Effects of sulfation on the activity of Ce0.67Zr0.33O2 supported Pt catalyst for propane oxidation

The sulfated Ce_0.67Zr_0.33O₂ support was prepared by impregnated with sulfuric acid solution, and the influence of sulfation on propane oxidation activity of the corresponding Pt supported catalysts was evaluated. Sulfation of the ceria–zirconia mixed oxides inhibits its intrinsic activity severely but promoted the Pt supported catalysts significantly. It is evidenced by CO adsorption that the interaction between sulfates and platinum makes the latter in more deficient states (Pt^δ+). These metastable Pt^δ+ species are liable to the atmosphere and act as active sites for propane oxidation.     

Na改性Pt/AlOOH对甲醛催化氧化反应活性的影响

具有晶面取向的阳极氧化AlOOH因其低温甲醛催化性能而被用于催化氧化甲醛体系。为丰富AlOOH表面羟基含量,采用Na₂CO₃为Na前体浸渍法改性载体,制备不同Na含量（0.13%、0.19%、0.30%、0.41%,质量分数）的Pt/Na_x/AlOOH催化剂。通过BET、FTIR、XPS、HRTEM等表征分析,发现加入Na后,Na/AlOOH的表面羟基更加丰富,Pt/Na_x/AlOOH催化剂的比表面积增大,拥有更小的Pt颗粒尺寸,表面Pt颗粒分散度提高,Pt0元素价态含量增加。当Na含量为0.41%时,催化剂Pt/0.41Na/AlOOH的Pt分散度高达56%。实验结果证明,Pt/0.41Na/AlOOH展现出最优的HCHO催化活性,60℃时HCHO转化率达100%。     

Kinetic study of support effect in the propane combustion over platinum catalyst

The support effect on the low-temperature propane combustion over platinum catalysts was investigated by kinetic study. The catalytic activity of supported platinum catalysts varied with the support material, and Pt/SiO₂–Al₂O₃ showed much higher activity than Pt/ZrO₂, as already reported. The reaction order for oxygen was negative and that for propane was positive. The reaction order for propane and oxygen also greatly depended on the support material: Pt/ZrO₂ gave anomalous reaction orders, i.e., –2.9 for oxygen and 3.4 for propane. Further, oxidized Pt/ZrO₂ showed a long-term change of the catalytic activity with time-on-stream, compared with oxidized Pt/SiO₂–Al₂O₃. From these results, it was concluded that high catalytic activity of platinum on acidic support is attributed to high ability to maintain the metallic state of platinum with high oxidation-resistance and high reducibility of platinum oxide.     

Effect of mixed support of carbon black and nanographite on the activity of Pt catalyst for ethanol oxidation

The effect of the mixed support of carbon black and nanographite (CG) on the electrocatalytic activity and stability of the CG supported Pt (Pt/CG) catalyst for ethanol oxidation was investigated. It was found that the electrocatalytic activity and stability of the Pt/CG catalyst for ethanol oxidation depend on the weight ratio of carbon black and nanographite because the carbon black has a large surface area and nanographite has high conductivity. The Pt/CG catalyst with a weight ratio of 10:1 produces the best electrocatalytic activity and stability of the Pt/CG catalyst for ethanol oxidation.     

The role of nitrogen in a carbon support on the increased activity and stability of a Pt catalyst in electrochemical hydrogen oxidation

Nitrogen-containing carbon materials were prepared by acetonitrile pyrolysis on carbon black and used as a support for a Pt catalyst. The Pt particles on N-containing carbon exhibited increased activity and stability in electrochemical hydrogen oxidation relative to Pt on pristine carbon black. The N-doped carbon had a graphitic structure and contained pyridinic and quaternary nitrogen species. The Pt nanoparticles were better-dispersed because of increased hydrophilicity induced by the nitrogen species. The Pt/N-containing carbon showed higher stability in a potential cycling test than Pt/C, because of an increased metal-support interaction. Using XPS and EELS mapping, we demonstrated that the metal-support interaction became stronger and more specific by adding nitrogen into carbon.     

添加剂有机胺对丙烯选择性氧化制丙烯醛催化剂活性的影响

采用共沉淀法制备丙烯选择性氧化制丙烯醛催化剂,考察有机胺的加入对丙烯选择性氧化制丙烯醛催化性能的影响。结果表明,添加有机胺后,催化剂活性在维持不变的情况下,选择性显著提高。采用扫描电镜、X射线衍射、吡啶吸附红外光谱和N₂物理吸附表征等对不同催化剂的物化性能进行表征。结果发现,添加有机胺后,催化剂比表面积略有下降,但催化剂表面的L酸性中心强度明显增加,对催化剂活性影响不大;另一方面,MoO₃结晶度的下降与(Co_0.7Fe_0.3)(MoO₄)结晶度的上升对催化剂选择性均是积极因素。同时孔容的减小以及大孔比例增加更有利于主反应产物的脱附,能抑制深度氧化物的生成。     

The effect of nickel on propane oxidation and sulfur resistance of Pt/Ce0.4Zr0.6O2 catalyst

The effect of nickel on propane oxidation and sulfur resistance of Pt/Ce_0.4Zr_0.6O₂ catalyst has been studied. Samples were characterized by X-ray diffraction, BET area, H₂ temperature programmed reduction. It has been found that the introduction of nickel not only enhances the surface area of the catalyst, but also decreases its reduction temperature. The nickel promoted catalyst is more active in complete oxidation of C₃H₈. Furthermore, the addition of nickel to the catalyst is able to improve the desorption amount of sulfur species under reducing atmosphere, which could decrease the accumulation of sulfur species in the catalyst. Consequently, the sulfur resistance of Pt/Ce_0.4Zr_0.6O₂ catalyst has been improved.     

Stability and performance of catalytic microreactors: Simulations of propane catalytic combustion on Pt

A pseudo-two-dimensional (2D) model is developed to analyze the operation of platinum-catalyzed microburners for lean propane-air combustion. Comparison with computational fluid dynamics (CFD) simulations reveals that the transverse heat and mass transfer is reasonably captured using constant values of Nusselt and Sherwood numbers in the pseudo-2D model. The model also reasonably captures the axial variations in temperatures observed experimentally in a microburner with a gap size. It is found that the transverse heat and mass transport strongly depend on the inlet flow rate and the thermal conductivity of the burner solid structure. The microburner is surface reaction limited at very low velocities and mass transfer limited at high velocities. At intermediate range of velocities (preferred range of reactor operation), mass transfer affects the microburner performance strongly at low wall conductivities, whereas transverse heat transfer affects stability under most conditions and has a greater influence at high wall conductivities. At sufficiently low flow rates, complete fuel conversion occurs and reactor size has a slight effect on operation (conversion and temperature). For fast flows, propane conversion strongly depends on residence time; for a reactor with gap size of , a residence time higher than 6 ms is required to prevent propane breakthrough. The effect of reactor size on stability depends on whether the residence time or flow rate is kept constant as the size varies. Comparisons to homogeneous burners are also presented.     

Oscillations in the oxidation of MIBK over a Pt/HFAU catalyst: role of coke combustion

The catalytic oxidation of methyl-isobutyl-ketone (MIBK) in low concentration (1340 ppm) was investigated over a Pt/HFAU catalyst. Two main reactions were observed: total oxidation into CO₂ and the formation of non-desorbed compounds (“coke”). The conversion into these products depends on the reaction temperature, high temperatures being favourable to the conversion into CO₂ and unfavourable to the conversion into coke. Oscillations in the conversion into CO₂ were observed at specific temperatures, which were explained by coke combustion.     

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.     

Roles of Pt and alumina during the combustion of coke deposits on propane dehydrogenation catalysts

Temperature programmed oxidation of coke deposited on Pt based propane dehydrogenation catalysts reveals that the deposited coke can be categorised into three groups according to their burning temperatures. When coke was separated from the catalyst, however, only one TPO peak could be observed. Experimental results suggest that γ-Al₂O₃ enhances the coke burning process by increasing coke surface area contacts to oxygen. Pt may also act as a catalyst for the coke combustion reaction. Experiments also show that changing dehydrogenation reaction temperature, variation of H₂/HC ratios, addition of only Sn or Sn and an alkali metal (Li, Na and K) can significantly affect the amount of each coke formed. Sample weight used in the temperature programmed oxidation (TPO) experiment also affects the resolution of TPO spectrum.     

用于丙烷催化燃烧的PdxPty-ZSM-5/Cordierite整体式催化剂

以ZSM-5分子筛、铝溶胶、硝酸钯、硝酸铂和水为原料制备分子筛浆料，采用真空抽提-一次涂覆法在堇青石蜂窝陶瓷载体表面制备出Pd_xPt_y-ZSM-5/Cordierite整体式催化剂，考察了Pd负载量、ZSM-5分子筛的硅铝比和Pd/Pt质量比对整体式催化剂的丙烷催化燃烧性能的影响，并用超声波振荡、SEM、XRD、H₂-TPR和C₃H₈-TPD等手段对整体式催化剂进行了表征。当球磨时间为60 min，分子筛浆料固含量为38%时，整体式催化剂的涂层上载量可达到178 g?L^-1，涂层脱落率低于0.5%。Pd₂Pt₃-ZSM-5/Cordierite整体式催化剂（贵金属总负载量为1.2 g?L^-1）对于丙烷的催化燃烧具有较好的催化活性（T₅₀=259℃，T₉₀=323℃）和稳定性，具有良好的工业应用前景，其中较低的ZSM-5分子筛硅铝比以及Pd和Pt之间的相互作用增加了对丙烷的吸附能力和表面活性氧物种的数量，从而提高了整体式催化剂的催化活性。     

MoOx/SBA-15丙烷选择氧化催化剂的研究

采用浸渍法制备了一系列不同Mo含量的MoOx/SBA-15催化剂,并考察了丙烷选择氧化生成醛类含氧化合物（甲醛、乙醛和丙烯醛）的催化剂性能,利用FT-IR和XRD等技术对催化剂及载体的物化性能进行了表征。结果表明,催化剂的活性主要取决于Mo的负载量,当x(Mo)=1.75%［n(Mo)∶n(Si)=1.75∶100］时,醛类选择性约30%,总醛收率为10.4%,高分散催化剂尤其有利于醛类含氧化合物的定向生成。     

Synthesis and activity of the Pt catalyst supported on CNT

Carbon nanotubes (CNT) were obtained by the decomposition of methane on a Ni catalyst supported on Al₂O₃. After the removal of the catalyst materials from CNT, a CNT-supported Pt catalyst was prepared, and this catalyst was characterized by XRD, XPS, and TEM. Activity of the CNT-supported Pt catalyst for hydrogenation of carbon–carbon double bonds at room temperature under the atmospheric pressure of hydrogen was examined. The CNT-supported Pt catalyst showed higher activity than the commercial Pt catalysts supported on activated carbon.     

Electrochemical promotion of the oxidation of propane on Pt/YSZ and Rh/YSZ catalyst-electrodes

The effect of electrochemical promotion (EP) or non-faradaic electrochemical modification of catalytic activity (NEMCA) was studied in the catalytic reaction of the total oxidation of propane on Pt and Rh films deposited on Y₂O₃-stabilized-ZrO₂ (or YSZ), an O²⁻ conductor, in the temperature range 420–520 °C. In the case of Pt/YSZ and for oxygen to propane ratios lower than the stoichiometric ratio it was found that the rate of propane oxidation could be reversibly enhanced by application of both positive and negative overpotentials (“inverted volcano” behavior), by up to a factor of 1350 and 1130, respectively. The induced rate increase Δr exceeded the corresponding electrochemically controlled rate I/2F of O²⁻ transfer through the solid electrolyte, resulting in absolute values of the apparent faradaic efficiency Λ=Δr/(I/2F) up to 2330. The Rh/YSZ system exhibited similar EP behavior. Abrupt changes in the oxidation state of the rhodium catalyst, accompanied by changes in the catalytic rate, were observed by changing the O₂ to propane ratio and catalyst potential. The highest rate increases, by up to a factor of 6, were observed for positive overpotentials with corresponding absolute values of faradaic efficiency Λ up to 830. Rate increases by up to a factor of 1.7 were observed for negative overpotentials. The observed EP behavior is explained by taking into account the mechanism of the reaction and the effect of catalyst potential on the binding strength of chemisorbed reactants and intermediates and on the oxidative state of the catalyst surface.     

Effect of sintering on the catalytic activity of a Pt based catalyst for CO oxidation: Experiments and modeling

The goal of this paper was to make the link between sintering of a 1.6% Pt/Al₂O₃ catalyst and its activity for CO oxidation reaction. Thermal aging of this catalyst for different durations ranging from 15 min to 16 h, at 600 and 700 °C, under 7% O₂, led to a shift of the platinum particle size distributions towards larger diameters, due to sintering. These distributions were studied by transmission electron microscopy. The number and the surface average diameters of platinum particles increase from 1.3 to 8.9 nm and 2.1 to 12.8 nm, respectively, after 16 h aging at 600 °C. The catalytic activity for CO oxidation under different CO and O₂ inlet concentrations decreases after aging the catalyst. The light-off temperature increased by 48 °C when the catalyst was aged for 16 h at 600 °C. The CO oxidation reaction is structure sensitive with a catalytic activity increasing with the platinum particle size. To account for this size effect, two intrinsic kinetic constants, related either to platinum atoms on planar faces or atoms on edges and corners were defined. A platinum site located on a planar face was found to be 2.5 more active than a platinum site on edges or corners, whatever the temperature. The global kinetic law {r (mol m⁻² s⁻¹) = 103 × exp(−64,500/RT)[O₂]^0.74[CO]^−0.5)} related to a reaction occurring on a platinum atom located on planar faces allows a simulation of the CO conversion curves during a temperature ramp. Modeling of the catalytic CO conversion during a temperature ramp, using the different aged catalysts, allows prediction of the CO conversion curves over a wide range of experimental conditions.     

Pt-Fe催化剂次表层Fe结构表面的CO氧化反应性能

利用紫外光电子能谱等表面科学方法,研究了Pt-Fe模型催化剂的次表层Fe结构[即Pt/Fe/Pt(111)结构]在不同条件下CO的吸附及其氧化反应。结果表明,Pt/Fe/Pt(111)结构在H_2气氛或者超高真空中是种稳定结构,最外层的原子与Pt(111)相同,是密排的铂原子面;但次表层的原子中有约0.5单层的铁原子,使费米边附近(0~2.0)e V的电子态密度明显低于Pt(111)表面,从而改变表面的CO和O_2吸附以及反应性能。程序升温的紫外光电子能谱结果显示,Pt/Fe/Pt(111)表面在(100~300)K,CO的吸附受温度的影响不明显,且O_2能够吸附、活化并使共吸附的CO发生氧化反应;当温度为300 K时,O_2无法在Pt/Fe/Pt(111)表面吸附、活化,所以CO氧化反应无法进行。Pt/Fe/Pt(111)结构虽然能有效地减弱CO的吸附从而避免CO毒化的问题,但O_2的吸附和活化也受到显著抑制并影响到一定条件下CO的氧化反应。     

乙醇在Pt/ZSM-5上催化氧化动力学

在内径为4 mm的石英管燃烧器中进行了富氧条件下乙醇在Pt/ZSM-5上的催化深度氧化动力学实验,反应温度控制在428 K以下,建立了Power-rate law模型和Langmuir-Hinshelwood模型来表征乙醇的低温深度氧化反应,Power-rate law模型和Langmuir-Hinshelwood模型的活化能分别为95.96和103.72 kJ·mol^-1,乙醇和氧气的反应级数分别为0.38和1.38。Langmuir-Hinshelwood模型中,乙醇的吸附常数比氧气的吸附常数大,说明乙醇在催化剂表面的吸附能力比氧气强,提高氧气的浓度比提高乙醇的浓度更有利于提高反应速率,这一点同样反映在氧气的反应级数比乙醇的反应级数大。     

Promoting and inhibiting effect of SO2 on propane oxidation over Pt/Al2O3

SO₂ adsorption, SO₂ oxidation and oxidation of propane with oxygen in the absence and the respective presence of SO₂ in the feed gas were studied over unsulfated and sulfated 1% Pt/γ-Al₂O₃.Results showed that the promoting effect of SO₂ in the reaction flux on C₃H₈ oxidation over 1% Pt/γ-Al₂O₃ depends on the presulfating temperature. Catalytic activity measurements and FTIR absorption spectra showed that during propane oxidation, Pt/support interfacial adsorbed species were formed at temperatures 25–300 °C, inhibiting C₃H₈ oxidation. However, at higher temperatures these Pt/support interfacial adsorbed species were oxidized, leading to Pt/support interfacial sulfate species, which strongly promote propane oxidation.