Preparation of noble metal nanocatalysts and their applications in catalytic partial oxidation of methane

A series of noble metal catalysts (Ru, Rh, Ir, Pt, and Pd) supported on alumina-stabilized magnesia were prepared and employed in partial oxidation of methane. The prepared catalysts were characterized using BET, SEM, TEM and H₂S chemisorption techniques. The results revealed that the Ru and Rh catalysts had the highest activity in catalytic partial oxidation of methane. Based on the obtained results the following order of activity was observed for different catalysts in partial oxidation of methane: Rh ～ Ru > Ir > Pt > Pd. The obtained results also showed a high catalytic stability without any decrease in methane conversion up to 50 h of reaction.     

Catalytic wet oxidation of p-chlorophenol over supported noble metal catalysts

Heterogeneous catalytic wet oxidation of aqueous p-chlorophenol (p-CP) solution was investigated at 453 K and 2.6 MPa in a slurry reactor. The performance of noble metal catalysts was compared with that of traditional manganese catalysts. Activated carbon supported catalysts showed significant higher activities for total organic carbon (TOC) reduction than those supported on alumina or cerium oxide. Pt was found to be the most active metal for p-chlorophenol oxidation. The activities of noble metal catalysts were found to correlate with heat of formation of metal oxides. CO₂ is the predominant oxidation product with formation of minor p-benzoquinone and acetic acid as intermediate compounds. Possible reaction pathway was also discussed.     

TPR study and catalytic performance of noble metals modified Al2O3, TiO2 and ZrO2 for low-temperature NH3-SCO

A series of γ-Al₂O₃, TiO₂ (anatase) and mt-ZrO₂ were impregnated with 1.0 wt.% of Cu or Fe and/or with 0.05 wt.% of Pt, Pd or Rh. The obtained samples were tested as catalysts of the selective catalytic oxidation of ammonia. An interesting class of zirconia and titania supported catalysts is based on copper. Modification of these catalysts with noble metals significantly decreased temperature of the ammonia oxidation. Platinum doped catalysts exhibited the highest activity, while rhodium based materials were the most selective catalysts in the studied temperature range. Catalytic performances of tested materials were consistent with their redox properties.     

Surface modification of Ni catalysts with trace Pt for oxidative steam reforming of methane

Hysteresis of catalytic performance with respect to temperature increasing and decreasing in oxidative steam reforming of methane (CH₄/H₂O/O₂/Ar = 40/30/20/10) over the monometallic Ni catalysts disappeared by the modification with Pt, and the additive effect of Pt by the sequential impregnation method (Pt/Ni) was much more significant than that by the co-impregnation method (Pt + Ni) in terms of catalytic performance and catalyst bed temperature profile. Characterization results by means of TEM, TPR, EXAFS, and FTIR suggest that the Pt atoms on the Pt/Ni catalysts were located more preferably on the surface to form a PtNi alloy than those on the Pt + Ni catalysts. The modification of Ni with Pt suppressed the oxidation of Ni species near the bed inlet in the oxidative steam reforming of methane at 1123 K, although the species on the monometallic Ni catalysts were oxidized under similar conditions. This can be due to the decreased oxidation rate of the species and the increased reduction rate caused by the surface modification of Ni with Pt. Consequently, the PtNi species can be maintained in the metallic state near the bed inlet, and the species can be the active site for the reforming reaction as well as the combustion reaction, which this leads to a lower bed temperature and smaller temperature gradient than those seen for the monometallic Ni catalysts.     

Hydroxylation of benzene with oxygen and hydrogen over catalysts containing Group VIII metals and heteropoly compounds

The vapor phase hydroxylation of benzene to phenol with a mixture of oxygen and hydrogen over silica supported bi-component catalysts containing Group VIII metals (M) and heteropoly compounds (HPC) was investigated. The productivity of the catalysts was ascertained for various metal and HPC combinations and a range of reaction conditions. The Pt–PMo₁₂/SiO₂ and Pd–PMo₁₂/SiO₂ catalysts of optimal composition provide up to 380 mol phenol/g-atom Pt or Pd/h. The observed catalysis appears to be associated with an interface between metal particles and those of the heteropoly compound, as illustrated by an HREM image of a Pt–PMo₁₂/SiO₂ sample.     

Dip-coating on TiO2 foams using a suspension of Pt–TiO2 nanopowder synthesized by laser pyrolysis—preliminary evaluation of the catalytic performances of the resulting composites in deVOC reactions

As an extension of a study to generate ceramic-metal nanosized composites further deposited on ceramic foams, here we describe a new route to prepare Pt–TiO₂ nanopowders of controlled metallic size and their further coating of TiO₂ foams. Their efficiency as catalysts in volatile organic compound elimination (deVOC) reactions was evaluated and compared to those of the corresponding classical unsupported mixed powders.Composite metal/ceramic nanopowders (Pt–TiO₂) were synthesized by laser pyrolysis using organo-metallic precursors. Successive dip-coatings on TiO₂ foams with aqueous slurries of nanodispersed Pt–TiO₂ particles were then achieved. Both foam-supported and unsupported Pt–TiO₂ grains of about 20 nm could be stabilized, confirming no significant particles coalescence after a thermal treatment at 460 °C. Both proved equally efficient catalysts for the total oxidation of methanol, selected as probe deVOC reaction, thereby demonstrating that the dispersion of the nanopowders over the preformed ceramics does not modify their catalytic performances.     

Hydrogen storage using heterocyclic compounds: The hydrogenation of 2-methylthiophene

Alkyl substituted thiophenes are promising candidates for hydrogen carriers, as their dehydrogenation reactions are known to occur under mild conditions. Four types of catalysts, including supported noble metals, bimetallic noble metals, transition metal phosphides and transition metal sulfides, have been investigated for 2-methylthiophene (2MT) hydrogenation and ring-opening. The major products were tetrahydro-2-methylthiophene (TH2MT), pentenes and pentane, with very little C₅-thiols observed. The selectivity towards the desired product TH2MT follows the order: noble metals > bimetallics > phosphides > sulfides. The best hydrogenation catalyst was 2% Pt/Al₂O₃ which exhibited relatively high reactivity and selectivity towards TH2MT at moderate temperatures. Temperature-programmed reaction (TPR) experiments revealed that pentanethiol became the major product, especially with HDS catalysts like CoMoS/Al₂O₃ and WP/SiO₂.     

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.     

Silicon nitride supported platinum catalysts for the partial oxidation of methane at high temperatures

The catalytic partial oxidation of methane has been studied over platinum silicon nitride supported catalysts in the temperature range of 900–1100°C at a contact time of 0.35 ms at atmospheric pressures. The feed consisted of a mixture of CH₄/O₂/N₂≈2/1/10. The catalysts were prepared by impregnation of platinum bis-acetyl-acetonate on silicon nitride powder (Si₃N₄). The different catalysts were characterized by chemical analysis, XPS and TEM. Minor particle sintering occurs during reaction. Metal losses were observed at 900°C, for catalysts containing 1.0 and 2.2 wt.% of platinum. A catalyst with a low amount of platinum (0.045 wt.%) appeared to be stable at 900°C, as no platinum loss was observed. The high stability of the 0.045 wt.% Pt/Si₃N₄ catalyst could be attributed to particular interactions between the metal and the support.     

Catalytic partial oxidation of ethane to ethylene and syngas over Rh and Pt coated monoliths: Spatial profiles of temperature and composition

The catalytic partial oxidation of C₂H₆ over Pt and Rh coated monolithic supports (4.7 wt% M/α-Al₂O₃ 45 PPI) was investigated with a capillary sampling technique for a range of C₂H₆/air ratios at constant inlet flow (～8 ms contact time), with and without H₂ addition. Effluent data clearly indicate the differences in product distribution between catalysts and equilibrium. Rh effectively converts the reactant mixtures to syngas with ～80% selectivity, whereas Pt produces C₂H₄ with ～55% C-atom selectivity, while neither produces thermodynamically favored C. Spatially resolved measurements provide direct evidence of the multi-zone nature of the reactors. With Rh, complete conversion of O₂ occurs to produce mostly CO, H₂ and H₂O within the first 3 mm of catalyst, followed by a reforming zone to produce additional syngas. Pt consumes O₂ more slowly, which results in a steady increase in temperature along the reactor. Ethylene formation correlates to reactor temperatures >750 °C, regardless of C/O, in line with the onset of homogeneous reactions. Hydrogen addition tests (C₂H₆/O₂/H₂=2/1/2) clearly exhibit preferential oxidation of H₂ with O₂ over Pt, which shifts the maximum in temperature upstream while preserving a portion of the C₂H₆ for C₂H₄ production. H₂ addition modifies the concentration and temperature profiles minimally on Rh. The main differences between catalysts are the high reforming and O₂ consumption activity with Rh compared to Pt, which are likely responsible for differences in C₂H₄ yields.     

XPS and EXAFS study of supported PtSn catalysts obtained by surface organometallic chemistry on metals: Application to the isobutane dehydrogenation

In this work, well defined alumina and silica supported Pt and PtSn catalysts were prepared by surface organometallic reactions and were characterized by TEM, XPS and EXAFS. These catalysts were tested in the catalytic dehydrogenation of isobutane. XPS results show that tin is found under the form of Sn(0) and Sn(II,IV), being the percentage of Sn(0) lower for alumina supported than for silica supported catalysts. Tin modified platinum catalysts, always show a decrease of approximately 1 eV in the BE of Pt, what would be indicative of an electron charge transfer from tin to platinum. When the concentration of Sn(0) is high enough, in our case Sn(0)/Pt ∼ 0.3, EXAFS experiments demonstrated the existence of a PtSn alloy diluting metallic Pt atoms, for both PtSn/γ-Al₂O₃ and PtSn/SiO₂. This PtSn alloy seems to be not active in the dehydrogenation reaction; however, it is very important for selectivity and stability, inhibiting cracking and coke formation reactions. The ensemble of our catalytic, XPS and EXAFS results, show that bimetallic PtSn/γ-Al₂O₃ catalysts, prepared via SOMC/M techniques, can be submitted to several sequential reaction–regeneration cycles, recovering the same level of initial activity each time and that the nature of the catalytic surface remains practically without modifications.     

Selective gas-phase conversion of maleic anhydride to propionic acid on Pt-based catalysts

Pt-based catalysts, supported on Al₂O₃, SiO₂ and SiO₂–Al₂O₃, were prepared by incipient wetness impregnation and tested in the gas phase hydrogenation of maleic anhydride at atmospheric pressure and 240 °C. In these conditions, the hydrogenolytic activity pattern was: Pt/SiO₂ > Pt/Al₂O₃ > Pt/SiO₂–Al₂O₃, which is just the opposite of the support acidity trend. These metal Pt-based catalysts showed high selectivity to propionic acid, which was always higher than 80%. The selectivity pattern to this product was: Pt/Al₂O₃ > Pt/SiO₂ > Pt/SiO₂–Al₂O₃. Both activity and selectivity patterns may be explained on the basis of metal-support interaction and support acidity.     

Self-oscillations of methane oxidation rate over Pd/Al2O3 catalysts: Role of Pd particle size

Oscillations of the methane oxidation rate were studied under methane-rich conditions on Pd/Al₂O₃ catalysts differing in Pd particle size. It was demonstrated that the temperature interval where oscillations occur narrows from 300–360 °C for the catalyst with Pd particle aggregates from 50–100 nm to 345–355 °C for the catalyst with isolated Pd particles of ~ 5 nm in size. At the same time, the period of oscillations showed ~ 6-fold increase. Structural transformations of Pd in the oscillation cycle were similar to those observed on bulk Pd used as a catalyst in the same reaction.     

Anodic catalysts for polymer electrolyte fuel cells: the catalytic activity of Pt/C,Ru/C and Pt-Ru/C in oxidation of CO by O2

The catalytic activity for oxidation of CO by O₂ was investigated on commercial Pt/C, Pt-Ru/C (Pt/Ru atomic ratio = 20, 3, 1, 1/3) and Ru/C. All samples contained 20 wt.% metal. Assuming equal surface and bulk composition, the number of surface Pt and Ru atoms was calculated from the average size of the supported metal particle as determined by TEM. On Pt-Ru/C alloys, the turnover frequency per Ru atom, N_Ru/molecules s⁻¹ Ru-atom⁻¹, was independent of chemical composition. This finding suggests that the active site in these alloys is Ru. In the temperature range 300–400 K, the turnover frequency per active metal atom was 50–300 times higher on Pt-Ru/C than on Pt/C. The turnover frequency was 400 times higher on Ru/C than on Pt/C at 313 K and 90 times higher at 353 K. Addition of water vapor to the reactant mixture left the catalytic activity of Ru/C unchanged but slightly increased the activity of Pt/C. On both catalysts the activation energy and reaction orders were nearly the same as in dry atmosphere. Conversely, the addition of water markedly decreased the activation energy for Pt-Ru(1 : 1)/C alloy (from 19 to 11 kcal mol⁻¹). These findings suggest that fuel cells equipped with Pt-Ru/C anodes perform better than cells with Pt/C anodes. They do so because Ru effectively oxidizes the carbon monoxide present as an impurity in the H₂-reformed fuel.     

Rapid syntheses of ultrafine LaMnO3 nano-crystallites with superior activity for catalytic oxidation of toluene

Supercritical water (sc-H₂O) reaction environment was evidenced with the capability to dramatically facilitate the solid-state reaction between hybrid oxides. This led to one-step and rapid (within several seconds) syntheses of ultrafine LaMnO₃ nano-crystallites (at ca. 6 nm) with no need of additional heat-treatment (literaturelly need to be heat-treated at 600–800 °C for 4–6 h in static air). The ultrafine LaMnO₃ was shown with remarkable surface area and distinct oxygen mobility and reducibility, which yielded an activation energy (Ea) in toluene oxidation at only ca. 54.3 kJ/mol, comparable to some noble metal catalysts.     

Preparation of binary washcoat deposited on cordierite substrate for catalytic applications

The deposition of binary M–ZrO₂ (M = Al₂O₃, SiO₂ or TiO₂) as secondary support on cordierite substrate by dip-coating was investigated and the as-prepared M–ZrO₂/cordierite was characterized by means of XRD and SEM techniques. After two successive dip-coating processes, the highest washcoat loading of 25.1% was achieved in Al₂O₃–ZrO₂/cordierite, followed by 18.7% in TiO₂–ZrO₂/cordierite and then 17.4% in SiO₂–ZrO₂/cordierite. The optimal parameters to prepare Al₂O₃–ZrO₂ washcoat on cordierite were investigated in detail. After introduction of noble metal active components (Rh and Pd) to the secondary support, the obtained Rh/M–ZrO₂/cordierite and Pd/M–ZrO₂/cordierite were further tested as monolithic catalysts for the decomposition of nitrous oxide and the deep oxidation of benzene, respectively.     

Efficient and selective conversion of glycidol to 1,2-propanediol over Pd/C catalyst

The present work deals with the catalytic hydrogenolysis of glycidol to 1,2-propanediol. Reactions were carried out in a closed steel reactor using noble metal based heterogeneous catalysts (Pd, Rh, Pt) under hydrogen pressure (1–8 bars) in the temperature range of 25–140 °C. Pd/C shows the highest glycidol conversion (96%) under solvent free conditions after 24 h with high selectivity to 1,2-propanediol (93%). The effect of the solvent was also investigated and it was demonstrated that ethanol reduces drastically oligomer production enhancing selectivity up to 99% with a significant reaction time reduction (6 h). The Pd/C catalyst shows high recyclability and could be reused several times (9 cycles) without losses in activity and selectivity.     

Trace precious metal Pt doped plate-type anodic alumina Ni catalysts for methane reforming reaction

A novel plate-type anodic alumina supported 17.9 wt% Ni/Al₂O₃/alloy showed a quick deactivation in daily start-up and shut down (DSS) steam reforming of methane (SRM) at 700 °C, because of the Ni oxidation reaction with steam. When 0.078 wt% Pt was doped, the catalyst exhibited self-activation and self-regeneration ability, while 3000 h continual and 500-time DSS stability was testified. Further, this Pt–Ni catalyst also showed excellent reactivity during carbon dioxide reforming of methane (CMR) and partial oxidation of methane reaction (POM). According to the TPR and XRD analyses, the H₂ spillover effect and the formation of Pt–Ni alloy were believed to be the main reason for the reactivity improvement of this catalyst.     

Electrodeposited Re-promoted Ni foams as a catalyst for the dry reforming of methane

The dry reforming of methane (DRM) utilizes carbon dioxide (CO₂) as the oxidizing agent in order to produce synthesis gas. Catalyst deactivation via coking, oxidation, and sintering has stymied the industrialization of catalysts for the DRM. Here, we utilized electrodeposition followed by de-alloying in order to synthesize metal alloy foams (5 m²/g). Through this process we have created the first electrodeposited DRM catalyst capable of converting more than 10,000 mL/g 1 h at near-equilibrium conversion. Rhenium promotion was observed over the entire temperature range studied (700–800 °C), with the most dramatic enhancement at 700 °C. After 50 h of reaction, no significant accumulation of carbonaceous deposits were detected, making electrodeposited structures a viable candidate for stable methane conversion catalysts.     

Investigations on the properties of ceria–zirconia-supported Ni and Rh catalysts and their performance in acetic acid steam reforming

The production of hydrogen via steam reforming of acetic acid was examined over Ni and Rh supported on a CeO₂–ZrO₂-mixed oxide. The catalysts were tested at 550–650–750 °C using steam/carbon = 3. Steam reforming, water gas shift, and decarboxylation are the main reactions taking place over the support alone. In parallel, dehydrogenation leads to the formation of carbon deposits on the surface of the mixed oxide. The addition of the metals enables the reforming reactions to proceed with high rates producing hydrogen yields close to thermodynamic equilibrium even at 650 °C. The oxygen exchange reactions are enhanced leading to much lower coke deposition. The nature of the metal affects not only the quantity but also the quality and the location of the carbon deposits, as evidenced from temperature-programing oxidation tests. The synergy of the support and metal is the key factor for the low coke deposition, which is even lower for the Rh catalyst.