The promoting effect of Pb on carbon supported Pt and Pt/Ru catalysts for electro-oxidation of ethanol

Carbon supported Pt/Pb and Pt/Ru/Pb catalysts were prepared by deposition of Pb on commercial Pt and Pt/Ru catalysts, respectively. It was found that after addition of Pb, the catalytic activity of Pt and Pt/Ru for ethanol oxidation increased greatly, especially at high potentials. It has been shown that decorating commercial Pt and Pt/Ru catalysts with Pb is a simple and effective way to prepare carbon supported Pt/Pb and Pt/Ru/Pb catalysts for ethanol oxidation. The physical properties of the catalysts were characterized by XRD, EDX and TEM, and it was found that no Pt/Pb and Pt/Ru/Pb alloys were formed.     

Analyzing the electroactive surface of gold nanopillars by electrochemical methods for electrode miniaturization

Nanostructured surfaces have recently gained in importance for electrochemical applications because of an enhanced surface area compared to planar substrates. Due to this property, structured substrates are well suited for electrochemical (bio-)sensors, capacitive coupling with electrogenic cells, and other bioelectronic applications. However, the relationship between electrolytically exposed and redox-active surface areas of nanostructured electrodes compared to planar electrodes is still under discussion. Here, we performed a series of comparative studies to elucidate processes taking place at the electrochemically active surface of gold nanopillars. The pillars, approximately 200 nm in height and 50 nm in diameter, were fabricated using template-assisted nanostructuring. The surface area increase compared to planar electrodes was determined by scanning electron microscopy (SEM), and the redox-active surface area of the same sample was derived from cyclovoltammetric studies. We found consistency between the SEM results and the electrochemically active surfaces determined by cyclic voltammetry of immobilized ferrocenylhexanethiol, immobilized cytochrome c, and oxidation/reduction of gold for small scan rates. Similar values were derived from the capacitance measured by cyclic voltammetry, whereas impedimetric measurements revealed values twice as high. Commonly used diffusion-controlled systems, such as hexacyanoferrate, showed a smaller increase of the electroactive surface area. Finally, we conclude that the sterically restricted diffusion of redox-active species leads to an inaccurate determination of the electroactive surface area of nanosized electrodes.     

Comparison of different promotion effect of PtRu/C and PtSn/C electrocatalysts for ethanol electro-oxidation

Well dispersed PtSn/C, PtRu/C and Pt/C electrocatalysts were synthesized by a modified polyol process and characterized by X-ray diffraction (XRD), transmission electron microscope (TEM) and inductively coupled plasma-atomic emission spectrometry techniques. XRD patterns show that Ru induces the contraction of Pt lattice parameter while Sn makes the Pt crystal lattice extended. Ethanol oxidation activities on the catalysts were studied via cyclic voltammetry (CV) and chronoamperometry (CA) methods at room temperature. It is found that the electrode potential plays an important role in the electrochemical behavior of ethanol oxidation on PtRu/C and PtSn/C catalysts. In the lower potential region, PtSn/C possesses higher performance for ethanol oxidation, while in the higher potential region PtRu/C is more active. The different promotion effects of PtSn/C and PtRu/C to ethanol oxidation can be explained by the structural effect and modified bi-functional mechanism in different potential region. Single cell test of a direct ethanol fuel cell (DEFC) was also carried out to elucidate the promotion effect of PtRu/C and PtSn/C catalysts on the ethanol oxidation at 90 °C.     

Pt decorating of PdNi/C as electrocatalysts for oxygen reduction

A low-cost and high performance catalyst consisting of Pt decorating PdNi/C (Pt-PdNi/C) for oxygen reduction is prepared by a two-stage route. The characterization techniques considered are X-ray diffraction (XRD), transmission electron microscopy (TEM) and energy dispersive X-ray analysis (EDX) technique. The results show that the Pt-PdNi/C catalyst has an average diameter of ca. 5 nm. The electrochemical activity for the ORR is evaluated from steady state polarization measurements, which are carried out in an ultra-thin layer rotating disk electrode (RDE). The RDE tests show that the Pt-PdNi/C catalyst has the highest ORR activity compared to pure Pt/C, Pd/C and PdNi/C catalysts. High electrocatalytic activities could be attributed to the synergistic effect between Pt and PdNi.     

Preparation and characterization of successively deposited Pt/Ru bimetallic electrocatalysts for the methanol oxidation

Two types of Pt/Ru electrocatalysts, which have different structural characteristics, were prepared with different synthetic routes. That is, Pt/Ru electrocatalysts were synthesized by the coreduction and successive deposition methods, respectively. The structural and catalytic properties of Pt/Ru electrocatalysts were characterized by XRD, TEM, voltammetry and chronoamperometry. From the XRD analysis, coreduced and successively deposited Pt/Ru electrocatalysts had an alloyed structure. TEM analyses showed that all the electrocatalysts had a highly dispersed state on the Vulcan XC-72R substrate. From the voltammetry, the coreduced electrocatalysts displayed higher catalytic activity than the successively deposited electrocatalysts for the electrooxidation of methanol. These results explain why coreduced catalysts are better able to dehydrogenate methanol and have a greater CO tolerance than the successively deposited ones. But chronoamperometry showed that successively deposited Pt/Ru electrocatalysts had stability similar to that of the coreduced ones. Although the successively deposited electrocatalysts showed lower catalytic activity than the coreduced ones, their enhanced catalytic activity was obtained by the successive deposition method in the comparison of methanol oxidation current density with pure platinum electrocatalyst.     

Enantioselective hydrogenation of ethyl pyruvate catalysed by Pt/graphite: Superior performance of sintered metal particles

A 5% Pt/graphite catalyst has been sintered in 5% H₂/Ar at 400, 500, 600, 700, 800, and 1000 K and cinchonidine-modified samples used to catalyse enantioselective ethyl pyruvate hydrogenation at 293 K and 30 bar pressure. Changes in catalyst morphology on sintering have been investigated by high resolution electron microscopy and cyclic voltammetry. The as-received catalyst contained small Pt particles aggregated into clusters. As the temperature was raised these clusters disaggregated; the resulting small particles grew, first showing enhanced crystallinity and better defined step and terrace topography, and later progressive faceting. Ultimately the particles were large and hexagonal. These processes were accompanied by a loss of surface area and a reduction in catalytic activity. Enantiomeric excess rose from 43% for as-received material to 63% for catalyst sintered at 700 K, and declined for higher sintering temperatures. The particle size distribution for the optimal catalyst peaked at 8 nm and most particles were substantially faceted. Chiral performance is interpreted in terms of enhanced enantioselectivity provided by edge sites in the Pt surface. Modification of chiral kink sites by alkaloid, to give diastereomeric enantioselective sites may have further enhanced the enantioselectivity. The investigation provides clear objectives for future catalyst design.     

聚苯胺修饰电极对甲醇的电催化氧化研究

应用电化学方法制备了Pt/PAn/GC电极,优化了苯胺在玻碳电极上的聚合条件,并对其进行了表征.结果表明,铂微粒在聚苯胺膜电极上具有很高的分散度,电极具有很大的比表面积,Pt/PAn/GC电极对甲醇电氧化的催化活性明显高于Pt/GC电极和Pt电极,在该电极上甲醇正向扫描和反向扫描时的氧化峰电流为58.68mA/cm2和50.00mA/cm2,为Pt/GC电极的1.6倍和1.7倍,为Pt电极的3.0倍和3.1倍,从而有效地提高了铂的催化活性,并得到在玻碳电极上聚合苯胺的最佳条件为扫描速度50mV/s,扫描上限1.2V.     

Low temperature CO pulse adsorption for the determination of Pt particle size in a Pt/cerium-based oxide catalyst

Unexpectedly large amounts of CO adsorption have resulted from a pulse adsorption experiment at 323 K, giving about 300% Pt dispersion in a Pt/cerium-based oxide catalyst. An in situ diffuse reflectance infrared Fourier transform spectroscopic investigation on a Pt/cerium-based oxide during CO adsorption has revealed that carbonate species on the cerium oxide surface are responsible for the unrealistically large CO adsorption at 323 K, as a result of CO spillover. Lowering the temperature to 195 K considerably diminished the amount of CO adsorption. The size of the Pt particles in the Pt/cerium-based oxide catalyst was determined by CO pulse adsorption at 195 K and showed good agreement with the particle size determined by X-ray diffraction and low energy ion scattering. This indicates that CO pulse adsorption at 195 K is a useful technique to reliably estimate the Pt particle size in a Pt/cerium-based oxide catalyst.     

用Pt/C催化剂通过浸渍-还原法制备疏水催化剂

选择XC-72R炭黑为载体,采用改进的浸渍-还原法制备了2~3 nm高分散度Pt/C催化剂。研究了还原温度、还原剂、pH和甲醛用量等工艺条件对Pt粒径大小及分散度的影响,采用透射电镜和X射线衍射等对催化剂进行表征。结果表明,提高溶液pH和反应温度、增加甲醛用量均有助于得到Pt粒子粒径较小的高分散度Pt/C催化剂,较佳的工艺条件为:用乙二醇与水为炭黑分散溶剂,反应温度80~90℃,pH≈11,甲醛用量80倍于PtCl62-物质的量,可以制备Pt粒子粒径在2 nm左右的高分散度Pt/C催化剂。     

Ｐｔ／Ｃ催化剂催化硝基苯加氢制对氨基苯酚工艺过程剖析

本文介绍了硝基苯催化加氢制对氨基苯酚的研究概况；探讨了在加氢工艺路线中的若干技术关键，如温度、氢分压、ｐＨ值及加氢深度等；评述了添加助剂提高对氨基苯酚收率的方法，并对其优缺点进行了讨论。     

Pt/PAn/GC电极的制备及对甲酸电催化氧化性能的研究

利用循环伏安法电聚合导电高分子聚苯胺，并制备了Pt／PAn／GC电极和Pt／GC电极，优化了苯胺在玻碳电极上的聚合条件，用在H2SO4中的循环伏安曲线对其进行了表征，Pt／PAn／GC电极的制备提高了Pt的分散度，增加了催化剂Pt的利用率。实验结果表明Pt／PAn／GC电极对甲酸电氧化的催化活性明显高于Pt／GC电极和Pt电极，正向扫描和反向扫描时对应的氧化峰电位分别是0．68V、0．45V。峰电流为54．23mA／cm^2和84．23mA／cm^2，为Pt／GC电极的修饰电极1．7倍和1．9倍，为Pt片电极的3．8倍和4．9倍，有效地提高了铂微粒的催化活性，并得到聚合苯胺的最佳条件为扫描速度50mV／s、扫描上限1．2V。     

Comparison of NO adsorbing ability and process on Pt/Mg/Al oxide catalysts prepared by different methods

Pt/Mg/Al metal oxide catalysts were prepared by impregnation and co-precipitation methods, respectively. These samples were characterized by BET, XRD and NO-TPD; their NO _X storage property and adsorbing intermediate species were investigated with NSC and FTIR. The results showed that the prepared methods exert significant influence on the physical structure properties and the adsorption abilities of NO. (Pt)/Mg/Al samples prepared by impregnation (IM) have larger specific areas and higher NO _X storage capacity than (Pt)/Mg/Al catalysts prepared by co-precipitation (CP). The intermediate species of NO adsorbing process indicated that NO was firstly adsorbed as bridged nitrites both on Pt/Mg/Al (IM) and on Pt/Mg/Al (CP), then on Pt/Mg/Al (IM) the nitrites transferred into monodentate and bidentate nitrate species while on Pt/Mg/Al (CP) the nitrites only transferred into monodentate nitrate species.     

The nature of activity enhancement for propane oxidation over supported Pt catalysts exposed to sulphur dioxide

The nature of the active sites, the role of the support, and the mechanism by which hydrocarbons are activated over supported Pt catalysts have been investigated for the combustion of propane in the presence and absence of SO₂. A strong enhancement in the activity for propane oxidation has been confirmed either when SO₂ is introduced with the propane or with a pre-sulphated alumina-supported catalyst. No equivalent effects were found with silica-supported catalysts. Fluorination of the alumina support also leads to an increase in activity. The addition of pulses of SO₂ into the propane-containing gas stream produces a very large, but short-lived, increase in activity in addition to a more gradual and progressive activity enhancement. Reasons for these different effects are discussed. Attempts to correlate the permanent enhancement in activity with the total acidity of the support were unsuccessful. It appears that the increase in activity is due to a more subtle effect and a model is presented in which the possible role of perimeter sites at the metal–support interface is emphasised.     

Performance of highly dispersed Pt/C catalysts for low temperature fuel cells

A novel technique based on intermittent microwave heating (IMH) is used to prepare highly dispersed Pt/C catalysts. It has been proved that more than 60% Pt on carbon can be prepared by one-step procedure. The average Pt clusters on carbon are less than 5 nm with very narrow size distribution. The catalysts prepared by the present method show better performance in low temperature fuel cells.     

The potential of zero total charge of Pt nanoparticles and polycrystalline electrodes with different surface structure: The role of anion adsorption in fundamental electrocatalysis

In the present paper anion effects are discussed on different shape-controlled Pt nanoparticles as well as on polycrystalline Pt electrodes of different surface structures. In particular, the potentials of zero total charge (pztc) were determined by using the CO displacement approach, both in sulphuric and perchloric media. The CO monolayer oxidative stripping was studied on the different samples. CO coverages were independent of the electrolyte provided that the true CO stripping charges, corrected for double layer contributions are compared to the charge involved only in the hydrogen adsorption region. The classical charge density normalization process is discussed and small changes are proposed. Then, criteria to evaluate the real surface area of platinum electrodes from charge measurements are proposed in both electrolytes.     

Model catalysts fabricated by electron beam lithography: AFM and TPD surface studies and hydrogenation/dehydrogenation of cyclohexene + H2 on a Pt nanoparticle array supported by silica

Pt nanoparticle model catalysts with 28 ± 2 nm diameters and 100 ± 2 nm square periodicity have been fabricated with electron beam lithography on silica substrates. The reactivity of the Pt/SiO₂ arrays was compared to a Pt foil for cyclohexene + H₂ at 100°C. The overall reactivity of the Pt particle arrays was higher by a factor of two, the selectivity towards dehydrogenation was three times higher, and the rate of deactivation was about the same as for the Pt foil. Since the primary difference between the nanoparticle array and the Pt foil was the interface between the Pt and the SiO₂, the interfacial region was most likely responsible for the changes in reactivity on the arrays. Using AFM, SEM, and TPD, the arrays were characterized before and after being exposed to reaction conditions. AFM images of a sample cleaned by ion sputtering showed that the pattern of the Pt nanoparticle array was replicated in the silica during the sputtering process. This revised version was published online in June 2006 with corrections to the Cover Date.     

Preparation of Low Loading Pt/C Catalyst by Carbon Xerogel Method for Ethanol Electrooxidation

Low platium loading Pt/C catalyst was prepared by direct Pt-embedded carbon xerogel method. The Pt content of the as-prepared Pt/C is about 4.32 wt% and has a typical polycrystalline phase. Textural and structural characteristics of the catalysts were characterized by XRD, EDS and BET. Pt-embedded in carbon xerogel increases the specific surface area and pore volume of the X-Pt/C during carbon gelation and the carbonization process. Electrochemical characteristics of the catalysts for ethanol electrooxidation were measured. The results indicated that the as-prepared 4.32 wt% Pt/C has higher mass current density in ethanol electrooxidation as compared to the 20 wt% Pt/C. This may be due to the high roughness of the Pt surface that is formed during the carbon gelation and carbonization process.     

On the determination of platinum particle size in carbon-supported platinum electrocatalysts for fuel cell applications

Using a conventional laboratory diffractometer, small angle X-ray scattering (SAXS) was used to determine the average platinum particle size in samples of carbon with a range of platinum loadings. The results obtained were compared with those obtained from wide-angle X-ray diffraction (WAXS) studies. SAXS was more effective than WAXS for determining the average platinum particle size in samples where the grains were so small that the resultant diffraction peaks in the WAXS profiles were too broad to accurately determine the peak width for use in the Scherrer equation.     

Determination of cyclodextrin inclusion constant for aromatic carbonyl compounds through spectrophotometric and electrochemical methods

α- and β-Cyclodextrins cavity inclusion constants (K_i) were determined for a series of benzaldehydes and acetophenones by using two different methods: Benesi-Hildebrand (BH) UV/vis spectroscopic method and electrochemical current (EC) method, determined by cyclic voltammetry. The values determined in the group of benzaldehydes varied from 322 ± 27 to 5688 ± 317 mol⁻¹ dm³ for UV/vis method, and 342 ± 19 to 7386 ± 142 mol⁻¹ dm³ for EC method. The values determined in the group of acetophenones varied from 2201 ± 88 to 9125 ± 251 mol⁻¹ dm³ for UV/vis method, and 1473 ± 33 to 7555 ± 187 mol⁻¹ dm³ for EC method. The equilibrium time estimated for UV/vis spectroscopic (BH) method was 240 min and for the cyclic voltammetry (EC) method was 310 min. Notably, despite their limitations, both methods were suitable and reliable for inclusion constant measurement, if the equilibrium time of the system is well established.     

Fitting the experimental conditions and characteristics of Pt/C catalyst for the selective hydrogenation of citral

A Pt catalyst supported on activated carbon was prepared and pretreated at different conditions. Both experimental conditions and catalyst characteristics were optimized. The influence of the textural properties of the support on the catalytic performance, based on the study of the internal and external diffusional limitations, is presented. The Pt-dispersion and its localization along the porosity of the support, strongly influences the activity and the product distribution. The production of valuable unsaturated alcohols is favored using catalysts with a Pt-particle size of around 8?nm working at a high hydrogen pressure and moderate temperatures. Secondary reactions are favored by increasing the temperature and the presence of active particles inside the mesopores of the support.