Characterization and Catalytic Performance of PtSn Catalysts Supported on Al2O3 and Na-doped Al2O3 in n-butane Dehydrogenation

PtSn/Al₂O₃ and PtSn/Al₂O₃–Na catalysts display important modifications of the metallic phase with respect to Pt/Al₂O₃ one. In this sense, TPR and XPS results show the presence of strong interactions between Pt and Sn, with probable alloy formation, which would be responsible for the decrease of the reaction rate and the increase of the activation energy in cyclohexane dehydrogenation. Besides the experiments of cyclopentane hydrogenolysis show that the alkali metal addition to bimetallic PtSn/Al₂O₃ catalysts completely eliminates the hydrogenolytic ensembles, which could be due to a geometric modification of the metallic phase. These important modifications in the nature of the metallic function due to the simultaneous addition of Na and Sn to Pt/Al₂O₃ are responsible for the excellent catalytic performance in the n-butane dehydrogenation, thus giving high conversions, selectivities to butenes higher than 95%, and lower deactivation capacity than those corresponding to bimetallic PtSn catalysts (with different Sn contents) supported on undoped alumina. The excellent stability of PtSn/Al₂O₃–Na catalysts would be due to a low carbon formation during the reaction, such as it was observed from pulse experiments.     

FTIR and XPS study of supported PtSn catalysts used for light paraffins dehydrogenation

A comparison between the characteristics of the metallic phase (studied by FTIR and XPS) of Pt and PtSn catalysts supported on Al₂O₃, K-doped Al₂O₃ and MgO (used for light paraffins dehydrogenation reactions) is reported in this paper. The beneficial effects produced by tin addition to platinum, both in the increase of the selectivity to propene and the low coke formation, would be related with the possible electronic modifications of Pt by Sn, with probable formation of alloys, mainly for Al₂O₃ and MgO supported bimetallic catalysts. On the other hand, the modification of the electronic state of Pt by Sn addition appears to be of a minor importance in bimetallic catalysts supported on K-doped Al₂O₃.     

Hydrogenation of (–)-Menthone, (+)-Isomenthone, and (+)-Pulegone with Platinum/Tin Catalysts

The hydrogenation of (-)-menthone, (+)-isomenthone, and (+)-pulegone over SiO₂-supported Pt and Pt-Sn catalysts was studied in this work. The modification with tin was performed by means of the techniques of surface organometallic chemistry on metals. This way of modifying the catalysts allowed stereoisomers of menthol to be obtained in a one-step process. The hydrogenation of these terpenones was favored by the presence of tin in the bimetallic phase.     

Platinum-tin and platinum-copper catalysts for autothermal oxidative dehydrogenation of ethane to ethylene

The addition of various metals to Pt-coated ceramic foam monoliths was examined for the autothermal oxidative dehydrogenation of ethane to ethylene at 900°C at contact times of 5 ms. The addition of Sn or Cu to Pt-monoliths enhanced both C₂H₆ conversions and C₂H₄ selectivities significantly, giving higher C₂H₄ yields. No deactivation or volatilization of the catalysts was observed. For Pt-Sn, an increase in the Sn/Pt ratio from 1/1 to 7/1 increased both the conversion and the selectivity. For Pt-Sn (Sn/Pt = 7/1) versus Pt alone the conversion increased by up to 6% and the selectivity up to 5% for an increase in optimal yield from 54.5% with Pt to 58.5% with Pt-Sn. XRD and XPS measurements showed that Pt existed in the form of PtSn and Pt₃Sn alloys. The 1/1 Pt-Cu catalyst showed comparable performance, with conversion increasing by 5% and selectivity by 3%. The addition of several other metals to Pt-monoliths decreased both C₂H₆ conversion and C₂H₄ selectivity in the order, Sn>Cu>Pt alone>Ag>Mg>Ce>Ni>La> Co. For oxidative dehydrogenation ofn-butane and isobutane, Pt-Sn and Pt-Cu also showed higher conversion than Pt.This research was partially supported by NSF under Grant CTS-9311295.     

Influence of the crystalline structure of ZrO2 on the metallic properties of Pt in Pt/WO3–ZrO2 catalysts

The influence of the crystalline structure of ZrO₂ on the metallic properties of Pt, when supported on WO₃–ZrO₂, was studied. Pt supported on tetragonal zirconia loses its metallic properties while when supported on monoclinic zirconia it presents good metallic activities. WO₂,^2- deposited on amorphous Zr(OH)₄ before calcination generates an active material for n‐butane isomerization. The larger the fraction of the tetragonal phase of zirconia in this material, the higher the isomerization activity and the lower the metallic activity of Pt. This revised version was published online in July 2006 with corrections to the Cover Date.     

芳烃加氢金属催化剂抗硫性研究的进展

介绍了在油品芳烃加氢过程中提高镍金属和贵金属催化剂抗硫性研究的进展，对镍催化剂，添加碱金属、碱土金属和其他组分，调节镍金属的还原度及形成镍硼合金等有一定的效果；对贵金属催化剂，铂和钯形成合金，改变金属的颗粒度和载体的酸碱性能及添加碱金属等常被采用。     

Deactivation and regeneration of Pt/Al2O3 catalysts during the hydrodechlorination of carbon tetrachloride

Deactivation and regeneration of Pt/Al₂O₃ catalysts during the hydrodechlorination of carbon tetrachloride were studied. The effect of reactant partial pressures and temperature on the catalyst deactivation was investigated. A deactivation model with residual activity was developed to quantify the kinetic deactivation parameters. The effect of the regeneration atmosphere was also investigated. Regeneration under air allowed for the full recovery of the catalytic performance of fresh catalysts while treatments under flowing hydrogen resulted in a superior catalytic performance, increasing both the initial and residual activities. This was ascribed to a combined effect, redispersion of the metallic phase and formation of surface defects.     

Building and characterization of catalysts on single crystal surfaces

The components of complex catalyst systems include transition metals, oxides, alkali metal or halogen additives and strongly chemisorbed sulfur or carbonaceous species. Modern surface science techniques identified the chemical and structural roles of these ingredients when used in combination with catalytic reaction rate studies. Using metal single crystal substrates, catalyst components have been deposited from the vapor phase and the complex catalyst system could be built this way. The Pt-Re-S, Rh-TiO₂, and Mo-Co-S systems are reviewed and the requirements for the proper surface structure and composition to obtain high reaction rates and selectivities are discussed.     

Preparation and catalytic use of platinum in magnetic core/shell nanocomposites

Platinum (Pt) nanoparticles show high activity as catalysts in various chemical reactions. The control of the morphology of Pt nanostructures can provide an opportunity to improve their catalytic properties. The preparation of Pt‐loaded iron‐oxide polyvinylbenzyl chloride nanocomposites was done in several stages: first by the formation of the core consisting of magnetite nanoparticles and second by the polymerization of vinylbenzyl chloride in the presence of the magnetic core particles. The third step is the amination of the chlorine group with ammonia, which leads to an ion exchange resin. Then, the Pt precursor (H₂PtCl₆) is attached by ion exchange. Finally, the Pt ions are reduced to Pt metal with NaBH₄. The obtained material can be dispersed easily and be used as a catalyst which can be separated after the reaction by magnetic fields. Characterization of the resulting metallic nanocomposites is evaluated by atomic absorption spectroscopy, thermal gravimetric analysis, transmission electron microscopy, infrared spectroscopy, and gas chromatography. The activity of Pt at magnetic core/shell nanocomposites was measured for the reduction reaction of cinnamaldehyde to cinnamyl alcohol. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

New Supported Pd and Pt Alloy Catalysts for Steam Reforming and Dehydrogenation of Methanol

The catalytic performances of supported Group 810 metal (Co, Ni, Ru, Pd, Ir and Pt) catalysts for steam reforming of methanol, CH₃OH + H₂O CO₂ + 3H₂, and dehydrogenation of methanol to methyl formate, 2CH₃ OH HCOOCH₃ + 2H₂, are markedly affected by the kinds of supports as well as the metals used. The selectivity for steam reforming and the formation of methyl formate was markedly improved when Pd or Pt were supported on ZnO, In₂O₃ and Ga₂O₃. The combined results of temperature-programmed reduction, XRD, XPS and AES revealed that Pd-Zn, Pd-In, Pd-Ga, Pt-Zn, Pt-In and Pt-Ga alloys were formed upon reduction. Over the catalysts having an alloy phase, the reactions proceeded selectively, whereas over the catalysts having a metallic phase, methanol was decomposed to carbon monoxide and hydrogen predominantly. It was shown that the reactivity of formaldehyde intermediate over the Pd and Pt alloys was markedly different from that over metallic Pd and Pt. Over Pd and Pt alloys, aldehyde species were stabilized and transformed into carbon dioxide and hydrogen or methyl formate by nucleophilic addition of water or methanol, respectively. By contrast, over metallic Pd and Pt, aldehyde species were rapidly decarbonylated to carbon monoxide and hydrogen.     

Performance and stability of Pt-based ternary alloy catalysts for PEMFC

Carbon-supported Pt-based ternary alloy electrocatalysts were prepared by incipient wetness method in order to elucidate the origin of the enhanced activity of oxygen reduction reaction in PEMFC. To measure the catalytic activity and stability of the cathode alloy catalysts (electrodes containing Pt loading of 0.3 mg/cm², 20 wt.% Pt/C, E-TEK), the I-V polarization curves were obtained. All alloy catalysts showed higher performances than Pt/C. It can be concluded that as platinum formed alloys with transition metals, the electronic state of Pt and the nearest neighbor Pt-Pt distance changes, which significantly influence the electrocatalytic activity for oxygen reduction.Long-term stability test was performed with the Pt₆Co₁Cr₁/C alloy catalyst for 500 h. According to XPS analysis, the lower oxide component with Pt₆Co₁Cr₁/C electrocatalyst provides a large portion of platinum in metallic species in the electrocatalyst and it seems to be mainly responsible for its enhanced activity towards oxygen reduction.     

XAFS study of the state of platinum in a sulfated zirconia catalyst

EXAFS and XANES data show that platinum, present in a Pt-SO₄-ZrO₂ catalyst, exists in the metallic state following calcination in air at 725°C for 2 h, and that no detectable change in the valence state of Pt occurs during use of the catalyst for hydrocarbon conversion at 150°C under hydrogen pressure. The metallic Pt is present in reasonably large crystals where the average coordination number of Pt is about 12.     

Influence of alkali metal doping on selectivity behaviour of platinum catalysts for hydrogenation of 2-butyne-1,4-diol

Hydrogenation of 2-butyne-1,4-diol to 2-butene-1,4-diol (B₂D) and butane-1,4-diol (B₁D) using Pt catalysts doped with alkali metals was studied. These catalysts showed higher selectivity to the olefinic diol (B₂D) compared to that with monometallic platinum catalyst. Among various alkali metals, Cs-doped catalyst showed highest selectivity (>99%) to B₂D. The selectivity to B₂D increased (up to 99.9%) with increase in the concentration of Cs from 0.25% to 1%. The increase in the basic strength of alkali doped catalysts measured by CO₂-TPD, would be responsible for the increase in electron density of Pt hence, faster desorption and higher selectivity to the intermediate olefinic diol (B₂D). The reaction parameters, such as temperature, H₂ pressure and substrate concentration have strong influence on the catalyst activity but almost no effect on the selectivity to B₂D.     

Confirmation of sulfur tolerance of bimetallic Pd–Pt supported on highly acidic USY zeolite by EXAFS

The sulfur tolerance (i.e., degree of sulfidation) of Pd and Pt in sulfided bimetallic Pd–Pt catalysts (Pd : Pt mole ratio of 4 : 1) supported on USY (ultrastable Y) zeolites (SiO₂/Al₂O₃ = 10.7, 48, and 310) was investigated using an extended X‐ray absorption fine structure (EXAFS) method. The sulfidation of the catalysts was done in a 1000 ppm H₂S–2% H₂/N₂ stream at 573 K for 0.5 h. In the Fourier transforms of Pd K‐edge and Pt L_III‐edge EXAFS spectra, both of the peaks due to metallic Pd and to metallic Pt for the Pd–Pt/USY (SiO₂/Al₂O₃ = 10.7) catalyst remained most after sulfidation. Further, the results of the Fourier transforms confirmed that the sulfur tolerance of both Pd and Pt decreased with increasing SiO₂/Al₂O₃ ratio, suggesting that Pd and Pt become sulfur‐tolerant when Pd–Pt bimetallic particles are supported on highly acidic USY zeolite. This revised version was published online in July 2006 with corrections to the Cover Date.     

MgAl2O4 spinel prepared by mechanochemical synthesis used as a support of multimetallic catalysts for paraffin dehydrogenation

The catalytic performance in n-butane dehydrogenation of bimetallic PtSn, PtGa and PtIn, and trimetallic PtSnIn and PtSnGa catalysts (with low metal contents) supported on a MgAl₂O₄ prepared by a novel mechanochemical synthesis was evaluated both in flow and pulse equipment. The influence of the addition of different promoters (Sn, Ga and In) to Pt on the activity, selectivity and deactivation in the n-butane dehydrogenation reaction was studied. Stability experiments through successive reaction-regeneration cycles were carried out for selected catalysts. In order to correlate the properties of the metallic phase of the catalysts with the catalytic behavior, several characterization techniques were used, such as test reactions of the metallic phase (cyclohexane dehydrogenation and cyclopentane hydrogenolysis), TPR, XPS, H₂ chemisorption and TEM. Bimetallic PtSn catalyst has a better catalytic behavior than PtIn and PtGa ones. For PtSnM (M: In or Ga) catalysts, whereas Ga addition to the bimetallic catalyst does not practically modify the dehydrogenation performance, the addition of In produces an increase of the activity and the selectivity to butenes. Characterization results indicate the presence of geometric effects for the PtSn catalyst, and geometric and electronic effects for PtIn and PtGa ones. For trimetallic catalysts, the presence of a close contact between Pt, Sn and In or Ga in both trimetallic catalysts was found, mainly due to geometric effects like blocking and dilution of the active sites by the promoters. In stability experiments, the trimetallic PtSnIn/MgAl₂O₄ catalyst clearly displays the best catalytic performance along reaction-regeneration cycles, though PtSnGa and PtSn catalysts also showed a very good behavior through the successive cycles. The characterization of these catalysts after cycles shows that their metallic phases are slightly modified along the cycles.     

Co/Al2O3 catalysts promoted with noble metals for production of hydrogen by methane steam reforming

The effect of noble metal addition on the catalytic properties of Co/Al₂O₃ was evaluated for the steam reforming of methane. Co/Al₂O₃ catalysts were prepared with addition of different noble metals (Pt, Pd, Ru and Ir 0.3 wt.%) by a wetness impregnation method and characterized by UV–vis spectroscopy, temperature programmed reduction (TPR) and temperature programmed oxidation (TPO) of the reduced catalysts. The UV–vis spectra of the samples indicate that, most likely, large amounts of the supported cobalt form Co species in which cobalt is in octahedral and tetrahedral symmetries. No peaks assigned to cobalt species from aluminate were found for the promoted and unpromoted cobalt catalysts. TPO analyses showed that the addition of the noble metals on the Co/Al₂O₃ catalyst leads to a more stable metallic state and less susceptible to the deactivation process during the reforming reaction. The Co/Al₂O₃ promoted with Pt showed higher stability and selectivity for H₂production during the methane steam reforming.     

Hydrogenation of Sunflower Oil over M/SiO2 and M/Al2O3 (M = Ni,Pd, Pt,Co, Cu) Catalysts

This work is aimed at evaluating the performance of several catalysts in the partial hydrogenation of sunflower oil. The catalysts are composed of noble (Pd and Pt) and base metals (Ni, Co and Cu), supported on both silica and alumina. The following order can be proposed for the effect of the metal on the hydrogenation activity: Pd > Pt > Ni > Co > Cu. At a target iodine value of 70 (a typical value for oleomargarine), the production of trans isomers is minimum for supported nickel catalysts (25.7–32.4 %, depending on the operating conditions). Regarding the effect of the support, Al₂O₃ allows for more active catalysts based on noble metals (Pd and Pt) and Co, the effect being much more pronounced for Pt. Binary mixtures of catalysts have been studied, in order to strike a balance between catalyst activity and product distribution. The results evidence that Pd/Al₂O₃–Co/SiO₂ mixture has a good balance between activity and selectivity, and leads to a very low production of trans isomers (11.8 %) and a moderate amount of saturated stearic acid (13.5 %). Consequently, the utilization of cobalt‐based catalysts (or the addition of cobalt to other metallic catalysts) could be considered a promising alternative for the hydrogenation of edible oil.     

Study on the properties of iron–cobalt alumina supported catalyst for ammonia

The addition of Co to Fe/Al₂O₃ increases the catalytic activity in NH₃ synthesis. The maximum effect is observed for 20% by weight of Co in the metallic phase. Bivalent cobalt atoms replace bivalent iron atoms (a similar ionic radius) in the crystal lattice. This process changes the reducibility of the samples. The Fe-Co compound and its formation results in the fairly high temperature of reduction (873 K) which is needed to prepare the most active catalyst. Changing the reactor atmosphere from reducing to inert causes the disappearance of free iron (escape of Fe to the crystal lattice of support with formation of a new compound with a spinel character). This is the effect of the iron-hydrogen interaction. The formation of an intermetallic iron-cobalt compound is crucial to the catalyst activity. This might be due to the surface restructuring by exposing the most active iron surface, Fe(111). The potassium addition in the form of KOH causes an increase in the catalytic activity. The increase is not as high as for a ‘super basic’ Fe-Co magnesium hydroxide carbonate supported catalyst studied earlier. A part of the potassium hydroxide is used to neutralize the acid sites on the surface of alumina.     

On the development of metallic inert anode for molten CaCl2–CaO System

Some fundamental aspects related to inert anode development in molten CaCl₂–CaO were investigated based on thermodynamic analysis, electrochemistry of metals and solubility of oxide measurements. The Gibbs free energy change of several key anodic reactions including electro-stripping of metals, electro-formation of metallic oxides, electro-dissolution of metallic oxides as well as oxygen and chlorine evolution was calculated and documented, for the first time, as a reference to develop metallic inert anode in chloride based melts. The anodic behaviors of typical metals (Ni, Fe, Co, Mo, Cu, Ag, and Pt) in the melt were investigated. The results confirmed the thermodynamic stability order of metals in the melts and revealed that surface oxide formation can increase the stability of the electrodes in CaO containing melt. Furthermore, solubility of several oxides (NiO, Fe₂O₃, Cr₂O₃, Co₃O₄, NiFe₂O₄) in pure CaCl₂ or CaCl₂–CaO melts was measured to evaluate the stability of oxide coating or a cermet inert anode in the melt. It was found that the solubility of NiO decreased with increasing CaO concentration, while that of Fe₂O₃ increased. Ni coated with NiO film had much higher stability during anodic polarization.     

Role of tungsten in supported Pt-W reforming catalysts Part I. Modification of platinum activity and selectivity by addition of tungsten

Bimetallic supported Pt-W catalysts are studied for 3-methylhexane reforming. An increase in the activity and selectivity in aromatization is found for Pt-low W/Al₂O₃ catalysts compared to the classical monometallic Pt/Al₂O₃ catalyst. Changes in activity and selectivity, for bimetallic catalysts, are attributed to tungsten moderator interaction effects between platinum and support which modify the metallic particle sizes. These changes are observed on Pt-high W/Al₂O₃ and Pt-W/SiO₂ catalysts. Superficial carbide formation and modification of the hydrogen chemisorption may be proposed to explain the reactivity of Pt-W catalysts under low hydrogen pressure.