纳米多孔钯、钯—金和钯-钌电极的制备及电催化活性
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摘要
直接液体燃料电池在手机、笔记本、音乐播放器等便携式电源领域具有广阔的应用前景,其能量转换效率高、对环境污染小、燃料来源范围宽广、储存以及运输方便等优点,已经得到世界范围内的重视和关注。如何降低贵金属用量、提高催化剂电活性以及寻找高效、价格低廉的非铂催化剂,是目前燃料电池商业化过程中亟待解决的核心问题。上世纪九十年代开始,有机小分子的电催化氧化研究就受到国内外许多科研机构的高度重视,深入研究有机小分子电催化氧化过程,对认识电化学现象,发展电极过程动力学,完善电化学氧化机理具有重要的科学与实践意义。铂、钯、金、银等贵金属对小分子的电催化性能已被广泛研究,探索电催化活性优良的修饰电极是一个十分重要的课题。
本文开展了用于甲醇、乙醇、甲酸、甲醛氧化和过氧化氢还原的新型电催化剂探索和研究,从添加络合剂,选用不同的还原剂来改进电催化剂性能,制备出结构新颖,催化活性高的新型催化剂,并通过扫描电子显微镜(SEM)、能量散射光谱(EDS)、循环伏安法(CV)、恒电位阶跃(CA)、线性扫描法(LSV)、交流阻抗法(EIS)等分析测试技术,对催化剂的结构、形貌、电化学性能等进行了详细具体研究。
本论文的主要内容和研究结论如下:
1.对钯电极的应用、研究进展和制备方法进行概述,阐述了甲醇、乙醇、甲酸、甲醛等有机小分子的电催化氧化以及过氧化氢的还原机理,得出催化剂纳米化是当前开发催化剂的主要思路。
2.确定了纳米钯系列催化剂的具体制备过程。本研究中以EDTA为添加剂,分别以甲醛、乙二醇、聚乙二醇为还原剂,利用水热法,通过改变溶液组成制备不同的纳米钯电极;以EDTA为络合剂和甲醛做还原剂制备出纳米钯电极,然后在此电极上恒电位沉积金,得到金修饰钯电极;以EDTA为络合剂、甲醛做还原剂制备出钯钌双金属电极。金属催化剂能够以纳米小颗粒直接沉积于钛基体表面,而且催化剂颗粒结构稳定。
3.利用扫描电子显微镜(SEM)和能谱分析(EDS)测试技术,对所制备的nanoPd、Au/nanoPd、nanoPdRu电极的结构与成分进行了表征和分析,主要结论如下:
(1)不同溶液组成制备的nanoPd电极:nanoPd/PEG催化剂颗粒大小不均匀,电极表面多孔结构也不是很明显,颗粒的边角轮廓模糊,整体感觉催化剂颗粒“淹没”于黑暗中。nanoPd-EDTA/PEG催化剂颗粒明显变小,粒子之间相互堆积连接到一起,呈现出较明显的蜂窝状结构,但仍有被“淹没”的痕迹。nanoPd-EDTA/HCHO电极纳米颗粒为大小均匀的球形,粒子直径约为60 nm,微小的钯催化剂颗粒在钛片表面紧密结合,形成纵横交错的立体多孔网状结构。nanoPd/EG电极也呈现出多孔网状结构,但催化剂颗粒大小不均匀。nanoPd/HCHO电极,催化剂颗粒之间孔隙较小,但粒径较大,平均粒径约为150 nm。
(2)Au/nanoPd电极:未沉积Au之前的nanoPd电极,Pd颗粒在钛基表面紧密结合,颗粒相互牢固地连接在一起形成多孔蜂窝状结构,且众多孔穴的形成为金颗粒的附着提供了大量位点,可以保障Au/nanoPd催化剂颗粒的高度稳定性。能谱分析结果表明,Pd的特征能量峰在2.9 keV,Au的特征峰处于2.1 keV和9.7 keV。
(3)PdRu电极:纳米颗粒在钛片表面相互连接形成三维立体网状结构,依附于钛基体表面紧密地覆盖一层催化剂颗粒,PdRu纳米粒子约100～150 nm,这种网状结构使电极拥有巨大的比表面积。
4.采用CV、LSV、CA、EIS等测试方法,在碱性介质中研究了纳米钯电极对甲醇、乙醇、甲酸、甲醛氧化、以及过氧化氢还原的电催化活性,并对电极动力学过程进行了分析研究,同时研究了金修饰的纳米钯电极对甲酸的电氧化活性以及钯钌双金属电极对乙醇氧化的催化活性,主要结论如下:
(1)在碱性溶液中循环伏安测试表明甲醇在nanoPd电极上氧化,起始氧化电位较低、阳极电流密度较大和抗CO毒化能力较强。电化学交流阻抗测试表明,甲醇在nanoPd电极上电氧化反应的阻抗值较低,甲醇浓度增加,电极阻抗值更低。
(2)乙醇在纳米Pd电极上氧化表现出较负的起始氧化电位,其中nanoPd-EDTA/HCHO电极正向扫描起始氧化电位为-0.788 V,阳极峰电流密度达到151 mA cm-2。交流阻抗测试结果显示,nanoPd-EDTA/HCHO电极在碱性溶液中对乙醇氧化具有较低的电荷传递电阻。
(3)利用循环伏安法研究了甲酸在不同反应液所制备的nanoPd电极上的电催化氧化,发现在1.0 mol L~(-1)NaOH+0.5 mol L~(-1)HCOOH溶液中,加入EDTA且以甲醛做还原剂的电极(nanoPd-EDTA/HCHO)上,甲酸氧化电流密度达132.00 mA cm-2,起始电位为-0.80V,表明电催化活性优于其它电极,同时研究了nanoPd-EDTA/HCHO电极对不同浓度甲酸电催化氧化,结果表明,在一定的甲酸浓度范围内,甲酸氧化的阳极电流密度随浓度的增加而增大。
(4) CV、LSV、CA、EIS法研究表明,所制备的nanoPd电极在碱性条件下,对甲醛氧化具有较好的电流稳定性和较高的电催化活性。
(5)nanoPd-EDTA/HCHO催化剂在1.0 mol L~(-1)NaOH溶液中对H2O2还原具有良好的电催化活性。这种nanoPd-EDTA/HCHO催化剂有望成为过氧化氢燃料电池的阴极催化剂。
(6) CV和LSV结果显示,金在nanoPd表面的沉积促进了Pd对甲酸氧化的电催化活性,起始电位提前,电流密度增大。EIS研究也表明,Au/nanoPd电极上甲酸氧化反应的电荷传递电阻更低。所以这种金修饰纳米钯电极(Au/nanoPd)对甲酸氧化有较高的电催化活性。
(7) CVs曲线显示所制备的电极(nanoPd, Pd_(99)Ru_1, Pd_(96)Ru_4, Pd_(87)Ru_(13)和Pd_(35)Ru_(75))在碱性溶液中对乙醇氧化具有很强的电催化活性,其中Pd87Ru13的氧化峰电流密度最大,峰电流平台最宽、起始氧化电位最负。进一步研究发现,随着乙醇浓度的增大(0.1-2.0 mol L~(-1)),电流密度平台呈增大的趋势。Pd_(87)Ru_(13)电极的阻抗值很低,乙醇在电极表面的氧化过程中电荷传递电阻较低。研究结果表明,Ru添加到Pd电极中改善了Pd对乙醇的电化学氧化活性。
虽然目前对有机小分子电催化活性的研究报道较多,但制备性能优良的新型催化剂仍是这一领域的重要研究内容。本文所制备的纳米钯、钯金、钯钌电极,催化剂颗粒具有新颖的结构,对甲醇、乙醇、甲酸、甲醛氧化以及过氧化氢还原具有优异的电催化活性。此类新颖的电极材料对今后燃料电池阴阳两极催化剂的制备、以及新型电化学传感器的研究开发开辟了新的思路,为制备纳米电催化剂的研究工作提供了一定的理论指导与前期探索经验,对研究小分子的电催化活性在理论上具有一定的借鉴与指导意义。
The direct liquid fuel cells have been paid high attention and investigated widely, due to the high energy efficiency, low-pollution, abundant sources, easy storage and transportation of fuels. The direct liquid fuel cells have broadly application fields in the mobile phones, laptops, music players and other portable power sources. The core issues of their commercialization are how to reduce the consumption of precious metal, or to enhance the catalytic activity and to search for high efficient and low-cost non-platium catalyst. Since the 20th century, electrocatalytic oxidation of small molecules has been highly attented by foreign research institutions, and it has important scientific and practical significance to understand the electrochemical phenomena, develop electrode kinetics and improve electro-oxidation mechanism. Platium, palladium, gold, silver and other precious metals on the electro-catalytic properties of small molecules have been studied extensively to explore their excellent electro-catalytic activity. This is a much challenging work.
In this work, we have prepared the novel electro-catalysts of nanoPd, Au/nanoPd and PdRu by the hydrothermal process using different reduction agents in the presence of EDTA. Then we have researched their electro- catalytic acfivity towards the oxidation of methanol, ethanol, formic acid, and formaldehyde and the reduction of hydrogen peroxide. The electro-activity has been investigated by the conventional electrochemical techniques including cyclic voltammetry(CV), chronoamperometric(CA), linear scanning voltammetry(LSV), electrochemical impedance spectroscopy(EIS), et al.The morphlogical stracture of the samples has been characterized by using the scanning electron micronscope(SEM) and energy scattering spectra(EDS).
The principal contents and research conclusions of this thesis are as follows:
1. The application, research progress and preparation of the Pd-coutaining catalysts are summarized, it is expounded the mechanism of small organic molecules oxidation such as methanol, ethanol, formic acid, formaldehyde and reduction activity like hydrogen peroxide. To develop nano catalysts is the main concept.
2. Make sure the preparation process of palladium series nanometer catalysts. In this thesis, different nanometer palladium electrodes are fabricated by the hydrothermal process with adding EDTA through formaldehyde, glycol or polyethylene. The gold modified nanometer palladium catalyst is preparated by the constant potentioal deposition. The binary palladium ruthenium metal electrodes are obtained with EDTA as a complexing agent and formaldehyde as a reducing agent. Results show that nano-metal catalysts particles are directly deposited on the surface of titanium substrate, and the catalysts have high stability.
3. Scanning electron microscopy(SEM), energy disperse spectroscopy (EDS), are employed to investigate the morphology and element compositions of nanoPd, Au/nanoPd, andPdRu.The main conclusions are as follows:
(1) Morphologies of the prepared samples have been examined by scanning electro microscopy(SEM) and characterized by nanoporous network structures. The sizes of the Pd nanoparticles for the nanoPd/PEG, nanoPd-EDTA/PEG, nanoPd-EDTA/HCHO, nanoPd/EG, and nanoPd-HCHO are around 230, 130, 60, 80, and 150 nm, respectively. Their SEM images show that the Pd nanoparticles are connected with each other to form a three-dimensional texture which provides a considerably large real surface area.
(2) For the preparation of the Au-modified nanoPd electrode: The porous structure of the nanoPd electrode offers plenty of sites and provides stable immobilization of the gold particles. Energy dispersed spectra of these samples indicate characteristic energy peaks of gold at ca. 2.1 and 9.7 keV, and palladium at ca. 3.1 and 3.25 keV.
(3) All samples present a similar three-dimensional texture which is formed by the interconnection of the particles on the Ti surface. A typical SEM image of samples shows that a porous network structure is observed and the size of the particles(PdRu) is ca. 100 ~150 nm. This porous structure provides a considerably large real surface area of the samples. Energy dispersed spectra of these samples indicate characteristic energy peaks of palladium at ca. 3.1 and 3.25 keV, and ruthenium at ca. 2.2 keV. In addition, the energy peak at around 4.5 keV is ascribed to the substrate Ti.
4 Electro-catalytic activity of the nanoPd for the oxidation of methanol, ethanol, formic acid, formaldehyde and the reduction of hydrogen peroxide in alkaline solution has been studied using CV, CA, LSV and EIS, and the catalytic activiyu of the electrode kinetic process is analyzed. In addition electro-oxidation of formic acid on the gold modified palladium and ethanol oxidation on palladium ruthenium electrode have bee n investi gated. The mai n results are as follows:
(1) Cyclic voltammetry (CV) and electrochemical impedance spectra (EIS) have been applied to evaluate the electrocatalytic acitivity of the nanoPd/Ti electrode towards methanol oxidation in alkaline solution. CV results show that the nanoPd /Ti electrode exhibits high anodic peak densities and a low onset potential for methanol oxidation. Also nanoPd /Ti electrode shows excellent CO tolerance during the oxidation of methanol. Nyquist and Bode plots of electrochemical impedance show that methanol electro-oxidation on the nanoPd /Ti exhibits low impedance values, and that with the increase of methanol concentrations, the impedance value for methanol electrooxidation decreases. The prepared nanoporous Pd electrode shows the significantly high electroactivity for methanol oxidation.
(2) The oxidation of ethanol on the nanoPd-EDTA/HCHO exhibits a high anodic peak(151mA cm~(-2)) and a low onset potential of -0.788V. According to the analysis for elecreochemial impedance spectra(EIS), the nanoPd-EDTA/HCHO shows very low charge transfer resistances in 1.0 mol L~(-1)NaOH cantaining various concentrations of ethanol.
(3) The electro-oxidation of formic acid on these Pd electrodes has been studied with cyclic voltammograms(CV) in the 1.0 mol L~(-1)NaOH+0.5 mol L~(-1)HCOOH solution. During the positive potential scan formic acid oxidation on the Pd-EDTA/HCHO exhibits a high anodic peak (132.0 mA cm-2) and a low onset potential of -0.98V , showing better electrocatalytic activity for formic acid oxidation than others. Effect of formic acid concentration on electrochemical characteristics of the nanoPd-EDTA/HCHO electrode is also investigated.
(4) Electrocatalytic activity of the nanoPd towards formaldehyde oxidation in alkaline media has been evaluated by cyclic voltammetry (CV), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS). Electrooxidation of formaldehyde on the nanoPd electrode takes place at a low onset potential of ca. -0.85 V (vs SCE) and large anodic current densities. Chronoamperometric data of the nanoPd electrode show high and stable anodic currents for formaldehyde oxidation. It is also observed that the steady-state current density shows a well linear increment with formaldehyde concentration in the range of 0 to 20 mmol L~(-1)formaldehyde. EIS investigation at different formaldehyde concentrations presents very low values of charge transfer resistances for formaldehyde oxidation on the nanoPd. Results show that the prepared nanoPd electrode is a highly efficient catalyst for formaldehyde oxidation in alkaline media.
(5) Electroactivity of the nanoPd-EDTA/HCHO catalyst towards the electroreduction of hydrogen peroxide in 1.0 mol L~(-1)NaOH solution has been evaluated by voltammetric techniques. Both linear scan voltammetric and chronoamperometric data present significantly large steady-state reduction current density with regard to the hydrogen peroxide electroreduction on the prepared nanoPd-EDTA/HCHO catalyst. Results show that the prepared nanoPd-EDTA/HCHO catalyst is a much more effective electrocatalyst for the electroreduction of hydrogen peroxide in alkaline media.
(6) Electrocatalytic activity of the nanoPd and Au/nanoPd towards formic acid in alkaline solution is evaluated by cyclic voltammetry(CV) and electrochemical impedance spectroscopy(EIS). CV results reveal that Au/nanoPd presents a low onset potential and high anodic peak densities, showing that the deposited gold on nanoPd electrode can enhance palladium catalyst for formic acid electrooxidation activity. Also Nyquist plots indicate that formic acid electrooxidation on the Au/nanoPd exhibits low impedance values. Results show that the prepared Au/nanoPd electrode is an effective electrocatalyst towards formic acid oxidation in alkaline media.
(7) CVs of the prepared electrocatalysts (nanoPd, Pd99Ru1, Pd96Ru4, Pd87Ru13 and Pd35Ru75) in alkaline media present extremely high anodic peaks towards ethanol oxidation. Among the prepared catalysts, Pd87Ru13 displays the (relatively) largest anodic peak current density, a wide peak current plateau and a most negative onset potential for ethanol oxidation. It is further found that the peak current plateau on the Pd87Ru13 catalyst becomes wider with the increase of ethanol concentration in the range of 0.1 to 2.0 mol L~(-1). This wide peak current plateau is also observed at higher potential scan rates. This would be ascribed to the different reaction rates between the oxidation of Pd itself and ethanol oxidation on the Pd87Ru13 catalyst. Nyquist plots of the Pd87Ru13 catalyst present low impedance values, showing that ethanol oxidation on the Pd87Ru13 catalyst has a low charge transfer resistance. The study demonstrates that the addition of an appropriate amount of Ru to Pd improves the electrocatalytic activity of the Pd catalyst for ethanol oxidation. The prepared porous Pd87Ru13 catalyst could be a good choice for the ethanol oxidation in the promising alcohol fuel cell.
Although the electro-catalytic activity of the small organic molecules has been extensively investigated, the new catalyst preparation is still an important work in this field. In the thesis the novel structure of porous palladium, palladium gold, pallaium ruthenium catalysts have been successfully prepared. Our study will be of signifacance in the development of direct liquid fuel cells and in the electrochemical study on the electro-oxidation of small molecules.
本文开展了用于甲醇、乙醇、甲酸、甲醛氧化和过氧化氢还原的新型电催化剂探索和研究,从添加络合剂,选用不同的还原剂来改进电催化剂性能,制备出结构新颖,催化活性高的新型催化剂,并通过扫描电子显微镜(SEM)、能量散射光谱(EDS)、循环伏安法(CV)、恒电位阶跃(CA)、线性扫描法(LSV)、交流阻抗法(EIS)等分析测试技术,对催化剂的结构、形貌、电化学性能等进行了详细具体研究。
本论文的主要内容和研究结论如下:
1.对钯电极的应用、研究进展和制备方法进行概述,阐述了甲醇、乙醇、甲酸、甲醛等有机小分子的电催化氧化以及过氧化氢的还原机理,得出催化剂纳米化是当前开发催化剂的主要思路。
2.确定了纳米钯系列催化剂的具体制备过程。本研究中以EDTA为添加剂,分别以甲醛、乙二醇、聚乙二醇为还原剂,利用水热法,通过改变溶液组成制备不同的纳米钯电极;以EDTA为络合剂和甲醛做还原剂制备出纳米钯电极,然后在此电极上恒电位沉积金,得到金修饰钯电极;以EDTA为络合剂、甲醛做还原剂制备出钯钌双金属电极。金属催化剂能够以纳米小颗粒直接沉积于钛基体表面,而且催化剂颗粒结构稳定。
3.利用扫描电子显微镜(SEM)和能谱分析(EDS)测试技术,对所制备的nanoPd、Au/nanoPd、nanoPdRu电极的结构与成分进行了表征和分析,主要结论如下:
(1)不同溶液组成制备的nanoPd电极:nanoPd/PEG催化剂颗粒大小不均匀,电极表面多孔结构也不是很明显,颗粒的边角轮廓模糊,整体感觉催化剂颗粒“淹没”于黑暗中。nanoPd-EDTA/PEG催化剂颗粒明显变小,粒子之间相互堆积连接到一起,呈现出较明显的蜂窝状结构,但仍有被“淹没”的痕迹。nanoPd-EDTA/HCHO电极纳米颗粒为大小均匀的球形,粒子直径约为60 nm,微小的钯催化剂颗粒在钛片表面紧密结合,形成纵横交错的立体多孔网状结构。nanoPd/EG电极也呈现出多孔网状结构,但催化剂颗粒大小不均匀。nanoPd/HCHO电极,催化剂颗粒之间孔隙较小,但粒径较大,平均粒径约为150 nm。
(2)Au/nanoPd电极:未沉积Au之前的nanoPd电极,Pd颗粒在钛基表面紧密结合,颗粒相互牢固地连接在一起形成多孔蜂窝状结构,且众多孔穴的形成为金颗粒的附着提供了大量位点,可以保障Au/nanoPd催化剂颗粒的高度稳定性。能谱分析结果表明,Pd的特征能量峰在2.9 keV,Au的特征峰处于2.1 keV和9.7 keV。
(3)PdRu电极:纳米颗粒在钛片表面相互连接形成三维立体网状结构,依附于钛基体表面紧密地覆盖一层催化剂颗粒,PdRu纳米粒子约100～150 nm,这种网状结构使电极拥有巨大的比表面积。
4.采用CV、LSV、CA、EIS等测试方法,在碱性介质中研究了纳米钯电极对甲醇、乙醇、甲酸、甲醛氧化、以及过氧化氢还原的电催化活性,并对电极动力学过程进行了分析研究,同时研究了金修饰的纳米钯电极对甲酸的电氧化活性以及钯钌双金属电极对乙醇氧化的催化活性,主要结论如下:
(1)在碱性溶液中循环伏安测试表明甲醇在nanoPd电极上氧化,起始氧化电位较低、阳极电流密度较大和抗CO毒化能力较强。电化学交流阻抗测试表明,甲醇在nanoPd电极上电氧化反应的阻抗值较低,甲醇浓度增加,电极阻抗值更低。
(2)乙醇在纳米Pd电极上氧化表现出较负的起始氧化电位,其中nanoPd-EDTA/HCHO电极正向扫描起始氧化电位为-0.788 V,阳极峰电流密度达到151 mA cm-2。交流阻抗测试结果显示,nanoPd-EDTA/HCHO电极在碱性溶液中对乙醇氧化具有较低的电荷传递电阻。
(3)利用循环伏安法研究了甲酸在不同反应液所制备的nanoPd电极上的电催化氧化,发现在1.0 mol L~(-1)NaOH+0.5 mol L~(-1)HCOOH溶液中,加入EDTA且以甲醛做还原剂的电极(nanoPd-EDTA/HCHO)上,甲酸氧化电流密度达132.00 mA cm-2,起始电位为-0.80V,表明电催化活性优于其它电极,同时研究了nanoPd-EDTA/HCHO电极对不同浓度甲酸电催化氧化,结果表明,在一定的甲酸浓度范围内,甲酸氧化的阳极电流密度随浓度的增加而增大。
(4) CV、LSV、CA、EIS法研究表明,所制备的nanoPd电极在碱性条件下,对甲醛氧化具有较好的电流稳定性和较高的电催化活性。
(5)nanoPd-EDTA/HCHO催化剂在1.0 mol L~(-1)NaOH溶液中对H2O2还原具有良好的电催化活性。这种nanoPd-EDTA/HCHO催化剂有望成为过氧化氢燃料电池的阴极催化剂。
(6) CV和LSV结果显示,金在nanoPd表面的沉积促进了Pd对甲酸氧化的电催化活性,起始电位提前,电流密度增大。EIS研究也表明,Au/nanoPd电极上甲酸氧化反应的电荷传递电阻更低。所以这种金修饰纳米钯电极(Au/nanoPd)对甲酸氧化有较高的电催化活性。
(7) CVs曲线显示所制备的电极(nanoPd, Pd_(99)Ru_1, Pd_(96)Ru_4, Pd_(87)Ru_(13)和Pd_(35)Ru_(75))在碱性溶液中对乙醇氧化具有很强的电催化活性,其中Pd87Ru13的氧化峰电流密度最大,峰电流平台最宽、起始氧化电位最负。进一步研究发现,随着乙醇浓度的增大(0.1-2.0 mol L~(-1)),电流密度平台呈增大的趋势。Pd_(87)Ru_(13)电极的阻抗值很低,乙醇在电极表面的氧化过程中电荷传递电阻较低。研究结果表明,Ru添加到Pd电极中改善了Pd对乙醇的电化学氧化活性。
虽然目前对有机小分子电催化活性的研究报道较多,但制备性能优良的新型催化剂仍是这一领域的重要研究内容。本文所制备的纳米钯、钯金、钯钌电极,催化剂颗粒具有新颖的结构,对甲醇、乙醇、甲酸、甲醛氧化以及过氧化氢还原具有优异的电催化活性。此类新颖的电极材料对今后燃料电池阴阳两极催化剂的制备、以及新型电化学传感器的研究开发开辟了新的思路,为制备纳米电催化剂的研究工作提供了一定的理论指导与前期探索经验,对研究小分子的电催化活性在理论上具有一定的借鉴与指导意义。
The direct liquid fuel cells have been paid high attention and investigated widely, due to the high energy efficiency, low-pollution, abundant sources, easy storage and transportation of fuels. The direct liquid fuel cells have broadly application fields in the mobile phones, laptops, music players and other portable power sources. The core issues of their commercialization are how to reduce the consumption of precious metal, or to enhance the catalytic activity and to search for high efficient and low-cost non-platium catalyst. Since the 20th century, electrocatalytic oxidation of small molecules has been highly attented by foreign research institutions, and it has important scientific and practical significance to understand the electrochemical phenomena, develop electrode kinetics and improve electro-oxidation mechanism. Platium, palladium, gold, silver and other precious metals on the electro-catalytic properties of small molecules have been studied extensively to explore their excellent electro-catalytic activity. This is a much challenging work.
In this work, we have prepared the novel electro-catalysts of nanoPd, Au/nanoPd and PdRu by the hydrothermal process using different reduction agents in the presence of EDTA. Then we have researched their electro- catalytic acfivity towards the oxidation of methanol, ethanol, formic acid, and formaldehyde and the reduction of hydrogen peroxide. The electro-activity has been investigated by the conventional electrochemical techniques including cyclic voltammetry(CV), chronoamperometric(CA), linear scanning voltammetry(LSV), electrochemical impedance spectroscopy(EIS), et al.The morphlogical stracture of the samples has been characterized by using the scanning electron micronscope(SEM) and energy scattering spectra(EDS).
The principal contents and research conclusions of this thesis are as follows:
1. The application, research progress and preparation of the Pd-coutaining catalysts are summarized, it is expounded the mechanism of small organic molecules oxidation such as methanol, ethanol, formic acid, formaldehyde and reduction activity like hydrogen peroxide. To develop nano catalysts is the main concept.
2. Make sure the preparation process of palladium series nanometer catalysts. In this thesis, different nanometer palladium electrodes are fabricated by the hydrothermal process with adding EDTA through formaldehyde, glycol or polyethylene. The gold modified nanometer palladium catalyst is preparated by the constant potentioal deposition. The binary palladium ruthenium metal electrodes are obtained with EDTA as a complexing agent and formaldehyde as a reducing agent. Results show that nano-metal catalysts particles are directly deposited on the surface of titanium substrate, and the catalysts have high stability.
3. Scanning electron microscopy(SEM), energy disperse spectroscopy (EDS), are employed to investigate the morphology and element compositions of nanoPd, Au/nanoPd, andPdRu.The main conclusions are as follows:
(1) Morphologies of the prepared samples have been examined by scanning electro microscopy(SEM) and characterized by nanoporous network structures. The sizes of the Pd nanoparticles for the nanoPd/PEG, nanoPd-EDTA/PEG, nanoPd-EDTA/HCHO, nanoPd/EG, and nanoPd-HCHO are around 230, 130, 60, 80, and 150 nm, respectively. Their SEM images show that the Pd nanoparticles are connected with each other to form a three-dimensional texture which provides a considerably large real surface area.
(2) For the preparation of the Au-modified nanoPd electrode: The porous structure of the nanoPd electrode offers plenty of sites and provides stable immobilization of the gold particles. Energy dispersed spectra of these samples indicate characteristic energy peaks of gold at ca. 2.1 and 9.7 keV, and palladium at ca. 3.1 and 3.25 keV.
(3) All samples present a similar three-dimensional texture which is formed by the interconnection of the particles on the Ti surface. A typical SEM image of samples shows that a porous network structure is observed and the size of the particles(PdRu) is ca. 100 ~150 nm. This porous structure provides a considerably large real surface area of the samples. Energy dispersed spectra of these samples indicate characteristic energy peaks of palladium at ca. 3.1 and 3.25 keV, and ruthenium at ca. 2.2 keV. In addition, the energy peak at around 4.5 keV is ascribed to the substrate Ti.
4 Electro-catalytic activity of the nanoPd for the oxidation of methanol, ethanol, formic acid, formaldehyde and the reduction of hydrogen peroxide in alkaline solution has been studied using CV, CA, LSV and EIS, and the catalytic activiyu of the electrode kinetic process is analyzed. In addition electro-oxidation of formic acid on the gold modified palladium and ethanol oxidation on palladium ruthenium electrode have bee n investi gated. The mai n results are as follows:
(1) Cyclic voltammetry (CV) and electrochemical impedance spectra (EIS) have been applied to evaluate the electrocatalytic acitivity of the nanoPd/Ti electrode towards methanol oxidation in alkaline solution. CV results show that the nanoPd /Ti electrode exhibits high anodic peak densities and a low onset potential for methanol oxidation. Also nanoPd /Ti electrode shows excellent CO tolerance during the oxidation of methanol. Nyquist and Bode plots of electrochemical impedance show that methanol electro-oxidation on the nanoPd /Ti exhibits low impedance values, and that with the increase of methanol concentrations, the impedance value for methanol electrooxidation decreases. The prepared nanoporous Pd electrode shows the significantly high electroactivity for methanol oxidation.
(2) The oxidation of ethanol on the nanoPd-EDTA/HCHO exhibits a high anodic peak(151mA cm~(-2)) and a low onset potential of -0.788V. According to the analysis for elecreochemial impedance spectra(EIS), the nanoPd-EDTA/HCHO shows very low charge transfer resistances in 1.0 mol L~(-1)NaOH cantaining various concentrations of ethanol.
(3) The electro-oxidation of formic acid on these Pd electrodes has been studied with cyclic voltammograms(CV) in the 1.0 mol L~(-1)NaOH+0.5 mol L~(-1)HCOOH solution. During the positive potential scan formic acid oxidation on the Pd-EDTA/HCHO exhibits a high anodic peak (132.0 mA cm-2) and a low onset potential of -0.98V , showing better electrocatalytic activity for formic acid oxidation than others. Effect of formic acid concentration on electrochemical characteristics of the nanoPd-EDTA/HCHO electrode is also investigated.
(4) Electrocatalytic activity of the nanoPd towards formaldehyde oxidation in alkaline media has been evaluated by cyclic voltammetry (CV), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS). Electrooxidation of formaldehyde on the nanoPd electrode takes place at a low onset potential of ca. -0.85 V (vs SCE) and large anodic current densities. Chronoamperometric data of the nanoPd electrode show high and stable anodic currents for formaldehyde oxidation. It is also observed that the steady-state current density shows a well linear increment with formaldehyde concentration in the range of 0 to 20 mmol L~(-1)formaldehyde. EIS investigation at different formaldehyde concentrations presents very low values of charge transfer resistances for formaldehyde oxidation on the nanoPd. Results show that the prepared nanoPd electrode is a highly efficient catalyst for formaldehyde oxidation in alkaline media.
(5) Electroactivity of the nanoPd-EDTA/HCHO catalyst towards the electroreduction of hydrogen peroxide in 1.0 mol L~(-1)NaOH solution has been evaluated by voltammetric techniques. Both linear scan voltammetric and chronoamperometric data present significantly large steady-state reduction current density with regard to the hydrogen peroxide electroreduction on the prepared nanoPd-EDTA/HCHO catalyst. Results show that the prepared nanoPd-EDTA/HCHO catalyst is a much more effective electrocatalyst for the electroreduction of hydrogen peroxide in alkaline media.
(6) Electrocatalytic activity of the nanoPd and Au/nanoPd towards formic acid in alkaline solution is evaluated by cyclic voltammetry(CV) and electrochemical impedance spectroscopy(EIS). CV results reveal that Au/nanoPd presents a low onset potential and high anodic peak densities, showing that the deposited gold on nanoPd electrode can enhance palladium catalyst for formic acid electrooxidation activity. Also Nyquist plots indicate that formic acid electrooxidation on the Au/nanoPd exhibits low impedance values. Results show that the prepared Au/nanoPd electrode is an effective electrocatalyst towards formic acid oxidation in alkaline media.
(7) CVs of the prepared electrocatalysts (nanoPd, Pd99Ru1, Pd96Ru4, Pd87Ru13 and Pd35Ru75) in alkaline media present extremely high anodic peaks towards ethanol oxidation. Among the prepared catalysts, Pd87Ru13 displays the (relatively) largest anodic peak current density, a wide peak current plateau and a most negative onset potential for ethanol oxidation. It is further found that the peak current plateau on the Pd87Ru13 catalyst becomes wider with the increase of ethanol concentration in the range of 0.1 to 2.0 mol L~(-1). This wide peak current plateau is also observed at higher potential scan rates. This would be ascribed to the different reaction rates between the oxidation of Pd itself and ethanol oxidation on the Pd87Ru13 catalyst. Nyquist plots of the Pd87Ru13 catalyst present low impedance values, showing that ethanol oxidation on the Pd87Ru13 catalyst has a low charge transfer resistance. The study demonstrates that the addition of an appropriate amount of Ru to Pd improves the electrocatalytic activity of the Pd catalyst for ethanol oxidation. The prepared porous Pd87Ru13 catalyst could be a good choice for the ethanol oxidation in the promising alcohol fuel cell.
Although the electro-catalytic activity of the small organic molecules has been extensively investigated, the new catalyst preparation is still an important work in this field. In the thesis the novel structure of porous palladium, palladium gold, pallaium ruthenium catalysts have been successfully prepared. Our study will be of signifacance in the development of direct liquid fuel cells and in the electrochemical study on the electro-oxidation of small molecules.
引文
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