The modification of SiO2 by various organic groups and its influence on the properties of cobalt-based catalysts for Fischer-Tropsch synthesis

SiO₂ was modified by various organic groups before the impregnation of cobalt precursor. These modified supports and the corresponding catalysts were characterized by BET, ²⁹Si CP MAS NMR, XRD, Raman, XPS and H₂-TPR. These characterizations clearly show the changes of morphology as well as reducibility of the catalysts. The organic modification of SiO₂ remarkably influences the reducibility and catalytic properties of Co catalysts. Co catalyst supported on (CH₃)₃-modified SiO₂ exhibits high activity and C₅⁺ hydrocarbon selectivity. However, COOH-, NH₂-, and NH₂(CH₂)₂NH-modified SiO₂ distinctly suppress the catalytic activity of Co catalysts.     

Characterization of Fischer–Tropsch Cobalt-Based Catalytic Systems (Co/SiO<Subscript>2</Subscript> and Co/Al<Subscript>2</Subscript>O<Subscript>3</Subscript>) by X-ray Diffraction and Magnetic Measurements

Results of the characterization of six Co-based Fischer–Tropsch (FT) catalysts, with 15% Co loading and supported on SiO₂ and Al₂O₃, are presented. Room temperature X-ray diffraction (XRD), temperature and magnetic field (H) variation of the magnetization (M), and low-temperature (5 K) electron magnetic resonance (EMR) are used for determining the electronic states (Co⁰, CoO, Co₃O₄, Co²⁺) of cobalt. Performance of these catalysts for FT synthesis is tested at reaction temperature of 240 °C and pressure of 20 bars. Under these conditions, 15% Co/SiO₂ catalysts yield higher CO and syngas conversions with higher methane selectivity than 15% Co/Al₂O₃ catalysts. Conversely the Al₂O₃ supported catalysts gave much higher selectivity towards olefins than Co/SiO₂. These results yield the correlation that the presence of Co₃O₄ yield higher methane selectivity whereas the presence of Co²⁺ species yields lower methane selectivity but higher olefin selectivity. The activities and selectivities are found to be stable for 55 h on-stream.     

CO hydrogenation towards higher alcohols catalysed on SiO2-grafted and zeolite-entrapped Ru,Co and RuCo bimetallic clusters: Their EXAFS and FTIR characterization and catalytic performances

Some Ru and Co carbonyl clusters in zeolite pores such as Ru₃(CO)₁₂/NaY, [HRu₆(CO)₁₈]^–/NaY, [Ru₆(CO)₁₈]^2–/NaX, Co₄(CO)₁₂/NaY and Co₆(CO)₁₆/NaY were prepared by the ship-in-bottle technique, and characterized by FTIR and EXAFS. The RuCo bimetallic carbonyl cluster was prepared by reductive carbonylation of the oxidized RuCo/NaY, which provides the proposed assignment to [HRUCo₃(CO)₁₂]/NaY. The tailored Ru, RuCo and Co catalysts were prepared by H₂ reduction from the precursors, e.g. Ru, RuCo bimetallic and Co carbonyl clusters impregnated on SiO₂ and entrapped in NaY and NaX zeolites. The RuCo bimetallic carbonyl cluster-derived catalysts showed substantially higher activities and selectivities for oxygenates such as C₁–C₅ alcohols in CO hydrogenation (CO/H₂ = 0.33-1.0, 5 bar, 519–543 K). By contrast, hydrocarbons such as methane were preferentially obtained on the catalysts prepared from Ru₆, Ru₃ and Co₄ carbonyl clusters and provided lower CO conversion and poor selectivities for oxygenates. The RuCo bimetals are proposed to be associated with the selective formation of higher alcohols in CO hydrogenation.     

Characterization of magnesium promoted Co/SiO2 catalysts

Co/SiO₂, Mg-Co/SiO₂, and Co-Mg/SiO₂ catalysts were prepared from nitrate precursors to get more insight into the effect of magnesium promotion on the cobalt catalyst. The desorption characteristics and reactivity of the catalysts towards synthesis gas were evaluated in a pulse micro reactor connected to an on-line quadrupole mass spectrometer. The presence of MgO both decreased the extent of reduction and increased the dispersion of cobalt. The reactivity results suggested that MgO promotion created new types of active sites, probably at the edge sites of cobalt and magnesium. The highest activity per metallic site available was obtained with a Mg: Co molar ratio of 1/2, i.e. with a high amount of edge sites. In accordance with previous results the formation of CO₂ was clearly suppressed in the presence of MgO, and methanol was formed in trace amounts.     

Ethene hydroformylation on Co/SiO2 catalysts

The results from ethene hydroformylation at 173°C showed that a Co(acac)₃/SiO₂ catalyst prepared from Co(acac)₃ precursor by gas‐phase deposition was three times as active as a catalyst prepared by impregnation from cobalt nitrate, but oxo‐selectivities were similar. The high propanal selectivities on the Co(acac)₃/SiO₂ seem to be related to the presence of highly dispersed active sites favouring CO insertion. As dispersion is decreased from 23 to 8% due to increasing metal content (from 5 to 16 wt%), oxo‐selectivity decreased from 39 to 25%. The activity of Co(acac)₃/SiO₂ remained unchanged during 68 h on stream. The gas‐phase deposition technique described here is a promising method for the preparation of active, selective and stable heterogeneous hydroformylation catalysts. This revised version was published online in July 2006 with corrections to the Cover Date.     

The long-term performance of Co/SiO2 catalysts in CO hydrogenation

The activity in terms of conversion of carbon monoxide was determined for Co/SiO₂ catalysts in CO hydrogenation over a reaction time of 120 h. The catalysts were prepared from nitrate (N) and carbonyl (CO) precursors. The conversion decreased rapidly during the first five hours, and thereafter moderately at a rate related to dispersion, i.e. the higher the dispersion the higher the rate of decrease. The active sites were blocked by wax and coke formed in the reaction, although some agglomeration of particles probably took place on the Co(CO)/SiO₂ catalysts. More carbon was accumulated on Co(CO)/SiO₂ than on Co(N)/SiO₂ during the reaction suggesting a need for frequent regeneration. The reduction-oxidation-reduction treatments indicated, however, that the regenerability of the Co(CO)/SiO₂ in terms of hydrogen uptake is poor, although the amounts adsorbed still remained higher than those for Co(N)/SiO₂.     

CO2 hydrogenation reactivity and structure of Rh/SiO2 catalysts prepared from acetate,chloride and nitrate precursors

Silica-supported Rh catalysts (Rh/SiO₂) were prepared from acetate, chloride and nitrate precursors by an impregnation method and were applied to CO₂ hydrogenation reaction. CO₂ conversion over the catalyst prepared from chloride precursor was lower than that over acetate or nitrate one, because of fewer active sites on catalysts, as estimated by H₂ chemisorption. The main product was CO over the catalysts prepared from acetate and nitrate, but it was CH₄ over the catalyst prepared from chloride precursor. Characterization of catalysts by TEM, FT-IR and XPS was carried out in order to elucidate the effect of metal precursor on the CO₂ hydrogenation reactivity. The results of XPS showed that the O atomic ratio to Rh on surface hydroxyl groups increased in the order: chloride<nitrate<acetate precursor. The ratio of hydroxyl groups to Rh particles on SiO₂ surface was expected to have a significant influence on the reactivity.     

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.     

Preparation of supported gold catalysts from gold complexes and their catalytic activities for CO oxidation

A phosphine-stabilized mononuclear gold complex Au(PPh₃)(NO₃) (1) and a phosphine-stabilized gold cluster [Aug(PPh₃)₈](NO₃)₃ (2) were used as precursors for preparation of supported gold catalysts. Both complexes 1 and 2 supported on inorganic oxides such as -Fe₂O₃, TiO₂, and SiO₂ were inactive for CO oxidation, whereas the 1 or 2/ oxides treated under air or CO or 5% h₂/Ar atmosphere were found to be active for CO oxidation. The catalytic activity depended on not only the treatment conditions but also the kinds of the precursor and the supports used. The catalysts derived from 1 showed higher activity than those derived from 2. -Fe₂O₃ and TiO₂ were much more efficient supports than SiO₂ for the gold particles which were characterized by XRD and EXAFS.     

Enhancing the Fischer–Tropsch Synthesis Activity of Co-based Catalysts by Adding ZrOx to the SiO2 Support and Chelating Ligands to the Co-precursor

Abstract  

Co/ZrO _x /SiO₂ catalysts with enhanced dispersion of Co⁰ and turnover frequency were successfully prepared combining two different promotion effects, i.e., modifications of SiO₂ surface with ZrO _x by liquid phase deposition and influencing coordination structure of Co species using chelating agents or glycols. The catalysts exhibited ~6.3-fold higher CO conversion than Co/SiO₂ and those promoted by organic additives or ZrO _x alone, indicating activity enhancement was induced by cooperation of these two promoters.     

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.     

Methanol synthesis over Cu/SiO2 catalysts

The rates of CO and CO/CO₂ hydrogenation at 4.2 MPa and 523 K are reported for a series of Cu/SiO₂ catalysts containing 2 to 88 wt.% Cu. These catalysts were prepared on a variety of silica sources using several different Cu deposition techniques. In CO/CO₂ hydrogenation, the rate of methanol formation is proportional to the exposed Cu surface area of the reduced catalyst precursor, as determined by N₂O frontal chromatography. The observed rate, 4.2×10^–3 mole CH₃OH/Cu site-sec, is within a factor of three of the rates reported by others over Cu/ZnO and Cu/ZnO/Al₂O₃ catalysts under comparable conditions. These results suggest that the ZnO component is only a moderate promoter in methanol synthesis. Hydrogenation of CO over these catalysts also gives methanol with high selectivity, but the synthesis rate is not proportional to the Cu surface area. This implies that another type of site, either alone or in cooperation with Cu, is involved in the synthesis of methanol from CO.     

Colloidal Co nanoparticles supported on SiO2: Synthesis, characterization and catalytic properties for steam reforming of ethanol

Colloidal Co nanoparticles with sizes in the 3–8 nm range were obtained by thermal decomposition of Co₂(CO)₈ in the presence of ligands and impregnated on SiO₂ to prepare SiO₂-supported Co nanocatalysts. The catalysts showed activity for the steam reforming of ethanol with higher values for smaller Co particles. H₂ adsorption results and Fourier transform infrared spectroscopy of adsorbed CO suggested that the fraction of accessible Co sites also depended on the synthesis conditions. Precipitation of the Co nanoparticles with methanol instead of ethanol before impregnation had a positive effect on the density of accessible Co sites to catalysis; similar result was verified by increasing the thermal treatment temperature under H₂ flow before the reaction. Based on the distribution of products with temperature of reaction, a mechanism for steam reforming of ethanol on SiO₂-supported Co nanocatalysts is suggested.     

Synergy of ruthenium and cobalt in SiO2-supported catalysts on ethylene hydroformylation

Dynamic hydroformylation of ethylene at atmospheric pressure and 150°C has been studied in a fixed bed reactor over ruthenium- and cobalt-containing SiO₂-supported catalysts (1% Ru loading). Any combination of ruthenium and cobalt precursors leads to significant improvement of hydroformylation activity with respect to those of monometallic catalysts. The optimal atomic ratio of Co:Ru is estimated to be 3:1 for ideal catalytic activity. A catalyst derived from Ru₃(CO)₁₂ and Co₂(CO)₈ is most active. A catalyst derived from metal carbonyls is generally more active than a catalyst prepared from metal salts. Metal chlorides retard the preparation of active catalysts in most cases. The catalysts studied exhibit fairly good catalytic stability. The determined rate enhancement of ethylene hydroformylation suggests a synergy of ruthenium and cobalt, which is understood as catalysis by bimetallic particles or ruthenium and cobalt monometallic particles in intimate contact. The synergy causes high ethylene hydrogenation activity while giving enhanced ethylene hydroformylation activity. Meanwhile, the potential of the ruthenium-based catalysts is evaluated from both catalytic performances and cost by comparison with the corresponding rhodium-based ones.     

The Inclusion of Organometallic Derivatives of Cyclotriphosphazenes Inside SiO2 Matrix and Their Conversion to Nanostructured Metal-Oxides and Phosphates

Organometallic derivatives of the cyclotriphosphazene N₃P₃[OC₆H₄CH₂CN·TiClCp₂]₆ (1), N₃P₃(O₆H₅)₅[OC₆H₄N·W(CO)₅] (2), N₃P₃[OC₆H₄CH₂CN·Mo(CO)₅]₆ (3), [N₃P₃(O₆H₅)₅(OC₅H₄N·CpRu(PPh₃)₂)][PF₆] (4), [N₃P₃(O₂C₁₂H₈)₂OC₅H₄N·Ag(PPh₃)][OSO₂CF₃] (5), N₃P₃[OC₆H₅]₅ [OC₅H₄N·Cu][PF₆] (6) and N₃P₃[OC₆H₄CH₂CN·CuCl]₆[PF₆]₆ (7),were incorporated inside SiO₂ through the sol–gel method. The metal–organic nanocomposites of the general formula N₃P₃[OC₆H₄CH₂CN·TiClCp₂]₆·nSiO₂ (G ₁ ), N₃P₃[OC₆H₄N·W(CO)₅]·nSiO₂ (G ₂ ), N₃P₃[OC₆H₄CH₂CN·Mo(CO)₅]₆·nSiO₂ (G ₃ ), N₃P₃(O₆H₅)₅OC₅H₄N·CpRu(PPh₃)₂][PF₆]·nSiO₂ (G ₄ ), [N₃P₃(O₂C₁₂H₈)₂OC₅H₄N·Ag(PPh₃)][OSO₂CF₃]·nSiO₂ (G ₅ ), N₃P₃[OC₆H₅]₅[OC₅H₄N·Cu][PF₆]·(SiO₂) _n (G ₆ ), and N₃P₃[OC₆H₄CH₂CN·CuCl]₆[PF₆]₆·(SiO₂) _n (G ₇ ), were characterized by IR spectroscopy; ¹²C, ³¹ P and ²⁹Si MAS NMR measurements as well as UV–Visible diffuse reflectance spectra, indicating the presence of the respective organometallic derivatives of the cyclotriphosphazene incorporated into SiO₂. Pyrolysis of these nanocomposites under air at 800 °C gives rise to nanostructured metal-oxides and metal phosphates incorporated into amorphous SiO₂, with the presence in some cases of complexes phase mixtures. From some precursors, we obtained metal-oxides/phosphates nanoparticles separated from the SiO₂ nanoparticles instead the oxides/phosphates nanoparticles inside the SiO₂ matrix. Additionally and for comparison purposes, we used the compound N₃P₃[NH(CH₂)₃Si(OEt)₃]₆ as gelator. Nanocomposites (G′ ₁ ), (G′ ₂ ) and (G′ ₃ ) exhibited mainly morphological differences while in some cases composition differences when using TEOS as gelator. Some simple metal-containing compounds as (O₃SCF₃)Ag(PPh₃)(HOC₅H₄N), [CuCl₂·NC₅H₄OH] and [CuCl₂·NCCH₂C₆H₄OH]—which are useful models of the most complexes (G ₅ ), (G ₆ ) and (G ₇ ) were also prepared and incorporated in amorphous silica. Their pyrolytic products were compared with those of more complex cyclotriphosphazene analogous. Interestingly, the pyrolysis of the nanocomposite [(O₃SCF₃)Ag(PPh₃)(HOC₅H₄N)][SiO₂] _n affords the firstly-reported materials containing Ag₂O along with SiO₂ nanoparticles.     

Characterization of bimetallic surface structures of highly active Rh-Sn/SiO2 catalysts for NO-H2 reaction by EXAFS

Rh-Sn/SiO₂ catalysts prepared by the reaction of (CH₃)₄Sn with Rh metal particles supported on SiO₂ have remarkably high activities for NO-H₂ reaction and NO dissociation. The bimetallic surface structure of Rh-Sn/SiO₂ composed of an isolated Rh atom surrounded by six Sn atoms, is presented by Rh K-edge and Sn K-edge EXAFS, FT-IR, TEM and CO adsorption.     

Ethanol Steam Reforming on Co/CeO2: The Effect of ZnO Promoter

A series of ZnO promoted Co/CeO₂ catalysts were synthesized and characterized using XRD, TEM, H₂-TPR, CO chemisorption, O₂-TPO, IR-Py, and CO₂-TPD. The effects of ZnO on the catalytic performances of Co/CeO₂ were studied in ethanol steam reforming. It was found that the addition of ZnO facilitated the oxidation of Co⁰ via enhanced oxygen mobility of the CeO₂ support which decreased the activity of Co/CeO₂ in C–C bond cleavage of ethanol. 3 wt% ZnO promoted Co/CeO₂ exhibited minimum CO and CH₄ selectivity and maximum CO₂ selectivity. This resulted from the combined effects of the following factors with increasing ZnO loading: (1) enhanced oxygen mobility of CeO₂ facilitated the oxidation of CH _x and CO to form CO₂; (2) increased ZnO coverage on CeO₂ surface reduced the interaction between CH _x /CO and Co/CeO₂; and (3) suppressed CO adsorption on Co⁰ reduced CO oxidation rate to form CO₂. In addition, the addition of ZnO also modified the surface acidity and basicity of CeO₂, which consequently affected the C₂–C₄ product distributions.     

Organometallics derived (Pd + Ln)/SiO2 catalysts for the reactions of synthesis gas conversion

C₃H₆ hydroformylation and CH₃OH synthesis on organometallics derived (Pd + Ln)/ SiO₂ and Pd/SiO₂ catalysts have been studied. The activity and selectivity towards methanol in CO + H₂ reaction were observed to increase for all the modified catalysts while both the hydroformylation activity and selectivity towards oxygenates in C₃H₆ hydroformylation decreased for the catalysts in comparison to those of Pd/SiO₂. The FTIR, TPD data and characteristic catalytic properties of the catalysts studied allow to suggest that C₃H₆ hydroformylation on (Pd + Ln)/SiO₂ catalysts occurs on monometallic Pd clusters without participation of mixed active sites and CO complexes activated thereon.     

Selective reduction of NOx with hydrocarbons over Co/MFI prepared by sublimation of CoBr2 and other methods

Co/MFI catalysts were prepared by various methods, including wet-ion exchange (WIE), either as such or in combination with impregnation (IMP), solid-state ion exchange (SSI), and sublimation (SUB) of CoCl₂ (at 700°C) or CoBr₂ (at 600°C) onto H/MFI. The catalysts were tested for the reduction of NO_x with CH₄ or iso-C₄H₁₀ in excess O₂. Below 425°C the SUB catalysts show the highest NO_x reduction activity with CH₄ or iso-C₄H₁₀. Above 425°C, the best performance is given by WIE. Below the temperature of maximum N₂ yield, a mixture of Fe/FER and WIE is superior to either catalyst. Addition of 10% H₂O to the feed drastically decreases the N₂ yield in NO_x reduction with CH₄, but increases the activity with iso-C₄H₁₀ under some conditions. Permanent damage of the zeolite lattice as a potential cause for the adverse effect of H₂O in the tests with CH₄ is eliminated, as the original activity is fully restored after calcination. A 100 h test with a wet iso-C₄H₁₀ feed shows excellent stability with a SUB catalyst prepared from CoBr₂.Characterization by XRD, H₂-TPR, and FTIR reveals that WIE contains isolated Co²⁺ and (Co–OH)⁺ ions that are only reducible at 700°C. SUB catalysts show additional TPR peaks at low temperature, including a feature at 220–250°C, ascribed to multinuclear Co oxo-ions. The formation of an NO_y chemisorption complex is most rapid on these catalysts. No oxidation states between Co⁰ and Co²⁺ are detectable; the one-step reduction of Co²⁺ to Co⁰ clusters could be a cause for the unique propensity of Co/MFI to reduce NO_x with CH₄.     

Preparation of Co/SiO<Subscript>2</Subscript> Using Several Glycols for Enhanced Fischer-Tropsch Synthesis Activity and Dispersion of Co<Superscript>0</Superscript> Nanoparticles with Unique Co<Superscript>0</Superscript> Particle Size Effect

Abstract  

Co/SiO₂ catalysts with highly dispersed Co⁰ and reducible Co were prepared by impregnation using an aqueous solution of Co nitrate containing ethylene glycol or its homologs. Addition of glycols enhanced FTS activity by a factor of 4. Particle size of Co⁰ decreased from 30 to below 6 nm, while TOF of the catalysts was independent of the Co⁰ particle size.