含钕类普鲁士蓝化学修饰电极对甲酸的电催化氧化研究
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摘要
直接甲酸燃料电池(DFAFC)是一种以甲酸为阳极燃料,并使其直接在电极上进行氧化反应从而转化出电能一种能源装置。DFAFC具有结构简单,燃料补充方便,效率高等一系列优点。在DFAFC中,阳极催化剂对甲酸的氧化效率以及电池的耐用性有着非常重要的影响。因此,寻找对甲酸电催化氧化具有高催化活性的催化剂是十分重要的研究课题。
基于以上原因,本文以含钕类普鲁士蓝修饰电极为基础,并复合了铂微粒、聚苯胺制备了几种多元混配物复合电极,这几种新型修饰电极对甲酸的电催化氧化均具有较高的催化活性,良好的抗毒化性以及稳定性,以其作为DFAFC的阳极催化剂具有很好的应用研究价值。
论文共分为四章:
第一章:综述
该部分主要介绍了化学修饰电极,以及多核过渡金属铁氰化物薄膜修饰电极及其制备应用。并简述了直接甲酸燃料电池的发展及存在的问题,对作为直接甲酸燃料电池中阳极催化剂载体的有机导电聚合物种类及聚苯胺的结构性质进行了详细的阐述。
第二章:首次用电沉积法制备了Nd-Fe-WO_4~(2-)氰桥混配物修饰铂电极(Nd-Fe-WO_4~(2-)/Pt),并通过SEM和XRD技术分别表征了该修饰电极的表面形貌和修饰物的晶相结构。采用循环伏安法和计时电流法研究了甲酸在该修饰电极上的电氧化行为,实验发现甲酸在修饰电极上的电催化氧化电流密度与裸铂电极相比增加了10余倍,而且CV回扫阳极电位边界对属于吸附中间体的反扫峰形状有很大影响。此外,还研究了支持电解质中H~+和SO_4~(2-)浓度变化对甲酸氧化过程伏安特性的影响。结果表明:甲酸电催化主氧化峰的电位随H~+浓度的增加而正向移动,随SO_4~(2-)浓度增加而负向移动;当这两种离子共存时,H~+的影响起主导作用。这表明甲酸在该修饰电极上电催化氧化反应的速率控制步骤是脱质子过程,而且SO_4~(2-)/HSO_4~-在电极表面的吸附有利于氧化反应正向进行。以上结论为解释甲酸的电催化氧化机理提供了新的实验依据。同时,计时电流曲线和电极稳定性实验均表明该修饰电极对甲酸的电催化氧化过程具有良好的催化活性和抗毒化能力。
第三章:本文采用电沉积法在Nd-Fe-WO_4~(2-)氰桥混配物修饰铂电极基底上制备了铂微粒/Nd-Fe-WO_4~(2-)氰桥混配物复合修饰铂电极(Pt/ Nd-Fe-WO_4~(2-)/Pt),用SEM表征了该电极的表面形貌。考察了沉积电位、沉积时间、氯铂酸浓度、起扫电位静息时间对甲酸电催化氧化的影响。并用循环伏安和计时电流法考察了该修饰电极对甲酸的电催化氧化性能,实验结果表明,甲酸在该修饰电极上的电催化氧化峰电流密度约是Nd-Fe-WO_4~(2-)/Pt电极的10倍,而且扫速在50 mV/s ~450 mV/s之间时,氧化电流密度与扫描速率的平方根在呈良好的线性关系。此外,还研究了回扫阳极边界对甲酸电催化氧化的影响,当回扫阳极电位较低时,毒性中间体的氧化溶出反应被抑制,不利于甲酸氧化反应的发生。
第四章本文采用电化学方法制备了聚苯胺分散铂微粒/Nd-Fe-WO_4~(2-)氰桥混配物复合修饰铂电极(PAn-Pt/ Nd-Fe-WO_4~(2-)/Pt),通过SEM对其进行了表征,并采用循环伏安法和计时电流法研究了甲酸在该电极上的电催化氧化行为。实验发现,甲酸在该修饰电极上的反应与温度密切相关,氧化电流密度与温度分别在25~40℃和45~55℃范围内呈良好的线性关系,且低温区温度系数约是高温区温度系数的4倍。扫描速度的平方根与甲酸电催化氧化电流密度呈良好的线性关系,说明甲酸在该修饰电极上的氧化反应是受扩散控制的,而且甲酸电催化氧化CV曲线中PtO与CO2的还原峰随回扫阳极电位边界的增加而逐渐增大。此外,这种将无机聚合物Nd-Fe-WO_4~(2-)膜与有机导电聚合物聚苯胺膜相结合,并与分散铂微粒共同修饰制备的新型复合电极的催化性能、稳定性、抗毒化性均与Pt/ Nd-Fe-WO_4~(2-)/Pt电极相当,由此可以得出这种复合聚合物Nd-Fe-WO_4~(2-)膜也具有良好的伏安性能。
Direct formic acid fuel cell (DFAFC) is a new energy installations, formic acid is adopted as its anode fuel and converted into electric energy by reacting on the electrode.DFAFC have a lot of advantages, such as the simple structure, high efficiency and high convenience of adding fuel, etc. Anode catalyst has great impact on the oxidation efficiency of formic acid and the durable property of the fuel cell in DFAFC. Therefore, looking for the catalyst possessed high catalytic activity becomes a very important research topic.
For the above reasons, based on contained-Nd Prussian blue analoge modified electrode, we prepared several multiple mixture modified electrodes complexed Pt particles and polyaniline. These newly modified electrodes were all possessed high catalytic activity, better tolerance to toxic intermediate contamination, and high stability to the electrocatalytic oxidation of formic acid. These electrodes will have excellent application and research value as anode catalyst of DFAFC.
There were four chapters in this paper:
Chapter one: This section mainly introduced the chemically modified electrode, the polynuclear transition metal hexacyanoferrates modified electrode, the preparation and application of polynuclear transition metal hexacyanoferrates modified electrode. The development and problems existed in DFAFC were introduced in brief, the kinds of organic conductive polymers, which acted as carrier of anode catalyst in DFAFC were also discussed. The structure and properties of polyaniline were described in detail.
Chapter two: Nd-Fe-WO_4~(2-) cyanide-bridged mixed complexes modified platinum electrode was successfully prepared by using electrodeposition method for the first time. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) were employed to characterize the morphology and crystalline lattice structure of the modified materials. Formic acid electrocatalytic oxidation behavior on this modified electrode was evaluated by means of cyclic voltammetry and chronoamperometry. The results indicated that the electrocatalytic oxidation current density of formic acid on modified electrode was about 10 times more than on bare Pt electrode,and CV anodic limit potential had significant effect on peak figuration of absorption intermediate in the reverse scan. Moreover, the influence of H~+ and SO_4~(2-) concentration in electrolyte solution on the voltammetric characteristics of formic acid electrocatalytic oxidation was also studied, it showed that the peak potential increased with increasing H~+ concentration, however, decreased with increasing SO_4~(2-) concentration, but being coexistence of H~+ and SO_4~(2-), the effect of H~+ played a dominant role. This phenomenon revealed that the rate-determining step of electrocatalytic oxidation of formic acid on modified electrode was correlative with deprotonation process, and the adsorption of SO_4~(2-)/HSO_4~- would promote the forward oxidation reaction. These conclusions provided new experimental evidences for explaining the mechanism of formic acid electrocatalytic oxidation. Meanwhile, the electrode stability experiments as well as chronoamperometry also demonstrated that the newly developed modified electrode possessed much better electrocatalytic activity and tolerance to toxic intermediate contamination.
Chapter three: Based on Nd-Fe-WO_4~(2-) cyanide-bridged mixed complexes modified platinum electrode, the new Pt/Nd-Fe-WO_4~(2-)/Pt modified electrode was prepared by means of electrodeposition. The morphology of this modified electrode was characterized by SEM. The effect factors of formic electrocatalytic oxidationon, such as deposition potential, deposition time, the concentration of H2PtCl6 and quiet time were investigated. Formic acid electrocatalytic oxidation behavior on this modified electrode was evaluated by means of cyclic voltammetry and chronoamperometry. The results indicated that the electrocatalytic oxidation current density of formic acid on the modified electrode was about 10 times more than that on Nd-Fe-WO_4~(2-)/Pt electrode, and when the scan rate was between 50 mV/s and 450 mV/s, oxidation current density of formic acid and the root of scan rate showed good linear relationship. Furthermore, the effect of anode limit in the reverse scan on formic acid electrocatalytic oxidation was also studied. When the anode limit was lower, the oxidation reaction of toxic intermediate was suppressed, it was not conducive to the oxidation reaction of formic acid.
Chapter four : PAn-Pt/ Nd-Fe-WO_4~(2-)/Pt modified electrode was successfully prepared by using electrochemical method, SEM was employed to characterize the morphology of electrode, formic acid electrocatalytic oxidation behavior on this modified electrode was evaluated by means of cyclic voltammetry and chronoamperometry. The results indicated that the reaction of formic acid on this modified electrode was closed related to temperature, the electrocatalytic oxidation current density and temperature showed good linear relationship between the range of 25~40℃and 45~55℃,and the temperature coefficient of low temperature area was about 4 times more than that in high temperature area. The good linearity between square root of scan rate and current density of formic acid electrocatalytic oxidation indicated that formic acid oxidation on the modified electrode was controlled by diffusion. The reduction peak of PtO and CO2 increased with increasing anode limit in the reverse scan at CV of formic acid electrocatalytic oxidation. Moreover, the catalytic activity, stability and tolerance to toxic intermediate contamination of the newly complex electrode, which composed with inorganic polymer Nd-Fe-WO_4~(2-) membrane, organic conductive polymer polyaniline film and platinum particles, were the same as Pt/ Nd-Fe-WO_4~(2-)/Pt electrode, so we could conclude that the Inorganic polymer Nd-Fe-WO_4~(2-) film also showed excellent voltammetry property.
基于以上原因,本文以含钕类普鲁士蓝修饰电极为基础,并复合了铂微粒、聚苯胺制备了几种多元混配物复合电极,这几种新型修饰电极对甲酸的电催化氧化均具有较高的催化活性,良好的抗毒化性以及稳定性,以其作为DFAFC的阳极催化剂具有很好的应用研究价值。
论文共分为四章:
第一章:综述
该部分主要介绍了化学修饰电极,以及多核过渡金属铁氰化物薄膜修饰电极及其制备应用。并简述了直接甲酸燃料电池的发展及存在的问题,对作为直接甲酸燃料电池中阳极催化剂载体的有机导电聚合物种类及聚苯胺的结构性质进行了详细的阐述。
第二章:首次用电沉积法制备了Nd-Fe-WO_4~(2-)氰桥混配物修饰铂电极(Nd-Fe-WO_4~(2-)/Pt),并通过SEM和XRD技术分别表征了该修饰电极的表面形貌和修饰物的晶相结构。采用循环伏安法和计时电流法研究了甲酸在该修饰电极上的电氧化行为,实验发现甲酸在修饰电极上的电催化氧化电流密度与裸铂电极相比增加了10余倍,而且CV回扫阳极电位边界对属于吸附中间体的反扫峰形状有很大影响。此外,还研究了支持电解质中H~+和SO_4~(2-)浓度变化对甲酸氧化过程伏安特性的影响。结果表明:甲酸电催化主氧化峰的电位随H~+浓度的增加而正向移动,随SO_4~(2-)浓度增加而负向移动;当这两种离子共存时,H~+的影响起主导作用。这表明甲酸在该修饰电极上电催化氧化反应的速率控制步骤是脱质子过程,而且SO_4~(2-)/HSO_4~-在电极表面的吸附有利于氧化反应正向进行。以上结论为解释甲酸的电催化氧化机理提供了新的实验依据。同时,计时电流曲线和电极稳定性实验均表明该修饰电极对甲酸的电催化氧化过程具有良好的催化活性和抗毒化能力。
第三章:本文采用电沉积法在Nd-Fe-WO_4~(2-)氰桥混配物修饰铂电极基底上制备了铂微粒/Nd-Fe-WO_4~(2-)氰桥混配物复合修饰铂电极(Pt/ Nd-Fe-WO_4~(2-)/Pt),用SEM表征了该电极的表面形貌。考察了沉积电位、沉积时间、氯铂酸浓度、起扫电位静息时间对甲酸电催化氧化的影响。并用循环伏安和计时电流法考察了该修饰电极对甲酸的电催化氧化性能,实验结果表明,甲酸在该修饰电极上的电催化氧化峰电流密度约是Nd-Fe-WO_4~(2-)/Pt电极的10倍,而且扫速在50 mV/s ~450 mV/s之间时,氧化电流密度与扫描速率的平方根在呈良好的线性关系。此外,还研究了回扫阳极边界对甲酸电催化氧化的影响,当回扫阳极电位较低时,毒性中间体的氧化溶出反应被抑制,不利于甲酸氧化反应的发生。
第四章本文采用电化学方法制备了聚苯胺分散铂微粒/Nd-Fe-WO_4~(2-)氰桥混配物复合修饰铂电极(PAn-Pt/ Nd-Fe-WO_4~(2-)/Pt),通过SEM对其进行了表征,并采用循环伏安法和计时电流法研究了甲酸在该电极上的电催化氧化行为。实验发现,甲酸在该修饰电极上的反应与温度密切相关,氧化电流密度与温度分别在25~40℃和45~55℃范围内呈良好的线性关系,且低温区温度系数约是高温区温度系数的4倍。扫描速度的平方根与甲酸电催化氧化电流密度呈良好的线性关系,说明甲酸在该修饰电极上的氧化反应是受扩散控制的,而且甲酸电催化氧化CV曲线中PtO与CO2的还原峰随回扫阳极电位边界的增加而逐渐增大。此外,这种将无机聚合物Nd-Fe-WO_4~(2-)膜与有机导电聚合物聚苯胺膜相结合,并与分散铂微粒共同修饰制备的新型复合电极的催化性能、稳定性、抗毒化性均与Pt/ Nd-Fe-WO_4~(2-)/Pt电极相当,由此可以得出这种复合聚合物Nd-Fe-WO_4~(2-)膜也具有良好的伏安性能。
Direct formic acid fuel cell (DFAFC) is a new energy installations, formic acid is adopted as its anode fuel and converted into electric energy by reacting on the electrode.DFAFC have a lot of advantages, such as the simple structure, high efficiency and high convenience of adding fuel, etc. Anode catalyst has great impact on the oxidation efficiency of formic acid and the durable property of the fuel cell in DFAFC. Therefore, looking for the catalyst possessed high catalytic activity becomes a very important research topic.
For the above reasons, based on contained-Nd Prussian blue analoge modified electrode, we prepared several multiple mixture modified electrodes complexed Pt particles and polyaniline. These newly modified electrodes were all possessed high catalytic activity, better tolerance to toxic intermediate contamination, and high stability to the electrocatalytic oxidation of formic acid. These electrodes will have excellent application and research value as anode catalyst of DFAFC.
There were four chapters in this paper:
Chapter one: This section mainly introduced the chemically modified electrode, the polynuclear transition metal hexacyanoferrates modified electrode, the preparation and application of polynuclear transition metal hexacyanoferrates modified electrode. The development and problems existed in DFAFC were introduced in brief, the kinds of organic conductive polymers, which acted as carrier of anode catalyst in DFAFC were also discussed. The structure and properties of polyaniline were described in detail.
Chapter two: Nd-Fe-WO_4~(2-) cyanide-bridged mixed complexes modified platinum electrode was successfully prepared by using electrodeposition method for the first time. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) were employed to characterize the morphology and crystalline lattice structure of the modified materials. Formic acid electrocatalytic oxidation behavior on this modified electrode was evaluated by means of cyclic voltammetry and chronoamperometry. The results indicated that the electrocatalytic oxidation current density of formic acid on modified electrode was about 10 times more than on bare Pt electrode,and CV anodic limit potential had significant effect on peak figuration of absorption intermediate in the reverse scan. Moreover, the influence of H~+ and SO_4~(2-) concentration in electrolyte solution on the voltammetric characteristics of formic acid electrocatalytic oxidation was also studied, it showed that the peak potential increased with increasing H~+ concentration, however, decreased with increasing SO_4~(2-) concentration, but being coexistence of H~+ and SO_4~(2-), the effect of H~+ played a dominant role. This phenomenon revealed that the rate-determining step of electrocatalytic oxidation of formic acid on modified electrode was correlative with deprotonation process, and the adsorption of SO_4~(2-)/HSO_4~- would promote the forward oxidation reaction. These conclusions provided new experimental evidences for explaining the mechanism of formic acid electrocatalytic oxidation. Meanwhile, the electrode stability experiments as well as chronoamperometry also demonstrated that the newly developed modified electrode possessed much better electrocatalytic activity and tolerance to toxic intermediate contamination.
Chapter three: Based on Nd-Fe-WO_4~(2-) cyanide-bridged mixed complexes modified platinum electrode, the new Pt/Nd-Fe-WO_4~(2-)/Pt modified electrode was prepared by means of electrodeposition. The morphology of this modified electrode was characterized by SEM. The effect factors of formic electrocatalytic oxidationon, such as deposition potential, deposition time, the concentration of H2PtCl6 and quiet time were investigated. Formic acid electrocatalytic oxidation behavior on this modified electrode was evaluated by means of cyclic voltammetry and chronoamperometry. The results indicated that the electrocatalytic oxidation current density of formic acid on the modified electrode was about 10 times more than that on Nd-Fe-WO_4~(2-)/Pt electrode, and when the scan rate was between 50 mV/s and 450 mV/s, oxidation current density of formic acid and the root of scan rate showed good linear relationship. Furthermore, the effect of anode limit in the reverse scan on formic acid electrocatalytic oxidation was also studied. When the anode limit was lower, the oxidation reaction of toxic intermediate was suppressed, it was not conducive to the oxidation reaction of formic acid.
Chapter four : PAn-Pt/ Nd-Fe-WO_4~(2-)/Pt modified electrode was successfully prepared by using electrochemical method, SEM was employed to characterize the morphology of electrode, formic acid electrocatalytic oxidation behavior on this modified electrode was evaluated by means of cyclic voltammetry and chronoamperometry. The results indicated that the reaction of formic acid on this modified electrode was closed related to temperature, the electrocatalytic oxidation current density and temperature showed good linear relationship between the range of 25~40℃and 45~55℃,and the temperature coefficient of low temperature area was about 4 times more than that in high temperature area. The good linearity between square root of scan rate and current density of formic acid electrocatalytic oxidation indicated that formic acid oxidation on the modified electrode was controlled by diffusion. The reduction peak of PtO and CO2 increased with increasing anode limit in the reverse scan at CV of formic acid electrocatalytic oxidation. Moreover, the catalytic activity, stability and tolerance to toxic intermediate contamination of the newly complex electrode, which composed with inorganic polymer Nd-Fe-WO_4~(2-) membrane, organic conductive polymer polyaniline film and platinum particles, were the same as Pt/ Nd-Fe-WO_4~(2-)/Pt electrode, so we could conclude that the Inorganic polymer Nd-Fe-WO_4~(2-) film also showed excellent voltammetry property.
引文
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