In situ Raman spectroscopy studies of catalysts

In situ Raman spectroscopy is rapidly becoming a very popular catalyst characterization method because Raman cells are being designed that can combine in situ molecular characterization studies with simultaneous fundamental quantitative kinetic studies. The dynamic nature of catalyst surfaces requires that both sets of information be obtained for a complete fundamental understanding of catalytic phenomena under practical reaction conditions. Several examples are chosen to highlight the capabilities of in situ Raman spectroscopy to problems in heterogeneous catalysis: the structural determination of the number of terminal M=O bonds in surface metal oxide species that are present in supported metal oxide catalysts; structural transformations of the MoO₃/SiO₂ and MoO₃/TiO₂ supported metal oxide catalysts under various environmental conditions, which contrast the markedly different oxide–oxide interactions in these two catalytic systems; the location and relative reactivity of the different surface M–OCH₃ intermediates present during CH₃OH oxidation over V₂O₅/SiO₂ catalysts; the different types of atomic oxygen species present in metallic silver catalysts and their role during CH₃OH oxidation to H₂CO and C₂H₄ epoxidation to C₂H₄O; and information about the oxidized and reduced surface metal oxide species, isolated as well as polymerized species, present in supported metal oxide catalysts during reaction conditions. In summary, in situ Raman spectroscopy is a very powerful catalyst characterization technique because it can provide fundamental molecular‐level information about catalyst surface structure and reactive surface intermediates under practical reaction conditions. This revised version was published online in August 2006 with corrections to the Cover Date.     

Hydrogen Production by Catalytic Hydrolysis of Sodium Borohydride with a Bimetallic Solid-State Co-Fe Complex Catalyst

The addition of the active non-noble metal species on a ligand can influence the catalytic performance of catalyst. In the present work, a new bi-metallic solid-state complex catalyst system, including 4-4’-methylene bis(2,6-diethyl) aniline-3,5-di-tert-butylsalisilaldimin ligand and Fe and Co metal salts are prepared for hydrogen generation by catalytic hydrolysis of NaBH₄. It was found that the Co/Fe mixture ratio, temperature, NaBH₄, and NaOH concentrations, all exert considerable influence on the catalytic effectiveness of Co–Fe complex catalyst towards the hydrolysis reaction of NaBH₄. The results suggested that the optimal mixture percentage of Co–Fe complex catalyst is 80:20. The obtained complex catalysts are characterized by XRD, FT-IR, and SEM techniques.     

Ge-modified Pt/SiO2 catalysts used in preferential CO oxidation (CO-PROX)

A bimetallic PtGe catalyst was prepared by a controlled surface reaction and studied for the PROX reaction. The good activity of the bimetallic catalyst can be assigned to the presence of a “noble metal-oxidized metal promoter” ensemble site in close contact, the noble metal (Pt) being the CO adsorption site and the oxidized metal promoter (Ge) the O₂ adsorption site. The stability of the PtGe clusters is confirmed by the EXAFS spectra and activity measurements in the preferential oxidation reaction that show similar values for samples subjected to different oxidation–reduction cycles.     

Polymerization studies using modified Ziegler-Natta catalysts: 3. The catalyst system

The catalyst system VOCl₃/Al(iBu)₃/THF has been examined and the role of the individual catalyst components investigated. Tetrahydrofuran is believed to undergo complex formation with the other catalyst components thus restricting reduction of the vanadium to V(IV). The complex VOCl₂.2THF has been isolated and, when used with tri-isobutyl-aluminium in the presence of excess tetrahydrofuran, shown to produce polymerization systems of comparable activity to the VOCl₃/Al(iBu)₃/THF systems. The kinetic behaviour of the VOCl₃/Al(iBu)₃/THF system has been investigated and shown to be consistent with a simple Ziegler-Natta kinetic scheme involving a rapid bimolecular decomposition of either a transition metal alkyl compound, or of a complex formed on interaction of a transition metal alkyl with an aluminium alkyl.     

Behaviour of Co-Mo-Al2O3 catalysts in the hydrodeoxygenation of phenols

The activity of a number of ring alkyl-substituted phenols in the direct hydrodeoxygenation reaction (i.e. C-O bond scission without prior ring hydrogenation) in the presence of a commercial Co-Mo-Al₂O₃ catalyst has been investigated. The results indicate that the catalytically active site is stereochemically demanding. It is proposed that the phenol ring hydrogenation and the direct hydrodeoxygenation reaction proceed on the same catalytic site. The ease of the direct hydrodeoxygenation reaction is retarded mainly when transfer of the substrate hydroxyl group onto a co-ordinatively unsaturated metal site on the catalyst is inhibited. This occurs when the catalyst hydroxyl group receptor site is occupied by a co-ordinating ligand (poison) or when substituents on the substrate direct the phenolic hydroxyl group away from this metal site. The catalytic behaviour of Co-Mo-Al₂O₃ can be ‘transformed’ to resemble more closely that of Ni-Mo-Al₂O₃ (high reductive capacity) when the reaction medium contains both excess H₂S and a co-ordinating ligand. It is proposed that this ‘transformed’ species is of importance in hydrodenitrogenation reactions in an H₂S-rich environment.     

Controlled modification of Pt/Al2O3 for the preferential oxidation of CO in hydrogen: A comparative study of modifying element

The catalytic performance of a series of Pt/Al₂O₃ catalysts, modified with Cr, Mn, Fe, Co, Ni, Cu and Sn, has been tested for the preferential oxidation of CO in hydrogen. The promoters were deposited onto the surface of a 5 wt.% monometallic Pt/Al₂O₃ catalyst using a controlled surface approach, to give a nominal promoter:Pt surface atomic ratio of 1:2 (corresponding to typically 0.15–0.25 wt.% of the promoting metal). The aim of this approach was to selectively create the Pt-promoter oxide interfacial sites considered to be important for the non-competitive dual-site mechanism proposed for such promoted catalysts. In this mechanism the promoting oxide is believed to act as an active oxygen provider, providing oxygen for the oxidation of the CO on the Pt. The catalysts were characterised using TEM, EDX, ICP-AES and CO chemisorption and results suggest that the promoter was successfully deposited on to the Pt surface. Even at the low loadings of promoter used, significant enhancement was observed in the catalytic performance of the PROX reaction in a simulated reformate mixture, for the Fe- and Co-promoted catalysts in particular (and to a lesser extent the Mn, Sn, Cu- and Ni-promoted catalysts), highlighting the successful preparation of the Pt-promoting metal oxide interfacial sites. The Mn-promoted catalyst, however showed no enhancement in the absence of water suggesting that the form of the promoting metal oxide may be particularly important for promotion of Pt for the PROX reaction.     

Chemisorption of C3 hydrocarbons on cobalt silica supported Fischer–Tropsch catalysts

Chemisorption of propene and propane was studied in a pulse reactor over a series of cobalt silica-supported Fischer–Tropsch catalysts. It was shown that interaction of propene with cobalt metal particles resulted in its rapid autohydrogenation. The reaction consists in a part of the propene being dehydrogenated to surface carbon and CH_x chemisorbed species; hydrogen atoms released in the course of propene dehydrogenation are then involved in hydrogenation of remaining propene molecules to propane at 323–423 K or in propene hydrogenolysis to methane and ethane at temperatures higher than 423 K. The catalyst characterization suggests that propene chemisorption over cobalt catalysts is primarily a function of the density of cobalt surface metal sites. A correlation between propene chemisorption and Fischer–Tropsch reaction rate was observed over a series of cobalt silica-supported catalysts. No propane chemisorption was observed at 323–373 K over cobalt silica-supported catalysts. Propane autohydrogenolysis was found to proceed at higher temperatures, with methane being the major product of this reaction over cobalt catalysts. Hydrogen for propane autohydrogenolysis is probably provided by adsorbed CH_x species formed via propane dehydrogenation. Propene and propane chemisorption is dramatically reduced upon the catalyst exposure to synthesis gas (H₂/CO = 2) at 323–473 K. Our results suggest that cobalt metal particles are probably completely covered by carbon monoxide molecules under the conditions similar to Fischer–Tropsch synthesis and thus, most of cobalt surface sites are not available for propene and propane chemisorption.     

Heterogeneous Pd catalyst for oxidative carbonylation of bisphenol A to polycarbonate

Polycarbonates (PCs) were prepared by oxidative carbonylation of bisphenol A and carbon monoxide, using a Pd‐polybipylidyl complex, Pd‐polyvinylpyridine complex, smectite‐supported Pd complex, or hydrotalcite‐supported Pd complex as a heterogeneous Pd catalyst to separate the PC solution and the Pd catalyst after the reaction. Propylene carbonate was used as a halogen‐free solvent. When Co(OAc)₂·4H₂O was used as the inorgano‐redox catalyst, all of the Pd compounds gave a good PC yield with the recycling potential of the catalyst. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and catalytic activity of polymer‐anchored metal complex for oxidation of cyclohexane

Catalytic oxidation of cyclohexane was investigated over polymer‐anchored Co(II) catalyst prepared by modification of polymer surface by NO_x and subsequent functinalization by amination. The catalyst characterized by various techniques, such as elemental analysis, atomic absorption spectroscopy, Fourier transform infrared spectroscopy (FT‐IR), thermo‐gravimetric analysis, and scanning electron microscopy confirmed the modification of polymer surface and bond formation between functionalized resin and metal ion. The oxidation of cyclohexane using molecular oxygen (O₂) as an oxidant was studied in the temperature and pressure range of 373–413 K and 1.0–1.4 MPa, respectively. The maximum cyclohexane conversion of 18.4% was obtained at 413 K and 1.2 MPa pressure. Cyclohexanone and cyclohexanol were found as the main reaction products with 93.0% selectivity. No appreciable change in catalytic activity and on product selectivity was observed after the catalyst recycled three times. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2127–2135, 2013     

Nanoengineering catalyst supports via layer-by-layer surface functionalization

Recent progress in the layer-by-layer surface modification of oxides for the preparation of highly active and stable gold nanocatalysts is briefly reviewed. Through a layer-by-layer surface modification approach, the surfaces of various catalyst supports including both porous and nonporous silica materials and TiO₂ nanoparticles were modified with monolayers or multilayers of distinct metal oxide ultra-thin films. The surface-modified materials were used as supports for Au nanoparticles, resulting in highly active nanocatalysts for low-temperature CO oxidation. Good stability against sintering under high-temperature treatment was achieved for a number of the Au catalysts through surface modification of the support material. The surface modification of supports can be a viable route to control both the composition and structure of support and nanoparticle interfaces, thereby tailoring the stability and activity of the supported catalyst systems.     

Silica-supported alloy catalysts for triglyceride hydrogenation: The preparation and properties of Pd–Ag and Pd–Ni systems

The binary metal systems Pd–Ag and Pd–Ni have been prepared on a silica support with a total metal loading of 2.5% (w/w). About a dozen catalysts were prepared in each series covering the range 0–100 at. % Pd. The catalysts were characterised by a number of techniques, principally temperature programmed reduction, differential scanning calorimetry and metal surface area measurement. The catalyst activity and selectivity were measured for the hydrogenation of soya bean oil in both stirred and shaken batch reactors at 1 atm H₂ pressure in the temperature range 100–160°C. The characterisation techniques provided strong evidence of alloying for both series of catalysts. The activity and selectivity measurements also provided supporting evidence of alloying, and the Pd–Ag system exhibited an activity maximum in the 90–100 at. % Pd range, while the Pd–Ni system maintained constant activity for alloys containing 0–60 at. % Ni. Trans-acid formation was suppressed by lower reduction temperature, and linolenate removal was improved at lower temperatures. However, it also appears that reaction rates were dominated largely by triglyceride diffusion effects.     

Development of platinum-free catalyst and catalyst with low platinum content for cathodic oxygen reduction in acidic electrolytes

Studies are presented of the kinetics and mechanism of oxygen electroreduction on CoPd catalysts synthesized on XC 72 carbon black. As shown both in model conditions and in tests with the cathodes of hydrogen–oxygen fuel cells with proton conducting electrolyte, the CoPd/C system features higher activity as compared to Co/C. It is found by means of structural analysis that CoPd alloy is formed in the course of the catalyst synthesis. This provides the higher catalytic activity of the binary systems. CoPd/C catalyst is also more stable in respect to corrosion than Pd on carbon black. Measurements on a rotating ring–disc electrode show that the CoPd/C system provides preferential oxygen reduction to water in the practically important range of potentials (E > 0.7 V). The similarity of the kinetic parameters of the oxygen reduction reaction on CoPd/C and Pt/C catalysts points to a similar reaction mechanism. The slow step of the reaction is the addition of the first electron to the adsorbed and previously protonated O₂ molecule. Studies of the most active catalyst in the fuel cell cathodes are performed. Binary PtCo catalysts (metal atomic ratio of 1 : 1) with low platinum content (7.3 wt.%) modified by phosphorus or sulfur are developed and studied. It is demonstrated that the specific activity of the PtCoS/C (Pt : S = 1 : 1) catalytic system for the O₂ reduction reaction exceeds that of a commercial Pt/C catalyst (E-TEK). The tolerance of the catalyst modified with sulfur is at least six times higher than that of Pt/C (E-TEK).     

Hydrogenation of aromatics under mild conditions on transition metal complexes in zeolites. A cooperative effect of molecular sieves

The hydrogenation of aromatics, i.e. benzene, toluene, -methylstyrene, anisole, and ethyl benzoate, can be carried out under a very low (1/12000) catalyst to substrate ratio, and mild reaction conditions (80°C, 6 atm of H₂O), on Rh and Ni organometallic complexes anchored on USY zeolites. A strong cooperative effect between the faujasite surface and the transition metal surface complex is thought to be responsible for the simultaneous enhancement of concentrations of arene and H₂ in the neighborhood of the catalytic centers, and for the observed electronic effects.     

Copolymerization of ethylene and styrene by homogeneous metallocene catalysts. 1. Theoretical studies with rac-ethylenebis-(tetrahydroindenyl)MCl2 [M=Ti, Zr] systems

A computational study of the ethylene-styrene copolymerization with rac-ethylenebis(tetrahydroindenyl)MCl₂ [M=Ti, Zr] systems using DFT methods is presented. The complexation, coordination and insertion energies for ethylene and styrene monomers as well as for the styrene-ethylene copolymerization steps into the catalytic active site models [Et₂(IndH₄)₂]MCH₃⁺ [M=Ti, Zr] were calculated. The goal of this study is to examine the influence of the metal atom [Ti, Zr] on the copolymerization activity. It could be concluded that zirconocene catalyst is much more active than the titanocene based catalyst. This could be explained by the higher steric congestion around the Ti as compared to the Zr complex. Furthermore, it was found that the primary styrene insertion gives rise to complexes in which the active sites are blocked by the phenyl ring in both metal atoms, so that only the secondary insertion of the styrene is possible. These facts might help to clarify the already published experimental results.     

Metal‐ion‐containing ionic liquid hydrogels and their application to hydrogen production

A cationic hydrogel synthesized from (3‐acrylamidopropyl) trimethyl ammonium chloride as poly[(3‐acrylamidopropyl) trimethyl ammonium chloride] [p(APTMACl)] was put into contact with the chloride salts of metals such as CoCl₂, NiCl₂, and CuCl₂ in ethanol. The metal‐loaded p(APTMACl) hydrogels were used as catalyst systems in hydrogen generation from the hydrolysis of sodium borohydride (NaBH₄) and ammonia borane. The activation energy values for the hydrolysis reaction were calculated for all of the catalyst systems and were found to be 53.43 and 26.74 kJ/mol for p(APTMACl)–[CoCl₄]^2? and p(APTMACl)–[NiCl₄]^2?, respectively. These activation parameters were better than values reported in the literature for the ionic liquid metal complexes of smaller molecules used for the same purpose. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40183.     

Testing of a Ni‐Al2O3 Catalyst for Methane Steam Reforming Using Different Reaction Systems

Ni‐Al₂O₃ catalyst activity was tested for methane steam reforming using two different reaction systems: a catalyst particle bed (0.42–0.5 mm catalyst particles diluted in SiC) with a surface area‐to‐volume ratio SA/V of 910 m^–1 and a porosity ? of 52 % and a catalyst‐coated metal monolith with an SA/V of 3300 m^–1 and an ? of 86 %. Under a steam‐to‐carbon ratio of 2.5 and at a temperature of 700 °C, the highest specific reaction rates were found for the catalyst‐coated monolith. The high SA/V and ?, together with the high rate of heat transfer of the metal monolith were found to be responsible of this optimum behavior. However, in both systems, the Ni‐Al₂O₃ catalyst suffered a catalyst deactivation during operation.     

Prevention of catalyst deactivation caused by coke formation in the methanation of carbon oxides

Prevention of catalyst deactivation in carbon monoxide methanation on a highly active Ni-based composite catalyst has been investigated. The composite catalyst, Ni-La₂O₃-Ru supported on silica, has greater activity than that of a Ni catalyst, but the decrease of the catalyst activity with reaction time is greater than that of the Ni catalyst, especially when the CO conversion is low. The reason for this behaviour is found in the relation between the amount of surface-carbon species and the degree of deactivation. When the CO methanation reaction is operated at above the temperature of complete CO conversion, catalyst deactivation is avoided. At such high temperatures the amount of surface-carbon species is small. The catalyst deactivation is considerably suppressed with a low concentration, e.g. 1–3 kPa, of additional CO₂ or CO₂ + H₂O. The cause of this suppression is considered to be the renewal of the covered surface with the carbon-species by the competitive adsorption of these additives.     

Characteristics of adsorbed CO and CH3OH oxidation reactions for complex Pt/Ru catalyst systems

Pt/Ru powder catalysts of the same nominal Pt to Ru composition were prepared using a range of methods resulting in different catalyst properties. Two PtRu alloy catalysts were prepared, one of which has essentially the same surface and bulk Pt to Ru composition, while the second catalyst is surface enriched with Ru. Two powders consisting of non-alloyed Pt phases and surfaces enriched with Ru were also prepared. The oxidation state of the surface Ru of the latter two catalysts is mainly metallic Ru or Ru-oxides. The catalyst consisting of Ru-oxides was formed at 500 °C. Part of this catalyst was then reduced in a H₂ atmosphere under “mild” conditions, thus catalyst properties such as particle size are not changed, as they are locked in during previous high temperature treatment. The oxidation kinetics of adsorbed CO (CO_ads) and solution CH₃OH were studied and compared to the Ru ad-metal state and Pt to Ru site distribution of the as-prepared catalysts. The kinetics of the CO_ads oxidation reaction were observed to be slower for the catalyst containing Ru-oxides as opposed to mainly Ru metal. The CH₃OH oxidation activities measured per Pt surface area, i.e., the catalytic activities are better (by ca. seven times) for the alloy catalysts than the non-alloyed Pt/Ru catalysts. The latter two catalysts showed essentially the same catalytic CH₃OH oxidation activities, i.e., independent of the Ru ad-metal oxidation state of the as-prepared catalysts. Furthermore, it is shown that CO_ads oxidation experiments can be used to extract characteristics that allow the comparison of catalytic activities for the CO_ads oxidation reaction and Pt to Ru site distribution for complex catalyst systems.     

Models of metal catalysts: beyond single crystals

Because solid catalysts are typically complex in structure and composition, researchers have often used structurally simple models in attempts to identify catalytic sites and understand reaction mechanisms. Among models of metal catalysts, single crystals are the prototypes, but, because they cannot represent support effects or the smallest metal clusters and cannot easily be used in long-term catalyst testing, they are complemented by other types of model catalysts, including metal particles on well-defined planar supports and nearly molecular clusters of a few metal atoms each on metal oxide and zeolite supports. This account is a comparison of the various types of model metal catalysts and a summary of the advantages and limitations of each. Examples of rhodium and of platinum catalysts are given to illustrate the catalyst types and connections between them. More data are needed as a basis for comparisons of the performance of the various model catalysts.     

Microgels as new support materials for heterogeneous cocatalysts in ethylene polymerization reactions

Microgels are monodisperse poly(organosiloxane) microparticles that can be functionalized at their surface. These materials were tested as supports for heterogeneous cocatalysts of the methylaluminoxane type and were used for the polymerizations of olefins with transition‐metal catalysts. The cocatalysts were synthesized directly on the surfaces of the microgel particles by the partial hydrolysis of trimethylaluminum and were then used for the activation of homogeneous catalyst precursors. Complexes of various chemical natures were successfully activated and optimized through variations in the Al/H₂O ratio used for the synthesis. Metallocene dichloride complexes and coordination compounds of iron and nickel were tested as catalysts for ethylene polymerization, and the results were compared with the results for the homogeneous systems and heterogeneous systems supported on silica gel (SiO₂). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3021–3029, 2002