Two-step pyrolysis process to synthesize highly dispersed Pt-Ru/carbon nanotube catalysts for methanol electrooxidation

Highly dispersed Pt-Ru particles with different atomic ratios supported on carbon nanotubes were synthesized using an easy two-step synthesis method including adsorption and pyrolysis. In this method, the functionalized carbon nanotubes act as adsorption sites for metallic ions and subsequently act as nucleation center for catalyst deposition in the pyrolysis process. The deposited Pt-Ru nanoparticles disperse on the carbon nanotubes surface uniformly, and the bulk composition of the Pt-Ru particles can be adjusted simply by changing atomic ratios of the metallic solution for adsorption. Finally, the electrocatalytic activity of the as-prepared catalysts supported on carbon nanotubes toward oxidation of methanol was studied. Results showed that their electrocatalytic activity, having long-term stability, strongly depends on the atomic ratio of Pt to Ru. The higher the concentration of Pt in the binary system is, the greater the electrocatalytic activity will be.     

Synthesis of highly dispersed Pt/C electrocatalysts in ethylene glycol using acetate stabilizer for methanol electrooxidation

Pt/C electrocatalysts were prepared from a solution of H₂PtCl₆ in ethylene glycol in the presence of XC-72 carbon by adding a small amount of sodium acetate as stabilizer. Repeated TEM images showed that the platinum nanoparticles were small and uniform in size and highly dispersed on XC-72 carbon supports when a small amount of sodium acetate solution was added to the synthesis solution. The Pt/C electrocatalysts exhibited very high electrocatalytic activity for liquid methanol oxidation. The effects of adding acetate on Pt particle size and size distribution are discussed. It is demonstrated that acetate can be used as a good stabilizer for preparing Pt/C catalyst with fine and uniform Pt particles.     

Electrocatalytic activities of graphite-supported platinum electrodes for methanol electrooxidation

Electrooxidation of methanol in 1 m NaOH at 30°C was studied on graphite-supported platinum electrodes prepared both in hydrogen and in air at various temperatures. Heating in hydrogen always produced higher surface area of Pt, and hence greater mass activity, than in air at a particular temperature. Nevertheless, both the graphite-supported platinum electrodes exhibited almost the same specific activity as a smooth Pt electrode for methanol electrooxidation irrespective of the preparation conditions. This indicates that the difference in mass activity is due to different surface areas produced by the different preparation methods. The Tafel slope of 110 mV decade^–1 on all the electrodes studied indicated that the first charge transfer process was the rate-determining step.     

Electrocatalytic oxidation of methanol and C1 molecules on highly dispersed electrodes Part II: Platinum-ruthenium in polyaniline

The oxidation of methanol and C1 molecules at electrodes modified with polyaniline and particles of platinum and ruthenium has been studied in aqueous HClO₄ electrolyte. The platinum and ruthenium particles were incorporated into the polyaniline film by electrochemical reduction. The activity for the oxidation of C1 molecules is higher for bimetallic electrodes than for polyaniline-coated electrodes modified with platinum alone. Indeed, a negative shift of more than 100 mV is observed as compared to the potential obtained with a polyaniline film modified by pure platinum. Moreover, the oxidation of methanol is faster and more complete on the Pt-Ru modified polyaniline electrode, since carbon dioxide is the main reaction product.     

Electrocatalytic oxidation of methanol and C1 molecules on highly dispersed electrodes Part 1: Platinum in polyaniline

The oxidation of methanol and C1 molecules was investigated on platinum-modified polyaniline electrodes. It was found that such electrodes are conducting even at 0.0 V vs RHE. They were found to have a higher electrocatalytic activity than bulk platinum electrodes. Moreover, the poisoning effect is drastically decreased as proved by in situ EMIRS studies which show no significant CO_ads signal. Finally, kinetic results show that the methanol electrooxidation is first order with respect to methanol and that the main oxidation product is formaldehyde.     

Pt supported on highly graphitized lace-like carbon for methanol electrooxidation

A simple solvothermal method has been used to synthesize highly graphitized lace-like carbon (GLC) using ethanol as the carbon source and Mg as reducing agent. The GLC is characterized by transmission electron microscopy, X-ray diffraction, N₂ adsorption, Raman spectroscopy and electrochemical techniques. The GLC synthesized at optimized conditions shows interlaced structure with an average thickness of 3 nm. Platinum on GLC electrocatalysts were prepared for methanol oxidation in acidic media for the first time. They show extremely higher activity for methanol oxidation compared to Pt/C electrocatalyst for the same Pt loadings. GLCs act as structural units to form mesopores and channels in the catalyst layers, which lead to the increase of the electrochemical active surface area and improvement in the mass transport by reducing the liquid sealing effect.     

CO and methanol electrooxidation on Pt/Ir/Pt multilayers electrodes

This work describes the CO and methanol electrooxidation over an Ir/Pt bilayer electrodeposited on a platinum polycrystalline substrate. In the blank acidic solution it was observed that the electrochemical behavior of both the polycrystalline Pt and Pt/Ir/Pt nanostructured electrodes were very similar. The electroactive area, calculated using the hydrogen desorption method, are the same for both materials. In order to investigate the effect of the thickness change of Ir interlayer, two different samples were prepared. One with 1 Ir monolayer and the second with 3 monolayers thick. CO stripping voltammograms showed a shift in the anodic peak potential towards the negative direction of 160 and 180 mV for Pt/Ir/Pt 3:1 and 1:1 ML, respectively, compared to polycrystalline Pt. Besides, for methanol electrooxidation, the Pt/Ir/Pt electrodes presented an increase of 170% in the peak current density compared to polycrystalline Pt. These results are in agreement with the calculated activation energies which were 31.5, 39.0 and 43.5 kJ mol⁻¹ for Pt/Ir/Pt 1:1, 3:1 ML and polycrystalline Pt electrodes, respectively. Using the electrochemical impedance spectroscopy, surprisingly, the Pt/Ir/Pt electrodes, did not exhibit the inductive arc which means that the poisoning of the electrode surface is not important in this case.     

The effect of plasma pre-treatment of carbon used as a Pt catalyst support for methanol electrooxidation

Vulcan XC-72 carbon black for use as a catalyst support was treated in three different plasma atmospheres, H₂, Ar and O₂. The results showed that the microstructure and surface functional groups were significantly changed after plasma treatment. Pt/C catalysts were prepared by chemical reduction of H₂PtCl₆ with HCHO and those with untreated and plasma treated carbon black supports were characterized and tested for methanol electrooxidation. TEM showed that the platinum nanoparticles on H₂ and Ar plasma treated carbon were uniform and well distributed. Those on untreated carbon were uniform in most regions but coalesced in others. On O₂ plasma treated carbon agglomeration of the platinum nanoparticles was significant. XRD showed that the catalysts were composed of face-centered cubic Pt nanoparticles and XPS showed that they were metallic with no oxides present. Cyclic voltammetry and chronoamperometry were used to study methanol electrooxidation on the Pt/C catalysts in a solution of 0.5 M H₂SO₄ + 0.5 M CH₃OH, and showed that the catalytic activity those using H₂ and Ar plasma treated carbon was higher than for the untreated one. Catalysts supported by O₂ plasma treated carbon showed no catalytic activity. The treatment atmosphere of carbon therefore had a large effect on the catalyst performance, with the H₂ plasma being the best.     

Pd-Co/CNT复合催化剂的制备及甲醇电氧化性能

以Pd Cl₂和Co(NO₃)₂为原料，采用分步乙二醇还原法制备了多壁碳纳米管负载Pd-Co复合纳米催化剂Pd-Co/CNT。利用TEM、XRD和XPS对催化剂的结构进行了表征，考察了其甲醇电氧化性能。结果显示，Co的引入使Pd催化剂的分散性得到改善，其电化学表面积可达39.7 m²/g。循环伏安测试表明，当Pd∶Co物质的量比为1∶0.2时，Pd-Co/CNT的甲醇氧化峰电流密度约为Pd/CNT的2.7倍。计时电流结果表明，Co的添加使催化剂的活性衰减比例由Pd/CNT的63.8%降至54.2%，显示出较强的抗中毒能力。Pd-Co复合催化剂性能的改善归因于Pd与Co之间的协同相互作用。     

Giant multilayer electrocatalytic effect investigation on Pt/Bi/Pt nanostructured electrodes towards CO and methanol electrooxidation

This work describes CO and methanol electrooxidation over Bi/Pt 1.2:1.2 or 10:10 ML electrodeposited on a bulk platinum substrate. It could be observed in a blank solution that the same features for bulk Pt and Pt/Bi/Pt MM and the hydrogen region were overlaid. The electroactive areas, calculated using the hydrogen desorption method, are the same for both bulk Pt and Pt/Bi/Pt MM electrodes. This is in agreement with AFM images and RMS values, which were the same for bulk Pt and Pt/Bi/Pt MM electrodes. CO stripping voltammograms showed a shift in the anodic peak potential towards the negative direction of 138 and 197 mV for Pt/Bi/Pt 10:10 and 1.2:1.2 ML, respectively, in comparison to bulk Pt. Moreover, for methanol electrooxidation the Pt/Bi/Pt 1.2:1.2 ML electrodes presented an enhancement of 315% and 22 times in the peak current density compared to bulk Pt using cyclic voltammetry and chronoamperometry techniques respectively. Using electrochemical impedance spectroscopy, it was possible to observe the lowest resistance charge transfer for Pt/Bi/Pt 1.2:1.2 ML compared to Pt/Bi/Pt 10:10 ML and bulk Pt respectively. We designate the Pt/Bi/Pt MM electrodes as a giant multilayer electrocatalytic (GME) system, due to their enhanced electrocatalytical properties.     

Direct methanol fuel cell with non-equipotential electrodes

Our model of a direct methanol fuel cell with straight channels is extended to take into account finite conductivity of current collector plates and local contact resistances. Co-flow conditions are assumed and the two cases are considered: (i) when load resistor is connected at the inlet of the feed channels and (ii) when it is connected at the outlet. In both cases voltage loss in the plates induces growth of current production close to the point of load connection. The increase in local current j is accompanied by the growth of local polarization voltages η^a and η^c of the anode and the cathode sides, respectively. Moving the point of load connection one can change the distribution of j,η^a and η^c along the channel. Local “spot” of contact resistance decreases local current and polarization voltages; in the rest part of the cell these values increase.     

PtRu nanoparticles supported on nitrogen-doped multiwalled carbon nanotubes as catalyst for methanol electrooxidation

Nitrogen-doped carbon nanotubes (N-CNT) obtained by plasma treatment were compared to the conventional acid-treated carbon nanotubes (O-CNT) as catalyst support for platinum-ruthenium (PtRu) nanoparticles in the anodic oxidation of methanol in direct methanol fuel cells. PtRu catalysts were prepared by an impregnation-reduction method from chloride precursors with metal loadings of 20 wt.%, and were characterised by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and electrochemical methods. Voltammetry and chronoamperometry studies showed that the performance of PtRu/N-CNT was significantly higher compared to PtRu/O-CNT and also to the commercial E-TEK PtRu/C catalyst, indicating that N-CNT are an interesting support material for fuel cell electrocatalyst. Nitrogen plasma treatment produced pyridinic and pyrrollic species on the CNT surface, which acts as the anchoring sites for the deposition of PtRu particles. A mechanism for the deposition of PtRu on N-CNT is tentatively proposed and discussed.     

Monodispersed hard carbon spherules as a catalyst support for the electrooxidation of methanol

Hard carbon spherules (HCS) were used as support of Pt nanoparticles as electrocatalyst for direct methanol fuel cells (DMFCs). Scanning electron microscopy (SEM) images show that the size of the Pt particles on HCS by reduction of K₂PtCl₆ with ethylene glycol is 4-5 nm. High-resolution transmission electron microscopy (HRTEM) study reveals that the Pt particles on the HCS surface have faceted crystalline structures. The size and aggregation of the Pt particles depend on the surface properties of the carbon support and the medium of the reduction reaction. Cyclic voltammetry and galvanostatic polarization experiments show that the Pt/HCS catalyst exhibits a higher catalytic activity in the electrooxidation of methanol than either the Pt/MCMB or the commercial Pt/Vulcan XC-72 catalyst does.     

Helical nanocoiled and microcoiled carbon fibers as effective catalyst supports for electrooxidation of methanol

We have demonstrated a new synthesis of twist-shaped nanocoiled and herringbone-type double microcoiled carbon fibers via catalytic chemical vapor deposition of acetylene over NiCuMgAl-layered double hydroxides. The materials were characterized by power X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and N₂ adsorption-desorption experiments. For the first time, the use of electrodes modified with platinum particles supported on as-grown helical carbon fibers was studied for electrocatalytic oxidation of methanol. Especially, the electrode supported on herringbone-type double microcoiled carbon fiber showed much larger Pt active surface area than that supported on commercial carbon black. Furthermore, such electrocatalyst has exhibited about fourfold enhancement of activity and excellent anti-poisoning ability, which is believed to be attributed to the combined beneficial effects of novel microstructure and special composition of as-grown helical carbon fibers.     

Direct room-temperature synthesis of a highly dispersed Pd nanoparticle catalyst and its electrical properties in a fuel cell

Highly dispersed palladium nanoparticles supported on bacterial cells were successfully prepared by a microbial method using the metal ion-reducing bacterium Shewanella oneidensis. Resting cells of S. oneidensis reduced soluble palladium(II) to insoluble palladium(0) at room temperature and neutral pH within 60 min when formate was provided as the electron donor. Transmission electron microscopy analysis of a thin section of S. oneidensis cells after exposure to a PdCl₂ solution revealed that palladium particles approximately 5–10 nm in size were deposited on the bacterial surface and in the periplasmic space. The initial concentrations of soluble palladium(II) and formate in the precursor solution strongly influenced the rate of palladium(II) reduction and the dispersity of biomass-supported palladium particles. The dried biomass-supported palladium was tested as an anode catalyst in a polymer electric membrane fuel cell for power production. The maximum power generation of the highly dispersed biomass-supported palladium particles was comparable to that of a commercial palladium catalyst.     

影响甲醇合成催化剂时空收率的因素

研究温度、压力、空速、原料气组成等对甲醇合成催化剂时空收率的影响 ,以及催化剂使用前后的时空收率 ,CO、 CO2 转化率 ,粗甲醇含水量 ,粗甲醇中杂质的变化规律。并对实验结果进行了数学关联和综合分析     

Electrodeposited Pd-Co catalyst for direct methanol fuel cell electrodes: Preparation and characterization

Pd-Co alloy has been recently proposed as a catalyst for the cathode of direct methanol fuel cells with both excellent oxygen reduction activity and methanol tolerance, hence electrodeposition of this alloy is an attractive approach for synthesizing porous metal electrodes with high methanol tolerance in direct methanol fuel cells. In this study, we electrodeposited two types of Pd-Co films onto Au substrates by applying different current density (−10 or −200 mA cm⁻²); and then characterized them in terms of morphology, composition, crystal structure, and catalytic activity. Pd-Co deposited at −10 mA cm⁻² was smooth and possessed smaller particles (ca. 10 nm), while that at −200 mA cm⁻² was dendritic (or rough) and possessed larger particles (ca. 50 nm). Both the Pd-Co alloys were found to be almost the same structure, i.e. a solid solution of ca. Pd₇Co₃ with Pd-skin, and also confirmed to possess comparable activity in oxygen reduction to Pt (potential difference at 1.0 μA cm⁻² was 0.05 V). As for methanol tolerance, cell-voltage was not influenced by addition of 1 mol dm⁻³ methanol to the oxidant solution. Our approach provides fundamental technique for synthesizing Pd-Co porous metal electrodes by electrodeposition.     

高分散镍硅催化剂对喹啉催化加氢的性能

以硝酸镍和硅溶胶为原料,采用蒸氨水热法,制得了一系列负载量为10%(以镍在催化剂中的质量分数计,下同)的镍硅酸盐衍生的Ni-PS-AEH-x(x代表不同焙烧温度,下同)催化剂,并用于喹啉选择性加氢制取1,2,3,4-四氢喹啉。通过考察不同镍基催化剂的加氢性能,发现Ni-PS-AEH-400催化性能最好。通过考察反应条件的影响,确定最佳反应条件为:底物与金属镍投料比(物质的量之比,下同)为30∶1、反应温度100℃、氢气压力3MPa、反应时间120min,此时喹啉转化率为99.0%,1,2,3,4-四氢喹啉收率为95.4%。采用FTIR、XRD、TEM、N2吸附-脱附、H2-TPR和XPS对催化剂结构、组成、形貌进行了表征,结果表明:镍硅酸盐结构使Ni-PS-AEH-400比表面积大、镍纳米粒子分散均匀,活性中心与载体间的相互作用力强,使其在喹啉加氢反应中具有较浸渍法制备Ni/SiO2-IMP更优异的催化性能。     

Mechanistic aspects of methanol oxidation on platinum-based electrocatalysts

An understanding of the overall mechanism of the electrooxidation of methanol is of considerable interest in relation to the optimization of the direct methanol fuel cell. This paper describes in detail the different steps in the oxidation of methanol on platinum-based electrocatalysts with the identification of the key adsorption steps and of the different intermediates involved. From these fundamental studies, it is shown how it is possible to design multimetallic electrocatalysts for the electrooxidation of methanol under experimental conditions suitable for fuel cell application.