Liquid phase selective hydrogenation of phthalic anhydride to phthalide over titania supported gold catalysts

Au/TiO₂ catalysts with different gold loadings were prepared by deposition–precipitation method and used for the liquid phase hydrogenation of phthalic anhydride. All the studied Au/TiO₂ catalysts exhibited excellent activity with high selectivity (>92%) to phthalide under mild reaction conditions (180 °C and 3.0 MPa H₂). Specially, catalysts with 2–3 wt.% gold loading were highly active and selective for the formation of phthalide. When reused, the catalyst showed a certain deactivation, but still was highly selective to phthalide. The deactivation was attributed to the leaching of gold, collapse of the pore structure and accumulation of organic species on the surface.     

Influences of preparation methods of ZrO2 support and treatment conditions of Cu/ZrO2 catalysts on synthesis of methanol via CO hydrogenation

ZrO₂ supports were prepared by different methods (conventional precipitation method, shortened as “CP”, and alcogel/thermal treated with nitrogen method, shortened as “AN”), and Cu/ZrO₂ catalysts were prepared by impregnation method. The supports and catalysts were characterized by BET, XRD, TEM and TPR. The effects of the preparation methods of ZrO₂ supports and the treatment conditions (calcination and reduction temperatures) of the catalyst precursors on the texture structures of the supports and catalysts as well as on the catalytic performances of Cu/ZrO₂ in CO hydrogenation were investigated. The results showed that the support ZrO₂-AN had larger BET specific surface area, cumulative pore volume and average pore size than the support ZrO₂-CP. Cu/ZrO₂-AN catalysts showed higher CO hydrogenation activity and selectivity of oxygenates (C₁–C₄ alcohols and dimethyl ether) than Cu/ZrO₂-CP catalysts. Calcination and reduction temperatures of supports and catalyst precursors affected the catalytic performance of Cu/ZrO₂. The conversion of CO and the STY of oxygenates were 12.7% and 229 g/kg h, respectively, over Cu/ZrO₂-AN-550 at the conditions of 300 °C, 6 MPa.     

The CO methanation over NaY-zeolite supported Ni/Co3O4, Ni/ZrO2, Co3O4/ZrO2 and Ni/Co3O4/ZrO2 catalysts

The CO methanation was studied over zeolite NaY supported Ni, Co₃O₄, ZrO₂ catalysts. The XRD, N₂ physisorption and SEM analysis were used in order to characterize the catalysts. Catalytic activities were carried out under a feed composition of 1% CO, 50% H₂ and 49% He between the 125 °C to 375 °C. Except for the Ni/Co₃O₄/NaY catalyst, all catalysts gave high surface area because of the presence of zeolite NaY. Average pore diameter of the catalysts fell into the mesopore diameter range. The highest CO methanation activity was obtained with Ni/ZrO₂/NaY catalyst at which the CO methanation was started after 175 °C and 100% CO conversion was obtained at 275 °C using the same catalyst.     

Synthesis of Ag promoted porous Fe3O4 microspheres with tunable pore size as catalysts for Fischer–Tropsch production of lower olefins

Ag promoted porous Fe₃O₄ microspheres with tunable pore size were synthesized via one-pot solvothermal method and employed as catalysts for Fischer–Tropsch synthesis. The introduction of Ag played an important role in regulating the pore size of catalysts and the dispersion of Fe. Comparable to unmodified catalyst in this system, Ag promoted Fe-based catalysts displayed excellent selectivity to lower olefins, particularly for Fe–0.9Ag with smaller pore size of 1.33 nm and Fe dispersion of 10.1%. The maximum selectivity to C₂ through C₄ olefins was 43.0 wt.%, and the selectivity to CH₄ was low to 14.8 wt.%.     

Higher alcohol synthesis from syngas over KCoMoP catalysts

Carbon modified K_xCo_0.75MoP (0 ≤ x ≤ 1.5) catalysts were prepared from a sol–gel method using citric acid as a complexant. The catalysts were evaluated with CO hydrogenation and characterized by XRD, XPS and CO₂-TPD techniques. Results show that the addition of cobalt accelerates the dispersion of catalytic components in phosphide catalysts while the participation of potassium in phosphide catalysts enhances the interaction between MoP and CoMoP and facilitates the rearrangement of electron density in different Mo species. In K₁Co_0.75MoP, a large number of Mo^4 + species resulted in high selectivity to C_2 + higher alcohol.     

Development of [60] fullerene supported on silica catalysts for the photo-oxidation of alkenes

Simple or successive incipient wetness impregnation followed by heating at 180 °C is proved an efficient preparation method for dispersing effectively onto the silica surface various amounts of C₆₀ in the range 1–4% (w/w). BET, XRD, DRS, TGA, microelectrophoresis and photoluminescence have been used to characterize the photocatalysts prepared. A high dispersion was obtained for the quite stable supported C₆₀ phase, comprised mainly from relatively small or medium size C₆₀ clusters/aggregates. The photocatalytic activity was assessed in the singlet oxygen oxidation of alkenes by examining the photo-oxygenation of 2-methyl-2-heptene as a probe reaction. The catalytic tests were carried out at 0–5 °C in CH₃CN, under oxygen atmosphere and using a 300 W xenon lamp as the light source. The heterogeneous catalysts obtained were proved to be active in the photocatalytic oxidation of olefins via a ¹O₂ ene reaction. The catalysts exhibited significant conversion, turnover number and turnover frequency values, substantially higher than those achieved over the unsupported C₆₀. The conversion increases with the amount of the supported C₆₀ up to a value equal to 3% (w/w) and then it decreases whereas turnover number and turnover frequency decreases monotonically as the amount of the supported C₆₀ increases. The easy separation of these solid catalysts from the reaction mixture, the high activity and stability as well as the retained activity in subsequent catalytic cycles, make these supported catalysts suitable for a small-scale synthesis of fine chemicals.     

Effect of impregnation sequence on performance of SiO2 supported Cu-Fe catalysts for higher alcohols synthesis from syngas

The effects of different impregnation sequences of copper and iron on the performance of Cu-Fe/SiO₂ catalysts for higher alcohols synthesis from syngas were investigated by N₂ adsorption, XRD, H₂-TPR, CO-IR, XPS, and CO hydrogenation reaction. The results indicate that the catalyst prepared by impregnation of support first with Fe and then with Cu exhibits the highest selectivity (36.1%) and space time yield (153.3 g·kg_cat^− 1·h^− 1) of alcohols. The CO conversion and alcohol selectivity of the catalysts was closely related to the content of surface Cu, and the ratio of surface contents of Cu to Fe, respectively.     

Solid state NMR investigation of silica aerogel supported Fischer–Tropsch catalysts

The Fischer–Tropsch (F–T) catalyst is the critical component for the F–T synthesis of a variety of hydrocarbons from syngas. Fischer–Tropsch cobalt, iron and ruthenium catalysts supported on silica aerogel have been prepared using a combination of sol–gel chemistry and vapor phase deposition methods. Solid state NMR spectroscopy, a very powerful technique for analyzing the structure and dynamics of various materials, was employed in the study of these F–T catalyst systems. The silica aerogel supported F–T catalysts have been investigated using both solid state ²⁹Si and ¹³C NMR methods. The silica aerogel's tetrahedral sub-unit structure and the influence of the loaded metal compounds have been observed. Three types of Si(O_1/2)₄ tetrahedral unit structure (Q₂, Q₃ and Q₄) are clearly resolved in the silica aerogel samples. The calcining process and the loading of metal compounds produce line broadening in the ²⁹Si spectra sufficient to prevent clear resolution of the three distinct Q_n spectral lines, but the broadened spectra indicate that the three Q sub-unit structures are still present. The ferrocene and ruthenocene molecules used in the vapor phase deposition method exhibit a rapid exchange within the silica aerogel support similar to what one would expect in the gas or liquid state.     

Investigation on textural and structural evolution of the novel crack-free equimolar Al2O3-SiO2-TiO2 ternary aerogel during thermal treatment

Crack-free mesoporous equimolar Al₂O₃-SiO₂-TiO₂ ternary nanocomposite aerogel has been synthesized using an ethanol supercritical drying technique. The effects of heat treatment temperatures on its textural and structural evolution during thermal treatment are investigated in this study. XRD results reveal that only anatase phase is detected in the as-dried ternary aerogel, whereas peaks corresponding to silica and alumina phase are not shown due to its much faster polymerization rate of titania precursor. Structural transition from boehmite to γ-Al₂O₃ begins to occur at 450 °C within the ternary aerogel, and this process is completed at nearly 615 °C. The needle-like reticulated γ-Al₂O₃ grows along the anatase backbone, however, it is not evident in the XRD patterns. The morphologies of the ternary aerogel become more homogeneous after the structural transition, as indicated by the SEM analysis, which is also consistent with the BET results. With the increase of heat temperature up to 1050 °C, the γ-Al₂O₃ phase disappears and no separate SiO₂ is detected. At the same time, the silica-alumina network originates in a structure of Al-O-Si, and the silicon atoms incorporate into the alumina phase in the γ-Al₂O₃ structure, disordering the alumina primary particles. When the heat treatment temperature increases to 1200 °C, mullitization begins to occur along the titania backbone, whereas silica crystallization happens at 1300 °C. The 600 °C calcinated ternary aerogel is typically mesoporous, showing high specific surface area (255.37 m²/g), suitable average pore diameter (22.83 nm) and large pore volume (1.34 cm³/g). Moreover, the ternary aerogels show high surface acid activity at temperatures below 1000 °C, which have future applications for ideal catalysts and catalyst supports at elevated temperatures.     

Promoting effect of Pd on H2 production from cellulose pyrolysis over mesocellular-foam-supported Ni catalysts

Noble-metal promoters have been added to catalysts for reactions such as steam-methane reforming, but have rarely been applied to systems that produce H₂ from larger, biomass-derived molecules, such as polyols or cellulose. We have previously found that nickel catalysts supported on mesocellular-foam-(MCF)-type silica catalyze H₂ formation during cellulose pyrolysis, and sought to increase their activity. Thus, palladium-promoted nickel catalysts supported on MCF were prepared, and their activities were tested in cellulose pyrolysis (RT → 800 °C, 40 °C/min) under dry argon. A thermogravimetric analyzer–mass spectrometer (TG–MS) was used to semi-quantitatively monitor the gases, especially H₂, that were released during pyrolysis over catalysts with and without Pd promoters. Although the Pd promoters had little impact on the fraction of H₂ in the product gas, adding ≥ 0.4 wt.% Pd enhanced the H₂ yield from cellulose pyrolysis by increasing the total gas yield from the reaction. Thus the promoter improved H₂ yield by enhancing the tar-cracking activity of the catalyst. A 5%Ni/MCF catalyst that was doped with 0.7 wt.% Pd yielded 85 cm³ H₂/g cellulose, which was 15% more H₂ than was obtained when the catalyst was 5%Ni/MCF.     

The effect of acetic acid pretreatment for cobalt catalysts prepared from cobalt nitrate

The effects of acetic acid pretreatment for dried catalysts prepared from cobalt nitrate were investigated. Cobalt catalyst prepared from cobalt nitrate, followed by treatment of 2.2 M acetic acid, namely CoN/2.2Ac catalyst, showed the highest CO conversion as well as the lowest CO₂ and CH₄ selectivities in liquid-phase Fischer–Tropsch synthesis. On the contrary, cobalt catalyst prepared from cobalt acetate exhibited poor catalytic activity due to very low reduction degree of supported cobalt. The higher catalytic activity for CoN/2.2Ac catalyst could be ascribed to the formation of the mixture of cobalt nitrate and cobalt acetate with suitable ratio between them during acetic acid treatment, which led to an optimum balance between the dispersion and reduction degree of supported cobalt, eventually realizing the higher catalytic activity. Various catalysts were characterized by XRD, TPR and H₂ chemisorption.     

Preferential CO oxidation over activated carbon supported catalysts in H2-rich gas streams containing CO2 and H2O

Selective CO oxidation (PROX) was studied at 423 K over 1% Pt–0.25% SnO_x and 1% Pt–1% CeO_x catalysts supported on un-oxidized and oxidized activated carbon (AC) using feed mixtures simulating the reformate coming from fuel processors. Effects of the addition of 15% CO₂ or (15% CO₂ + 10% H₂O) into feed mixtures containing 1% CO, 1% O₂, 60% H₂ and He were determined for nine different AC-supported catalysts, and the results were compared with those obtained with pure H₂-rich feed. Unlike other PROX catalysts having oxide supports, introduction of CO₂ into pure feed drastically increased CO conversion on all nine catalysts supported on oxidized or un-oxidized AC regardless of impregnation strategy.1% Pt–0.25% SnO_x supported on HNO₃-oxidized AC stands out as a potential candidate for commercial use in PROX since it yields 100% CO conversion under realistic feed conditions. 1% Pt–1% CeO_x catalysts prepared by sequential or co-impregnation and supported on air-oxidized AC also give 100% CO conversion in H₂-rich feed containing (CO₂ + H₂O) during extended run times and hence hold promise as PROX catalysts.     

NO SCR with propane and propene on Co-based alumina catalysts prepared by co-precipitation

Homogeneous dispersions and small size of deposited high-content cobalt on alumina were achieved by the co-precipitation method and were well maintained on the cobalt-based binary alumina catalysts with Zn, Ag, Fe, Cu or Ni as modifiers. The component and concentration of deposited cobalt species were characterized by UV–vis, EDX and XPS spectra and found to be greatly related to the Co loading, calcination temperatures and the type of additive metals. The optimal Co loading of 8 wt% and calcination temperatures of 800 °C were demonstrated. With respect to the single cobalt-based alumina catalyst, the surface concentration of Co²⁺ on the binary catalysts with addition of Fe, Cu, Ag or Ni was all reduced and accompanying with part conversion of Co²⁺ to Co₃O₄ on the Fe and Ni-modified catalysts. A slight enhanced surface Co²⁺ concentration was only achieved on the Zn-promoted catalyst. It was also demonstrated that for the case of Cu and Fe the additive metals themselves participated in the activation of propene. The octahedral and tetrahedral Co²⁺ ions were suggested as the common active sites. A maximum deNOx activity of 96% was observed on the 8Co4ZnA800 catalyst at the reaction temperatures of 450 °C, and the catalytic performance on the cobalt-based binary alumina catalysts can be described as fellows: CoZn > CoAg, CoNi > Co Cu > CoFe. Based on the in situ DRIFT spectra, different reaction intermediates R–ONO and –NCO besides –NO₂ were formed on the 8Co4ZnA800 and 8Co4FeA800 samples, respectively, demonstrating their dissimilar reaction mechanisms.     

Kinetic study of Fischer–Tropsch process on titania-supported cobalt–manganese catalyst

An active cobalt–manganese catalyst was prepared by co-precipitation method, and was also tested for hydrogenation of carbon monoxide to light olefins. The catalyst was characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM) and Brunauer–Emmett–Teller (BET) surface area techniques. The kinetic experiments on a well-characterized Co–Mn/TiO₂ catalyst were performed in a fixed-bed micro-reactor, and were also conducted in a temperature range of 190–280 °C, pressure range of 1–10 bar, H₂/CO feed ratio (mol/mol) range of 1–3 and a space velocity range of 2700–5200 h^?1. Two kinetic expressions based on Langmuir–Hinshelwood–Houngen–Watson (LHHW) mechanism were observed to fit the experimental data accurately for Fischer–Tropsch synthesis reaction. The kinetic parameters were estimated with non-linear regression method. Activation energies obtained were 35.131 and 44.613 kJ/mol for optimal kinetics models.     

Rhodium complexes supported on nanoporous activated carbon for selective hydroformylation of olefins

Activated carbon with nanoporous structure, high surface area (2500 m²/g) and total pore volume (2.35 cm³/g) was prepared from Mango seed shell (Mangifera indica L.) via chemical activation method and used as support to impregnate active hydroformylation rhodium complexes HRhCO(PPh₃)₃ and Rh(acac)(CO)₂. The prepared catalysts were characterized by XRD, SEM, TEM, NMR, IR, TGA, and N₂ adsorption/desorption techniques. The supported catalysts have shown excellent selectivity for aldehydes (~ 99%) in the hydroformylation of olefins with good stability and recyclability up to 4 cycles.     

Hydrogenation of carbon monoxide to methane over mesoporous nickel-M-alumina (M = Fe,Ni, Co,Ce, and La) xerogel catalysts

Mesoporous nickel(30 wt%)-M(10 wt%)-alumina xerogel (30Ni10MAX) catalysts with different second metal (M = Fe, Ni, Co, Ce, and La) were prepared by a single-step sol–gel method for use in the methane production from carbon monoxide and hydrogen. In the methanation reaction, yield for CH₄ decreased in the order of 30Ni10FeAX > 30Ni10NiAX > 30Ni10CoAX > 30Ni10CeAX > 30Ni10LaAX. Experimental results revealed that CO dissociation energy of the catalyst and H₂ adsorption ability of the catalyst played a key role in determining the catalytic performance of 30Ni10MAX catalyst in the methanation reaction. Optimal CO dissociation energy of the catalyst and large H₂ adsorption ability of the catalyst were favorable for methane production. Among the catalysts tested, 30Ni10FeAX catalyst with the most optimal CO dissociation energy and the largest H₂ adsorption ability exhibited the best catalytic performance in terms of conversion of CO and yield for CH₄ in the methanation reaction. The enhanced catalytic performance of 30Ni10FeAX was also due to a formation of nickel–iron alloy and a facile reduction.     

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.     

Solvent free synthesis of chalcone and flavanone over zinc oxide supported metal oxide catalysts

Liquid phase Claisen–Schmidt condensation between 2′-hydroxyacetophenone and benzaldehyde to form 2′-hydroxychalcone, followed by intramolecular cyclisation to form flavanone was carried out over zinc oxide supported metal oxide catalysts under solvent free condition. The reaction was carried out over ZnO supported MgO, BaO, K₂O and Na₂O catalysts with 0.2 g of each catalyst at 140 °C for 3 h. Magnesium oxide impregnated zinc oxide was observed to offer higher conversion of 2′-hydroxyacetophenone than other catalysts. Further MgO impregnated with various other supports such as HZSM-5, Al₂O₃ and SiO₂ were also used for the reaction to assess the suitability of the support. The order of activity of the support is ZnO > SiO₂ > Al₂O₃ > HZSM-5. Various weight percentage of MgO was loaded on ZnO to optimize maximum efficiency of the catalyst system. The impregnation of MgO (wt%) in ZnO was optimized for better conversion of 2′-hydroxyacetophenone. The effect of temperature and catalyst loading was studied for the reaction.     

Kinetics studies of nano-structured cobalt–manganese oxide catalysts in Fischer–Tropsch synthesis

The nano-structured cobalt/manganese oxide catalyst was prepared by thermal decomposition of [Co(NH₃)₄CO₃]MnO₄ precursor, and was tested for the Fischer–Tropsch reaction (hydrocarbon forming) in a fixed-bed micro-reactor. Experimental conditions were varied as follow: reaction pressure 1–10 bar, H₂/CO feed ratio of 1–2 and space velocity of 3600 h^?1 at the temperature range of 463.15–523.15 K. On the basis of carbide and/or enolic mechanisms and Langmuir–Hinshelwood–Hougen–Watson (LHHW) type rate equations, 30 kinetic expressions for CO consumption were tested and interaction between adsorption HCO and dissociated adsorption hydrogen as the controlling step gave the most plausible kinetic model. The kinetic parameters were estimated with non-linear regression method and the activation energy was 80.63 kJ/mol for optimal kinetic model. Kinetic results indicated that in Fischer–Tropsch synthesis (FTS) rate expression, the rate constant (k) has been increased by decreasing the catalyst particle size. The catalyst characterization was carried out using different methods including powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and Brunauer–Emmett–Teller (BET) surface area measurements.     

Production of silica aerogel microparticles loaded with ammonia borane by batch and semicontinuous supercritical drying techniques

Silica aerogel microparticles were prepared by supercritical drying and used as support for hydrogen-storing ammonia borane (AB). The formation of aerogel microparticles was done using two different processes: batch supercritical fluid extraction and a semicontinuous drying process. Silica aerogel microparticles with a surface area ranging from 400 to 800 m²/g, a volume of pores of 1 cm³/g, and a mean particle diameter ranging from 12 to 27 μm were produced using the two drying techniques. The particle size distribution (PSD) of the microparticles was influenced by shear rate, amount of catalyst, hydrophilic–hydrophobic solvent ratio and hydrophobic surface modification. In particular, irregular aerogel particles were obtained from hydrophilic gels, while regular, spherical particles with smooth surfaces were obtained from hydrophobic gels. AB was loaded into silica aerogel microparticles in concentrations ranging from 1% till 5% wt. Hydrogen release kinetics from the hydride-loaded aerogel was analyzed with a volumetric cell at 80 °C. By stabilization of AB into the silica aerogel microparticles, an improvement of the release rate of hydrogen from AB was observed.