Catalytic hydrogen transfer of ketones over atomic layer deposited highly-dispersed platinum nanoparticles supported on multi-walled carbon nanotubes

Hydrogen transfer of ketones, catalyzed by highly-dispersed platinum nanoparticles supported on multi-walled carbon nanotubes (MWCNTs), was studied. Pt nanoparticles were deposited on gram quantities of non-functionalized MWCNTs by atomic layer deposition (ALD) at 300 °C, using (methylcyclopentadienyl) trimethylplatinum and oxygen as precursors. TEM analysis showed that ~ 1.4 nm Pt nanoparticles were highly dispersed on MWCNTs. The heterogeneous hydrogen-transfer reactions of acetophenone indicated that an acetophenone conversion of 100% and a 1-phenylethanol selectivity of 99.0% could be obtained with a ketone to Pt mass ratio of 24,690 and a ketone to KOH mass ratio of 22 at 150 °C for 5 h. The selectivity of the Pt/MWCNT catalyst was higher than that of the commercial Pt/C catalyst, due to the highly-dispersed, uniform Pt nanoparticles and the unique porous structures of the Pt/MWCNT catalyst. The high stability of the Pt/MWCNT catalyst was demonstrated by reutilization of the catalyst. The high reactivity and selectivity of this catalyst for hydrogen transfer reduction were also demonstrated for other ketones.     

Catalytic reforming—the impact of process and regeneration conditions on catalyst cycle duration and product quality at the Rijeka Oil Refinery

The impact of catalytic reforming and catalyst regeneration process parameters on cycle duration and product quality was investigated. Overall data were based on catalyst manufacturer data and process data of the Platforming plant at the Rijeka Oil Refinery (Croatia). Used catalyst was Pt–Re on high purity aluminia as carrier.For the reformate octane number of 99 the reduction of charge from the designed 90 m³/h to 75 m³/h results in the lowering of the Start of Run reactor temperature from 515.2 to 511.0 °C with a hydrogen/hydrocarbon ratio of 7.3:1 and 23 bar at the high pressure separator. Knowing the maximal inlet reactor temperatures at Platforming of around 528 °C for the existing catalyst type, it turns out that the temperature range of catalyst usability goes up from 12.8 to 17.1 °C. In this way, from a cycle duration of 116 days, we come to a more acceptable duration of 198 days. Such cycle duration enables two catalyst regenerations per year.Catalyst cycle duration, as well as the quality of catalytic reforming products, greatly depends on the way catalyst regeneration is carried out. This relates to the distribution of active metal sites on catalyst fines after the coke, deposited on the catalyst, had been burned out. Regeneration process itself must be adjusted to the maximum allowed operating pressure and the maximum volume flow of gas phase through the high pressure catalytic section.     

Effect of Temperature and Water on the Selective Oxidation of H<Subscript>2</Subscript>S to Elemental Sulfur on a Macroscopic Carbon Nanofiber Based Catalyst

Abstract  

Carbon nanofibers were synthesized on graphite felt substrate by catalytic decomposition of ethane. The preshaped material was efficiently used as catalyst support for the active phase NiS₂ in the direct oxidation of H₂S into elemental sulfur. The catalyst was extremely active, selective, and stable at 60 °C in a fixed bed reactor due to the high resistance of carbon nanofiber based catalyst to the solid sulfur loading. This is explained by the specific mode of sulfur deposition, involving the role of water in the sulfur transport and the hydrophobic nature of the support.     

Catalytic combustion of formaldehyde on gold/iron-oxide catalysts

A series of gold/iron-oxide catalysts for catalytic combustion of formaldehyde were prepared by co-precipitation. The catalyst containing 7.10 wt% of gold exhibited the highest catalytic activity. On this catalyst, the catalytic combustion reaction of formaldehyde proceeded at considerable rates at 20 °C and complete burn-off of formaldehyde was achieved at 80 °C. The catalysts were stable and remained active in the presence of moisture and are good substitutes for the noble metals (Pt, Pd) catalysts. The structure of catalysts, the valence state of gold and the size of gold particles were investigated by X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy techniques. Gold atoms with fractional positive charge (Au^δ+) were found to exist in the catalyst and play an important role in the catalytic activity. Interaction between active species and support also provided important contribution to the valence state of gold and the activity for the catalytic combustion of HCHO.     

Hydrogen production by aqueous-phase reforming of ethanol over nickel catalysts prepared from hydrotalcite precursors

Derived hydrotalcite catalysts, with different Ni loadings, were prepared and tested in aqueous-phase reforming of ethanol. Upon calcination of the hydrotalcite-like compounds, there was formation of MgO periclase-type phase, where both nickel and aluminum oxides are well dispersed. The mixed oxides showed only one reduction peak in temperature range of 900–1000 °C. The catalytic tests were carried out in a batch reactor with an aqueous solution of 1 wt.% ethanol at different temperatures (200, 230 and 250 °C). The derived hydrotalcite catalysts showed high activity, with 65% of ethanol conversion at 230 °C, high hydrogen selectivity and lower methane production than alumina supported nickel catalyst.     

Size and Shape Dependence on Pt Nanoparticles for the Methylcyclopentane/Hydrogen Ring Opening/Ring Enlargement Reaction

Abstract  

Monodisperse Pt nanoparticles (NPs) with well-controlled sizes in the range between 1.5 and 10.8 nm, and shapes of octahedron, cube, truncated octahedron and spheres (~6 nm) were synthesized employing the polyol reduction strategy with polyvinylpyrrolidone (PVP) as the capping agent. We characterized the as-synthesized Pt nanoparticles using transmission electron microscopy (TEM), high resolution TEM, sum frequency generation vibrational spectroscopy (SFGVS) using ethylene/H₂ reaction as the surface probe, and the catalytic ethylene/H₂ reaction by means of measuring surface concentration of Pt. The nanoparticles were supported in mesoporous silica (SBA-15 or MCF-17), and their catalytic reactivity was evaluated for the methylcyclopentane (MCP)/H₂ ring opening/ring enlargement reaction using 10 torr MCP and 50 torr H₂ at temperatures between 160 and 300 °C. We found a strong correlation between the particle shape and the catalytic activity and product distribution for the MCP/H₂ reaction on Pt. At temperatures below 240 °C, 6.3 nm Pt octahedra yielded hexane, 6.2 nm Pt truncated octahedra and 5.2 nm Pt spheres produced 2-methylpentane. In contrast, 6.8 nm Pt cubes led to the formation of cracking products (i.e. C₁–C₅) under similar conditions. We also detected a weak size dependence of the catalytic activity and selectivity for the MCP/H₂ reaction on Pt. 1.5 nm Pt particles produced 2-methylpentane for the whole temperature range studied and the larger Pt NPs produced mainly benzene at temperatures above 240 °C.     

Catalytic enhancement of platinum supported on zeolite beta for toluene hydrogenation by addition of palladium

This work focused on the preparation, characterization and catalytic performance of a bimetallic platinum–palladium catalyst for toluene hydrogenation. A catalyst with 3 wt% loading of each metal was prepared by co-impregnation on zeolite beta in proton form and denoted as 3Pt3Pd/HBEA. The structure of HBEA was retained after catalyst preparation and the metal occupied strong acidic sites of the zeolite. Compared to monometallic 3Pt/HBEA, the 3Pt3Pd/HBEA exhibited smaller Pt particle size due to better dispersion on the support. The catalytic performance of the bimetallic catalyst at various temperatures indicated that the presence of Pd enhanced toluene hydrogenation of Pt catalyst at high temperature. The most suitable temperature for toluene hydrogenation on 3Pt3Pd/HBEA was 150 °C for which a complete toluene conversion was obtained with methylcyclohexane as the only product.     

Promotion Effects of Platinum and Ruthenium on Carbon Nanotube Supported Cobalt Catalysts for Fischer–Tropsch Synthesis

Abstract  

Carbon nanotube supported nano-size monometallic and noble metal (Pt and Ru) promoted cobalt catalysts were prepared by incipient wetness impregnation (IWI) using solution of cobalt nitrate and characterized by nitrogen adsorption isotherm, X-ray diffraction (XRD), temperature programmed reduction, in situ magnetic method and TEM. Analysis of the magnetization and H₂-TPR data suggested promotion with platinum and ruthenium significantly decreased the cobalt species reduction temperature. TEM and XRD results showed that the presence of noble metal promoters had no significant effect on the size of cobalt for carbon naotube as catalytic support. Promotion of cobalt carbon nanotube-supported catalysts with small amounts of Pt and Ru resulted in slight increase in Fischer–Tropsch cobalt time yield. The Pt and Ru promoted cobalt catalyst exhibited carbon monoxide conversion of 37.1 and 31.4, respectively. C₅+ hydrocarbon selectivity was attained at 80.0%. The Pt promoted cobalt supported on carbon nanotube yielded better catalytic stability than that of the monometallic cobalt catalyst.     

Outstanding efficiency of indium in bimetallic catalysts for hydroconversion of bioacids to bioalcohols

Step by step reduction of acetic acid (AA) to ethanol was investigated over novel bimetallic catalysts (PtIn/Al₂O₃) for the processing of VFAs (volatile fatty acids) that can be produced simply by thermochemical or biological biomass degradation. A fixed bed flow-through reactor was applied with hydrogen stream at 21 bar total pressure in the temperature range of 220–380 °C. AA hydroconversion activity of the parent alumina supported Pt catalyst and the yield of selectively produced alcohol can be increased drastically by In₂O₃ addition. Appearance of metallic indium creating a bimetallic catalyst can direct the consecutive catalytic reduction to ethanol formation inhibiting hydrodecarbonylation. Comparing the In-containing bimetallic catalysts studied recently, NiIn-catalyst showing similar activity to that of the PtIn-catalyst can be a cheap substitute for the expensive Pt catalysts in the reduction carboxylic acids.     

Promoting Effect of Pt Addition to V2O5/ZrO2 Catalyst on Reduction of NO by C3H6

The effect of Pt addition to a V₂O₅/ZrO₂ catalyst on the reduction of NO by C₃H₆ has been studied by FTIR spectroscopy as well as by analysis of the reaction products. Pt loading promoted the catalytic activity remarkably. FTIR spectra of NO adsorbed on the catalysts doped with Pt show the presence of two different types of Pt sites, Pt oxide and Pt cluster, on the surface. The amount of these sites depends on Pt contents and the catalyst state. Pt atoms highly disperse on the surface as Pt oxide at low Pt content, being aggregated into Pt metal clusters by increasing Pt amount or reducing the catalysts. The spectral behavior of V=O bands on the surface also supports the formation of Pt clusters. It is concluded that Pt promotes the NO–C₃H₆ reaction through a reduction–oxidation cycle between its oxide and cluster form.     

Hydrogenation and Ring Opening of Aromatic and Naphthenic Hydrocarbons Over Noble Metal (Ir,Pt, Rh)/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Catalysts

Abstract  

The hydrogenation and ring opening of model hydrocarbons and of naphtha was studied over commercial noble metal (Ir, Pt, Rh)/Al₂O₃ catalysts. The experiments were performed in a fixed bed reactor at temperatures between 220 and 350 °C and pressures of 1.1 and 5.0 MPa, respectively. The product distribution was determined and the cetane number was calculated. The Pt catalyst is very active for hydrogenation of aromatics but does not catalyse the ring opening of naphthenes. The Ir and Rh catalysts are active for both hydrogenation of aromatics and ring opening of naphthenes. Experiments with toluene, m-xylene, propyl-benzene, and methylcyclohexane indicate that ring opening follows a selective mechanism, where the cleavage of bisecondary carbon bonds is favoured. This results in predominant formation of branched paraffins. The product distribution as well as cracking of long-chain hydrocarbons, which increase at temperatures above 260 °C, lead to an insignificant boost in the cetane number, as confirmed by experiments using real naphtha as feedstock.     

Effect of calcination temperature on catalytic properties of PtSnNa/ZSM-5 catalyst for propane dehydrogenation

The effect of calcination temperature on catalytic performance of PtSnNa/ZSM-5 catalysts for propane dehydrogenation was studied. It was found that when the calcination temperature was in the range of 400–500 °C, structure and acidity of the catalyst did not change obviously. In contrast to this, with the increase of calcination temperature, the specific surface area and pore volume dramatically decreased, while the mean pore diameter increased. Under these conditions, more framework aluminum atoms were removed from tetrahedral positions, which weakened the interactions between Sn species and carrier. Meantime, the degree of Pt sintering and the destruction of Pt active sites with “sandwich structure” were aggravated, which was disadvantageous to the reaction. When the catalyst was calcined at 500 °C, the interactions between Pt and Sn were strengthened, thus improving the catalytic stability and reaction selectivity evidently. Moreover, it should be remarked that the phenomenon of slow Pt sintering was not clearly observed even though the reaction temperature of it was higher than the calcination one.     

Selective Ring-Opening of Methylcyclopentane Over Titania-Supported Monometallic (Pt, Ir) and Bimetallic (Pt–Ir) Catalysts

An investigation of the selective ring-opening of methylcyclopentane (MCP) was conducted for the first time on Pt/TiO₂, Ir/TiO₂ and Pt?CIr/TiO₂ catalysts with low amounts of noble metals (0.5?wt%) over a temperature range of 180?C400?°C under hydrogen at atmospheric pressure. The catalysts were prepared by impregnation or co-impregnation and characterized by different physico-chemical techniques, including SEM, XRD, H₂-TPR, N₂-sorption, TEM and elemental analysis. The metallic particles were highly dispersed on the TiO₂ support at isodispersion of ~1?nm. The particles exhibited icosahedral Mackay structures limited by (111) planes. The catalytic results show that the activity in the MCP was strongly influenced by the intrinsic nature of the metal and by the temperature. The most active catalyst was Ir/TiO₂. The order of the reactivity as a function of the temperature and total conversion was Ir/TiO₂ 180?°C (???=?2?%)?>?Pt?CIr/TiO₂ 220?°C (???=?27.8?%)?>?Pt/TiO₂ 260?°C (???=?9.9?%). Under these conditions, all of the catalysts exhibited the ability to open the ring of MCP with an atom economy, without unwanted products of cracking and ring-enlargement reactions. The synergy between Pt?CIr bimetallic particles was assessed by the total conversion of MCP, whereas the ring-opening results indicated that the reaction took place on Ir sites. These results suggest that the bimetallic catalyst contained separate entities of two metals. Increased reaction temperatures led to reduced reaction selectivity with respect to ring-opening of MCP versus the cracking side reaction.     

Biomorphic SiC pellets as catalyst support for partial oxidation of methane to syngas

Biomorphic silicon carbide (bioSiC) pellets prepared from carbonized millet were employed as nickel catalyst support for the partial oxidation of methane to syngas in a fixed-bed quartz reactor at 800 °C. To reduce the loss of nickel active component during the reaction, alumina was used to modify the bioSiC surface. The temperature programmed reduction reveals that the alumina modification can evidently increase the reduction temperature of nickel oxide and therefore enhance the interaction between nickel and support. Due to the enhanced interaction, the nickel component becomes stable and difficult to migrate on the support surface. As a result, the modified bioSiC catalyst shows higher catalytic activity and stability than the unmodified. Compared with the catalyst supported on powdered SiC, the pelletized catalyst shows higher activity, especially at high gas hourly space velocity.     

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.     

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.     

Platinum supported on reduced graphene oxide as a catalyst for hydrogenation of nitroarenes

Reduced graphene oxide (RGO)-supported platinum (Pt) catalyst was prepared by simple ethylene glycol (EG) reduction and used for hydrogenation of nitroarenes. Characterizations showed that EG as a reductant exhibited more advantages than the widely used hydrazine hydrate to fabricate monodispersed, small sized Pt nanoparticles on the surface of RGO. The yield of aniline over the Pt/RGO-_EG catalyst reached 70.2 mol-_AN/(mol-_Pt min) at 0 ^oC, which is 12.5 and 19.5 times higher than that of multi-walled carbon nanotube- and active carbon-supported Pt catalysts, respectively. When the reaction temperature was increased to 20 ^oC, the catalytic activity of Pt/RGO-_EG jumped to 1138.3 mol-_AN/(mol-_Pt min), and it was also extremely active for the hydrogenation of a series of nitroarenes. The unique catalytic activity of Pt/RGO-_EG is not only related to the well dispersed Pt clusters on the RGO sheets but also the well dispersion of Pt/RGO-_EG in the reaction mixture.     

Highly Active and Selective Nickel–Platinum Catalyst for the Low Temperature Hydrogenation of Maleic Anhydride to Succinic Anhydride and Synthesis of Succinic Acid at 40 °C

Abstract  

PtNi bimetallic and Ni monometallic catalysts supported on HY–Al₂O₃, HX–Al₂O₃, ZSM-5–Al₂O₃, USY–Al₂O₃, Beta–Al₂O₃ and Al₂O₃ were prepared and evaluated for the hydrogenation of maleic anhydride in the temperature range of 40–150 °C. Results from flow reactor studies showed that supports strongly affected the catalytic properties of different bimetallic and monometallic catalysts. The results showed that the HY–Al₂O₃ support exhibited the highest activity and selectivity. Using NiPt/Al₂O₃–HY catalyst and performing the reaction, it was possible to carry out the lowest reaction temperature ever carried at 100% conversion. Adding a small amount of Pt (0.5) to the Ni (5%)/Al₂O₃–HY catalyst that is effective for increasing the selectivity and activity. We also found that PtNi is an efficient catalyst for the one-pot conversion of maleic acid into succinic acid with 100% conversion at 40 °C.     

Synthesis of nitrogen-doped multilayer graphene from milk powder with melamine and their application to fuel cells

We reported on the facile synthesis of N-doped multilayer graphene (N-MLG) from milk powder that uses melamine as a nitrogen-doping source with Fe²⁺ ions as catalytic growth agents. We showed that milk powder could be used as a precursor for large-scale N-MLG synthesis through heat treatment at 1000 °C under N₂ atmosphere for 45–120 min. In addition, heating time has a remarkable effect on N content and type in N-MLG. The resulting N-MLG exhibited higher catalytic activity than undoped graphene and carbon nanotubes (CNTs), as well as comparable catalytic activity to commercial Pt/C catalyst toward oxygen reduction reaction (ORR). Furthermore, the catalytic activity was sensitive to N content and type, particularly the ratio of pyridinic-N to total N atoms. Results showed that Fe atoms in N-MLG were found to function not as synergetic catalysts for ORR but as catalytic growth agents for N-MLG formation, thereby promoting and stabilizing N atoms. The present method could lead to the synthesis of bulk amounts of N-MLG, which is promising for applications in electrochemical energy devices, such as fuel cells and metal–air batteries.     

Differences in coke burning-off from Pt–Sn/Al2O3 catalyst with oxygen or ozone

Pt–Sn/γ-Al₂O₃ catalysts with different Sn loadings were prepared by incipient wetness coimpregnation of γ-Al₂O₃ with H₂PtCl₆ and SnCl₂. The Pt–Sn interaction was tested by temperature-programmed reduction and the catalytic activity was measured by cyclohexane dehydrogenation. The catalysts were coked by cyclopentane at 500 °C and totally or partially decoked with O₂ at 450 °C or O₃ at 125 °C. Coke deposits were studied by TPO and the catalytic activity of coked catalysts, partially or totally regenerated, by cyclohexane dehydrogenation.The TPO with O₃ shows that coke combustion with O₃ starts at a low temperature and has a maximum at 150 °C, that is a compensation between the increase of the burning rate and the rate of O₃ decomposition when increasing the temperature. Meanwhile O₂ burns coke with a maximum at 500 °C. When performing partial decoking with O₃ (125 °C) the remaining coke is more oxygenated and easier to burn than the coke that remains after decoking with O₂ (450 °C).After burning with O₃ the dehydrogenation activity of the fresh catalyst is recovered, while after burning with O₂ the activity is higher than that of the fresh catalyst. The burning with O₃ practically does not change the original Pt–Sn interaction while the burning with O₂ produces a decrease in the interaction, producing free Pt sites with higher dehydrogenation capacity.The differences in coke combustion with O₃ and O₂ are due to the different form of generation of activated oxygen, the species that oxidizes the coke. O₃ is activated by the γ-Al₂O₃ support at low temperatures firstly eliminating coke from the support while O₂ is activated by Pt at temperatures higher than 450 °C and the coke removal starts on the metal. Then, the recovery of the Pt catalytic activity as a function of coke elimination is faster with O₂ than with O₃.