Effect of Si-Doping on Thermal Stability and Diesel Oxidation Activity of Pt Supported Porous γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Monolithic Catalyst

Abstract  

A series of different contents of Si-stabilized aluminas with high thermal stability were synthesized by the coprecipitation method and were used as the support of Pt diesel oxidation catalysts. The physicochemical properties of SiO₂–Al₂O₃ (SA) and the catalytic performance of Pt/SiO₂–Al₂O₃ (Pt/SA) were characterized in detail by TG–DTA, XRD, infrared spectroscopy, N₂ adsorption, NMR, CO-TPD, and the catalytic activity evaluation of CO and C₃H₆ oxidations as well as NO reduction in simulating diesel exhaust. The results indicate that the presence of Si can remarkably enhance the thermal stability and phase transition temperature of alumina. It was also found that the catalytic activity is virtually independent of surface area, and only appropriate amount of Si doping can improve the diesel oxidation activity, as compared to pure Pt/Al₂O₃ under the same conditions as a result of the better dispersion of Pt on SA–W supports.     

Formation of carbon nanotubes through ethylene decomposition over supported Pt catalysts and silica-coated Pt catalysts

Ethylene decomposition was performed over supported Pt catalysts to fabricate composites of Pt metal nanoparticles and carbon nanotubes (CNTs). All supported Pt catalysts (Pt/carbon black, Pt/CNT, Pt/MgO, Pt/Al₂O₃ and Pt/SiO₂) showed catalytic activity for ethylene decomposition at 973 K to form CNTs. Pt metal particles were found at tips of CNTs. These results indicate that Pt metal particles have catalytic activity for growth of CNTs through hydrocarbon decomposition. A broad range (5-50 nm) of CNT diameters were formed from the use of supported Pt metal catalysts although Pt metal particles in the catalysts before ethylene decomposition were relatively uniform in size (2-5 nm). These results imply that Pt metal particles in the catalysts aggregated during ethylene decomposition at 973 K. Aggregation of Pt metal particles in catalysts during ethylene decomposition could be suppressed by covering catalysts with silica layers that were a few nanometers thick. Silica-coated Pt catalysts showed high activity for ethylene decomposition to form CNTs with uniform diameters (8-10 nm) despite the uniform coverage of Pt metal particles with silica layers.     

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.     

Preparation of Carbon Nanotube-Supported Pt Metal Particles Covered with Silica Layers and Their Application to Electrocatalysts for PEMFC

Carbon nanotube (CNT)-supported Pt metal nanoparticles were covered with silica layers by hydrolysis of 3-aminopropyl-triethoxysilane (APTES) and/or tetraethoxysilane (TEOS). The hydrolysis of only APTES resulted in a uniform coverage of silica layers on Pt/CNT, but the thickness of the silica layers was very thin (<1 nm). Pt/CNT could also be coated with silica layers of a few nanometers in thickness by hydrolysis of TEOS, but exposed surfaces of CNTs in the sample were frequently observed. In contrast, the successive hydrolysis of APTES and TEOS brought about a uniform coverage of silica layers of a few nanometers in thickness on Pt/CNT. The silica-coated Pt/CNT showed high catalytic activity for electrochemical reactions in aqueous H₂SO₄ electrolyte, in spite of a uniform coverage of Pt metal with silica layers. In addition, the coverage of Pt/CNT with silica layers improved its durability in electrochemical reactions.     

Selective Production of 2-Phenylhexane from Benzene and <Emphasis Type="Italic">n</Emphasis>-Hexane Over Pt- and Ga-Modified Zeolites

Abstract  

Alkylation of benzene with n-hexane was performed over H-ZSM-5 and monometallic Ga- and Pt- and bimetallic Ga- and Pt-modified ZSM-5. The influence of the particle size and the method of incorporation of Ga (during hydrothermal synthesis, by solid-state ion exchange, or by liquid-state ion exchange) was determined. The presence of Pt and well-dispersed extraframework Ga in H-ZSM-5 increased the selectivity in alkylation and suppressed cracking reactions. Well-dispersed Pt particles led to better catalytic performance. The method of Ga incorporation played an important role in obtaining higher selectivity to alkylation products and in the suppression of side reactions. Up to 93% selectivity in alkylation (of which >95% was to 2-phenylhexane) was reached over 2 wt% Pt/H-Ga^fZSM5, in which Ga occupied framework positions. We propose that the close proximity of very small Pt nanoparticles and Ga–(OH)–Si acid sites results in the optimal bifunctional catalyst for selective production of 2-phenylhexane from benzene and n-hexane. During the reaction, the catalyst deactivated, most probably due to the sintering of the Pt particles.     

Reducibility of Platinum Supported on Nanostructured Carbons

The nanostructure of graphite like carbon, i.e. carbon nanofibers (CNF), carbon nanotubes (CNT) and carbon nanoplatelets (CNP), displayed a significant influence on the reducibility of platinum deposited on these carbons. The onset temperature for reduction increased from 461 K for Pt/CNF to 466 K for Pt/CNP and 487 K for Pt/CNT. The retarded reduction for Pt/CNT was related to the higher amount of acidic oxygen surface groups on this support resulting in a strong stabilization of the cationic platinum species. A higher reduction temperature for that sample increased the amount of metallic platinum, however the platinum particle size was larger (2–11 nm) compared to that of Pt/CNF and Pt/CNP (both 1–3 nm). The orientation of the graphene sheets had a significant influence on the selectivity for cinnamaldehyde hydrogenation: Pt/CNP resulted in a higher selectivity towards cinnamyl alcohol compared to Pt/CNF.     

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.     

Ultra-fine Pt nanoparticles supported on 3D porous N-doped graphene aerogel as a promising electro-catalyst for methanol electrooxidation

Three dimensional porous nitrogen-doped graphene aerogel (3D-NGA) was successfully fabricated via a combined hydrothermal self-assembly, thermal treatment and template-removing process. The as-synthesized Pt/3D-NGA catalysts exhibit an interconnected 3D porous structure, high N-doped level and uniform dispersion of Pt NPs. In studying the electrocatalytic performance of samples towards methanol electrooxidation, we found that Pt/3D-NGA hold a high electrochemical active surface area (ECSA) of 90.7 m² g^− 1 and better catalytic activity as well as stability compared to Pt/G and Pt/3D-GA catalysts. Our studies provide a simple approach to synthesize 3D metal or metal oxide/graphene-based composites, holding great potential for fuel cell applications.     

Biobutanol Dehydrogenation to Butyraldehyde over Cu,Ru and Ru–Cu Supported Catalysts. Noble Metal Addition and Different Support Effects

Abstract  

n-Butanol dehydrogenation to butyraldehyde was studied using Ru, Cu and Ru–Cu catalysts supported on ceria, titania and zirconia. Among the monometallic Cu and Ru supported catalysts, the non-noble catalytic systems recorded higher conversions and butyraldehyde selectivities than the noble catalysts. Furthermore, the 5Cu/ZrO₂ catalyst had the best catalytic activity and selectivity. This behaviour is related to the good metal phase dispersion on the zirconia structure. The addition of Ru reduced this catalyst’s performance because Ru incorporation weakened the Cu-support interaction and favoured the sintering of the Cu metal crystallites.     

Behavior of Pt Atoms on Oxide Supports During Reduction Treatments at Elevated Temperatures,Characterized by Aberration Corrected Stem Imaging

Abstract  

Aberration-corrected scanning transmission electron microscopy at the sub-?ngstr?m resolution allows imaging the structure of catalytic materials at the single atom level and permits fundamental studies of the behavior of heavy metal catalytic species as a result of elevated temperature gas-treatments. The present study is aimed at understanding the development of clusters and nanoparticles of Pt on γ-alumina during reduction treatments of a pre-oxidized highly dispersed catalyst. A special built ex situ reactor and a specimen holder allowing cyclic anaerobic transfer between the reactor and microscope were used for the study. The number of atoms in a nascent cluster can be determined along with the general shape of the cluster. Reduction experiments without air exposure of the sample showed that although clusters are formed at 500 °C, many Pt atoms are not associated with the cluster and are still dispersed on the catalyst support. After a 700 °C reduction, all of the Pt atoms are associated with the clusters. Movement of the clusters on the catalyst support is different depending upon the catalyst support.     

Catalytic CO Oxidation on Individual (110) Domains of a Polycrystalline Pt Foil: Local Reaction Kinetics by PEEM

Abstract  

The reaction kinetics of catalytic CO oxidation on individual grains of a polycrystalline Pt foil has been studied simultaneously by photoemission electron microscopy (PEEM) and mass spectroscopy (MS), in the pressure range ~10⁻⁵ mbar. By processing the video-PEEM images of ongoing catalytic reaction, the kinetic transitions were tracked for individual [110]-oriented domains. The obtained local kinetic phase diagrams were contrasted to those obtained from global MS activity measurements. These data and the observation of reaction front propagation on different Pt(110) domains indicate a quasi-independent behaviour of the crystallographic domains. The observed front propagation velocities and the degree of their anisotropy on Pt foil corroborate earlier observations on Pt(110) single crystals, confirming our concept of using Pt foil to monitor and compare different surface terminations in parallel.     

Direct dehydrogenation of n-butane over Pt/Sn/M/γ-Al2O3 catalysts: Effect of third metal (M) addition

A series of Pt/Sn/M/γ-Al₂O₃ catalysts with different third metal (M = Zn, In, Y, Bi, and Ga) were prepared by a sequential impregnation method for use in the direct dehydrogenation of n-butane to n-butene and 1,3-butadiene. In the direct dehydrogenation of n-butane, Pt/Sn/Zn/γ-Al₂O₃ catalyst showed the best catalytic performance. Catalytic performance decreased in the order of Pt/Sn/Zn/γ-Al₂O₃ > Pt/Sn/In/γ-Al₂O₃ > Pt/Sn/γ-Al₂O₃ > Pt/Sn/Y/γ-Al₂O₃ > Pt/Sn/Bi/γ-Al₂O₃ > Pt/Sn/Ga/γ-Al₂O₃. The catalytic performance increased with increasing metal–support interaction and Pt surface area of the catalyst.     

Influences of Mesoporosity Generation in ZSM-5 and Zeolite Beta on Catalytic Performance During <Emphasis Type="Italic">n</Emphasis>-Hexane Isomerization

Abstract  

Catalytic performance of Pt impregnated parent and desilicated nano-crystalline zeolites, ZSM-5 and Beta for n-hexane isomerization was studied. Difference in channel systems of the zeolites and absence/presence of mesopores therein were found to be reflected in product distributions. ZSM-5 was desilicated by NaOH and zeolite Beta with tetramethylammonium hydroxide (TMAOH.) Desilication was found to afford comparable catalytic performance to that of the parent counterpart at reaction temperature lower by 25 °C. Observed product distributions could be substantiated with characterizations such as ammonia TPD, surface area determination and SEM. Desilicated zeolite Beta was seen to be less prone to coking as deduced from the TGA study. Location of Pt with reference to proton sites within the channels and that inside the pores viz a viz external surface also have been discussed briefly.     

Pt/IrO2/CNT anode catalyst with high performance for direct methanol fuel cells

Carbon nanotube immobilized IrO₂ (IrO₂/CNT) was prepared by a simple oxidation method with hydrogen peroxide as an oxidant and used as an improved catalyst support to load active Pt to prepare Pt/IrO₂/CNT anode catalyst for direct methanol fuel cell. Electrochemical measurement revealed that Pt/IrO₂/CNT exhibits much higher activity for methanol oxidation and better CO tolerance than Pt/CNT. The anodic peak current of methanol oxidation on Pt/IrO₂/CNT (873.1A g_Pt^− 1) is 2.6 times that of Pt/CNT catalyst (335.7A g_Pt^− 1). The enhanced performance of Pt/IrO₂/CNT is attributed to the fact that IrO₂ improves the dispersion of Pt nanoparticles, and lowers the charge transfer resistance in methanol electrooxidation.     

Electrochemical deposition of Pt nanoparticles on CNTs for fuel cell electrode

In order to increase the performance of fuel cell electrode, carbon nanotubes (CNTs) were used as support instead of conventional carbon black, and the Pt catalyst was synthesized by using electrochemical deposition (ECD) method which has recently been adopted as a synthetic tool of metal nanoparticles. CNTs used in this paper were grown directly on carbon paper by chemical vapor deposition (CVD) of acetylene. Highly dispersed and nano-sized Pt particles were electrochemically deposited on CNTs surface, which would simplify the manufacturing process of membrane-electrode-assembly (MEA). Pt particles on CNTs were investigated by SEM and TEM. The particle size of Pt is less than 2 nm, which is relatively small compared to that of conventional wet impregnated catalyst (2–8 nm). CO chemisorption results show that the amounts of catalytic sites are about three times larger in Pt/CNT prepared by ECD than those in conventional wet-impregnated one. The mass activity of the former catalyst for oxygen reduction is more than three times higher compared to that of the latter one. This paper was presented at the 11th Korea-Japan Symposium on Catatysis held at Seoul, Korea, May 21–24, 2007.     

Electro-catalytic oxidation of CO on Pt catalyst supported on carbon nanotubes pretreated with oxidative acids

Characteristics of nanosized Pt electro-catalyst deposited on carbon nanotubes (CNTs) were studied with CO-stripping voltammogram and chronoamperometry measurements. The CNTs were pretreated by oxidation in HNO₃, mixed HNO₃ + H₂SO₄ and H₂SO₄ + K₂Cr₂O₇ solution, respectively, to enable surface modification. Well-homogenized Pt particles (average size: ≈3 nm) were loaded onto the pretreated CNT samples by a modified colloidal method. TEM, BET, FTIR and XRD techniques were used to characterize the physicochemical properties of the pretreated CNT samples. In the electro-oxidation of CO, all the Pt/CNT samples showed lower on-set as well as peak potentials than the conventional Pt/XC-72 electro-catalyst, indicating that the Pt/CNT samples were more resistant to CO poisoning and could be superior anode electro-catalyst for the proton exchange membrane fuel cells (PEMFCs). Moreover, we found that the pretreatment of CNTs in mixed HNO₃ + H₂SO₄ solution was very beneficial for the performance enhancement of Pt/CNT electro-catalyst; the catalyst obtained as such gave the lowest peak potential and the highest catalytic activity for the electro-oxidation of CO. Larger amount of oxygen-containing functional groups, higher percentage of mesopores, and higher graphitic crystallinity of the pretreated CNTs were considered crucial for the performance enhancement, e.g., by strengthening the interaction between Pt nanoparticles and the CNT support and enhancing the mass diffusion in the electro-chemical reaction.     

Oxidative Dehydrogenation Properties of Novel Nanostructured Polyoxovanadate Based Materials

Abstract  

A comparative study of the catalytic oxidative dehydrogenation of propane by a novel polyoxovanadate based open-framework material (Co-POV)—[Co₃V₁₈O₄₂(H₂O)₁₂(XO₄)]·24H₂O (X = V, S), which is composed of nanometer size vanadium oxide clusters interlinked by cobalt oxide {–O–Co–O–} motifs, showed that Co-POV has superior catalytic property as compared to its individual metal oxide constituents, vanadium oxide and cobalt oxide, and their mixture, with high propylene selectivity.     

Effect of heat treatment on the performance of TiO2-Pt/CNT catalysts for methanol electro-oxidation

TiO₂-Pt/CNT catalysts before and after heat treatment were prepared. Their catalytic activities for methanol and CO electro-oxidation were studied in detail. The results showed that the proper amount of hydrous TiO₂ in TiO₂-Pt/CNTs (e.g. heated at 200 °C for 2 h) was favorable for enhancing the catalytic activity of Pt/CNTs, which provided evidence for bi-functional mechanism. The studies on the catalysts with different TiO₂/Pt molar ratio displayed that the optimum molar ratio varied with the increase of heat treatment temperature. It was found that the optimum molar ratio of TiO₂/Pt was at 1:2 for the catalysts without heat treatment and was at 1:1 for the catalysts by heat treatment at 500 °C. This fact was ascribed to the difference in compact degree between TiO₂ and Pt/CNTs before and after heat treatment. Considering the influence of heating temperature, it was found that TiO₂-Pt/CNT catalyst heated at 200 °C for 2 h had better catalytic activity for methanol oxidation.     

The First Case of Competitive Heterogeneously Catalyzed Hydrogenation using Continuous-Flow Fixed-Bed Reactor System: Hydrogenation of Binary Mixtures of Activated Ketones on Pt-Alumina and on Pt-Alumina-Cinchonidine Catalysts

Abstract  

Under the experimental conditions of the Orito reaction the competitive hydrogenations of four binary mixtures of ethyl pyruvate (EP), methyl benzoylformate (MBF), pyruvic aldehyde dimethyl acetal (PA) and 2,2-diethoxyacetophenone (DAP) on unmodified Pt/Al₂O₃ (racemic hydrogenation) and catalyst modified by cinchonidine (chiral hydrogenation) were studied using continuous-flow fixed-bed reactor system (CFBR). Conversions of chiral and racemic hydrogenations were determined under 4 MPa H₂ pressure, at 293 K using toluene/acetic acid 9/1 as solvent. In the competitive chiral hydrogenation of MBF + EP and DAP + PA binary mixtures (S1 + S2) a new phenomenon was observed: namely the EP and PA are hydrogenated faster than MBF and DAP, whereas in racemic one the MBF and DAP are hydrogenated faster than the former ketones. The phenomenon verified for the first time in CFBR is dependent on the adsorption mode of the surface complexes of various compositions (S1–Pt, S2–Pt, S1–CD–Pt, S2–CD–Pt, CD = cinchonidine). In the chiral hydrogenation of DAP a rate decrease, i.e., “ligand deceleration” was observed instead of rate enhancement.