結合石墨烯氧化物及金屬鐵氰化物應用於電化學感測器

Incorporation of Metal Hexacyanoferrate on Graphene oxide and its Electrochemical Sensor Applications

葉懷澤(Huai-Tse Yeh)

指導教授 ： 陳生明

國立臺北科技大學/工程學院/化學工程研究所/碩士(2014年)

https://doi.org/10.6841/NTUT.2014.00057

摘要

以電化學方法在還原態石墨烯氧化物(RGO)修飾玻璃碳電極(GCE)上製備花型鐵氰化釔(YHCF)顆粒修飾薄膜，一開始以不同莫耳比例的硝酸釔及鐵氰化鉀來控制YHCF的顆粒型態，利用掃描電子顯微鏡(SEM)和能量色散型X射線裝置(EDX)和紅外線光譜學(IR)和X光繞射法(XRD)來研究RGO/YHCF複合材料的表面型態及組成，利用循環伏安法(CV)及線性掃描伏安法(LSV)來偵測RGO/YHCH修飾電極對對乙醯氨基酚(PA)的電催化活性，此外，此修飾電極可實際應用於偵測市售的對乙醯氨基酚片。

我們開發了一個簡單的電化學方法合成星型結構的鐵氰化鑥(LuHCF)，控制LuHCF的平均大小在7+8μM，在將LuHCF固定在RGO/GCE上，LuHCF顆粒的尺寸大小及表面形態是由沉積時間來控制，該LuHCF的表面型態由掃描電子顯微鏡(SEM)、紅外光譜(IR)和能量色散譜測定(EDX)，LuHCF/RGO/GCE的電化學阻抗比LuHCF/GCE及GCE還來的小，以循環伏安法及電流分析法測定後發現此複合膜修飾電極對水楊酸(SA)有良好的電催化活性，經計算後其偵測極限與靈敏度分別為0.49 μA and 77.2 μA mM-1cm-2，不僅如此，還可對市售的阿斯匹靈及水楊酸軟膏實際偵測，且具有良好的穩定性。

第三部分在此我們研發對尼古丁有高靈敏度的鐵氰化鈀(PdHCF)與石墨烯氧化物複合材料感測器，利用電化學方法將鐵氰化鈀顆粒電沉積析出，再利用循環伏安法(CV)、定電位計時安培法、電化學阻抗譜(EIS)和掃描式電子顯微鏡(SEM)對此材料進行電催化活性及表面形態研究。這種結合PdHCF/GO複合電極具有對尼古丁良好的電催化活性，膜上的GO具有很大的比表面積及增加PdHCF奈米粒子之電子轉移能力，此修飾電極對尼古丁的偵測線性範圍從8 μM到240 μM，靈敏度經測試後為1.208 μA μM-1cm-2，且修飾薄膜具有良好的穩定性。

關鍵字

花型鐵氰化釔 ； 還原態石墨烯氧化物 ； 電化學 ； 電催化活性 ； 對乙醯氨基酚 ； 鐵氰化鑥水楊酸 ； 鐵氰化鈀 ； 石墨烯氧化物 ； 尼古丁 ； 計時安培法

並列摘要

Herein, we report a template free and surfactant less electrochemical approach for the preparation of flower-like yttrium hexacyanoferrate (YHCF) particles on reduced graphene oxide (RGO) modified glassy carbon electrode (GCE). The morphology of YHCF particles has been controlled by varying the molar ratio of Y(NO3)2 and K3Fe(CN)6 for the first time. The surface morphology of as-prepared RGO/YHCF composite was characterized using SEM, EDX, IR and XRD methods. The electrocatalytic activity of the RGO/YHCF composite modified GCE towards paracetamol (PA) oxidation has been investigated by using cyclic voltammetry (CV) and linear sweep voltammetry (LSV). Besides, the practical feasibility of the fabricated modified GCE has been demonstrated through the determination of PA from commercially purchased paracetamol tablets.

First time we developed a facile electrochemical route for the synthesis of Lutetium hexacyanoferrate (LuHCF) building of stars like structure. The controlled synthesis of LuHCF particles having star like structure with average size of 7 + 8 μm. The LuHCF micro stars building is decorated on graphene oxide (GO) modified GCE. The electrochemical route is continued for the preparation of LuHCF/reduced graphene oxide (RGO) composite modified GCE. The size and morphology of the as synthesised LuHCF micro stars were controlled by depositing time. The LuHCF micro stars building was characterized by scanning electron microscopy (SEM), Infra-red spectroscopy, and energy dispersive spectroscopy. The charge transfer resistant value of LuHCF/RGO/GCE has smaller than LuHCF and unmodified GCE. The composite modified GCE has excellent electro catalytic activity towards salicylic acid (SA). The electro catalytic measurements were performed with cyclic voltammetry and amperometric methods. The detection limit and sensitivity of the SA sensor has been calculated as 0.49 μA and 77.2 μA mM-1cm-2 respectively. The reported GCE has excellent real time application with commercially purchased aspirin tablets and salicylic acid ointment. Moreover, the reported composite has long term storage stability.

Herein, we report highly sensitive amperometric nicotine (NIC) sensor using composite of palladium hexacyanoferrate (PdHCF) with graphene oxide (GO) modified GCE. The PdHCF particle was deposited using electrochemical route. The electro catalytic measurements and surface morphology of the as prepared composite was studied using cyclic voltammetry (CV), amperometry, electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (FESEM) respectively. This PdHCF incorporated GO composite modified GCE (PdHCF/GO) exhibits a prominent electro catalytic activity towards the voltammetric determination of NIC. The presence of the GO in the film enhances the surface coverage concentration and also increases the electron transfer rate constant, of the PdHCF nanoparticles. The modified electrode shows the linear range of 8 μM to 240 μM for NIC. The sensitivity has been found as 1.208 μA μM-1cm-2. Moreover the proposed film has long term stability.

並列關鍵字

Flower-like YHCF ； Reduced Graphene oxide ； electrochemical ； electrocatalytic activity ； paracetamol ； LuHCF ； micro star ； Salicylic acid ； palladium hexacyanoferrate ； graphene oxide ； nicotine ； amperometry

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