Preparation and electrochemical performance of Au-Pt nanoparticles/graphene-cellulose microfiber composite electrodes
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摘要: 石墨烯和金属纳米是优异的导电纳米材料，为构建具有高效活性表面积的电化学传感界面，以玻碳电极作为导电基底，采用滴涂法结合一步电沉积成功制备了Au-Pt纳米颗粒/还原氧化石墨烯-纤维素微纤维(Au-Pt NPs/RGO-CMF)复合材料。SEM、原子力显微镜(AFM)、EDS和拉曼光谱分析表明，Au-Pt纳米颗粒均匀分布在RGO-CMF的薄层上，同时实现了氧化石墨烯(GO)还原为RGO。以铁氰化钾作为氧化还原探针对界面的电化学性质进行研究，在优化的实验条件下(循环伏安法电沉积：电位为−1.2~0 V，周期为20，电解质pH值为6，滴涂GO-CMF体积为8 μL)，得到Au-Pt NPs/RGO-CMF复合材料的高效活性表面积(3.54 cm2)远远优于裸玻碳电极(1.52 cm2)。表明构建界面具有高的电催化活性，为传感器的进一步应用提供理论支持。Abstract: The graphene and metal nano-materials are excellent conductive nanomaterials. In order to construct an electrochemical sensing interface with high-efficiency active surface area, glassy carbon electrode was used as a conductive substrate, and Au-Pt nano particles/reduced graphene oxide-cellulose microfiber (Au-Pt NPs/RGO-CMF) composites were successfully prepared by drip coating combined with one-step electrodeposition. The SEM, atomic force microscopy (AFM), EDS and Raman spectroscopy analysis show that Au-Pt nanoparticles are uniformly distributed on the thin layer of RGO-CMF, and at the same time, graphene oxide (GO) reduce to RGO. Using potassium ferricyanide as a redox probe to study the electrochemical properties of the interface, under optimized experimental conditions (cyclic voltammetry electrodeposition: Potential is −1.2-0 V, period is 20, electrolyte pH value is 6, drops coated GO-CMF volume is 8 μL), the high-efficiency active surface area of Au-Pt NPs/RGO-CMF composites (3.54 cm2) is much better than that of bare glassy carbon electrode (1.52 cm2). It shows that the constructed interface has high electrocatalytic activity, which provides theoretical support for the further application of the sensor.
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Key words:
- graphene oxide /
- cellulose microfiber /
- Au-Pt nanoparticles /
- composites /
- electrochemical properties
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图 1 Au-Pt纳米颗粒/还原氧化石墨烯-纤维素微纤维(Au-Pt NPs/RGO-CMF)复合膜修饰电极的制备过程
Figure 1. Preparation process of Au-Pt nano particles/reduced graphene oxide-cellulose microfiber (Au-Pt NPs/RGO-CMF) composite film modified electrode
图 2 氧化石墨烯(GO)、GO-CMF、Au NPs/RGO-CMF、Pt NPs/RGO-CMF、Au-Pt NPs/RGO和Au-Pt NPs/RGO-CMF复合膜的SEM图像
Figure 2. SEM images of graphene oxide (GO), GO-CMF, Au NPs/RGO-CMF, Pt NPs/RGO-CMF, Au-Pt NPs/RGO and Au-Pt NPs/RGO-CMF composite films
图 3 GO-CMF和Au-Pt NPs/RGO-CMF复合膜的2D和3D原子力显微镜(AFM)图像
Figure 3. 2D and 3D atomic force micro-scopy (AFM) images of GO-CMF and Au-Pt NPs/RGO-CMF composite films
图 4 Au-Pt NPs/RGO-CMF复合膜的SEM图像(a)和EDS图谱(b)
Figure 4. SEM image (a) and EDS spectrum (b) of Au-Pt NPs/RGO-CMF composite film
图 5 GO、GO-CMF和Au-Pt NPs/RGO-CMF复合膜的拉曼光图谱
Figure 5. Raman spectra of GO, GO-CMF and Au-Pt NPs/RGO-CMF composite films
图 6 Au NPs、Pt NPs和Au-Pt NPs/RGO-CMF复合膜修饰玻碳电极(GCE)的循环伏安(CV)曲线(扫描速度为50 mV/s，沉积周期为20)
Figure 6. Cyclic voltammetry (CV) curves of Au NPs, Pt NPs and Au-Pt NPs/ RGO-CMF composite films modified glassy carbon electrodes (GCE) (Scanning speed is 50 mV/s, deposition period is 20)
图 7 不同修饰的GCE电极的CV曲线(a)和电化学阻抗(EIS) (b)图谱(内插图：峰电流Ipa的趋势；CV 扫描速度为0.1 V/s)
Figure 7. CV curves (a) and electrochemical impedance spectra (EIS) (b) of different modified electrodes (Inset: Trend of peak current Ipa; CV scanning speed is 0.1 V/s)
图 8 不同扫描速率下Au-Pt NPs沉积电位(a)、沉积周期(b)、电解质pH值(c)和GO-CMF复合材料的滴涂量(d)对5 mmol/L Fe(CN)63−峰值电流的影响
Figure 8. Influence of Au-Pt NPs deposition potential (a), deposition cycle (b), electrolyte pH value (c) and amount of drip coating of GO-CMF composites (d) at different scanning speeds on peak current of 5 mmol/L Fe(CN)63−
图 9 不同扫描速率下Au-Pt NPs/RGO-CMF复合膜修饰GCE的CV曲线(扫描速率a~g依次为0.05、0.075、0.1、0.125、0.15、0.175、0.2 mV/s) (a)；Au-Pt NPs/RGO-CMF复合膜修饰GCE的峰值电流与扫描速率的函数关系(用于计算有效活性表面积) (b)
Figure 9. CV curves of Au-Pt NPs/RGO-CMF composite films modified GCE in 0.2 mol/L KCl containing 5 mmol/L Fe(CN)63− at different scanning speeds (Scanning speed a–g are 0.05, 0.075, 0.1, 0.125, 0.15, 0.175, 0.2 mV/s) (a); Function relationship between peak current and scan rate of Au-Pt NPs/RGO-CMF composite films modified GCE (Used to calculate effective active surface area) (b)
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