Use of catalytic reactions to probe Mg-Al mixed oxide surfaces

The atmospheric hydroformylations of ethylene and propylene were investigated over SiO₂-supported Rh₄(CO)₁₂, Co₂(CO)₈, Rh₂Co₂(CO)₁₂ and RhCo₃(CO)₁₂-derived catalysts. The bimetal cluster-derived catalysts showed excellent activities for the formation of oxygenates. In situ IR study on partially dehydroxylated SiO₂-supported RhCo₃(CO)₁₂ suggested that the bimetal cluster framework may be preserved after decarbonylation under H₂ at 623 K and may be recarbonylated at room temperature. A strong physisorption of RhCo₃ (CO)₁₂ on SiO₂ is proposed, due to a nucleophilic attack of surface oxygen on the Co atoms, which promotes a metal-support interaction and thus stabilizes the bimetal cluster framework. A subcarbonyl bimetal cluster is thought to be the actual catalytic species on the surface.     

A highly active bimetallic supported Rh–Co hydroformylation catalyst prepared from RhCl3 and Co2(CO)8

The preparation of a highly active bimetallic SiO₂‐supported Rh–Co catalyst from RhCl₃ and Co₂(CO)₈ (Rh:Co= 1 : 3 atomic ratio) has been studied by IR spectroscopy and ethylene hydroformylation, etc. Two steps are involved in the preparative process: (1) surface‐mediated synthesis of Rh⁺(CO)₂/SiO₂ from calcined RhCl₃/SiO₂; (2) impregnation of Rh⁺(CO)₂/SiO₂ with a Co₂(CO)₈ solution followed by H₂ reduction at 623 K. The IR results of reductive carbonylation of calcined RhCl₃/SiO₂ have been compared to those of uncalcined RhCl₃/SiO₂ at 373 K. In situ IR observations, extraction results and elemental analysis suggest that approximately 50% of RhCl₃ are transformed to Rh₂O₃ on the SiO₂ surface and that calcined RhCl₃/SiO₂ is converted to a mixture of [Rh(CO)₂Cl]₂ and [Rh(CO)₂O₂ (O_s: surface oxygen) under CO at 373 K. When this SiO₂‐supported mixture was submitted to impregnation with a Co₂(CO)₈ solution at room temperature, IR study and elemental analysis show that [Rh(CO)₂Cl]₂ reacts easily with Co₂(CO)₈ on the surface to give RhCo₃(CO)₁₂, whereas [Rh(CO)₂O₂ does not react with Co₂(CO)₈. Catalytic study in steady‐state ethylene hydroformylation shows that a catalyst thus derived is more active than a catalyst derived from RhCo₃(CO)₁₂/SiO₂ and a catalyst derived by coimpregnation of [Rh(CO)₂Cl]₂ and Co₂(CO)₈ on SiO₂. This result suggests that the high rhodium dispersion of [Rh(CO)₂O₂ plays a crucial role in the formation of highly dispersed bimetallic Rh–Co sites. This revised version was published online in July 2006 with corrections to the Cover Date.     

SiO2‐supported bimetallic Rh–Co catalysts derived from [Rh(CO)2Cl]2 and cobalt carbonyls

According to the results of IR characterization and catalytic study in ethylene hydroformylation, bimetallic Rh–Co catalysts can be efficiently prepared from [Rh(CO)₂Cl]₂ and cobalt carbonyls by co‐impregnation on SiO₂. The reaction of Co₂(CO)₈ with [Rh(CO)₂Cl]₂ (Rh : Co = 1 : 3 atomic ratio) gives rapidly RhCo₃(CO)₁₂ on the surface of SiO₂. Although Co₄(CO)₁₂ is not reactive with [Rh(CO)₂Cl]₂ on SiO₂ to form directly RhCo₃(CO)₁₂, an equivalent bimetallic catalyst can be easily obtained from ([Rh(CO)₂Cl]₂ + Co₄(CO)₁₂)/SiO₂ or its derivative (Rh⁺ + Co²⁺)/SiO₂ (Rh : Co = 1 : 3 atomic ratio) under reducing conditions. This revised version was published online in July 2006 with corrections to the Cover Date.     

FT-IR studies of decarbonylation and recarbonylation of [Pt3(CO)6] 5 2− supported on dehydrated SiO2

Decarbonylation of [Pt₃(CO)₆]₅ on SiO₂ at 373 K produced [Pt₃(t-CO)₃]₅ species, where all the terminal CO remained. Complete decarbonylation at 423 K was not observed, which led to aggregation at 473 K. The interaction of some Pt with SiO₂ inhibited complete recarbonylation to [Pt₃(CO)₆]₅.     

Alkali-treatment of ZSM-5 zeolites with different SiO2/Al2O3 ratios and light olefin production by heavy oil cracking

Four kinds of ZSM-5 zeolites with different SiO₂/Al₂O₃ ratios are alkali-treated in 0.2 M NaOH solution for 300 min at 363 K. Changes to the compositions, morphologies, pore sizes, and distributions of the zeolites are compared before and after alkali-treatment. The changes observed are largely influenced by the SiO₂/Al₂O₃ ratios with which the zeolites are synthesized. A possible mechanism of desilication during alkali-treatment is proposed. The SiO₂/Al₂O₃ ratio of zeolites is found to influence the yield of light olefins that use heavy oil as feedstock. Alkali-treated ZSM-5 zeolites produce higher yields of light olefins compared to either untreated zeolites or the industry catalyst CEP-1. It is believed that alkali-treatment introduces mesopores to the zeolites and improves their catalytic cracking ability. ZSM-5 zeolites with SiO₂/Al₂O₃ ratios of 50 also present superior selectivity toward light olefins because of their optimized hierarchical pores.     

A TPD study of H2 ON Ru/SiO2 and Ru-Cu/SiO2

In H₂ TPD from Ru/SiO₂, two desorption peaks were observed. Both exchanged H for D in sequential dosing experiments. These hydrogen adsorption states were also found for Ru-Cu/SiO₂, along with another, higher temperature state at 400–500 K. This last state was neither exchangeable with nor replaceable by deuterium subsequently dosed at 150 K. The three chemisorption states are attributed to hydrogen held at the interface between Ru and SiO₂ (< 300 K), adsorbed on Ru particles (310–380 K), and held at the Ru-Cu interface (> 400 K).     

CO hydrogenation over a RhVO4/SiO2 catalyst after H2 reduction

The hydrogenation of CO over a RhVO₄/SiO₂ catalyst has been investigated after H₂ reduction at 773 K. A strong metal–oxide interaction (SMOI) induced by the decomposition of RhVO₄ in H₂ enhanced not only the selectivity to C₂ oxygenates but also the CO conversion drastically, compared with an unpromoted Rh/SiO₂ catalyst. The selectivity of the RhVO₄/SiO₂ catalyst was similar to those of conventional V₂O₅‐promoted Rh/SiO₂ catalysts (V₂O₅–Rh/SiO₂), but the CO dissociation activity (and TOF) was much higher than for V₂O₅–Rh/SiO₂, and hence the yield of C₂ oxygenates was increased. This revised version was published online in July 2006 with corrections to the Cover Date.     

Generation of alkyl fragments on Rh/SiO2 and VO x -promoted Rh/SiO2

The adsorption of ethylene on Rh/SiO₂ and Rh-VO _x /SiO₂ has been studied by transmission FTIR spectroscopy. For C₂H₄ chemisorption at 298 K on Rh/SiO₂ molecularly adsorbed C₂H₄ and ethylidyne species are identified. It has been found that ethylidyne can be hydrogenated toward surface ethyl species in a reversible reaction at room temperature. On Rh-VO _x /SiO₂ the fragmentation of C₂H₄ into methylene species has been observed during C₂H₄ adsorption at 298 K.On leave from Zentralinstitut für Physikalische Chemie, Rudower Chaussee 5, O-1199 Berlin, Germany.     

Low temperature selective catalytic reduction of NO by NH3 over V2O5 supported on TiO2–SiO2–MoO3

The V₂O₅ catalysts supported on TiO₂–SiO₂–MoO₃ (TSM) prepared by the coprecipitation method were investigated for the selective catalytic reduction (SCR) of NO by NH₃ at low temperatures. The V₂O₅/TSM catalyst with 7–13 wt% SiO₂ was found to exhibit a superior SCR activity and a good sulfur tolerance at low temperatures (<250 °C). The presence of highly active polymeric vanadates formed by the incorporation of MoO₃ to TiO₂–SiO₂ and superior redox properties seems to enhance SCR activity, and furthermore the very lower SO₂ oxidation activity due to the higher acidity leads to the remarkable improvement of sulfur tolerance.     

Synthesis and reaction mechanism of Ti3SiC2 ternary compound by carbothermal reduction of TiO2 and SiO2 powder mixtures

The present study aims to investigate synthesis of Ti₃SiC₂ from TiO₂ and SiO₂ powder mixtures by carbothermal reduction method. Equilibrium TiO₂–SiO₂–C ternary phase diagram was used to predict the conditions for the formation of Ti₃SiC₂ at 1800 K under Ar atmosphere. A reactant mixture with a TiO₂:SiO₂ molar ratio of 1.5 and a C content of 68.75 mol% (26.86 wt%) was initially selected among the thermodynamically favorable reactant compositions for the experimental studies. Two different C sources, graphite flakes and pyrolytic C coating, were used to synthesize Ti₃SiC₂ at 1800 K under Ar atmosphere. When graphite flakes were used, the products contained a trace amount of Ti₃SiC₂ phase along with major TiC and minor SiC phases. Whereas, pyrolytic C coating on the oxide particles resulted in the products with much higher Ti₃SiC₂ contents owing to the close contact between the reactants. Optimal C concentration for the C coated oxide mixtures with a TiO₂:SiO₂ molar ratio of 1.5 was determined to be 30.05 wt% under the experimental conditions studied. Ti₃SiC₂ content of the products obtained from this reactant was observed to increase with reaction time to 31 wt% at 75 min beyond which it gradually decreased. XRD studies indicated that the product with the highest ternary carbide content also contained TiC and a trace amount of SiC. SEM-EDS analyses showed that this sample essentially consisted of spherical fine TiC particles and Ti₃SiC₂ nanolaminates. Equilibrium thermodynamic analysis of the TiO₂–SiO₂–C system suggested that the reaction of solid Ti₂O₃ with SiO and CO gases may play a dominant role in the formation of Ti₃SiC₂.     

Aromatization of ethanol on Mo2C/ZSM catalysts

The reaction of ethanol was investigated on Mo₂C, Mo₂C/SiO₂ and Mo₂C/ZSM-5 catalysts at temperature ranging 573–973 K under atmospheric pressure. Mo₂C and Mo₂C/SiO₂ catalyzed only the decomposition of ethanol to H₂, ethylene, acetaldehyde and different hydrocarbons. The main reaction pathway on pure ZSM-5 is the dehydration reaction yielding ethylene, small amounts of hydrocarbons and aromatics. Deposition of Mo₂C on zeolite greatly enhanced the yield of benzene and toluene by catalyzing the aromatization of ethylene formed in dehydration process of ethanol.     

Determination of the promoting effect of nano SiO2 and H3PO4@nano SiO2 in the thiocyanation of N-containing aromatic compounds under solvent-free conditions

Silica nanoparticles/ammonium thiocyanate (nano SiO₂/NH₄SCN) and H₃PO₄ embedded on nano silica (H₃PO₄@nano SiO₂) in the presence of NH₄SCN were found to be effective systems for the thiocyanation of some arylamines and indoles to afford their corresponding thiocyanated adducts at 70°C under solvent-free conditions. The recovery and reusability of nano SiO₂ as a prompting system have been investigated. A simple procedure for the synthesis of H₃PO₄@nano SiO₂ has also been represented. In addition, a plausible mechanism of thiocyanation has also been suggested.     

X-ray photoelectron spectroscopy of the cement clinker phases tricalcium silicate and β-dicalcium silicate

We have used X-ray photoelectron spectroscopy (XPS) to investigate both tricalcium silicate (Ca₃SiO₅, C₃S) and β-dicalcium silicate (Ca₂SiO₄, β-C₂S), the principal components of cement clinkers. In addition to showing how the two phases may be characterised and differentiated, we show how the sensitivity of these phases to atmospheric carbon dioxide and moisture may, as a result of improper sample preparation, lead to erroneous results. The observed alteration processes of the clinker minerals shed light upon the aging process of cement clinker during storage.     

Skeletal isomerization of 1-butene over ferrierite and ZSM-5 zeolites: influence of zeolite acidity

Three ferrierite (FER) and five ZSM-5 (MFI) zeolites with SiO₂Al₂O₃ ratio ranging from 27 to 2000 are tested as catalysts for the skeletal isomerization of 1-butene at 350–450°C and atmospheric total pressure in order to study the influence of acidity and pore structure of zeolite on conversion and selectivity. The catalytic and NH₃ temperature-programmed desorption results from FER and MFI catalysts with the same SiO₂/Al₂O₃ ratio reveal that the pore structure of FER zeolite rather than its acidity may play an important role in achieving high selectivity for the skeletal isomerization of 1-butene to isobutene.     

Partial oxidation of CH4 at low pressure over SiO2 prepared from Si

The oxidation of CH₄ with O₂ at low pressure was carried out over SiO₂ prepared from metal Si. The Si showed only total oxidation activity while the Si partly oxidized to SiO₂ showed high selectivities to CH₃OH and HCHO. The results on SiO₂ prepared from Si were compared with those over commercial silicas. The role of SiO₂ in the CH₄ oxidation was discussed.     

Role of support in reforming of CH4 with CO2 over Rh catalysts

The reforming of CH₄ with CO₂ over supported Rh catalysts has been studied over a range of temperatures (550–1000 K). A significant effect of the support on the catalytic activity was observed, where the order was Rh/Al₂O₃>Rh/TiO₂>Rh/SiO₂. The catalytic activity of Rh/SiO₂ was promoted markedly by physical mixing of Rh/SiO₂ with metal oxides such as Al₂O₃, TiO₂, and MgO, indicating a synergetic effect. The role of the metal oxides used as the support and the physical mixture may be ascribed to the promotion in dissociation of CO₂ on the surface of Rh, since the CH₄ + CO₂ reaction is first order in the pressure of CO₂, suggesting that CO₂ dissociation is the rate-determining step. The possible model of the synergetic effect was proposed.     

EXAFS investigations of lanthana-promoted Rh/SiO2 catalysts

EXAFS investigations at the Rh K edge of lanthana-promoted Rh/SiO₂ catalysts showed that the local environment of the Rh ions in the oxidic catalyst precursor state did not depend on the La₂O₃ content and resembled that of Rh₂O₃. No LaRhO₃ formation could be detected. In the reduced state, EXAFS as well as H₂ and CO chemisorption demonstrated that La₂O₃ increased the Rh dispersion. Covering of the Rh metal particles by La₂O₃ was minor, because during catalyst preparation, La was impregnated prior to Rh.     

Fe effect on the optical properties of TiO2:Fe2O3 nanostructured composites supported on SiO2 microsphere assemblies

The effect of Fe ion concentration on the morphological, structural, and optical properties of TiO₂ films supported on silica (SiO₂) opals has been studied. TiO₂:Fe₂O₃ films were prepared by the sol-gel method in combination with a vertical dip coating procedure; precursor solutions of Ti and Fe were deposited on a monolayer of SiO₂ opals previously deposited on a glass substrate by the same procedure. After the dip coating process has been carried out, the samples were thermally treated to obtain the TiO₂:Fe₂O₃/SiO₂ composites at the Fe ion concentrations of 1, 3, and 5 wt%. Scanning electron microscopy (SEM) micrographs show the formation of colloidal silica microspheres of about 50 nm diameter autoensembled in a hexagonal close-packed fashion. Although the X-ray diffractograms show no significant effect of Fe ion concentration on the crystal structure of TiO₂, the μ-Raman and reflectance spectra do show that the intensity of a phonon vibration mode and the energy bandgap of TiO₂ decrease as the Fe⁺³ ion concentration increases.     

Direct Solvothermal Formation of Nanocrystalline TiO2 on Porous SiO2 Adsorbent and Photocatalytic Removal of Nitrogen Oxides in Air over TiO2–SiO2 Composites

Solvothermal decomposition of titanium(IV) tert-butoxide (TTB) in toluene at 573 K in the presence of silica gel (SiO₂) with continuous stirring yielded a titanium(IV) oxide (TiO₂)–SiO₂ composite in which agglomerates of nanocrystalline TiO₂ were deposited on the surfaces of SiO₂ particles. Various TiO₂–SiO₂ composites having different TiO₂ contents can be synthesized by changing the ratio of TTB and SiO₂, and the composites had large surface areas corresponding to porous properties of SiO₂. These TiO₂–SiO₂ composites were used for photocatalytic removal of nitrogen oxides in air and their photocatalytic performances were compared with those of other TiO₂–SiO₂ samples prepared by different methods. Solvothermally synthesized 74 wt.%TiO₂–SiO₂ composite exhibited excellent photocatalytic performance (almost stoichiometric removal of NO _x (98%) and very low NO₂ release (0.3%)) attributable to high photocatalytic activity of TiO₂ and high adsorption property of SiO₂. Lesser performance of 74 wt.%TiO₂–SiO₂ composites prepared by other methods suggested that pore-mouth plugging of SiO₂ by TiO₂ and lower level of mixing of TiO₂ and SiO₂ decreased photocatalytic performance of the composites.     

Hydrogen Spillover in Ga2O3–Pd/SiO2 Catalysts for Methanol Synthesis from CO2/H2

The hydrogenation of CO₂ was investigated on Ga₂O₃-promoted Pd/SiO₂ catalyts and mechanical mixtures of Ga₂O₃/SiO₂ and Pd/SiO₂ catalysts (H₂/CO₂ = 3; P = 3.0 MPa; T = 523 K). By means of the latter it was possible to demonstrate that atomic hydrogen, H_s, can be generated by Pd⁰ far from Ga₂O₃, and move (spill-over) there to reach the other reactive species (formates) and complete the reaction cycle. The reaction results indicate that (as also evidenced by in situ FTIR) the Ga₂O₃-Pd/SiO₂ catalyst works as a true bi-functional system. The metal-promoter intimacy is not decisive in terms of the catalytic chemistry of the system, but the closeness between the Pd crystallites and the Ga₂O₃ surface patches boost the activity, owing to a minimized effort in the H_s supply to the latter.