Channel effect ofnC6 aromatization on Pt/KL catalysts

Designed Pt/KL catalysts were prepared and characterized by CO chemisorption and XRD. Pulse catalytic tests usingn-hexane as the probe were performed. The results showed that Pt particles located in the L-zeolite channels were fundamental for aromatization, and the spatial effect of the channels was essential for dehydrocyclization. Obstruction of the channels, while having no influence on the high Pt dispersion, affects the product distribution ofnC₆ in addition to a sharp reduction in reactivity.     

Sulfur- and water-tolerance of Pt/KL aromatization catalysts promoted with Ce and Yb

Different Pt/KL catalysts containing rare earth (RE; Ce and Yb) promoters were prepared by two techniques, incipient wetness impregnation (IWI) and vapor phase impregnation (VPI). The catalysts were tested for the activity and the selectivity of n-hexane aromatization to benzene under clean, sulfur-containing, and water-containing feeds at 500 °C. It was observed that the catalysts prepared by the VPI technique exhibited much higher activity and selectivity than those prepared by IWI. It was also found that although under clean conditions, the addition of Ce or Yb caused a decrease in activity, in the presence of sulfur the addition of Ce and to a lesser extent Yb, significantly inhibited catalyst deactivation.

The influence of water in the feed was investigated by contacting the catalysts for 1 h to a feed containing 3 mol.% water. After this treatment, all the catalysts exhibited a significant activity loss. This loss was more pronounced for the catalyst prepared by the VPI method. The catalyst prepared by IWI already had suffered a significant deactivation before the water treatment, so the activity drop was not so pronounced. The sample prepared by VPI not only showed a drop in activity immediately after the water treatment but it became more susceptible to deactivation afterwards. By contrast, the Ce-promoted catalyst showed a more stable activity after the water treatment.

All catalysts were characterized before and after reaction by a number of techniques. In agreement with previous studies, FT-IR of adsorbed CO and chemisorption results indicated that the VPI method resulted in higher Pt dispersion than that obtained by the IWI method. After reaction in the presence of sulfur, the Ce-promoted Pt/KL catalyst showed a higher resistance to metal agglomeration and a lower rate of coke formation than the unpromoted Pt/KL. On all the catalysts, the amount of carbon deposits was greater in the presence of sulfur and after exposure to water vapor than under the reaction with clean feeds. This difference is explained in terms of metal particle growth and location in the zeolite.     

Infrared spectroscopy of carbon monoxide adsorbed on Pt/L zeolite

A series of 0.6 wt% Pt/MBaL zeolites, where M is Li, Na, K, Rb or Cs, were prepared and characterized by transmission electron microscopy, chemisorption, and infrared spectroscopy of adsorbed carbon monoxide. Greater than 90% of the exposed platinum in the samples is associated with small clusters, less than 7 Å across, inside the zeolite channels. The remaining fraction of exposed platinum is on 100–500 Å crystallites outside the channels. Adsorption of carbon monoxide on the platinum at 25 °C produces a broad infrared band whose maximum shifts from 2065 to 2025 cm^–1 as the alkali cations in the zeolite are changed from Li to Cs. This shift is indicative of electron transfer between the cations and the platinum clusters. Heating the Pt/L catalysts to 225 °C produces new infrared bands at 2020–2015, 1975, and 1935–1920 cm^–1. The appearance of these low-frequency bands strongly suggests that the CO-covered platinum clusters change their structure during heating. We propose that the new structure is one in which the carbon monoxide molecules insert into spaces between the framework atoms of the L zeolite.     

IR spectroscopic study of Pt/Kl zeolites using adsorption of CO as a molecular probe

FTIR spectra of CO adsorbed on Pt/KL catalysts show that the relative band intensities and the total dispersion markedly depend on the catalyst preparation method (ion exchange, incipient wetness impregnation or co-impregnation with KCl). The CO stretching frequency of the dominant band for linear CO is shifted to higher wavenumbers, parallel with the proton concentration in the reduced catalyst, which is derived independently from the intensity of the IR bands of the OH groups. The results are in accordance with the model that electron-deficient platinum particles are platinum-proton adducts.On leave from: N.D. Zelinsky Institute of Organic Chemistry, Academy of Sciences, Moscow, USSR.     

不同Pt前体制备Pt/CeO2催化剂对其结构及性能的影响

Pt与载体间的相互作用会影响到本征Pt纳米粒子的催化活性,不同Pt前体制备Pt/CeO₂催化剂会使其表现出完全不同的催化性能。分别采用金属胶体粒子原位沉积法、浸渍法以及浸渍还原的方式制备了Pt/CeO₂催化剂,通过X 射线衍射、程序升温还原、X射线光电子能谱以及高分辨透射电镜对催化剂进行表征,在CO氧化以及甲苯燃烧反应中评价催化剂活性。结果表明,胶体粒子原位沉积法制备Pt/CeO₂催化剂,能够将优先合成好的Pt纳米粒子直接以金属态Pt⁰的形式负载到载体表面,且保证其高度均匀分散,丰富的表面Pt⁰很好地充当了CO、甲苯反应时的活化位点,催化剂表现出优异的性能;浸渍还原法中,Pt纳米粒子之间会发生团聚现象,同时部分Pt又以Pt²⁺的形式与CeO₂之间形成了Pt-O-Ce相互作用,载体表面暴露Pt⁰含量的下降是催化剂表现出较弱活性的主要原因;浸渍法中,以Pt离子对Pt进行负载,Pt完全以Pt²⁺的形式参与到Pt-O-Ce键成键中,表面Pt⁰缺失,催化剂表现出明显的失活现象。Pt/CeO₂催化剂中,起主要活性作用的是金属态Pt⁰,胶体粒子原位沉积法能够实现Pt⁰的直接负载,对于提高Pt基催化剂中Pt的利用率,降低Pt资源消耗都具有重要意义。     

Ion-dipole interactions between adsorbed CO and support cations in Pt/K-LTL

The adsorption of carbon monoxide on a non-acidic Pt/K-LTL catalyst has been studied by diffuse reflectance and transmission IR spectroscopy. The CO spectrum is strongly dependent on the experimental conditions. Adsorption on the small Pt clusters in the presence of water gives linear-CO bands between 2060 and 1990 cm^–1 and a bridging-CO band around 1800 cm^–1. In the absence of water, the linear bands are red shifted to about 1940 and 1720 cm^–1, respectively. The frequency shift is attributed to an ion-dipole interaction between adsorbed CO and support cations. The ion-dipole interaction is screened by the adsorbed water leading to a smaller red shift in the CO stretching frequency.     

Preparation and characterization of Pt/silicalite catalysts with high Pt loadings

Methods for preparing Pt/silicalite catalysts are described. Equilibration of silicalite, a pentasil zeolite, in aqueous solutions of Pt(NH₃), Cl₂ containing excess ammonia resulted in Pt/silicalite catalysts with Pt loadings of ≥7 wt%. The Pt/silicalite catalysts were characterized by hydrogen chemisorption, X-ray diffraction and transmission electron microscopy. The characterization studies showed that the majority of the Pt in the heavily loaded catalysts was located in the silicalite pores, and the Pt dispersions in these catalysts exceeded 0.8.     

合成对氨基苯酚Pt/C催化剂失活的研究

硝基苯催化加氢合成对氨基苯酚反应中,加氢Pt/C催化剂的稳定性决定生产成本。实验结果表明,催化剂循环使用10次,将失活催化剂过滤,在60%的硝酸溶液中加热回流3 h,用去离子水充分洗涤后,催化剂可恢复部分活性。第一次硝酸活化处理后,催化剂还可以使用4次左右。采用原子吸收、BET、SEM及XRD等测试方法对新鲜催化剂和经过重复实验的催化剂进行表征,结果表明,催化剂失活的主要原因为有机物覆盖在催化剂表面造成表面积下降和孔堵塞,致使催化剂丧失活性中心。在催化剂使用过程中,活性组分Pt流失及Pt 金属晶粒长大也会导致催化剂失活。     

Contribution to the mechanism of NO reduction by CO over Pt/NaX zeolite

The reaction of NO + CO was studied over Pt/NaX prepared by the decomposition of [Pt(NH₃)₄]²⁺. The decomposition was carried out via calcination followed by reduction, by vacuum decomposition, and by decomposition in hydrogen, by ways which are known to lead to the formation of Pt clusters of different sizes and location. The NO reduction by CO was studied under static conditions for longer (20–30 min) and shorter (100 s) time intervals, and the reaction was followed by temperature programmed decomposition (TPD) of species adsorbed during the preceding isothermal reactions. The effect of various NO/CO ratios and of added oxygen was examined. The reactions of N₂O + CO were compared with those of NO + CO. The increasing size of Pt clusters enhances the reduction of NO by CO, but it is complicated at lower reaction temperatures (below 230°C) by the poisoning of active Pt centres, especially by adsorbed CO. Smaller Pt clusters exhibit higher preference towards NO adsorption from NO + CO mixtures than the larger Pt clusters. The incomplete reduction of NO to N₂O proceeds under our experimental conditions below 230°C, and is accompanied by the formation of adsorbed species. N₂O formation is enhanced by the increased NO/CO ratio and by the addition of oxygen. The reduction of nitrous oxide occurs much slower than that of nitric oxide, and therefore N₂O could play a role only as a surface intermediate in the CO + NO reaction.     

Enantioselective hydrogenation of ethyl pyruvate Long-term performance of chirally modified Pt/zeolite catalysts

The long-term performance of 5 wt.% Pt/zeolite catalysts (HNaY with different degrees of ion exchange) modified with (−)cinchonidine was studied. The enantioselective hydrogenation of ethyl pyruvate to R(+)ethyl lactate was used as the model reaction. The Pt/zeolites are effective catalysts for long-term use, if the chiral modifier is added before each cycle of hydrogenation. The optimal ratio between the amount of catalyst and chiral modifier essentially depends on both the specific Pt surface area of the catalyst and the solvent used. It is found that the use of acetic acid as solvent results in a higher long-term performance than cyclohexane. This is due to the competitive adsorption between the chiral auxiliary and acetic acid on the Pt surface. Furthermore, the acidity of the solvent results in a weakening of the (−)cinchonidine/Pt interaction, which prevents an overloading of the Pt surface area with (−)cinchonidine or its decay products. This effect was determined by means of differential thermal analysis and elemental analysis. When cyclohexane is used as the solvent, the long-term performance is significantly improved by raising the carrier acidity.     

正十二烷在Pt/ZSM-22和Pt/ZSM-23上的加氢异构反应性能

采用常规水热合成法合成了ZSM-22和ZSM-23分子筛,进而制备了分别含有上述分子筛的催化剂,并借助XRD、SEM、NH3-TPD和Py-IR表征了这两种分子筛和催化剂的结构和酸性,同时以正十二烷为模型化合物,采用固定床反应器研究了Pt/ZSM-22和Pt/ZSM-23催化剂上正十二烷加氢异构反应性能。结果表明,在这种模型反应基础上,催化剂的反应活性和选择性主要取决于催化剂的酸量和酸强度以及酸分布,相对而言,ZSM-22分子筛催化剂由于其弱酸和中等强度酸的含量较高,具有更佳的异构化选择性。     

Hydrogen spill-over effect on Pt/WO3 anode catalysts

The experimental evidence and mechanism of ‘hydrogen spill-over’ on Pt/WO₃ is reviewed and the application of this catalyst system for the evolution of hydrogen, anodic oxidation, hydrogenation and the anodic oxidation of small molecules and impure H₂ is discussed. It is suggested that further work on preparation techniques to ensure the maximisation of Pt/WO₃ interfaces and other analogous systems should lead to even higher catalyst activity and applications.     

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.     

Stability of carbon monoxide adsorbed on nanoparticle Pt and Pt/Ru electrodes in sulfuric acid media

Pt and Pt/Ru nanoparticle electrodes were used as substrates for studies of stability of chemisorbed CO and its interactions (exchange) with carbon monoxide and hydrogen gas admitted to sulfuric acid solution, which served as the supporting electrolyte for these measurements. The surface bound, radioactive CO was obtained after decomposition of ¹⁴C labeled methanol or formic acid from the same solution. The stability and/or exchange of the surface bound CO was examined after (i) the ¹⁴CCO containing electrolyte was replaced by the clean supporting electrolyte (to remove the CO solute from the bulk) and (ii) after hydrogen and, separately, non-radioactive CO was admitted to the cell. We found no displacement of adsorbed CO due to the exchange of electrolyte or introduction of hydrogen to the cell. However, non-radioactive CO rapidly displaced the adsorbed ¹⁴CCO on the surface leaving behind a monolayer of chemisorbed but non-radioactive CO. Both results were independent of the electrode potential applied and they neither dependent on the source of surface CO, that is, whether it was deposited from methanol or formic acid solutions.     

Changes in the selective hydrogenation of citral induced by copper addition to Ru/KL catalysts

Bimetallic Ru–Cu catalysts supported on KL zeolite have been prepared by coimpregnation with ionic precursors and characterized by several methods, such as temperature-programmed reduction, CO and hydrogen chemisorption, nitrogen adsorption, infrared spectroscopy of chemisorbed CO and microcalorimetry of CO adsorption. The catalytic behavior of the samples was analyzed in the selective hydrogenation of citral in the liquid phase, at 323 K and 5 MPa. The presence of bimetallic entities as well as of segregated copper species was recognized by the TPR measurements. The CO-FTIR and microcalorimetry results evidence that the higher the Cu/Ru atomic ratio the larger the surface heterogeneity, with formation of Cu^δ+ species. Bimetallic catalysts are more active than the monometallic ruthenium catalyst in the hydrogenation of citral, but this activity decreases with the increasing of copper concentration. In addition, selectivity towards citronellal decreases as the copper content increases, in opposite trend to the selectivity toward geraniol and nerol. For low copper loading (Cu/Ru ≈ 0.4) formation of a surface alloy is discussed. This surface structure is particularly active for hydrogenation of the conjugated CC double bond of citral. For Cu/Ru = 0.8 and Cu/Ru = 1.2 samples, three-dimensional islands of segregated copper seem to cover, in part, the surface alloy. This latter surface structure is less active than the preceding one for hydrogenation of the CC double bond, but more selective for hydrogenation of the CO group of citral.     

Heptane Dehydrocyclization Over Pt/KL Catalysts Doped with Barium or Lanthanum

Several 1 wt% Pt/KL catalysts doped with different concentrations of either BaO or La₂O₃ were prepared by successive impregnation of a zeolite KL and then characterized by H₂-O₂ titration, TPR, CO–FTIR, TEM-XEDS and XPS. Catalytic activity measurements in the hydroconversion of n-heptane showed that barium highly enhances the aromatization activity of Pt/KL, the more so the higher the barium concentration. The yield to aromatics increases to a lesser degree by adding 1 wt% La, but it is little modified at higher La concentrations. The CO–FTIR results suggest that the promoter effect of barium is related to an electron enrichment of Pt produced by the BaO Pt⁰ interaction which, according to the TEM–XEDS and XPS results, is more favored than the La₂O₃ Pt interaction.     

Kinetics of heptane reforming on Pt/L zeolite

The kinetics of heptane reforming over 0.64% Pt/KBaL have been measured over a wide range of conditions from 390 to 475 ° C, 0.05 to 1.00 atm heptane, and 0.2 to 25.0 atm hydrogen. Below about 6 atm H₂, the catalyst deactivates due to carbon fouling of the platinum particles. The reaction rate increases with hydrogen pressure under these conditions, presumably because this accelerates the rate of carbon hydrogenation off the metal surface. Above 6 atm H₂, no deactivation occurs. The activation energies and reaction orders in heptane and hydrogen at high H₂ pressure are: 39 kcal/mol, 0.7 and –1.9 for hydrogenolysis; 60 kcal/mol, 0.6 and –2.8 for isomerization; and 58 kcal/mol, 0.4 and –2.7 for dehydrocyclization. These kinetics are the same as those observed over platinum on nonacidic supports, and indicate that the reaction mechanism on Pt/KBaL is no different from that on monofunctional Pt catalysts.     

On the deactivation of Pt/L-zeolite catalysts

Pt/L-zeolite catalysts have a unique activity forn-hexane aromatization to benzene. There have been proposals which attribute this to electronic and to geometric origins of the L-zeolite. Recently, the uniqueness of the L-zeolite support has been understood to derive from the ability to stabilize very small particles in a non-acidic environment and it has been proposed that a further stabilization against deactivation (by geometric constraint of bimolecular coke precursor reactions) is what distinguishes these catalysts relative to SiO₂ supported small Pt particles. We have investigated the initial deactivation rate of four Pt/L-zeolite catalysts and a Pt/SiO₂ reference during reaction ofn-hexane, neopentane and 2-methyl-2-pentene. In all cases, the relative rates of deactivation correlate with the apparent acidity (as determined by competitive benzene/toluene hydrogenation) suggesting that the deactivation stabilization may have an electronic component.     

Effect of chemisorbed carbon monoxide on Pt/C electrode on the mechanism of the hydrogen oxidation reaction

The influence of poisoning of Pt catalyst by CO on the kinetics and mechanism of H₂ oxidation reaction (HOR) at Pt/C electrode in 0.5 mol dm⁻³ HClO₄, saturated with H₂ containing 100 ppm CO, was examined with rotating disc electrode (RDE) at 22 °C. Commercial carbon black, Vulcan XC-72 was used as support, while Pt/C catalyst was prepared by modified polyol synthesis method in an ethylene glycol (EG) solution. The kinetically controlled current (I_k) for the HOR at Pt/C decreases significantly at CO coverage (Θ_CO) > 0.6. For Θ_CO < 0.6 the HOR takes place through Tafel-Volmer mechanism with Tafel reaction as rate-determining step at the low CO coverage, while Volmer step controls the overall reaction rate at the medium CO coverage. When CO coverage is higher then 0.6, Heyrovsky-Volmer mechanism is operative for the HOR with Heyrovsky as the rate-determining step (rds).     

CO-induced decomposition of small Pt particles in K-LTL zeolite

Reduced Pt/K-LTL has been studied with XAFS spectroscopy before and after CO admission at room temperature. The results of the EXAFS data-analysis show that after reduction very small platinum metal particles are present consisting of five to six atoms. CO admission at room temperature leads to complete decomposition of the platinum metal particles and the formation of a platinum carbonyl cluster most probably stabilised by the zeolite walls. Modelling shows that the platinum carbonyl cluster just fits inside the pores of the zeolite-LTL. Analysis of the white line intensities of platinum L_II and L_III X-ray absorption edges reveals that after reduction and in the presence of chemisorbed hydrogen the platinum metal particles in Pt/K-LTL have 0.12% more d-band vacancies than bulk platinum metal. This value increases to 0.34% after CO admission implying-backdonation from platinum to CO, a positive charge on Pt in the newly formed cluster or a combination of both. The results of this study have a large impact on the interpretation of existing literature FTIR CO data obtained on Pt/K-LTL. The results question the validity of CO chemisorption carried out to determine the dispersion of very small platinum particles.