催化裂化再生器中铂助燃剂催化活性的测定(Ⅰ)——在新助燃剂上CO氧化的反应动力学

研究了催化裂化再生条件下铂助燃剂上ＣＯ氧化反应动力学。在排除了反应管及稀释剂的催化氧化作用后，测定了铂含量为１０－６ｇ／ｇ的国产新助燃剂上的反应动力学数据，得出了在氧过量时一氧化碳和氧的反应级数分别为１和０．５。给出了６６０℃下的反应速度常数值及其置信区间。     

Characterization of bimetallic NaY-supported Pt-Pd catalyst by EXAFS,TEM and TPR

NaY-supported bimetallic Pt-Pd catalysts have been studied by TEM, TPR and EXAFS. Small, randomly mixed particles are formed in the zeolite cages. When the Pt content is increased, a Pt core structure appears and the dispersion increases. Particle diameters are about 1–2 nm for bimetallic samples.     

硝基苯加氢制备对氨基苯酚的工艺要素研究

在稀硫酸介质中,Pt/C催化,硝基苯加氢还原、转位得到目标化合物对氨基苯酚。工艺要素研究表明:硝基苯20mL,氢气压力为1kPa的水封压力,温度85～90℃,十六烷基三甲基溴化铵用量为0.1g,2%Pt/C催化剂0.5g,反应时间为5h时,所得产品质量达到并优于日本JISK4144 1986标准要求。     

High utilization platinum deposition on single-walled carbon nanotubes as catalysts for direct methanol fuel cell

This research aims to enhance the activity of Pt catalysts, thus to lower the loading of Pt metal in fuel cell. Highly dispersed platinum supported on single-walled carbon nanotubes (SWNTs) as catalyst was prepared by ion exchange method. The homemade Pt/SWNTs underwent a repetition of ion exchange and reduction process in order to achieve an increase of the metal loading. For comparison, the similar loading of Pt catalyst supported on carbon nanotubes was prepared by borohydride reduction method. The catalysts were characterized by using energy dispersive analysis of X-ray (EDAX), transmission electron micrograph (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectrum (XPS). Compared with the Pt/SWNTs catalyst prepared by borohydride method, higher Pt utilization was achieved on the SWNTs by ion exchange method. Furthermore, in comparison to the E-TEK 20 wt.% Pt/C catalyst with the support of carbon black, the results from electrochemical measurement indicated that the Pt/SWNTs prepared by ion exchange method displayed a higher catalytic activity for methanol oxidation and higher Pt utilization, while no significant increasing in the catalytic activity of the Pt/SWNTs catalyst obtained by borohydride method.     

Heterogeneous asymmetric reactions. 23. Enantioselective hydrogenation of ethyl pyruvate over cinchonine- and α-isocinchonine-modified platinum catalysts

The enantioselective hydrogenation of ethyl pyruvate to (S)-ethyl lactate over cinchonine- and -isocinchonine-modified Pt/Al₂O₃ catalysts was studied as a function of modifier concentration and reaction temperature. The maximum enantioselectivities obtained under the applied mild conditions were 89% ee using cinchonine (0.014 mmoldm^–3, 1 bar H₂, 23°C, 6% AcOH in toluene), and 76% ee in the case of -isocinchonine (0.14 mmoldm^–3, 1 bar H₂, –10°C, 6% AcOH in toluene). Since -isocinchonine of rigid structure exists only in anti-open conformation these data provide additional experimental evidence to support the former suggestion concerning the dominating role of anti-open conformation in these cinchona-modified enantioselective hydrogenations.     

Dehydrogenation of Cyclohexene on Platinum Nanoclusters on a Thin Film of Al2O3/NiAl(100)

Using a scanning-tunneling microscope, reflection high-energy electron diffraction and photoelectron spectra with synchrotron radiation, we investigated the temperature dependence of the dehydrogenation of cyclohexene (C₆H₁₀) adsorbed on Pt nanoclusters supported on an ultra-thin film of Al₂O₃/NiAl(100). The Pt clusters, grown by vapor deposition, are structurally ordered and exhibit a mean diameter 2.2 nm and height 0.4 nm. The progress of dehydrogenation was monitored through the temporal variation of C 1s photoelectron spectra; analysis of these features revealed that the dehydrogenation of cyclohexene with increasing sample temperature occurs as a sequential process beginning around 150 K, a temperature significantly less than that for Pt single-crystal surfaces. The dehydrogenation behavior, particularly the decomposition into elemental carbon, is found to vary with Pt coverage.     

The SMSI between supported platinum and CeO2–ZrO2–La2O3 mixed oxides in oxidative atmosphere

CeO₂–ZrO₂–La₂O₃ (CZL) mixed oxides were prepared by citric acid sol–gel method. The as-received gel was calcined at 500, 700, 900 and 1050 °C to obtain the so-called C5, C7, C9 and CK, respectively. The C5, C7 and C9 powders were impregnated with H₂PtCl₆ and then calcined at 500 °C to prepare P5C5, P5C7 and P5C9, respectively. The impregnated CK powders were calcined at 500, 700 and 900 °C to prepare P5CK, P7CK and P9CK, respectively. The XRD and XPS analyses show that the surface distribution of Pt is evidently influenced by the structural and textural properties of the support. The CO adsorption followed by FTIR reveals that the dispersion and the chemisorption sites of Pt are reduced as the calcination temperature of CZL support increases. The chemisorption ability of the CK samples is even completely deactivated. The encapsulation mechanism, which has been applied to explain the so-called strong metal–support interaction (SMSI) after reductive treatment, is introduced here to demonstrate the abnormal observations though the samples were prepared in oxidative atmosphere. The HRTEM results also confirm this explanation. The effects of oxygen vacancies, the chemisorption sites on the Pt surface and Pt/Ce interfacial sites on the three-way catalytic activities are discussed.     

Pt/TiO_2光催化制氢的初步研究

对无氧条件下Pt/TiO_2光催化重整甲醇制氢的基本步骤进行简化,在同一体系中进行了光催化剂的合成和光催化制氢的两步反应。基于正交设计法对该复杂体系进行了分析,得到Pt载量、甲醇/水体积、灯距、前反应时间这4种影响因素的3个不同水平对放氢速率的影响。确定了最佳实验条件为Pt载量0.5％(mol)、甲醇/水体积比5:1、灯距12 cm、前反应时间3h。分析结果表明,Pt载量对放氢速率的影响最大。实验获得的最高放氢速率为5.84 ml·h~(-1)·g~(-1)。     

Formation of isocyanic acid during the reaction of mixtures of NO, CO and H2 over supported platinum catalysts

On-line infrared spectroscopy has been used to show that isocyanic acid, HNCO, is a substantial primary product of the reaction between NO, CO and H₂ over a Pt/SiO₂ catalyst. At 230°C it accounts for more than 40% of the CO converted. No isocyanic acid is seen when Al₂O₃ is placed downstream of Pt/SiO₂, or when using a Pt/Al₂O₃ catalyst under the same conditions, due to rapid hydrolysis of HNCO on the alumina. Isocyanic acid may exist as a trace intermediate in automobile catalytic converters during their warm-up phase but it is unlikely to emerge from the pore system of aluminabased catalysts.     

Oxidation and reforming reactions of CH4 on a stepped Pt(5 5 7) single crystal

The oxidation and reforming kinetics of methane by O₂, CO₂ and H₂O were studied on a stepped Pt(5 5 7) single crystal from 623 to 1050 K under methane rich conditions. The rate of carbon deposition was followed by ex-situ Auger electron spectroscopy under non-oxidative conditions. The apparent activation energy for methane decomposition was significantly lower than the apparent barriers measured for both total oxidation, CO₂ and H₂O reforming. Total oxidation of methane to CO₂ and H₂O followed by combined dry and steam reforming (combined combustion-reforming) led to CO production rates which were higher than direct CO₂ or H₂O reforming rates. The enhanced rates are most likely due to the ability of adsorbed oxygen to prevent carbon nucleation and/or scavenge carbon enabling the reforming reaction to turnover on a larger fraction of sites. Comparable amounts of carbon were found by Auger electron spectroscopy measurements after both direct dry or steam reforming, while combined oxidation-reforming had considerable less carbon. During direct dry or steam reforming, CO₂ and H₂O serve only to scavenge adsorbed atomic carbon, while in the presence of oxygen, carbon is removed by both combustion and reforming routes.