Selective hydrogenation of cinnamaldehyde to cinnamyl alcohol with carbon nanotubes supported Pt-Co catalysts

The Pt-Co catalysts supported on carbon nanotubes (CNTs) have been prepared by wet impregnation and the selective hydrogenation of cinnamaldehyde (CMA) to the corresponding cinnamyl alcohol (CMO) over the catalysts has been studied in ethanol at different reaction conditions. The results show that Pt-0.17 wt%Co/CNTs catalyst exhibits the highest activity and selectivity at a reaction temperature of 60 °C under a pressure of around 2.5 MPa, and 92.4% for the conversion of CMA and 93.6% for the selectivity of CMA to CMO, respectively. The selective hydrogenation for the CO double bond in CMA would be improved as increasing the H₂ pressure, and the selective hydrogenation for the CC double bond in CMA is enhanced as increasing the reaction temperature. In addition, these catalysts have also been characterized using transmission electron microscopy (TEM), energy dispersive X-ray spectrometry (EDS), X-ray photoelectron spectroscopy (XPS), H₂-temperature programmed reduction (H₂-TPR) and H₂-temperature programmed desorption (H₂-TPD) techniques. The results show that Pt particles are dispersed more homogeneously on the outer surface of the nanotubes, while the strong interaction between Pt and Co would improve the increasing of activated hydrogen number because of the hydrogen spillover from reduced Pt⁰ onto CNTs and increase the catalytic activity and selectivity of CMA to CMO.     

Selective hydrogenation of furfural to furfuryl alcohol over catalysts prepared via sonochemistry

Copper-chromite oxide and TiO2-supported copper-chromite oxide catalysts are prepared by various methods. They are characterized with ICP, BET, XRD, XPS, SEM, and TEM, etc. Their catalytic performance for liquid phase hydrogenation of furfural to furfuryl alcohol is also valuated. The catalysts prepared by ultrasound exhibit good performance. Catalytic activity of TiO2-supported catalysts is higher than that of catalyst without TiO2, notwithstanding they are all prepared by ultrasound. It is worth stressing that after reduced the TiO2-supported catalysts, which are X-ray amorphous, display good performance at 140 degrees C, while the catalysts without TiO2 show no activity under the same condition. Obtained results indicate that the catalytic performance of catalysts depends upon the amount of reducible copper ions and the activity decay is related to the loss of metal elements on the surface of catalyst.     

Sonochemical enantioselective hydrogenation of ethyl pyruvate over platinum catalysts

Chiral sonochemical hydrogenation of an aliphatic -ketoester, ethyl pyruvate to ethyl lactate was carried out over various platinum catalysts in different solvents under atmospheric hydrogen pressure. The reaction rates and the enantiomeric excesses were determined over Pt/C, Pt/SiO₂ and Pt/K-10 catalysts both under conventional and sonochemical conditions. The effect of ultrasounds on the catalytic activity and enantioselectivity was tested applying sonochemical pretreatment before the reaction. The ultrasonic irradiation was found to be highly advantageous in these hydrogenations. After insonation of the catalysts, the enantioselectivity was highly improved over Pt/SiO₂ and Pt/K-10 catalysts. In addition, the reactions took place in quantitative yield and with complete chemoselectivity and the hydrogenation rates increased with one order of magnitude despite the very mild (atmospheric hydrogen pressure, room temperature) experimental conditions.     

Asymmetric sonochemical reactions enantioselective hydrogenation of alpha-ketoesters over platinum catalysts

The sonochemical enantioselective hydrogenation of different alpha-ketoesters to the corresponding hydroxy derivatives over cinchona modified Pt catalysts is described. Ultrasonic irradiation was found to be beneficial in improving the optical yields. Besides studying the reaction rates and enantioselectivities, the effect of ultrasonics on the catalyst-modifier system and the scale-up of the process will also be considered.     

Synthesis of single- and multi-wall carbon nanotubes over supported catalysts

The quantities of deposited carbon were measured and the quality of the nanotubes was characterized by means of transmission electron microscopy and scanning tunneling microscopy. The inner and outer diameters of the nanotubes were also measured and the diameter distribution histograms were established. The multi-wall straight and coiled nanotubes were found to be quite regular with an average inner (outer) diameter of 4–7 nm (15–25 nm) and with lengths up to 50 μm. The walls contain concentric cylindrical graphene sheets separated by the graphitic interlayer distance. The single-wall nanotubes were found as bundles of hundreds of aligned straight 1-nm-diameter nanotubes with lengths up to 1-μm. The influence of various parameters such as the method of catalyst preparation, the nature and the pore size of the support, the nature of the metal, the quantity of catalyst active particles, and the reaction conditions on the nanotubes formation were studied. The numbers and dimensions of the catalyst active particles dispersed on the support were found to be of importance in regulating the shape of the produced nanotubes. Following these results, a model of growth mechanism was suggested for the nanotubes obtained by this method. Received: 5 January 1998     

Carbon-silica composites supported Pt as catalyst for asymmetric hydrogenation of ethyl 2-oxo-4-phenylbutyrate

Mesoporous carbon-silica composites supported Pt nanoparticle catalysts (Pt/MCS) were firstly applied to the heterogeneous asymmetric hydrogenation of ethyl 2-oxo-4-phenylbutyrate (EOPB). A series of different silica contents were investigated in the fabrication of this mesoporous material. When the volume of added tetraethyl orthosilicate (TEOS) during the preparation of composites is 8 mL, Pt/MCS-8 holds carbon and silica as the main components and possesses relatively strong acidity, mesoporous structures with micropores, appropriate Pt nanoparticle size and high dispersibility showing by XRD, XPS, TPD, N₂ sorption and TEM. These properties cause its good catalytic performance in the heterogeneous asymmetric hydrogenation of EOPB with the enantiomeric excess value and conversion up to 85.6% and 97.8%, respectively.     

Morphological effect of lanthanum-based supports on the catalytic performance of Pt catalysts in crotonaldehyde hydrogenation

Rod-like and particle-like La₂O₂CO₃ and La₂O₃ were obtained via morphology-preserved thermal transformation of the La(OH)₃ precursors. La₂O₂CO₃- and La₂O₃-supported Pt catalysts were prepared by impregnation method and tested in the liquid-phase crotonaldehyde hydrogenation reaction. The textural and physicochemical properties of the samples were studied by a series of techniques including XRD, TG-DSC, N₂ adsorption–desorption, TEM and HRTEM, IR spectrum, H₂-TPD, and H₂-TPR. Even after 600 °C reduction, Pt particles of about 0.8–2.8 nm interplayed with support surface to form Pt-doped interface, thereby preventing the catalysts from migration and affording a high dispersion of platinum. The specific exposed crystal-facets and surface oxygen species depending on the shape of the support affected the preferential deposition of Pt species and the metal-support interaction. Thus, Pt catalysts performed different physicochemical properties and catalytic performance relying on the morphology and structure of the supports. During the cycle experiment, severe deactivation was observed for NP-supported catalysts with an increased selectivity due to the aggregation and growth of Pt particles. Meantime, the NR-supported catalysts retained relatively high reactivity as a consequence of the crystal-facet confinement of rod-shaped lanthanum supports.     

MOFs-derived carbon covered alumina (CCA) supported Pt nanoparticles as catalyst for enantioselective hydrogenation

A one-step approach was developed to prepare carbon covered alumina (CCA) material by using Al-based MOFs (Al-PCP) as sacrificial template. Pt/CCA nanoparticle catalysts were characterized by using XRD, TGA, XPS, N₂ sorption, SEM, TEM and elemental analysis and revealed that they retained the mesostructure with high Pt dispersion and had a CCA structure. Moreover, after reduced at 800 °C, Pt/CCA-800 afforded the highest enantiomeric excess (84.8%) after chirally modified with cinchonidine at the second time reaction and can be recycled for more than 8 times without distinct loss of activity or enantioselectivity in the asymmetric hydrogenation of ethyl 2-oxo-4-phenylbutyrate.     

Pt/TiO2催化剂的载体结构对甲醇催化氧化性能的影响

二氧化钛载体包括二氧化钛纳米管阵列(TNTAs)和二氧化钛纳米线阵列(TNWAs)两种,载体的结构不同对催化性能有一定的影响。然而,Pt负载在TNTAs和TNWAs催化性能的比较鲜有报道。本文通过微波法制备了Pt/TNTAs和Pt/TNWAs两种催化剂,结果表明,Pt/TNTAs催化甲醇氧化效果要优于Pt/TNWAs。相较于Pt/TNWAs, Pt/TNTAs的优越催化性能可能与纳米管的限域效应有关。可见,载体的结构对催化剂的性能有很大的影响。     

Ultrasonics in heterogeneous metal catalysis: sonochemical chemo- and enantioselective hydrogenations over supported platinum catalysts

Sonochemical chemo- and enantioselective hydrogenations over supported platinum catalysts are described. We disclose our results with respect to a sonochemical modification of the chemoselective hydrogenation of cinnamaldehyde over supported platinum catalysts, and the asymmetric hydrogenation of ethyl pyruvate promoted by various ultrasonic pretreatments. The ultrasonic pretreatment of the supported platinum catalysts was found to be highly beneficial in almost every case, improving both the catalytic activity and selectivity. The effect of additional experimental variables, such as hydrogen pressure, catalyst support, temperature and the ultrasonic insonation time were also studied. The enantioselectivity of the hydrogenation of ethyl pyruvate increased up to 97.1% ee. In the case of cinnamaldehyde hydrogenation, the selective preparation of cinnamyl alcohol became possible. The theoretical aspects of the working mechanisms in comparison with 'silent' reactions will also be provided.     

Effect of Sn on methane decomposition over Fe supported catalysts to produce carbon

In this work, alumina-supported Sn containing Fe catalysts were investigated in CVD reactions (Chemical Vapor Deposition) using methane for carbon production. The catalysts were prepared with 10 wt.% of Fe (as Fe₂O₃) and 3, 6 and 12 wt.% of Sn (as SnO₂) supported on Al₂O₃ named hereon Fe10Sn3A, Fe5Sn6A and Fe10Sn12A, respectively. These catalysts were characterized by SEM, TPCVD, TPR, TG, Raman, XRD and ⁵⁷Fe and ¹¹⁹Sn Mössbauer spectroscopy. Methane reacts with Fe10A catalyst (without Sn) in the temperature range 680?C900°C to produce mainly Fe⁰, Fe₃C and 20 wt.% of carbon deposition. TPR and TPCVD clearly showed that Sn strongly hinders the CH₄ reaction over Fe catalyst. ⁵⁷Fe Mössbauer suggested that in the presence of Sn the reduction of Fe^?+?3 by methane becomes very difficult. ¹¹⁹Sn Mössbauer showed Sn^?+?4 species strongly interact with metallic iron after CVD, producing iron-tin phases such as Fe₃SnC and FeSn₂. This interaction Sn?CFe increases the CVD temperatures and decreases the carbon yield leading to the production of more organized forms of carbon such as carbon nanotubes, nanofibers and graphite.     

Carbon nanotubes supported Pt-Ni catalysts and their properties for the liquid phase hydrogenation of cinnamaldehyde to hydrocinnamaldehyde

The Pt-Ni catalysts supported on CNTs have been prepared by wet impregnation and the selective hydrogenation of cinnamaldehyde (CMA) to the corresponding hydrocinnamaldehyde (HCMA) over the catalysts has been studied in ethanol at different reaction conditions. The results show that Pt-0.34 wt% Ni/CNTs catalyst exhibits the highest activity and selectivity at a reaction temperature of 70 °C under a pressure of around 2.0 MPa, and 98.6% for the conversion of CMA and 88.2% for the selectivity of CMA to HCMA, respectively. The selective hydrogenation for the CC bond in CMA would be improved as increasing the reaction temperature, and the hydrogenation for the CO bond in CMA is enhanced as increasing the H₂ pressure. In addition, these catalysts have also been characterized using TEM-EDS, XPS, H₂-TPR and H₂-TPD techniques. The results show that Pt particles are dispersed more homogeneously on the outer surface of the nanotubes, while the strong interaction between Pt and Ni would improve the increasing of activated hydrogen number because of the hydrogen spillover from reduced Pt⁰ onto CNTs and increase the catalytic activity and selectivity of CMA to HCMA.     

Homogeneous and heterogeneous asymmetric reactions: Part 11. Sonochemical enantioselective hydrogenation of trifluoromethyl ketones over platinum catalysts

Enantioselective sonochemical hydrogenation of alpha,alpha,alpha-trifluoromethyl ketones, namely, 1,1,1-trifluoroacetophenone and 1,1,1-trifluoro-phenylacetone was carried out over various platinum catalysts modified by cinchonidine in different solvents. Both compounds yielded the (R)-alcohol as major product. The reaction rates and the enantiomeric excesses were determined over Pt/C, Pt/SiO2, Pt/K-10 and Pt/Al2O3 catalysts under conventional conditions. Since Pt/Al2O3 exhibited the best catalytic performance the effect of ultrasound on the catalytic activity and enantioselectivity was tested using this catalyst applying different sonochemical pretreatments. These methods included a pretreatment before the reaction in hydrogen and oxygen or both. The ultrasonic irradiation was found to be highly advantageous in the case of trifluoroacetophenone, whereas only moderate changes were observed using trifluoro-phenylacetone. After insonation of the catalyst, the enantioselectivity was considerably improved. Both the aerobic and anaerobic sonochemical pretreatments resulted in significant improvement in optical yield (up to 49% and 17% ee, at room temperature under 10 bar in 1,2-dichlorobenzene). In parallel, the hydrogenation rates increased to a small extent (1.1-1.2-fold increase) after hydrogenative ultrasonic pretreatment, whereas the rates decreased by a factor of 1.5-2 after aerobic insonation. To obtain more insight into the process, the effect of insonation time on the activity and enantioselectivity and actual changes of the catalyst were also studied.     

Ultrasonics in chemoselective heterogeneous metal catalysis sonochemical hydrogenation of unsaturated carbonyl compounds over platinum catalysts

The hydrogenation of unsaturated aldehydes was studied over ultrasonically pretreated silica supported platinum catalyst. In the hydrogenation of cinnamaldehyde a remarkable reaction rate and cinnamyl alcohol selectivity increase was observed. Using other unsaturated aldehydes the reaction rate and unsaturated alcohol selectivity increased moderately.     

An in situ Mössbauer study on the metal-support interaction of supported iron catalysts for CO hydrogenation

Iron supported catalysts were investigated by in situ Mössbauer spectroscopy. Results showed that MSI can be vell Interpreted as a combination of the dispersion effect and the chemical interaction effect.     

Surface studies of supported model catalysts

Metal particles grown by vapour deposition on clean and well-defined oxide surfaces are used as model catalysts. These new model catalysts allow, unlike metal single crystals, a study of size and support effects in heterogeneous catalysis. The structure, the electronic properties and the reactivity of these supported model catalysts have been studied, in situ, by a large number of surface science techniques. In order to get relevant information from those studies it is necessary to control the nucleation and growth in order to get uniform collections of metal particles. The preparation conditions and the characterisation methods will be reviewed. Particles with well-defined shapes are obtained by epitaxial growth at high temperature on clean ordered surfaces. The electronic properties of the small metal particles depend not only on their size but also on their shape. The chemisorption properties are strongly related to the surface structure of the particles. The interplay between the surface structure, the local electronic properties and the adsorption energy will be discussed for CO chemisorption. The presence of the support plays an important role in the control of the particle morphology. Furthermore, it can increase the adsorption rate. The intrinsic heterogeneity of the supported model catalysts has to be taken into account to understand in detail the catalytic reactions. The reaction rate cannot be considered as an average on the different crystalline facets present on the particle. Finally, we will discuss the possibility to study in situ and at the atomic level simple chemical reactions on supported catalysts.     

XPS characterization of supported Ziegler-Natta catalysts

Surface analytical technique ESCA (electron spectrometer for chemical analysis) has been used for analysis of catalysts used in propylene polymerization. As a result of this analysis it has been shown that productivity of a catalyst can be correlated to Ti/Mg atomic ratio that indicates dispersion of titanium atoms on magnesium support. A quantitative indicator of productivity, i.e. “titanium index” has also been evaluated for studied catalysts.     

Asymmetric sonochemical reactions. Enantioselective hydrogenation of α-ketoesters over platinum catalysts

The sonochemical enantioselective hydrogenation of different α-ketoesters to the corresponding hydroxy derivatives over cinchona modified Pt catalysts is described. Ultrasonic irradiation was found to be beneficial in improving the optical yields. Besides studying the reaction rates and enantioselectivities, the effect of ultrasonics on the catalyst–modifier system and the scale-up of the process will also be considered.     

Structural studies of supported tin catalysts

Tin oxide was supported on aluminium oxide, titanium oxide, magnesium oxide and silicon oxide, and the resulting interactions between the components in the prepared samples and after reduction were characterized by Mössbauer spectroscopy. It was observed that in the oxide state, tin is present as SnO₂ on alumina, magnesia and silica, but on titania tin occupies Ti sites in the structure. After hydrogen treatment at high temperatures, tin is reduced from Sn(4) to Sn(2) on alumina and titania; it is reduced from Sn(4) to Sn(0) on silica, and is practically not reduced on magnesia. These results reveal the degree of interaction between tin and the different supports studied.