钴化合物/有序介孔碳复合材料在电化学传感器中的应用
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摘要
近年来,碳基纳米材料以其良好的导电性和化学稳定性被广泛地应用在分析和电化学工艺中。自1999年首次成功合成有序介孔碳(OMC)这种新型碳材料以来,因其具有均一可调的孔结构、较高的比表面积,较大的孔容以及化学惰性这一系列优良的特性,它在分析中的应用倍受关注。此外,OMC可以很容易地通过价格低廉的硬模板法制得,并且在二氧化硅模板被完全去除的情况下无任何杂质污染。尤其是利用OMC作为催化载体时,它能大大增强催化剂的活性并能促进被分析物质的电子传递。因此,在电化学和电分析领域中研究OMC复合材料修饰电极受到了越来越多的关注。在本论文中,我们首次研究了新型碳材料OMC作为双核酞菁钴和介孔四氧化三钴材料的催化载体,主要包括以下几个方面的研究:
首先,我们用三嵌段共聚物P123做模板剂,正硅酸乙酯做硅源,通过溶胶-凝胶法制得了介孔氧化硅SBA-15。然后再以SBA-15为硬模板,蔗糖和硝酸钴为前驱物分别得到了OMC和介孔Co3O4材料。并用XRD,SEM,TEM和N2-吸脱附等手段对其进行了表征。
其次,我们制备了OMC/Co3O4/Nafion/GC修饰电极,并研究了该电极对水合肼的催化氧化作用。结果表明,该修饰电极对水合肼展示出很好的催化效果,且检测的灵敏度显著提高,这与该复合物中OMC和Co3O4之间存在良好的协同效应有关。该修饰电极对水合肼的测定获得了较低的检出限(0.07μM)、较快的响应时间(4 s)和较宽的线性范围(4 ~ 320μM),使该电极有望成为有效检测水合肼的电化学传感器。
此外,我们采用离子交换的方法成功地制备了一种新型的复合物修饰电极,即利用双核磺化酞菁钴(bi-CoPc)和阳离子交换剂双十二烷基二甲基溴化铵(DDAB)产生离子交换作用,首次制备了一种新型的有序介孔碳(OMC)复合物修饰电极(bi-CoPc/DDAB/OMC/GC)。我们通过紫外可见光谱(UV-vis),电子扫描显微镜(SEM)和电化学方法表征了此复合膜,并研究了它的电催化作用。结果表明,在有OMC的存在时增强了bi-CoPc的电子转移能力,进一步的研究发现bi-CoPc/DDAB/OMC膜在中性溶液中对氧气具4电子的电催化还原作用,能在较低的浓度下对血红蛋白(Hb)进行检测,此外作为2-巯基乙醇(2-ME)的安培检测传感器,有着较宽的线性范围2.5×10-6 M ~ 1.4×10-4 M,较高的灵敏度16.5μA mM-1和较低的检出限0.6μM (S/N=3)。这些都表明了此种新型的复合材料有较广阔的应用前景,将有可能在生物燃料电池,生物传感器和环境传感器等领域得到发展和应用。
In recent years, carbon based nanomaterials have been widely used in both analytical and industrial electrochemistry because of their good conductivity and chemical stability. Since one kind of novel carbon materials, i.e. ordered mesoporous carbon(OMC) was synthesized in 1999, intensive attention has been paid on the analytical application of OMC, because of its uniform and tailored pore structure, high specific surface area, large pore volume and chemical inertness. Besides, OMC can be easily prepared via the hard templating strategy with low cost and free from any impurities if the template silica walls are removed. Especially, the utilization of novel mesoporous carbon materials as a catalyst support could enhance the catalyst activity and promote the electron transfer of some analytes. Hence, more and more attention was focused on the electrochemistry and electrocatalysis of the composite materials based on OMC modified electrodes. In this paper, we have investigated the novel OMC was employed as the support for bi-CoPc and Co3O4 catalyst by the first time. This dissertation mainly consists of the following several aspects:
Firstly, we obtained the mesoporous silica SBA-15 via Sol-gel process with a triblock copolymer surfactant P123 as template and tetraethyl orthosilicate (TEOS) as organosiloxane precursor. The OMC and porous single crystals Co3O4 can be prepared using mesoporous silica SBA-15 as the hard template and using sucrose and cobaltous nitrate as the precursors, respectively. The obtained mesoporous materials were characterized by XRD, SEM, TEM and N2 adsorption–desorption.
Secondly, fabrication of the OMC/Co3O4/Nafion composite modified electrode and its application in electrocatalysis of hydrazine hydrate oxidation are studied. The modified electrode showed a good electrocatalytic response towards hydrazine hydrate and the detection sensitivity was improved dramatically because of the excellent synergistic effect in the composite. The results indicate that OMC/Co3O4/Nafion/GC electrode could be a promising candidate for effectively electrochemical sensors for the detection of hydrazine hydrate due to its very lower detection limit (0.07μM) , fast response (4 s) and wider linear range (4 ~ 320μM).
Thirdly, a new ordered mesoporous carbon (OMC) composite modified electrode was fabricated for the first time. Binuclear cobalt phthalocyaninehexasulfonate sodium salt (bi-CoPc) can be adsorbed onto didodecyldimethylammonium bromide (DDAB)/OMC film by ion exchange. UV-vis spectroscopy, scanning electron microscopy (SEM) and electrochemical methods were used to characterize the composite film. The cyclic voltammograms demonstrate that the charge transfer of bi-CoPc is promoted by the presence of OMC. Further study indicated that bi-CoPc/DDAB/OMC film is the excellent electrocatalyst for 4-electron reduction of oxygen in a neutral aqueous solution and for hemoglobin (Hb) reduction at lower concentrations. Additionally, as an amperometric 2-mercaptoethnaol (2-ME) sensor, this modified electrode shows a wider linear range (2.5×10-6 M to 1.4×10-4 M), high sensitivity (16.5μA mM-1) and low detection limit of 0.6μM (S/N=3). All these confirm the fact that the new composite film may have wide potential applications in biofuel cells, biological and environmental sensors.
首先,我们用三嵌段共聚物P123做模板剂,正硅酸乙酯做硅源,通过溶胶-凝胶法制得了介孔氧化硅SBA-15。然后再以SBA-15为硬模板,蔗糖和硝酸钴为前驱物分别得到了OMC和介孔Co3O4材料。并用XRD,SEM,TEM和N2-吸脱附等手段对其进行了表征。
其次,我们制备了OMC/Co3O4/Nafion/GC修饰电极,并研究了该电极对水合肼的催化氧化作用。结果表明,该修饰电极对水合肼展示出很好的催化效果,且检测的灵敏度显著提高,这与该复合物中OMC和Co3O4之间存在良好的协同效应有关。该修饰电极对水合肼的测定获得了较低的检出限(0.07μM)、较快的响应时间(4 s)和较宽的线性范围(4 ~ 320μM),使该电极有望成为有效检测水合肼的电化学传感器。
此外,我们采用离子交换的方法成功地制备了一种新型的复合物修饰电极,即利用双核磺化酞菁钴(bi-CoPc)和阳离子交换剂双十二烷基二甲基溴化铵(DDAB)产生离子交换作用,首次制备了一种新型的有序介孔碳(OMC)复合物修饰电极(bi-CoPc/DDAB/OMC/GC)。我们通过紫外可见光谱(UV-vis),电子扫描显微镜(SEM)和电化学方法表征了此复合膜,并研究了它的电催化作用。结果表明,在有OMC的存在时增强了bi-CoPc的电子转移能力,进一步的研究发现bi-CoPc/DDAB/OMC膜在中性溶液中对氧气具4电子的电催化还原作用,能在较低的浓度下对血红蛋白(Hb)进行检测,此外作为2-巯基乙醇(2-ME)的安培检测传感器,有着较宽的线性范围2.5×10-6 M ~ 1.4×10-4 M,较高的灵敏度16.5μA mM-1和较低的检出限0.6μM (S/N=3)。这些都表明了此种新型的复合材料有较广阔的应用前景,将有可能在生物燃料电池,生物传感器和环境传感器等领域得到发展和应用。
In recent years, carbon based nanomaterials have been widely used in both analytical and industrial electrochemistry because of their good conductivity and chemical stability. Since one kind of novel carbon materials, i.e. ordered mesoporous carbon(OMC) was synthesized in 1999, intensive attention has been paid on the analytical application of OMC, because of its uniform and tailored pore structure, high specific surface area, large pore volume and chemical inertness. Besides, OMC can be easily prepared via the hard templating strategy with low cost and free from any impurities if the template silica walls are removed. Especially, the utilization of novel mesoporous carbon materials as a catalyst support could enhance the catalyst activity and promote the electron transfer of some analytes. Hence, more and more attention was focused on the electrochemistry and electrocatalysis of the composite materials based on OMC modified electrodes. In this paper, we have investigated the novel OMC was employed as the support for bi-CoPc and Co3O4 catalyst by the first time. This dissertation mainly consists of the following several aspects:
Firstly, we obtained the mesoporous silica SBA-15 via Sol-gel process with a triblock copolymer surfactant P123 as template and tetraethyl orthosilicate (TEOS) as organosiloxane precursor. The OMC and porous single crystals Co3O4 can be prepared using mesoporous silica SBA-15 as the hard template and using sucrose and cobaltous nitrate as the precursors, respectively. The obtained mesoporous materials were characterized by XRD, SEM, TEM and N2 adsorption–desorption.
Secondly, fabrication of the OMC/Co3O4/Nafion composite modified electrode and its application in electrocatalysis of hydrazine hydrate oxidation are studied. The modified electrode showed a good electrocatalytic response towards hydrazine hydrate and the detection sensitivity was improved dramatically because of the excellent synergistic effect in the composite. The results indicate that OMC/Co3O4/Nafion/GC electrode could be a promising candidate for effectively electrochemical sensors for the detection of hydrazine hydrate due to its very lower detection limit (0.07μM) , fast response (4 s) and wider linear range (4 ~ 320μM).
Thirdly, a new ordered mesoporous carbon (OMC) composite modified electrode was fabricated for the first time. Binuclear cobalt phthalocyaninehexasulfonate sodium salt (bi-CoPc) can be adsorbed onto didodecyldimethylammonium bromide (DDAB)/OMC film by ion exchange. UV-vis spectroscopy, scanning electron microscopy (SEM) and electrochemical methods were used to characterize the composite film. The cyclic voltammograms demonstrate that the charge transfer of bi-CoPc is promoted by the presence of OMC. Further study indicated that bi-CoPc/DDAB/OMC film is the excellent electrocatalyst for 4-electron reduction of oxygen in a neutral aqueous solution and for hemoglobin (Hb) reduction at lower concentrations. Additionally, as an amperometric 2-mercaptoethnaol (2-ME) sensor, this modified electrode shows a wider linear range (2.5×10-6 M to 1.4×10-4 M), high sensitivity (16.5μA mM-1) and low detection limit of 0.6μM (S/N=3). All these confirm the fact that the new composite film may have wide potential applications in biofuel cells, biological and environmental sensors.
引文
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