不同体系Pd/C催化剂的制备及对甲酸的电催化氧化

采用不同体系制备了碳载Pd催化剂(Pd/C),发现在乙二醇体系中制备的Pd/C催化剂对甲酸氧化具有最负的峰电位和最低的起始氧化电位,Tafel斜率最小为155mV,并且在1h的计时电流曲线测试表明,用乙二醇体系制备的Pd/C-3催化剂具有较高的稳定电流。TEM结果可以看出,用乙二醇体系制备的Pd/C催化剂Pd粒子在活性碳表面分散得最好,Pd粒径的大小约为4～5nm。     

碳载PdPt催化剂的制备及对甲酸的电催化氧化性能

采用液相还原法制备了碳载PdPt催化剂(PdPt/C),电化学测试结果表明,尽管pd/C催化剂比PdPt/C催化剂对甲酸氧化具有更高的电催化活性,但长时间稳定性实验发现,甲酸在Pd/C催化剂上的氧化电流随时间衰减得很快,而PdPt/C催化剂对甲酸的氧化表现出更好的稳定性,比在Pd/C催化剂上有更高的稳定电流.     

碳载体的碱处理对Pd/C催化剂电催化活性的影响

采用处理与未处理的活性炭分别制备Pd/C催化剂,运用循环伏安法和计时电流法来检测两种Pd/C催化剂对甲酸的电催化氧化活性和稳定性。结果表明,用NH3.H2O处理过的活性炭所制备的Pd/C催化剂在对甲酸的电催化氧化的活性上和稳定性上都有不同程度的提高。     

Pd-TiO_2/C催化剂对甲酸的电催化氧化

用液相还原法制备Pd-TiO2/C催化剂。用循环伏安法(CV)和线性扫描法(LSV)考察了催化剂对甲酸的电催化氧化活性。通过计时电流曲线检测催化剂对甲酸的稳定性。结果表明Pd/TiO2/C催化剂中Pd粒子电化学比表面积增大,Pd-TiO2/C催化剂稳定,催化活性比Pd/C催化剂有较大幅度的提高。     

Pd与碳纳米管复合材料的制备及对甲酸催化氧化研究

以多壁碳纳米管(MWCNTs)为载体,采用电化学方法可控制备Pd纳米材料和Pd/MWCNTs复合纳米材料,研究对甲酸催化反应中的催化能力和催化效率。循环伏安法(CV)和计时电流法(CA)表明:与相同方法制备的Pd纳米粒子相比,Pd与MWCNTs复合纳米材料对甲酸电化学氧化的正向氧化峰电流密度较高,对甲酸氧化表现出较高的催化活性和催化稳定性。     

络合还原法制备的Pd/C催化剂对甲酸氧化的电催化性能

分别以硼氢化钠和乙二醇为还原剂,经络合还原法制备了炭载钯（Pd/C）催化剂。透射电镜（TEM）和X射线粉末衍射谱（XRD）结果表明,以乙二醇为还原剂制备的Pd/C催化剂中Pd粒子具有较小的粒径、均匀的粒径分布和较大的相对结晶度,Pd粒子的平均粒径和相对结晶度分别为4.2±2 nm和1.88。电化学测试结果显示,以乙二醇为还原剂制备的Pd/C催化剂具有较大的电化学活性面积,对甲酸氧化表现出较高的电催化活性和稳定性。     

载体的碱处理对Pd/C催化剂电催化性能的影响

将活性炭放入质量分数为10%的NaOH溶液中进行预处理,然后将其与未处理的活性炭分别作为载体制备Pd/C催化剂。对比两种催化剂的电化学性能发现,预处理的活性炭所制备的Pd/C催化剂,在甲酸电催化氧化活性和稳定性方面好于未处理的活性炭所制备的Pd/C催化剂。     

络合还原法制备Pd/C催化剂及甲酸电催化氧化性能

分别以硼氢化钠和乙二醇为还原剂,经络合还原法制备了炭载钯(Pd/C)催化剂。透射电镜(TEM)和X射线粉末衍射谱(XRD)结果表明,以乙二醇为还原剂制备的Pd/C催化剂中Pd粒子具有较小的粒径、均匀的粒径分布和较大的相对结晶度,Pd粒子的平均粒径和相对结晶度分别为(4.2±2)nm和1.88。电化学测试结果显示,Pd/C催化剂具有较大的电化学活性面积,对甲酸氧化表现出较高的电催化活性和稳定性。     

热活化提升Pd/C催化剂甲酸电氧化性能的研究

通过微波辅助多元醇方法以XC-72碳黑作为基体材料制备了Pd/C材料,对其进行惰性气氛下热活化处理,制备了热活化Pd/C催化剂,并对不同温度制备的Pd/C催化剂的电催化甲酸氧化反应的性能进行了探究。在电化学测试中,热活化后的Pd/C催化剂的电催化活性和长时间运行稳定性都得到了显著提升。此外,在对热活化温度优化后,发现当热活化温度达到500℃时,所制备的Pd/C-500℃催化剂的甲酸电氧化活性和稳定性达到最佳水平。分析认为,催化性能的提升来源于Pd纳米颗粒的结晶性的提高,以及更强的金属载体的相互作用。     

超声震荡对负载型Pd催化剂制备的作用

采用了两种方法制备了Pd/C-1-GC和Pd/C-2-GC两种催化剂。比较了在制备催化剂的不同过程采用超声震荡分散制备的催化剂Pd/C-2-GC对活性组分Pd分散的作用,发现在制备催化剂的整个过程都使用超声震荡制备的催化剂Pd/C-2-GC更有利于Pd的分散,Pd/C-2-GC催化剂对甲酸的氧化具有更高的电催化氧化活性和稳定性。     

Highly active carbon-supported PdNi catalyst for formic acid electrooxidation

A new carbon-supported PdNi (PdNi/C) catalyst is prepared by a simple simultaneous reduction reaction with sodium borohydride in glycol solution. The results show that the performance of PdNi/C catalyst for formic acid oxidation is greatly improved compared with that of Pd/C. X-ray diffraction (XRD) results show that Ni exists in the catalyst both as NiO and as PdNi alloy. The value of the apparent activation energy shows that the activity of formic acid oxidation on the PdNi/C is more sensitive to temperature compared with Pd/C.     

Nanoporous PdNi/C Electrocatalyst Prepared by Dealloying High‐Ni‐content PdNi Alloy for Formic Acid Oxidation

To improve the electrochemical performance of Pd‐based catalysts for formic acid oxidation, a carbon supported nanoporous PdNi catalyst is prepared by dealloying high‐Ni‐content PdNi alloy nanoparticles in acid solution. The structure of nanoporous PdNi/C catalyst is characterized by X‐ray diffraction, transmission electron microscopy and X‐ray photoelectron spectroscopy. The electrocatalytic results show that the activity of the nanoporous PdNi/C catalyst is higher than that of nonporous Pd/C catalyst. The results demonstrate that the carbon‐supported nanoporous PdNi catalyst has a potential for application in direct formic acid fuel cells.     

Formic acid oxidation by carbon-supported palladium catalysts in direct formic acid fuel cell

The oxidation of formic acid by the palladium catalysts supported on carbon with high surface area was investigated. Pd/C catalysts were prepared by using the impregnation method. 30 wt% and 50 wt% Pd/C catalysts had a high BET surface area of 123.7 m²/g and 89.9 m²/g, respectively. The fuel cell performance was investigated by changing various parameters such as anode catalyst types, oxidation gases and operating temperature. Pd/C anode catalysts had a significant effect on the direct formic acid fuel cell (DFAFC) performance. DFAFC with Pd/C anode catalyst showed high open circuit potential (OCP) of about 0.84 V and high power density at room temperature. The fuel cell with 50 wt% Pd/C anode catalyst using air as an oxidant showed the maximum power density of 99 mW/cm². On the other hand, a fuel cell with 50 wt% Pd/C anode catalyst using oxygen as an oxidant showed a maximum power density of 163 mW/cm² and the maximum current density of 590 mA/cm² at 60 °C.     

Synthesis of Pd/C Catalyst by Modified Polyol Process for Formic Acid Electrooxidation

Pd catalyst supported on Vulcan XC‐72 carbon black was prepared by a modified polyol process. Its performance was compared with that of Pd/C catalyst prepared by impregnation reduction method by using NaBH₄ as a reducing agent for formic acid electrooxidation. Their physical characterisations were tested by means of energy dispersive analysis of X‐ray, X‐ray diffraction and transmission electron micrographs. Their activities were presented by cyclic voltammetry and chronoamperometry. The results show that the particle sizes of Pd/C catalysts prepared by modified polyol process and impregnation reduction method are 3.9 and 7.9 nm, respectively. The size dispersion of the former is narrower and more homogeneous than that of the latter. However, both of Pd/C catalysts display the characteristic diffraction peaks of a Pd face‐centred cubic (f.c.c.) crystal structure. The results of electrochemical measurements present that the Pd/C catalyst prepared by modified polyol process has the higher electrocatalytic activity and stability for formic acid electrooxidation in comparison to the Pd/C one by impregnation reduction method due to the particle size effect, and its peak current density of CV and the current of chronoamperometric curve at 1,000 s reach 33.2 and 11.2 mA cm^–2, respectively.     

碳纳米管载PtPb、PtBi纳米催化剂对甲酸抗CO中毒的研究

混酸法预处理了载体碳纳米管（CNTs）,采用两步法制备PtPb/CNTs和PtB i/CNTs催化剂。以甲酸为研究对象,首次采用循环伏安法长时间连续性扫描的方法研究催化剂的抗CO中毒能力。研究发现,添加了Pb、B i金属后,增强了Pt/CNTs催化剂性能,如甲酸的起始氧化电位明显降低、氧化电流密度增大且抗毒性能增强。PtPb/CNTs、PtB i/CNTs催化甲酸的起始氧化电位都低于Pt/CNTs（0.099V）,依次为-0.108和-0.004V（Vs.Ag/AgC l）;在0.6V处,PtPb/CNTs、PtB i/CNTs催化氧化甲酸产生的电流密度都明显大于Pt/CNTs（0.79 mA/cm2）,依次为3.10和1.77mA/cm2;PtPb/CNTs、PtB i/CNTs催化剂的寿命依次为Pt/CNTs催化剂的4倍和5倍。本文主要进行燃料电池电催化剂材料的研究,对于制造新型电催化剂有一定的探索作用。     

Characterization and application of electrodeposited Pt, Pt/Pd, and Pd catalyst structures for direct formic acid micro fuel cells

In this work, we study the preparation, structural characterization, and electrocatalytic analysis of robust Pt and Pd-containing catalyst structures for silicon-based formic acid micro fuel cells. The catalyst structures studied were prepared and incorporated into the silicon fuel cells by a post CMOS-compatible process of electrodeposition, as opposed to the more common introduction of nanoparticle-based catalyst by ink painting. Robust, high surface area, catalyst structures consisting of pure Pt, pure Pd, and Pt/Pd = 1:1 were obtained. In addition, Pt/Pd catalyst structures were obtained via spontaneous deposition on the electrodeposited pure Pt structure. The catalyst structures were characterized electrochemically using cyclic voltammetry and chronoamperometry. All Pd-containing catalyst structures facilitate formic acid oxidation at the lower potentials and deliver higher oxidation currents compared to pure Pt catalyst structures. Fuel cells of these catalyst structures show that pure Pd catalyst structures on the anode exhibit the highest peak power density, i.e. as high as 28.0 mW/cm². The MEMS compatible way of catalyst electrodeposition and integration presented here has yielded catalyst structures that are highly active towards formic acid oxidation and are sufficiently robust to be compatible with post-CMOS processing.     

Performance characterization of direct formic acid fuel cell using porous carbon-supported palladium anode catalysts

Palladium particles supported on porous carbon of 20 and 50 nm pore diameters were prepared and applied to the direct formic acid fuel cell (DFAFC). Four different anode catalysts with Pd loading of 30 and 50 wt% were synthesized by using impregnation method and the cell performance was investigated with changing experimental variables such as anode catalyst loading, formic acid concentration, operating temperature and oxidation gas. The BET surface areas of 20 nm, 30 wt% and 20 nm, 50 wt% Pd/porous carbon anode catalysts were 135 and 90 m²/g, respectively. The electro-oxidation of formic acid was examined in terms of cell power density. Based on the same amount of palladium loading with 1.2 or 2 mg/cm², the porous carbon-supported palladium catalysts showed higher cell performance than unsupported palladium catalysts. The 20 nm, 50 wt% Pd/porous carbon anode catalyst generated the highest maximum power density of 75.8 mW/cm² at 25 °C. Also, the Pd/porous carbon anode catalyst showed less deactivation at the high formic acid concentrations. When the formic acid concentration was increased from 3 to 9 M, the maximum power density was decreased from 75.8 to 40.7 mW/cm² at 25 °C. Due to the high activity of Pd/porous carbon catalyst, the cell operating temperature has less effect on DFAFC performance.