CO tolerance and catalytic activity of Pt/Sn/SnO2 nanowires loaded on a carbon paper

Electrochemical activities and structural features of Pt/Sn catalysts supported by hydrogen-reduced SnO₂ nanowires (SnO₂NW) are studied, using cyclic voltammetry, CO stripping voltammetry, scanning electron microscopy, and X-ray diffraction analysis. The SnO₂NW supports have been grown on a carbon paper which is commercially available for gas diffusion purposes. Partial reduction of SnO₂NW raises the CO tolerance of the Pt/Sn catalyst considerably. The zero-valence tin plays a significant role in lowering the oxidation potential of CO_ads. For a carbon paper electrode loaded with 0.1 mg cm⁻² Pt and 0.4 mg cm⁻² SnO₂NW, a conversion of 54% SnO₂NW into Sn metal (0.17 mg cm⁻²) initiates the CO_ads oxidation reaction at 0.08 V (vs. Ag/AgCl), shifts the peak position by 0.21 V, and maximizes the CO tolerance. Further reduction damages the support structure, reduces the surface area, and deteriorates the catalytic activity. The presence of Sn metal enhances the activities of both methanol and ethanol oxidation, with a more pronounced effect on the oxidation current of ethanol whose optimal value is analogous to those of PtSn/C catalysts reported in literature. In comparison with a commercial PtRu/C catalyst, the optimal Pt/Sn/SnO₂NW/CP exhibits a somewhat inferior activity toward methanol, and a superior activity toward ethanol oxidation.     

Ethanol oxidation on the ternary Pt-Rh-SnO2/C electrocatalysts with varied Pt:Rh:Sn ratios

Ternary Pt-Rh-SnO₂/C electrocatalysts with the atomic ratio Pt:Rh:Sn = 3:1:x, where x varies from 2 to 6, were synthesized using the modified polyol method followed by thermal treatment. Several techniques used to characterize these electrocatalysts showed they were composed of homogeneous PtRh alloy and SnO₂, having all three constituents coexisting in single nanoparticles with the average particle size around 1.4 nm and a narrow size distribution. While all the electrocatalysts investigated exhibited high catalytic activity for ethanol oxidation, the most active one had the composition with the Pt:Rh:Sn = 3:1:4 atomic ratio. These ternary-electrocatalysts effectively split the C-C bond in ethanol at room temperature in acidic solutions, which is verified using the in situ IRRAS technique.     

Ethanol oxidation on novel, carbon supported Pt alloy catalysts—Model studies under defined diffusion conditions

The structure, surface composition and activity/selectivity for ethanol oxidation of carbon supported Pt alloy catalysts with different composition and catalyst loading, which were synthesized via the polyol-route, were investigated and characterized by microscopic/spectroscopic methods (TEM, EDX, XRD) and electrochemical (RDE, on-line DEMS) measurements under well-defined transport and diffusion conditions. The performance of the polyol-type Pt/C (20 wt.%), PtRu/C (20, 40 and 60 wt.%), and Pt₃Sn/C (20 wt.%) catalysts was compared with that of commercial Pt/C, PtRu/C and Pt₃Sn/C (E-Tek) catalysts. The metal particle sizes of the polyol-type catalysts are significantly smaller than those of the corresponding commercial catalysts, nevertheless both the mass specific activities and, more pronounced, the inherent, active surface area specific activities are lower than those of the commercial catalysts, which is related to the lower degree of alloy formation in the polyol-type catalysts. For all catalysts, incomplete ethanol oxidation to C2 products (acetaldehyde and acetic acid) prevails under conditions of this study, CO₂ formation contributes by ≤1% for potentiostatic reaction conditions. The lower activity of the polyol-type catalysts is mainly due to the lower activity for acetaldehyde formation. Implications and further strategies for fuel cell applications are discussed.     

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.     

Preparation of SnO2-CNTs supported Pt catalysts and their electrocatalytic properties for ethanol oxidation

SnO₂-carbon nanotubes (CNTs) composites were prepared by sol-gel method, and characterized by scanning electron microscopy and X-ray diffraction. Due to high stability in diluted acidic solution, SnO₂-CNTs composites were selected as the catalyst support and second catalyst for ethanol electrooxidation. The electrocatalytic properties of the SnO₂-CNTs supported platinum (Pt) catalyst (Pt/SnO₂-CNTs) for ethanol oxidation have been investigated by typical electrochemical methods. Under the same mass loading of Pt, the Pt/SnO₂-CNTs catalyst shows higher electrocatalytic activity and better long-term cycle stability than Pt/SnO₂ catalyst. Additionally, the effect of the mass ratio of CNTs to SnO₂ on the electrocatalytic activity of the electrode for ethanol oxidation was investigated, and the optimum mass ratio of CNTs to SnO₂ in the Pt/SnO₂-CNTs catalyst is 1/6.3.     

Low-temperature mild partial oxidation of ethanol over supported platinum catalysts

Supported platinum catalysts containing 1.2% Pt loaded on Al₂O₃ (1.2% Pt/Al₂O₃) and 1.9% Pt loaded on ZrO₂ (1.9% Pt/ZrO₂) were prepared by incipient wetness impregnation and sol–gel method, respectively. The activity of these catalysts in the partial oxidation of ethanol (POE) was examined in a fixed-bed reactor in a temperature range between 373 and 473 K. The results indicated that significant ethanol conversion (C_EtOH > 50%) was found at the low reaction temperature with a feed ratio of O₂/EtOH ratio >0.75. Oxygen molecules introduced in reactant were completely consumed in POE reactions performed. H₂, H₂O, CO and CO₂ were the major products detected. The selectivity of hydrogen (S_H2) and CO (S_CO) varied significantly with reaction conditions. High selectivity of hydrogen (S_H2 > 95%) and low selectivity of CO (S_CO  0%) were found from a mild oxidation at T_R = 373 K over Pt/ZrO₂. However, these two selectivities were drastically deteriorated through oxidation at high T_R, high O₂/EtOH ratio or over Pt/Al₂O₃ catalyst.     

Structure sensitivity of dimethylamine deep oxidation over Pt/Al2O3 catalysts

The deep oxidation of dimethylamine (DMA) was studied over Pt/Al₂O₃ catalysts with small (1 nm) and large (7.8–15.5 nm) Pt crystallite sizes. The turnover frequency (TOF) was higher for the large than for the small Pt crystallites, indicating that the reaction is structure sensitive. Two kinetic models were used to interpret the obtained results, i.e., the Mars van Krevelen and a mechanism based on the adsorption of oxygen and adsorption of dimethylamine on different active sites were employed. Both models showed that the activation energy for the oxygen chemisorption rate constant (k_o) decreased with increasing of Pt crystallite size and that the activation energy for the surface reaction rate constant (k_i) was independent of the Pt crystallite size. The structure sensitivity may be explained by differences in the reactivity of the oxygen adsorbed on these Pt crystallites.The Mars van Krevelen model fits the TOF values very well at concentrations of DMA higher than 1500 ppm, while in the lower concentrations region, the model under predicts the experimental data. The model based on the adsorption of oxygen and DMA on different active sites fits the experimental data quite well over the whole temperature and concentration range. The fitted values of the Henry adsorption constant are independent of the Pt crystallite size.     

MnOx/Pt/Al2O3 catalysts for CO oxidation in H2-rich streams

The catalytic activity of Pt on alumina catalysts, with and without MnO_x incorporated to the catalyst formulation, for CO oxidation in H₂-free as well as in H₂-rich stream (PROX) has been studied in the temperature range of 25–250 °C. The effect of catalyst preparation (by successive impregnation or by co-impregnation of Mn and Pt) and Mn content in the catalyst performance has been studied. A low Mn content (2 wt.%) has been found not to improve the catalyst activity compared to the base catalyst. However, catalysts prepared by successive impregnation with 8 and 15 wt.% Mn have shown a lower operation temperature for maximum CO conversion than the base catalyst with an enhanced catalyst activity at low temperatures with respect to Pt/Al₂O₃. A maximum CO conversion of 89.8%, with selectivity of 44.9% and CO yield of 40.3% could be reached over a catalyst with 15 wt.% Mn operating at 139 °C and λ = 2. The effect of the presence of 5 vol.% CO₂ and 5 vol.% H₂O in the feedstream on catalysts performance has also been studied and discussed. The presence of CO₂ in the feedstream enhances the catalytic performance of all the studied catalysts at high temperature, whereas the presence of steam inhibits catalysts with higher MnO_x content.     

Promotion effect of Sn in alumina-supported Pt catalysts for CO-PROX

In this work we have studied the effect of the addition of Sn to alumina-supported Pt catalysts towards the catalytic performance in CO-PROX reaction. Monometallic Pt and Sn catalysts supported on alumina, and bimetallic Pt–Sn supported on alumina (with Pt/Sn atomic ratios of 1.92, 0.53 and 0.28) was prepared by successive impregnation, with high dispersion of the metal. The addition of Sn to Pt does not substantially increase the activity in CO-PROX at low temperatures; however, the temperature interval where the CO conversion is maximum was significantly increased. The optimum Pt/Sn atomic ratio was found to be 0.53. In a wide operation window with respect to temperature, the catalyst with optimum Pt to Sn ratio shows a maximum CO conversion of 78% for λ = 2 with constant selectivity (about 40%) and with 31%CO yield. In the presence of either CO₂ or H₂O the performance of Sn promoted catalyst was seen to show improved activity.     

Pt催化丙烷脱氢过程中结焦反应的粒径效应与Sn的作用

用乙二醇还原法制备了Pt颗粒平均粒径分别为2.0、4.6、12.1 nm的Pt/Al₂O₃催化剂,同时用浸渍法制备了PtSn/Al₂O₃双金属催化剂,并考察了各催化剂在丙烷脱氢过程中的结焦行为。分别用H₂化学吸附、透射电镜、热重分析、元素分析、红外光谱、拉曼光谱等手段对催化剂进行了表征。表征结果显示,催化剂金属上的结焦速率与Pt金属颗粒粒径密切相关。具有较小Pt颗粒的催化剂金属上的结焦速率明显大于具有较大Pt颗粒的催化剂。具有较小Pt颗粒的催化剂上生成的焦含有较少的氢,其石墨化程度也较高。本研究中PtSn/Al₂O₃催化剂金属上的结焦速率高于Pt/Al₂O₃催化剂,并且在双金属上生成的焦具有更高的石墨化程度。结合Pt/Al₂O₃催化剂上的结焦机理,对高性能丙烷脱氢催化剂提出了新的概念设计。     

A novel dual thin-layer flow cell double-disk electrode design for kinetic studies on supported catalysts under controlled mass-transport conditions

We present a novel dual thin-layer flow cell double-disk electrode design, which due to its high collection efficiency in combination with a reasonable time resolution allows highly sensitive measurements of electro-active species generated during electrochemical reactions on the working electrode. Most important, it allows for rapid changes of the electrolyte during the measurements, which in combination with a thin-film electrode, where an inert glassy carbon substrate is covered by a thin film of carbon-supported noble metal catalyst, makes it particularly useful for kinetic studies on electrocatalytic fuel cell reactions under realistic conditions (continuous reaction, continuous electrolyte flow) and on realistic materials (supported catalysts).The performance of the set-up and its suitability for kinetic studies, in particular for transient experiments involving rapid electrolyte exchange, are demonstrated in potentiodynamic and transient potentiostatic measurements for the oxygen reduction reaction on carbon-supported Pt catalysts and, for comparison, on Pt-free Vulcan carbon supports.     

CO oxidation and CO2 reduction on carbon supported PtWO3 catalyst

The activity of a carbon supported PtWO₃ (PtWO₃/C) catalyst in the CO oxidation and CO₂ reduction reactions was evaluated in sulfuric acid solution at room temperature.Cyclic voltammetry combined with on-line mass spectrometry shows that the oxidation of both saturated CO adlayer and dissolved CO on PtWO₃/C material commences at rather low potentials, ca. 0.18 and 0.12 V vs. RHE, respectively. However, the low-potential process seems to involve only a minor fraction of the CO adlayer, the major part of the adsorbed CO layer being oxidised at the potentials as high as those for pure Pt catalysts—ca. 0.7 V vs. RHE. PtWO₃/C material was found to reversibly de-activate upon a prolonged exposure to the CO-saturated solution due to the inhibition of the hydrogen tungsten bronze formation.The reduction of CO₂ on PtWO₃/C leads to the formation of an adsorbate - presumably CO - on the Pt sites of the catalyst. Although the rate of the adsorbate build-up on PtWO₃/C at 0.1 V is lower than that on pure Pt/C, our results indicate that upon a prolonged exposure of the PtWO₃/C electrode to a CO₂-saturated solution a complete poisoning of the Pt sites with the adsorbate is likely to occur at room temperature.     

Electrooxidation of acetaldehyde on carbon-supported Pt, PtRu and Pt3Sn and unsupported PtRu0.2 catalysts: A quantitative DEMS study

The oxidation of acetaldehyde on carbon supported Pt/Vulcan, PtRu/Vulcan and Pt₃Sn/Vulcan nanoparticle catalysts and, for comparison, on polycrystalline Pt and on an unsupported PtRu_0.2 catalyst, was investigated under continuous reaction and continuous electrolyte flow conditions, employing electrochemical and quantitative differential electrochemical mass spectroscopy (DEMS) measurements. Product distribution and the effects of reaction potential and reactant concentration were investigated by potentiodynamic and potentiostatic measurements. Reaction transients, following both the Faradaic current as well as the CO₂ related mass spectrometric intensity, revealed a very small current efficiency for CO₂ formation of a few percent for 0.1 m acetaldehyde bulk oxidation under steady-state conditions on all three catalysts, the dominant oxidation product being acetic acid. Pt alloy catalysts showed a higher activity than Pt/Vulcan at lower potential (0.51 V), but do not lead to a better selectivity for complete oxidation to CO₂. C–C bond breaking is rate limiting for complete oxidation at potentials with significant oxidation rates for all three catalysts. The data agree with a parallel pathway reaction mechanism, with formation and subsequent oxidation of CO_ad and CH _{x, ad} species in the one pathway and partial oxidation to acetic acid in the other pathway, with the latter pathway being, by far, dominant under present reaction conditions.     

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.     

Pt／尼龙催化剂在硝基苯加氢中的应用

民了Ｐｔ／尼龙催化剂,成功地将其用作硝苯加氢一中成对氨基苯酚的催化剂,同时研究了金属负载量、催化剂还原方法、共催化剂、金属铂结晶颗粒的大小及分布与Ｐｔ／尼催化剂的活性和选择性的关系。     

Electrochemical characterization of the electrooxidation of methanol,ethanol and formic acid on Pt/C and PtRu/C electrodes

Methanol, ethanol and formic acid electrooxidations in acid medium on Pt/C and PtRu/C catalysts were investigated. The catalysts were prepared by a microwave-assisted polyol process. Cyclic voltammetry and chronoamperometry were employed to provide quantitative and qualitative information on the kinetics of methanol, ethanol and formic acid oxidations. The PtRu/C catalyst showed higher anodic current densities than the Pt/C catalyst and the addition of Ru reduced the poisoning effect.     

Selective CO oxidation in the presence of hydrogen over supported Pt catalysts promoted with transition metals

Selective CO oxidation in the presence of excess hydrogen was studied over supported Pt catalysts promoted with various transition metal compounds such as Cr, Mn, Fe, Co, Ni, Cu, Zn, and Zr. CO chemisorption, XRD, TPR, and TPO were conducted to characterize active catalysts. Among them, Pt-Ni/γ-Al₂O₃ showed high CO conversions over wide reaction temperatures. For supported Pt-Ni catalysts, Alumina was superior to TiO₂ and ZrO₂ as a support. The catalytic activity at low temperatures increased with increasing the molar ratio of Ni/Pt. This accompanied the TPR peak shift to lower temperatures. The optimum molar ratio between Ni and Pt was determined to be 5. This Pt-Ni/γ A1₂O₃ showed no decrease in CO conversion and CO₂ selectivity for the selective CO oxidation in the presence of 2 vol% H₂O and 20 vol% CO₂. The bimetallic phase of Pt-Ni seems to give rise to stable activity with high CO₂ selectivity in selective oxidation of CO in H₂-rich stream.     

Pt/Al_2O_3催化剂失活分析及再生处理

介绍了苯加氢制环己烷过程中的Pt/Al2 O3 催化剂酸中心的产生、积碳、机械杂质的覆盖及水、硫、一氧化碳等对催化剂活性、选择性、寿命的影响 ,以及催化剂失活后的再生方法