附水中ClO₄-,对ClO₄-的印迹因子α为1.8,对几种常见共存离子的选择性因子β>5.8,是潜在的高选择性吸附和回收ClO₄-的功能材料。      

基于Pd/Fe3O4/rGO纳米复合材料的H2O2无酶传感器

环境监测、食品工业、临床、制药等领域对过氧化氢(H_2O_2)的快速、准确检测有极大的需求,而电化学检测方法由于灵敏度高、响应快、检测限低等特点被认为是最理想的H_2O_2检测方法.本文利用电化学沉积的方法将Pd纳米颗粒沉积到四氧化三铁/石墨烯(Fe_3O_4/rGO)纳米复合材料修饰的玻碳电极表面,形成基于新型磁性纳米复合材料的H_2O_2无酶传感器;并采用循环伏安和计时安培电流等方法对修饰电极的电化学性能进行了表征.结果表明:制备的Pd/Fe_3O_4/r GO/GCE对H_2O_2的催化还原显示出较好的电催化活性,Pd纳米颗粒和Fe_3O_4/rGO在催化H_2O_2还原的过程中表现出了良好的协同作用.测定H_2O_2的线性范围为0.05~1 m M和1~2.6 m M两段,最低检测限达到3.918μM(S/N=3).并且该传感器具有较高的灵敏度和较好的重现性和抗干扰性,具有一定的实际应用价值.     

Fe3O4/ 聚吡咯复合材料的制备及表征

以化学沉淀法制备Fe₃O₄ 纳米粒子, 采用乙醇对Fe₃O₄ 纳米粒子表面进行处理, 使其表面有机化, 然后通过乳液原位复合制备Fe₃O₄ / 聚吡咯复合材料。利用TEM, XPS, 四探针测试仪和震荡磁力计对其进行表征和检测。结果表明: 经醇处理的Fe₃O₄ 纳米粒子的分散性得到明显改善, Fe₃O₄ 纳米粒子被包覆在聚吡咯层内, 包覆层厚度为10 nm 左右, 复合材料具有优良的电性能和磁性能, 电导率e= 7. 69 s/ cm～13. 6 s/ cm, 饱和磁强度M_s= 12. 06 emu/ g～24. 38 emu/ g, 矫顽力H_c= 11 Oe～41 Oe。其环境稳定性明显优于纯聚吡咯。      

Fe3O4/MXene/WPU复合膜的制备及其电磁屏蔽性能

实现高电磁屏蔽性能的同时降低反射是目前电磁屏蔽材料所追求的。采用一步水热法合成直径为30～40μm,厚度为70～200 nm的Fe₃O₄纳米片,利用红外光谱、X射线衍射仪、扫描电子显微镜表征发现结晶度良好。改变Fe₃O₄纳米片含量,喷涂制备的Fe₃O₄/MXene/WPU复合膜的反射值能低至4.3 dB,反射功率(R)从0.81降至0.63,透射功率(T)仅为10^-3数量级。同样,采用水热法制备了直径为180～200 nm、分散性良好的Fe₃O₄纳米微球。同等Fe₃O₄含量下纵向对比发现,含Fe₃O₄纳米片的复合膜电磁屏蔽性能稍高于含Fe₃O₄纳米球的复合膜。     

磁性介孔TiO2/氧化石墨烯复合材料的制备及其对U(Ⅵ)的吸附

以氧化石墨烯（GO）、纳米Fe₃O₄、钛酸四丁酯（TBOT）为原料,合成了磁性介孔TiO₂/GO（Fe₃O₄@TiO₂/GO）复合材料,用其处理浓度为10 mg·L-1的含U（Ⅵ）废水。研究了Fe₃O₄@TiO₂/GO复合材料中GO含量、溶液初始pH值、Fe₃O₄@TiO₂/GO复合材料投加量、反应时间、U（Ⅵ）初始浓度及共存离子对U（Ⅵ）吸附的影响。结果表明:在pH值为6、GO质量分数为60wt%、Fe₃O₄@TiO₂/GO复合材料投加量为10 mg的条件下,Fe₃O₄@TiO₂/GO复合材料对U（Ⅵ）的吸附效果最佳,较同等条件下磁性介孔Fe₃O₄@TiO₂复合材料和GO的吸附量分别高了10.99 mg·g-1和1.91 mg·g-1。Fe₃O₄@TiO₂/GO复合材料对U（Ⅵ）的吸附180 min即达到平衡,准二级动力学模型和Freundlich吸附等温模型能很好地描述其吸附过程。解吸实验表明,经5次吸附-解吸后,U（Ⅵ）的吸附率仍高达90.86%,说明Fe₃O₄@TiO₂/GO复合材料具有较高的循环利用性能。      

Fe2O3/TNTs纳米复合材料的生物合成及其光催化性能研究

采用Shewanellaoneidensis MR-1合成Fe₂O₃/TNTs纳米复合材料,通过高分辨透射电子显微镜、扫描电子显微镜、X射线衍射仪、X射线光电子能谱仪、紫外-可见分光光度计等对Fe₂O₃/TNTs的结构和性能进行表征。结果表明,Fe₂O₃成功负载在TiO₂纳米管上;在紫外光照射下,Fe₂O₃/TNTs在60min内对苯胺蓝的脱色率可达到97.5%,表现出较好的光催化活性。Shewanellaoneidensis MR-1协同Fe₂O₃/TNTs纳米复合材料对苯胺蓝脱色率较So.neidensis MR-1提高了1.63%。     

Fe3O4-MWCNTs在环氧树脂中的定向排列

用共沉淀法制备了具有超顺磁性Fe₃O₄-MWCNTs（多壁碳纳米管）复合粒子,加入环氧树脂（EP）中,在0.6 T的弱定磁场下固化成型。采用TEM研究其定向程度及分散性,并进行动态热机械分析、差热分析和导热率测试。结果表明,MWCNTs表面包覆了磁性Fe₃O₄纳米粒子,Fe₃O₄-MWCNTs复合物按照首尾衔接的方式沿着磁场方向定向排列。Fe₃O₄-MWCNTs/EP纳米复合材料表现出明显的各向异性,垂直于Fe₃O₄-MWCNTs轴向导热率低于平行方向的导热率,Fe₃O₄-MWCNTs的加入对于平行方向的导热率影响不大。Fe₃O₄-MWCNTs的加入使环氧树脂的储能模量变小,损耗模量变大,损耗因子均大于纯环氧树脂,表现出良好的阻尼性能。当Fe₃O₄-MWCNTs与EP质量比为0.3%时,损耗因子在20 ℃的温域内大于0.7,最高值达到1.16。     

石墨烯/银纳米颗粒复合材料的制备及其对双氧水的电化学检测

以氧化石墨烯(GO)和硝酸银为原材料,聚乙烯吡咯烷酮(PVP)为还原剂和稳定剂,通过水热法制备出还原氧化石墨烯/银纳米颗粒(rGO/AgNPs)复合材料。采用透射电子显微镜(TEM)、X射线衍射(XRD)及紫外-可见分光光度计(UV-Vis)对rGO/AgNPs复合材料的形貌、组成和结构进行表征。同时,将rGO/AgNPs复合材料修饰到玻碳电极表面制备出过氧化氢(H_2O_2)电化学传感器,通过循环伏安法(CV)和计时安培响应法(i-t)对传感器进行电化学性能测试。实验结果表明:制备的rGO/AgNPs传感器具有较好的电化学性能,其对H_2O_2检测的灵敏度为340.6μA·(mmol/L)~(-1)·cm~(-2),响应时间为3s,最低检测极限为7.5μmol/L(S/N=3),线性检测范围为20~4950μmol/L(线性相关系数为R=0.9973)。     

Voltammetric detection of bisphenol a by a chitosan-graphene composite modified carbon ionic liquid electrode

In this paper 1-ethyl-3-methylimidazolium tetrafluoroborate based carbon ionic liquid electrode (CILE) was fabricated and further modified with chitosan (CTS) and graphene (GR) composite film. The fabricated CTS-GR/CILE was further used for the investigation on the electrochemical behavior of bisphenol A (BPA) by cyclic voltammetry and differential pulse voltammetry. A well-defined anodic peak appeared at 0.436 V in 0.1 mol/L pH 8.0 Britton-Robinson buffer solution, which was attributed to the electrooxidation of BPA on the modified electrode. The electrochemical parameters of BPA on the modified electrode were calculated with the results of the charge transfer coefficient (α) as 0.662 and the apparent heterogeneous electron transfer rate constant (k_s) as 1.36 s^− 1. Under the optimal conditions, a linear relationship between the oxidation peak current of BPA and its concentration can be obtained in the range from 0.1 μmol/L to 800.0 μmol/L with the limit of detection as 2.64 × 10^− 8 mol/L (3σ). The CTS-GR/CILE was applied to the detection of BPA content in plastic products with satisfactory results.     

氨基-β-环糊精-石墨烯-二茂铁修饰电极对多巴胺的电化学行为研究

利用制备的氨基-β-环糊精-石墨烯-二茂铁(β-CD-NH2/GNs/Fc)复合膜修饰电极,研究了多巴胺(DA)的电化学行为。结果表明,该复合膜修饰电极在pH值=7.00的磷酸盐缓冲溶液(PBS)中对DA有良好的电催化性能,DA的氧化峰电流在0.1～100μmol/L浓度范围内呈良好的线性关系,检出限为8.5×10-8mol/L。结果表明该修饰电极具有较高的检测灵敏度,可用于实际样品的检测。     

氮掺杂多孔碳负载铜钴纳米复合材料的制备及其电催化性能EI北大核心CSCD

先以ZIF-8作为前驱体采用简单的高温炭化法制备出氮掺杂多孔碳纳米多面体(NPC),再通过一步化学还原法将铜和钴颗粒负载到多孔碳上,成功制备出Cu@Co/NPC纳米复合材料。运用X射线粉末衍射仪、透射电子显微镜和X射线光电子能谱等手段对复合材料进行表征,将该复合材料修饰到玻碳电极表面上,研究其对肼的电化学响应。结果表明,Cu@Co/NPC纳米复合材料发挥出协同作用,从而对肼展现出比单一组分修饰电极更优异的电催化作用。在优化的实验条件下,复合材料修饰电极与肼的浓度在5~1850μmol/L范围内呈良好的线性关系,检测限达0.08μmol/L。此外,该复合材料修饰电极测定肼的稳定性、重现性以及选择性均较好,已被成功用于环境水样中肼的检测,结果令人满意。     

A methyl parathion electrochemical sensor based on Nano-TiO2, graphene composite film modified electrode

A methyl parathion electrochemical sensor based on nano-TiO₂ and graphene composite film modified glassy carbon electrode has been developed. The electrochemical behavior of MP at the sensor was investigated by cyclic voltammetry and linear sweep voltammetry. Scanning electron microscopy was used to characterize the surface morphology of nano-TiO₂ and graphene composite film. Compared with a bare glassy carbon electrode or a mono-film modified electrode, the redox peak currents of methyl parathion on the composite film modified electrode improved greatly, indicating that the sensor showed good catalytic effects. The optimal experimental condition was obtained. The results indicated that the linear sweep voltammetry responses of methyl parathion, in pH 5.2 acetate buffer solution with open-circuit accumulation for 2 min, were linear with concentrations of methyl parathion in two ranges of 0.002～5 μM and 5～100 μM. The linear equations were i_Pc(μA) = 0.0136 + 4.965c_MP(μM) (R₁² = 0.9911) and i_Pc(μA) = 21.87 + 0.8206c_MP(μM) (R₂² = 0.9914), respectively. The detection limit was 1.0 nM (S/N = 3). The sensor exhibited high sensitivity and good reproducibility as well as certain anti-interference ability. It was applied to the determination of residual MP in fresh apple sample with the recovery of 92%～102%. The result was satisfactory.     

Determination of pentachlorophenol at carbon nanotubes modified electrode incorporated with beta-cyclodextrin

A facile and reliable electrochemical technique at beta-cyclodextrin incorporated carbon nanotubes modified glassy carbon electrode (beta-CD/CNTs/GCE) was proposed for determination of pentachlorophenol (PCP). The electrochemical behavior of PCP at the beta-CD/CNTs/GCE was investigated by cyclic voltammetry and linear sweep voltammetry. The beta-CD/CNTs/GCE showed good analytical performance characteristics in electrocatalytic oxidation of PCP, compared with the simple carbon nanotube modified electrode (CNTs/GCE) and bare glassy carbon electrode (GCE). After accumulation for 5 min on beta-CD/CNTs/GCE, the peak current increased linearly with the concentration of PCP in the range from 8.0 x 10(-7) to 1.04 x 10(-5) mol/L. The detection limit was 4.0 x 10(-8) mol/L at 3 sigma level. The proposed electrode presented good repeatability for the determination of PCP in artificial wastewater, and the recovery was 97%-103%. This modified electrode combined the advantages of carbon nanotubes and supramolecular cyclodextrin, leading to new capabilities for electrochemical detection of PCP.     

MnO2纳米棒-还原石墨烯复合修饰玻碳电极用于苋菜红的检测

利用电化学还原法制备MnO₂纳米棒-还原石墨烯复合修饰电极（MnO₂ NRs-ErGO/GCE）用于苋菜红的检测。采用SEM和XRD分别对修饰电极材料进行微观形貌和成分结构表征。通过循环伏安法考察了苋菜红在裸电极、ErGO/GCE和MnO₂ NRs-ErGO/GCE上的电化学行为,并对测定条件如pH值、富集电位、富集时间进行了优化。结果表明,MnO₂ NRs-ErGO增大了GCE电化学活性面积,提高了苋菜红的电化学氧化响应。在最优的检测条件下,MnO₂ NRs-ErGO/GCE线性扫描伏安法检测苋菜红线性范围为2.0×10^-8~1.0×10^-5 mol/L和1.0×10^-5~4.0×10^-4 mol/L,检测限为1.0×10^-8 mol/L。MnO₂ NRs-ErGO/GCE用于真实饮料样品检测,获得满意结果。     

导电分子印迹膜化学修饰电极的制备及其对胭脂红的电化学检测

报道了一种聚丙烯酰胺(PAAM)-植酸(PA)-聚多巴胺(PDA)导电分子印迹膜(PAAM-PA-PDA MIP)化学修饰电极的制备、表征及其在电化学定量检测食品添加剂胭脂红(P4R)中的应用。即通过原位电聚合和碱液洗脱的方法在玻碳电极(GCE)表面制得具有分子识别作用的导电分子印迹膜(PAAM-PA-PDA MIP)化学修饰电极,并利用SEM、循环伏安法(CV)及交流阻抗法(EIS)对该导电分子印迹膜化学修饰电极的表面形貌和电化学性能进行表征。研究结果表明该方法所制备的导电分子印迹膜化学修饰电极具有良好的电化学检测性能和应用前景,其对P4R的线性检测区间为10~200 μmol/L,灵敏度为0.085 A/mol/L,检测限可达23.6 nmol/L,并可有效地应用于P4R实际样品的分析检测。      

Fabrication of nano-porous hydroxyapatite modified electrode and its application for determination of p-chlorophenol

Nano-porous hydroxyapatite (HAp) modified electrode was fabricated by simply electrodepositing HAp onto the glassy carbon electrode (GCE) from the electrolytes solution containing Ca(NO3)2 4H2O and NH4H2PO4, the resulting electrode (nano-HAp/GCE) was characterized with scanning electron microscopy (SEM). The electrochemical behavior of p-chlorophenol (p-CP) at nano-HAp/GCE was studied by cyclic voltammetry. The electrode displayed selective and enhanced electroanalytical response towards p-CP, obviously because p-CP is accumulated at the electrode. For the greater sensitivity, a semi-derivative technique was adopted to obtain the current signal. The results indicated that the nano-HAp/GCE exhibits substantial enhancement in electrochemical sensitivity for p-CP due to its large surface area and particular adsorbability. After accumulation of 4 min for p-CP on nano-HAp/GCE, the peak height was linearly related to the concentration of p-CP in the range of 1.0 x 10(-8) to 1.0 x 10(-7) mol L(-1). The detection limit was 4.0 x 10(-9) mol L-(1) at 3sigma level. Based on this, the modified electrode was successfully applied in water samples with low cost and high sensitivity.