Size-controlled synthesis and impedance-based mechanistic understanding of Pd/C nanoparticles for formic acid oxidation

This work provides a detailed electrochemical impedance study for formic acid electro-oxidation on size-controlled Pd/C nanoparticles, the synthesis of which was done by a simple protocol using ethylene glycol as a reducing agent. By controlling KOH concentration, this strategy provides a synthesis method for Pd nanoparticles with a selective size range of 3.9–7.5 nm. The as-prepared Pd nanoparticles exhibited size-dependent electrochemical property and electrochemical characterizations of four different Pd/C nanocatalysts (3.9, 5.2, 6.1, and 7.5 nm) showed that Pd particle with average size of 6.1 nm has the highest formic acid oxidation activity. Electrochemical impedance-based characterizations of formic acid oxidation on Pd/C suggested that at high potentials the adsorbed oxygen species could block the catalyst surface and inhibit the oxidation reaction, as reflected by the negative polarization resistance. Unlike Pd/C, the intermediate adsorbed CO species (CO_ads) plays a critical role for formic oxidation on Pt/C and thus the impedance spectra of Pd/C and Pt/C appear different potential-dependent patterns in the second quadrant. The issue of CO was investigated by an impedance investigation of Pd/C in a mixture of formic acid containing dissolved CO.     

钛基纳米多孔钯电极的制备及对甲酸氧化的电活性

采用水热法,通过改变溶液组成制备了5种不同的钛基纳米多孔钯电极(Pd/PEG、Pd-EDTA/PEG、Pd-EDTA/HCHO、Pd/EG和Pd/HCHO)。扫描电镜图(SEM)分析表明,加入络合剂乙二胺四乙酸(EDTA)后,钯颗粒均匀,粒径明显减小,仅有60 nm左右。利用循环伏安法研究了甲酸在这些电极上的电催化氧化,发现在1.0 mol/L NaOH+0.5 mol/L HCOOH溶液中,加入EDTA且以甲醛作还原剂的电极(Pd-EDTA/HCHO)对甲酸氧化电流密度达132.00 mA/cm2,甲酸氧化的起始电位为-0.85 V,表明电催化活性优于其他电极。同时研究了Pd-EDTA/HCHO电极对不同浓度甲酸电催化氧化,结果表明,在一定甲酸浓度范围内,甲酸氧化的阳极电流密度随浓度的增加而增大。     

PdNi/C催化剂的制备及对甲酸的电催化氧化

采用化学还原法,在乙二醇体系中制备了碳载PdNi催化剂(PdNi/C),与相同方法制备的Pd/C催化剂比较,发现PdNi/C催化剂对甲酸氧化具有较负的峰电位和较高的峰电流,且起始氧化电位也较低。计时电流曲线测试表明,与Pd/C催化剂相比,甲酸在PdNi/C催化剂上的氧化电流密度随时间衰减得比较慢,且具有较高的稳定电流。     

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。     

Time-efficient microwave synthesis of Pd nanoparticles and their electrocatalytic property in oxidation of formic acid and alcohols in alkaline media

In this study time-efficient size controlled synthesis of stable Pd nanoparticles was carried out using microwave heating method by the decomposition of palladium chloride with glucose in aqueous medium using poly(ethyleneglycol) as capping agent. The benefit of the synthesis is that it was achieved in only 20 s. The synthesized Pd nanoparticles were characterized by UV–Visible spectroscopy, transmission electron microscopy, X-ray diffraction, and particle size analysis. The relative rates of electro-oxidation of formic acid, methanol and ethanol measured by cyclic voltammetry showed that efficiency of Pd nanoparticles as catalyst followed the order: formic acid < methanol < ethanol. The current–voltage characteristics improved with increase in either electrolyte (NaOH) or fuel concentrations but decreased with further increase in NaOH concentration.     

Electrosynthesis of Pd/Au hollow cone-like microstructures for electrocatalytic formic acid oxidation

Pd/Au hollow cone-like microstructures (HCMs) have been electrodeposited on indium tin oxide (ITO) using a two-step protocol, which involves the nucleation pulse and succedent constant potential reduction in the presence of metal precursors and polyvinylpyrrolidone (PVP). Scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscope (XPS) were used to characterize the Pd/Au HCMs. The electrochemical results (cyclic voltammetry and chronoamperometry) testify that the Pd/Au HCMs exhibit significantly higher electrocatalytic activity and stability for the oxidation of formic acid than that of Pd/Au solid microhemispheres (SMHs). These attractive features are attributable to the unique hollow structures of Pd/Au with much higher electrochemical active surface areas and the exposure of favorable planes. Our work points to a new path for the preparation of Pd/Au HCMs, which are promising as electrocatalysts in direct formic acid fuel cell (DFAFC).     

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.     

Sonochemical synthesis of Pt-doped Pd nanoparticles with enhanced electrocatalytic activity for formic acid oxidation reaction

Pt-doped Pd nanoparticle catalysts (Pd _n Pt, n is 12, 15 and 19) supported on carbon were synthesized by an ultrasound assisted polyol method. The catalysts were characterized by X-ray diffraction, transmission electron microscopy, and energy dispersive X-ray spectroscopy. The electrochemical activity of the electrocatalysts was investigated in terms of formic acid oxidation reaction (FAOR) at low concentration of formic acid in 0.1 M perchloric acid at room temperature. Formic acid oxidation on the Pd _n Pt/C commences at lower potential than a commercial Pt/C. Pd₁₉Pt/C catalyst showed the highest catalytic activity in FAOR compared to that of other catalysts. The obtained electrochemical results from voltammograms indicate that Pt-doped Pd catalysts can be a promising candidate for the anode material in direct formic acid fuel cells. The synthesis procedure is not only a very facile route but also a mass producible method for preparing carbon supported alloy nanoparticles.     

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.     

Au/Pd core-shell nanoparticles with varied hollow Au cores for enhanced formic acid oxidation

A facile method has been developed to synthesize Au/Pd core-shell nanoparticles via galvanic replacement of Cu by Pd on hollow Au nanospheres. The unique nanoparticles were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, ultraviolet–visible spectroscopy, and electrochemical measurements. When the concentration of the Au solution was decreased, grain size of the polycrystalline hollow Au nanospheres was reduced, and the structures became highly porous. After the Pd shell formed on these Au nanospheres, the morphology and structure of the Au/Pd nanoparticles varied and hence significantly affected the catalytic properties. The Au/Pd nanoparticles synthesized with reduced Au concentrations showed higher formic acid oxidation activity (0.93 mA cm^-2 at 0.3 V) than the commercial Pd black (0.85 mA cm^-2 at 0.3 V), suggesting a promising candidate as fuel cell catalysts. In addition, the Au/Pd nanoparticles displayed lower CO-stripping potential, improved stability, and higher durability compared to the Pd black due to their unique core-shell structures tuned by Au core morphologies.     

Improved electrocatalytic performance of Pd nanoparticles with size-controlled Nafion aggregates for formic acid oxidation

This work focuses on the effect of Nafion ionomer aggregation within the Pd catalytic electrode on electrocatalytic oxidation of formic acid. By a simple heat-treatment, the particle sizes of both Nafion ionomers in Nafion solution and congeries formed between Pd nanoparticles and Nafion ionomers in the catalyst ink decrease and their size distribution becomes narrow. Heat treatment of the catalyst ink leads to a significantly enhanced catalytic activity for formic acid oxidation on the Pd catalytic electrode. Such an enhancement is ascribed to the improvement in catalyst utilization verified by CO stripping voltammograms and to the decrease in charge-transfer resistance of oxidation reaction confirmed by impedance analysis. Typical XPS analysis shows that there are at least two kinds of Pd and S surface states within the catalytic electrode with the ink pre-heated at 25 °C and only one kind of Pd and S surface state at 80 °C, indicative of a better dispersion between Pd nanoparticles and smaller Nafion ionomers at a higher heat treatment temperature. Furthermore, the decrease in congeries size within the anode catalyst ink leads to a significant decrease in Nafion loading within the catalytic layer and a remarkable improvement in direct formic acid fuel cell's performance.     

Controlled synthesis of Pt-decorated Au nanostructure and its promoted activity toward formic acid electro-oxidation

Highly active Pt-decorated Au nanoparticles on carbon support with Pt:Au mole ratio ranging from 1:10 to 1:2 was successfully synthesized based on successive reduction strategy. The successful formation of this structure was suggested by transmission electron microscopy, UV-vis and voltammetry analyses. The electrocatalytic activity of this decorated structure toward formic acid oxidation surprisingly increases despite the low amount of Pt being used. At 0.1 V, the specific activity of PtAu/C with Pt/Au mole ratio 1:8 was more than one order of magnitude higher than the conventional Pt/C. The enhancement was attributed to the less Pt ensemble sites that the decorated structure possesses (ensemble effect) and the increase in the Pt atom reactivity on Au nanocrystal. The formic acid oxidation mechanism on this decorated structure was also elucidated using electrochemical impedance spectroscopy technique. It is proposed that besides the dehydrogenation reaction pathway happening on clean Pt sites, the reactive intermediate i.e. formate species could also be oxidized by the adsorbed water species on Pt at higher potential.     

Preparation of high performance Pd catalysts supported on untreated multi-walled carbon nanotubes for formic acid oxidation

Due to the inherent inertness of carbon nanotubes (CNTs), one of the most significant challenges in the preparation of CNT-supported catalysts is achieving a uniform deposition of nanoparticles on the surface of the nanotubes. In this paper, we report on the preparation and characterization of Pd nanoparticles supported on untreated multi-walled carbon nanotubes (MWCNTs), synthesized in the presence of glutamate. The results of Raman spectroscopy revealed that this synthetic procedure does not have a detrimental effect on the surface structure of MWCNTs. Transmission electron microscopy (TEM) measurements indicated that the dispersion of Pd nanoparticles on untreated-MWCNTs in the presence of glutamate were uniform, and a narrow particle size was observed. X-ray diffraction (XRD) patterns indicated that the Pd/MWCNT catalyst possessed a face-centered cubic crystal structure. Cyclic voltammetry and chronoamperometry tests demonstrated that the obtained Pd/MWCNT catalyst displayed superior electrocatalytic activity and stability in formic acid oxidation, as compared to both a Pd/MWCNT catalyst synthesized without glutamate and a Pd catalyst on acid-oxidized MWCNTs, under otherwise identical experimental conditions. These results indicate that the catalyst developed in this study is a superior candidate for direct formic acid fuel cells (DFAFCs).     

钯/纳米石墨片复合材料的制备及其对甲醇的电催化性能

用改进的Hummers方法和机械剥离法制备纳米石墨片,以硼氢化钠为还原剂,采用一步法制备蠕虫状Pd纳米颗粒/纳米石墨片。结果表明这种新型的纳米石墨片的制备方法简单快速、温和高效。11.5 nm的Pd纳米颗粒能良好地分散在纳米石墨片上,且复合材料在碱性条件下对甲醇具有良好的催化活性和抗毒化性能,比相同条件下制备出的Pd负载在传统的改进Hummers方法制备的氧化石墨烯和商业炭黑Vulcan XC-72的催化性能更佳。     

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。     

Facile fabrication of elongated polymer micro/nano discs and their surface adhesiveness

The key factor of polymer particles using as a drug carrier is the ability to adhere to the surface of the target sites in order to optimize the drug delivery efficiency. To this end, shape of the particles is one of the essential parameters since nonspherical particles such as discs theoretically have more contact surface area than spherical particles. We herein propose a facile method to fabricate elongated polymer micro/nano discs by combining phase separation and a roll-to-roll coating process with a stretching method. By roll-to-roll coating, biodegradable poly(lactide-co-glycolide) (PLGA) discs formed on polyvinyl alcohol (PVA) film can be instantly stretched by uniaxial stretcher. The effect of stretching temperature and percentage of film elongation on the particle morphology was studied. The results showed that the PLGA discs can be elongated and the aspect ratio of 2.3 can be achieved with 600% elongation at 80°C, reflecting the increase of estimated contact surface area by 1.8 times. The adhesion efficiency of these elongated discs was compared with discs before stretching, spheres, and elongated spheres by using the water-dropping test. The elongated discs showed the best result among these particles and their adhesion efficiency are strongly related to estimated contact surface area.     

碳载体处理对Pd催化氧化甲酸的影响

采用饱和Co盐浸渍碳黑,然后高温热处理.发现处理后的碳黑微孔体积减少,介孔体积增加,更适于作为催化剂的载体.用处理后的碳黑制备的碳载Pd催化剂比未处理的碳黑做载体制备的催化剂对甲酸氧化具有更高的电催化活性.XRD结果可以看出,经Co盐浸渍处理过的碳黑中含有一定量的Co,有助于金属Pd在碳黑表面的分散,增加活性金属的电化...     

Vapour phase hydrogenation of olefins by formic acid over a Pd/C catalyst

It has been found that ethylene and propylene could be effectively hydrogenated by formic acid vapour over a Pd/carbon catalyst at low temperatures (<440 K). Surface hydrogen formation from formic acid is the rate-determining step for this hydrogenation reaction. Interaction of this hydrogen with the olefins is then fast. The conversion of formic acid in the presence of either of the olefins at any temperature is higher than in their absence. This has been explained by a much lower surface hydrogen concentration in the presence of the olefins. Direct experiments have confirmed that hydrogen inhibits the formic acid decomposition. Water vapour addition has a small positive effect on the decomposition of formic acid as well as on the hydrogenation of the olefins with formic acid. Catalysts consisting of gold supported on carbon or titania are both active in the production of hydrogen from formic acid. However, in contrast to the Pd/C catalyst, neither gives hydrogenation of the olefins with this acid.     

Investigation of formic acid oxidation on Ti/IrO2 electrodes

A model has been proposed according to which the voltammetric charge involved in the Ti/IrO₂ electrodes is due to two contributions: a faradaic contribution due to surface redox activities at the IrO₂ coating and a non-faradaic contribution due to the charging of electrical double layer (). The later has been proposed as a tool for the estimation of the relative surface area of the Ti/IrO₂ electrodes.Differential electrochemical mass spectrometry (DEMS) measurements using H₂¹⁸O has demonstrated that we are dealing with an active electrode in which the surface redox couple IrO₃/IrO₂ acts as mediator in the oxidation of formic acid (FA).From the voltammetric measurements using different IrO₂ loading and FA concentrations, the kinetic parameters of FA oxidation via the surface redox couple IrO₃/IrO₂ have been determined.Finally a model has been proposed considering that FA oxidation at Ti/IrO₂ anodes is controlled by mass transfer. The good agreement between the experimental results and the model indicates that the surface reaction between FA and the electrogenerated IrO₃ is a fast reaction.