Skeletal Isomerization of n-Pentane over Platinum-Promoted Tungstophosphoric Acid Supported on MCM-41

Skeletal isomerization of n-pentane in the presence of hydrogen has been studied over Pt-promoted H₃PW₁₂O₄₀ (TPA)/MCM-41 bifunctional catalyst. A series of solid acid catalysts with different loading amount of TPA and Pt were prepared and characterized by XRD, FT-IR and XPS. The optimal catalytic activity of Pt-TPA/MCM-41 was observed with 2% Pt and 30% TPA. According to the cracked products distribution, this is typical of a monomolecular bifunctional metal-acid mechanism. Further, catalysts with different combination of noble metals (Pt, Pd and Ru), heteropoly acids (HPAs) (TPA, tungstosilicic acid (TSA), and molybdophosphoric acid (MPA)) and supports (MCM-41, SBA-1 and SiO₂) were also synthesized and their catalytic performances were compared.     

Preparation of platinum-doped hollow spheres and their electrocatalytic activity in water electrolysis

Pure TiO₂ hollow spheres were prepared by using poly(styrene-methacrylic acid) latex particles as template; thereafter, titania hollow spheres were coated by platinum with an appropriate amount of choloroplatinic acid solution to obtain Pt/TiO₂ catalysts. The morphology and structure of nonstructural Pt/TiO₂ hollow spheres were characterized by BET, XRD, TGA, SEM and TEM analysis. In the samples, a remarkably uniform layer of Pt consisting of particles from 5 to 70 nm in size was formed over TiO₂ hollow spheres. We found the electrocatalytic nature of the samples by cyclic voltammetric experiment in acidic solution. The anodic peak current density of 20 wt% Pt-loaded TiO₂ hollow particles was observed 2.5 times higher than that of 5 wt% Pt/TiO₂ in the same experimental condition. Also, the anodic current density of 20 wt% Pt/TiO₂ hollow spheres calcined at various temperatures followed the order: 400 °C≈500 °C>600 °C. The electrocatalytic activity of the Pt-loaded TiO₂ hollow spheres depends on the amount of atomic platinum present in the sample; a higher concentration of platinum results in a larger current density value in anodic sweep, resulting in more oxygen production during electrolysis. Pt/TiO₂ hollow sphere catalysts have also shown long term electrocatalytic stability in acidic media.     

Preparation and Characterization of Pt/Al-ZSM-5 Catalysts and their Reactivities for the Oxidation of CO with N2O at Low Temperatures

Al-ZSM-5 was prepared by treating H-ZSM-5 with an aqueous solution of Al(NO₃)₃ and used as a support for Pt catalysts. The Pt-loaded Al-ZSM-5 acts as an efficient catalyst for CO oxidation with N₂O at 273 K. TEM investigations revealed that Pt clusters with an average particle size of around 1–1.5 nm were homogeneously dispersed within Al-ZSM-5. Moreover, FT-IR and XPS analyses indicated that the small Al₂O₃ clusters formed within Al-ZSM-5 plays a significant role in the formation of highly dispersed Pt clusters within the pore structure of the ZSM-5 zeolite, leading to the high catalytic activity of Pt/Al-ZSM-5 as compared to Pt/ZSM-5.     

Enhancement of the catalytic oxidation of hydrogen-lean chlorinated VOCs in the presence of hydrogen-supplying compounds

The complete catalytic oxidation of trichloroethylene (TCE) over alumina-supported noble metal catalysts (Pt and Pd) and in the presence of hydrogen-rich compounds, i.e. water, hexane and toluene was evaluated. Experiments were performed at conditions of lean TCE concentration (around 1000 ppm) in air, between 250 and 550°C in a conventional fixed-bed reactor. Hexane and toluene were added to the feedstream in a concentration of around 1000 ppm and water concentration varied from 1000 to 15 000 ppm. TCE oxidation occurred faster in the presence of hexane and toluene over both catalysts. Over palladium catalysts, water did not alter catalytic activity, whereas over platinum catalysts water enhanced TCE oxidation at low temperatures (<400°C) but inhibited it at higher temperatures (>400°C). Selectivity to HCl was much improved by feeding water as a hydrogen-supplying reactant; 7500 ppm of water enhanced HCl outputs from 39.4 to 78.0% with Pd, and from 37.5 to 58.9% with Pt. Selectivities to C₂Cl₄, formed by chlorination of the feed, and Cl₂ were greatly reduced. On the other hand water promoted complete oxidation of TCE to CO₂, and thus reduced selectivity to CO. In the presence of hexane and toluene, formation of HCl was also enhanced. Hexane showed higher inhibition ability than toluene over both catalysts for the C₂Cl₄ and Cl₂ formation. Unlike in the presence of water, selectivity to CO increased, as a consequence of partial oxidation of both hydrocarbons.     

Performance of Pt/MgAPO-11 Catalysts in the Hydroisomerization of n-dodecane

MgAPO-11 molecular sieves with varying Mg contents synthesized by the hydrothermal method were used as supports for bifunctional Pt/MgAPO-11 catalysts. MgAPO-11 molecular sieves and the corresponding catalysts were characterized by X-ray diffraction (XRD), X-ray fluorescence spectroscopy (XRF), temperature-programmed desorption of NH₃ (NH₃-TPD), differential thermogravimetric (DTG) analysis, temperature-programmed reduction of H₂ (H₂-TPR), H₂ chemisorption and catalytic reaction evaluation. The results indicated that the acidity generated via the substitution of Mg²⁺ for Al³⁺ in the framework increased with the Mg content. Acting as acidic components, the MgAPO-11 molecular sieves loaded with Pt were tested in the hydroisomerization of n-dodecane. Optimum isomer yield was obtained over the Pt/MgAPO-11 catalyst that had neither the highest acidity nor the highest Pt loading among the tested catalysts. In fact, the activity and the isomer yield both could attain a maximum on 0.5 wt.% Pt/MgAPO-11 catalysts with differing Mg contents. A lower Mg content resulted in an insufficient acidity, whilst a higher Mg content weakened the dehydrogenation/hydrogenation function of the Pt. These inappropriate balances between the acidic and the metallic functions of the catalysts would lead to low activities and isomer yields. On the other hand, the 0.5 wt.% Pt/MgAPO-11(3) catalyst was found to have a good balance between the acidic and the metallic functions, and thus exhibited both high activity and isomer yield in comparison with the conventional 0.5 wt.% Pt/SAPO-11 catalyst.     

Support Effects in Nerol Hydrogenation over Pt/SiO<Subscript>2</Subscript>, Pt/H-Y and Pt/H-MCM-41 Catalysts

Chemoselective hydrogenation of nerol was investigated over Pt/SiO₂, Pt/H-Y and Pt/H-MCM-41 catalysts. The initial total reaction rates decreased in following order: Pt/H-Y > Pt/SiO₂ > Pt/H-MCM-41. Nerol hydrogenation was found to be an apparent structure sensitive reaction. The selectivities to citronellol at 30% conversion of nerol were 65%, 55% and 25% over Pt/SiO₂, Pt/H-MCM-41 and Pt/H-Y, respectively.     

Effect of Nickel Addition on Ceria‐Supported Platinum Catalysts for Medium‐Temperature Shift Reaction in Fuel Processors

Medium‐temperature shift reaction (MTS, 280–340 °C) has received much attention for use in fuel processors. In this study, bifunctional Pt‐Ni/CeO₂ catalysts were prepared by different Pt (0.1–0.5 %) and Ni (5–20 %) loadings, and investigated for MTS reaction. X‐ray diffraction, N₂ adsorption and temperature‐programmed reduction tests were used to characterize the prepared samples. The results showed that Pt‐Ni bimetallic catalysts have higher CO conversion in comparison to Pt/CeO₂ monometallic catalyst. Furthermore, the sequential synthesis method of Pt and Ni impregnation was preferred to the simultaneous one, which is due to the better Pt dispersion on catalytic surface. Steam to carbon ratio variations study showed the maximum CO conversion to be in the range of 4.5.     

Preparation of Pt-loaded TiO2 nanofibers by electrospinning and their application for WGS reactions

Preparation of Pt-loaded TiO₂ nanofibers and their catalytic performance for water gas shift (WGS) reactions have been explained in this work. The Pt-loaded TiO₂ nanofibers were obtained by electrospinning poly-ethylene oxide (PEO) aqueous solutions containing Ti(OH)_n slurry and Pt nanoparticles at room temperature, followed by calcination at 773 K for 4 h. The calcined nanofibers were rougher than the nanofibers of PEO/Ti(OH)_n/Pt due to the PEO degradation and oxidation of Ti(OH)_n to TiO₂. Diameters of the Pt-loaded TiO₂ nanofibers ranged between 200 and 900 nm. Catalytic activity of the Pt-loaded TiO₂ nanofibers for water gas shift (WGS) reactions was evaluated and it was observed that their activity was 5–7 times higher than that of a bulk catalyst. Such improvement is attributed to the larger surface area of the nanofiber catalyst compared to that of the bulk catalyst. To the best of our knowledge, this is the first demonstration of a synthesis of Pt-loaded TiO₂ nanofibers from a Ti(OH)_n nanoparticle slurry using electrospinning and its application to WGS reactions.     

The synergic effects of highly selective bimetallic Pt-Pd/SAPO-41 catalysts for the n-hexadecane hydroisomerization

The hydroisomerization of n-hexadecane over Pt-Pd bimetallic catalysts is an effective way to produce clean fuel oil. This work reports a useful preparation method of bimetallic bifunctional catalysts by a co-impregnation or sequential impregnation process. Furthermore, monometallic catalysts with loading either Pt or Pd are also prepared for comparison. The effects of the metal species and impregnation order on the characteristics and catalytic performance of the catalysts are investigated. The catalytic test results indicate that the maximum iso-hexadecane yield over different catalysts increases as follows: Pt/silicoaluminophosphate SAPO-41iso-hexadecane yield of 89.4% when the n-hexadecane conversion is 96.3%. Additionally, the Pt-Pd/SAPO-41 catalyst also presents the highest catalytic activity and best stability even after 150 h long-term tests.     

Synthesis of p‐aminophenol from the hydrogenation of nitrobenzene over metal–solid acid bifunctional catalyst

BACKGROUND: A single‐step conversion of nitrobenzene (NB) to p‐aminophenol (PAP) through catalytic hydrogenation is a widely used synthesis route for PAP. The main shortcoming of this route is the use of sulfuric acid for rearrangement of the phenylhydroxylamine (PHA) intermediate. In this paper, S₂O₈^2?/ZrO₂ (PSZ) solid acid and Pt‐S₂O₈^2?/ZrO₂ (Pt‐PSZ) bifunctional catalysts were prepared for the synthesis of PAP in non‐acid medium. RESULTS: Calcination temperature has a substantial effect on the acidity, structure and activity for PHA rearrangement of PSZ. The highest PAP yield was 33.8% over PSZ calcined at 823 K when the reaction was carried out in water at 423 K. A high PAP yield of 23.9% was achieved by a single‐step reaction of nitrobenzene over Pt‐PSZ bifunctional catalysts. CONCLUSION: PSZ solid acid exhibits high activity for PHA rearrangement. Perfect tetragonal ZrO₂ and much stronger acid sites play important roles in catalytic activity. Inhibiting the hydrogenation activity by reducing the amount of Pt loading on Pt‐PSZ can improve the competition of PHA rearrangement on acid sites with hydrogenation of PHA on metal active sites, resulting in better selectivity to PAP. Copyright © 2008 Society of Chemical Industry     

Characterization of the Active Sites on Pt-Loaded ZSM-5 (Pt/ZSM-5) Prepared by an Ion-Exchange Method for the Oxidation of CO at Low Temperatures

Highly dispersed Pt-loaded ZSM-5 (Pt/ZSM-5) catalysts were prepared by a combination of ion-exchange and thermal pretreatment in different temperatures under vacuum. Highly dispersed ion-exchanged Pt²⁺ ions were reduced into Pt⁺ and then Pt⁰, sustaining their high dispersion state with an increase in the thermal pretreatment temperatures up to 773 K. Thus, prepared Pt⁰ highly dispersed in the cavities of ZSM-5 exhibited high catalytic activity for the oxidation of CO with N₂O at 273?K. However, pretreatment at temperatures higher than 973 K led to the aggregation of highly dispersed Pt⁰ clusters, resulting in a decrease in the catalytic activity for low-temperature oxidation.     

The construction of nitrogen-doped graphitized carbon–TiO2 composite to improve the electrocatalyst for methanol oxidation

The exploration of advanced catalyst supports is a promising route to obtain electrocatalysts with high activity and durability. Herein, the nitrogen-doped graphitized carbon/TiO₂ composite was fabricated and explored as support for the Pt catalyst. The composite support was constructed by carbonization of polypyrrole/TiO₂ using cobalt nitrate and nickel nitrate as graphitizing catalysts. The resulting catalyst shows enhanced electrocatalytic performance for methanol electrooxidation compared with the commercial Pt/C catalyst. The enhancement can be ascribed to combinatory effect of N-doped graphitized carbon and TiO₂, in which the tolerance to CO-poisoning and the intrinsic kinetics of methanol oxidation reaction were simultaneously improved by the bifunctional effect and the modification of the electronic structure. As a result, the as-developed nitrogen-doped graphitized carbon/TiO₂ composite present attractive advantages for the application in fuel cell electrocatalyst.     

Low-temperature catalytic combustion of trichloroethylene over cerium oxide and catalyst deactivation

Cerium oxide catalysts prepared by a thermal decomposition method using the salt nitrate as precursor were tested for the catalytic combustion of trichloroethlyene (TCE), as a model of chlorinated volatile organic compounds (CVOCs). CeO₂ catalysts calcined at different temperature were found to possess high catalytic activity for catalytic combustion of TCE, and CeO₂ calcined at 550 °C was the most active catalyst and the complete combustion temperature (T_90%) of TCE was 205 °C. Effects of systematic variation of reaction conditions, including space velocity, inlet TCE concentration and water concentration on TCE catalytic combustion were investigated. Additionally, the stability and deactivation of CeO₂ catalysts were studied by various characterization methods (such as TG/DTA, EDS, XRD, Raman and XPS) and other assistant experiments.     

Oxidation state of platinum clusters during the reduction of NOx with propene and propane

The oxidation state of platinum supported on mesoporous SiO₂ and Al₂O₃ with MCM-41 type structure during the reduction of NO_x with propene or propane was investigated using in situ X-ray absorption spectroscopy. Platinum supported on MCM-41 (SiO₂) was reduced at low and oxidized at high reaction temperatures when propene was used as reducing agent, while it was found to be always oxidized in Pt/MCM-41 (Al₂O₃). When propane was used as reducing agent significant NO conversion was not observed over Pt/MCM-41 (SiO₂) and on both supports platinum was in an oxidized state. At the successive adsorption of the reactants, the prereduced catalysts were oxidized after NO adsorption and reduced after addition of the hydrocarbons. Addition of oxygen re-oxidized the catalysts, while the presence of water vapor did not influence the oxidation state.     

Photocatalytic Water Splitting on Visible Light-responsive TiO2 Thin Films Prepared by a RF Magnetron Sputtering Deposition Method

The development of visible light-responsive TiO₂ (Vis-TiO₂) thin films has been achieved by applying a radio-frequency magnetron sputtering deposition (RF-MS) method. Pt-loaded Vis-TiO₂ thin films act as photocatalysts to decompose water involving sacrificial reagent such as methanol or silver nitrate even under visible light (λ ≧ 420 nm) irradiation. It was also found that Pt-loaded Vis-TiO₂ thin films decompose pure water into H₂ and O₂ stoichiometrically under light irradiation of wavelengths longer than 390 nm. Vis-TiO₂ thin films exhibit columnar structures perpendicular to the substrate and a declined composition of the O/Ti ratio from the surface (O/Ti = 2.00) to bottom (O/Ti = 1.93). This unique structure (anisotropic structure) of Vis-TiO₂ can be considered an important factor in the modification of the electronic properties of Vis-TiO₂ thin films, enabling the absorption of visible light. Furthermore, the effect of the Pt loadings on the photocatalytic activity of the TiO₂ thin films was investigated and the optimum Pt loading was determined to be 21 μ g/cm² as Pt metal     

Adsorption and interaction of NO, C3H6 and O2 on Pt, Zr, Nb-MCM-41—FTIR study

Adsorption of NO, O₂ and C₃H₆ on the MCM-41 matrices with Nb and Zr loaded with Pt has been studied by the FTIR spectroscopy to characterize these materials as catalysts in the selective reduction of NO with propene. Two types of the catalysts have been studied differing by the methods of Zr and Nb introduction: either by one-pot (group 1) or by post-synthesis impregnation (group 2) and hence by the location of Nb and Zr in the framework (group 1) or extra framework (group 2). It has been found that the positions of these metals in the MCM-41 matrix determine the platinum dispersion, acidic–basic properties and influence the interaction of NO + O₂ + C₃H₆ with the catalyst surfaces. The fact that the Pt dispersion is much higher in group 2 materials has been revealed by results of XRD patterns and TEM images. According to the explanation proposed, the presence of Lewis acid–base pairs in the group 2 of catalysts has strongly activated chemisorption of propene, whereas Lewis basicity, characterized by 2-PrOH dehydrogenation on the samples containing transition metals introduced during the synthesis (group 1), has enhanced chemisorption of nitrite species on platinum. It has been proved that nitrite species have not been stored on Pt/Zr/MCM-41 samples, whereas they have been stabilized on Pt/Zr/Nb/MCM-41 containing BrØnsted acidic centres.     

Isomerization and Hydrocracking of n-Decane over Bimetallic Pt–Pd Clusters Supported on Mesoporous MCM-41 Catalysts

n-Decane hydroconversion has been investigated on bifunctional catalysts comprising bimetallic Pt–Pd clusters supported on an AlMCM-41 (n_Si/n_Al = 23) mesoporous molecular sieve. The catalytic activity of the bimetallic Pt–Pd catalysts is higher than that of the monometallic Pt and Pd catalysts. The good balance between the two catalytic functions, namely acid sites and metal sites, also results in a higher isomer yield at a substantially lower reaction temperature. Moreover, cracking on the metal sites (hydrogenolysis) is largely suppressed over certain bimetallic catalysts.     

Towards understanding the bifunctional hydrodeoxygenation and aqueous phase reforming of glycerol

Kinetically coupled reactions of glycerol in water over bifunctional Pt/Al₂O₃ catalysts are explored as a function of the Pt particle size and the reaction conditions. Detailed analysis of the reaction network shows that “reforming” and hydrodeoxygenation require the presence of a bifunctional catalyst, i.e., the presence of an acid–base and a metal function. The initial reaction steps are identified to be dehydrogenation and dehydration. The dehydrogenation of hydroxyl groups at primary carbon atoms is followed by decarbonylation and subsequent water gas shift or by disproportionation to the acid (and the alcohol) followed by decarboxylation. Hydrogenolysis of the C–O and C–C bonds in the alcohols does not occur under the present reaction conditions. Larger Pt particles favor hydrodeoxygenation over complete deconstruction to hydrogen and CO₂.     

Preparation of PtHY catalysts: Influence on the catalytic properties of the complexes used as platinum precursors

Three cation complexes: [Pt(NH₃)₄]²⁺, [Pt(NH₃)₂ (H₂O)₂]²⁺ and [Pt(H₂O)₄]²⁺ were used for the preparation of 0.6 wt.-% PtHY catalysts. The platinum dispersion depended on the platinum complex used as a precursor and, for a given complex, on the conditions of activation. The platinum dispersion of the catalysts prepared from the tetra-aquo platinum complex was very low, but this could be related to the great lability of the water ligands. It was also this lability which explained why the platinum dispersion was about twice as low for PtHY catalysts prepared from the diaquo-diammine complex than for those prepared from the tetra-ammine complex. However in the case of the two latter complexes, the activation conditions influenced the platinum dispersion in the same way: a highly marked effect of the calcination conditions and a small effect of the subsequent treatment under hydrogen flow. The behaviour of the PtHY catalysts for the bifunctional transformation of n-heptane did not depend on the platinum precursor. The activity and the selectivity of these catalysts depended only on their hydrogenating activity.