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21.
Shampa Kandoi Jeff Greeley Marco A. Sanchez-Castillo Steven T. Evans Amit A. Gokhale James A. Dumesic Manos Mavrikakis 《Topics in Catalysis》2006,37(1):17-28
A microkinetic model for methanol decomposition on platinum is presented. The model incorporates competitive decomposition
pathways, beginning with both O–H and C–H bond scission in methanol, and uses results from density functional theory (DFT)
calculations [Greeley and Mavrikakis, J. Am. Chem. Soc. 124 (2002) 7193, Greeley and Mavrikakis, J. Am. Chem. Soc. 126 (2004)
3910]. Results from reaction kinetics experiments show that the rate of H2 production increases with increasing temperature and methanol concentration in the feed and is only nominally affected by
the presence of CO or H2 with methanol. The model, based on the values of binding energies, pre-exponential factors and activation energy barriers
derived from first principles calculations, accurately predicts experimental reaction rates and orders. The model also gives
insight into the most favorable reaction pathway, the rate-limiting step, the apparent activation energy, coverages, and the
effects of pressure. It is found that the pathway beginning with the C–H bond scission (CH3OH→H2COH→HCOH→CO) is dominant compared with the path beginning with O–H bond scission. The cleavage of the first C–H bond in methanol
is the rate-controlling step. The surface is highly poisoned by CO, whereas COH appears to be a spectator species. 相似文献
22.
Larry N. Lewis Chris A. Sumpter Mark Davis 《Journal of Inorganic and Organometallic Polymers》1995,5(4):377-390
The Command-Cure concept is defined for a curable formulation as one with long work-like at ambient temperature and rapid cure time at elevated temperature. This concept is explored for a curable silicone system, cured via hydrosilylation. CODMCl2 complexes (COD=1.5-cyclo-octadiene:M=Pt. Pd) are reacted with beta-cyclodextrin (-CD) to make 11 inclusion compounds,M=Pd.2;M=Pt.4. Compounds2 and4 were analyzed by1H NMR and X-ray powder diffraction. Their catalytic ability was evaluated in a model system as well as a polymeric system that gels upon cure. Surprisingly, the Pd analog2 was a good command-cure catalyst whereas the guest compound CODPdCl2,1, was not active in the hydrosilylation reaction. The Pt analog,4, was an effective command-cure catalyst while the corresponding guest. CODPtCl2,3, was too active at low temperature in the hydrosilylation reaction. Additional Pt compounds and one Rh inclusion compound were evaluated as command cure catalysts. These inclusion compounds were: 11 -CD:[CODRhCl]2,5: 11 -CD:CpPtMe3,6 (Cp=cyclopentadienyl): 12 -CD:MeCpPtMe3,7; 12 -CO:CODPtMe2,8. The effectiveness of4 8 was evaluated in a number of silicone systems. 相似文献
23.
A cyclic voltammetric study of the behaviour of Br– and Br–
3 at Pt electrodes, in the potential range between hydrogen and oxygen evolution, is described. Different experiments were carried out, in the presence of Br– and Br–
3, in which the ratio between the species has been kept constant and equal to 1. The halide concentration was varied between 4 × 10–6 and 1 × 10–3 and mol dm–3, at constant ionic strength, in 1 M HclO4 as well as in 1 M NaClO4 adjusted to a pH of 2. Underpotential deposition of Br is observed at potentials as low as –0.125 V vs SCE. The adsorption parameters of Br species were determined from the adsorption/desorption peak pair in the hydrogen adsorption/desorption region, and from the oxide reduction peak data. In the absence of oxygen adsorption, a relatively high coverage of the electrode surface is attained. A Langmuir-type adsorption is observed under the different experimental conditions. 相似文献
24.
The catalytic activity of Pt catalysts supported on high surface area tin(IV) oxide in the complete oxidation of CH4 traces under lean conditions at low temperature was studied in the absence and in the presence of water (10 vol.%) or H2S (100 vol.ppm). Their catalytic properties were compared to those of Pd/Al2O3 and Pt/Al2O3. In the absence of H2S in the feed, Pt/SnO2appears as a very promising catalyst for CH4 oxidation, being even significantly more active under wet conditions than the best reference catalyst, Pd/Al2O3. Catalysts steamed-aged at 873 K were also studied in order to simulate long term ageing in real lean-burn NGV exhaust conditions. To this respect, Pt/SnO2 is slightly less resistant than Pd/Al2O3. In the presence of H2S, Pt/SnO2catalysts are rapidly and almost completely poisoned, comparably to Pd/Al2O3and the catalytic activity is hardly restored upon oxidising treatment below 773 K. A synergetic effect between Pt and specific surface SnO2sites active in CH4oxidation is proposed to explain the superior catalytic behaviour of Pt/SnO2. 相似文献
25.
A.J. Dickinson L.P.L. Carrette J.A. Collins K.A. Friedrich U. Stimming 《Journal of Applied Electrochemistry》2004,34(10):975-980
This paper describes the effects of varying the Pt to Ru ratio in carbon-supported catalysts for methanol oxidation as a function of temperature. Previously these effects were studied in isolation, but now it is shown that the composition of a given catalyst as a function of temperature is extremely important for its activity towards methanol oxidation. Platinum rich 3:2 atomic ratio catalysts perform better than a 1:1 catalyst at 25 °C, where only Pt is believed to be active towards methanol dehydrogenation, since this process is a highly thermally activated process on Ru sites. This result is reversed at 65 °C, where the 1:1 catalyst displays much higher currents across the entire range of polarization. This may result from methanol dehydrogenation occurring on both Ru and Pt sites at higher temperatures. At an intermediate temperature, 45 °C, the 3:2 catalyst is seen to perform better at lower current values, while the 1:1 catalyst is superior at higher current densities, with the crossover occurring at 62 A g–1. As a consequence, when designing fuel cell catalysts, the composition of the catalyst employed should be tailored with respect to the exact operating conditions, in order to promote optimum fuel cell performance. 相似文献
26.
We present dynamic studies of surface reactions using video-Field Ion Microscopy (FIM) along with Pulsed Field Desorption
Mass Spectrometry (PFDMS). Catalytic water formation is followed using rhodium and platinum 3D field emitter crystals for
the oxidation of hydrogen with either oxygen (Rh) or NO (Pt). Strongly non-linear dynamics are observed with nanoscale spacial
resolution. For both reactions quasi-oscillatory behaviour exists under certain conditions of temperatures and partial pressures.
An influence of the probing electric field is observed and possibly essential in establishing oscillatory behaviour. Local
chemical probing of selected surface areas with up to 400 atomic surface sites proves catalytic water formation to take place.
Since water ions (H2O+/H3O+) cause image formation of the O2–H2 reaction on Rh, respective videos provide space-time resolved information on the catalytically active sites. Atom-probe data
also reveal that the surface of the Rh sample reversibly switches from a metallic to an oxidized state during oscillations.
As to the NO–H2 reaction on Pt, fast ignition phenomena are observed to precede wave fronts. After catalytic water formation, NO molecules
diffuse into emptied areas and cause high image brightness. Depending on the size of the Pt crystal, the reaction may ignite
in planes or kinked ledges along the <100> zone lines. Thus FIM provides clear experimental evidence that kinks are more reactive
than steps in the catalytic NO + H2 reaction. Pt surface oxidation occurs and has probably been underestimated in previous FIM studies. 相似文献
27.
Steam reforming of isobutane on a 0.5% Pt–Ce0.8Gd0.2O1.9 catalyst was carried out from 300 to 700 °C under integral conditions with a gas hourly space velocity (GHSV) of 12,000 h−1. The major products were H2, CO2, CO and CH4. The other products produced were ethane, ethylene, propane and propylene with a total molar composition of less than 1.5%.
A complete conversion of isobutane was achieved at 700 °C, Kinetic data was obtained by changing the partial pressure of the
reactants and the temperature under differential conditions with a GHSV of 55,400 h−1. This was done after observing stable isobutane steam reforming for 160 h and under conditions where the mass transfer limitations
were insignificant. An empirical Langmuir–Hinshelwood type model that best fit the kinetic data available was developed. 相似文献
28.
通过对双加压法硝酸装置铂网使用情况和铂网脱边事故的统计,分析了氧化炉采用平编三元网存在的问题;论述了经编二元网的特性和优点;计算了铂网的生产强度和接触时间,确定了铂网丝径;总结了硝酸装置使用经编二元网的运行效果和经济效益,结果表明,吨酸氨耗降低了2.48kg,铂耗降低了10mg,经编二元网优于平编三元网。 相似文献
29.
为实现对铂电阻温度传感器的自动测试,设计了基于ZigBee的铂电阻的测试系统.多个高精度微型铂电阻测试节点组网后把测试数据通过汇聚节点传输到计算机.在Windows的开发平台下,利用Delphi7.0+ SQL Server2000技术进行软件研发,实现了铂电阻数据的自动采集、处理、传输、管理、性能评判等功能为一体的自... 相似文献
30.