The interaction of cobalt species with alumina on Co/Al2O3 catalysts prepared by atomic layer deposition

Alumina supported cobalt catalysts were prepared by atomic layer deposition (ALD) of cobalt acetylacetonate precursors (Co(acac)₂ and Co(acac)₃). The main modes of interaction between the acetylacetonate precursors and the support were found to be the exchange reaction between the alumina OH-groups and the acac-ligands of the precursor and dissociative adsorption on coordinatively unsaturated Al³⁺ sites. The amount of precursor that could adsorb on the support was determined by steric hindrance. Samples were prepared using 1–5 reaction cycles, i.e. subsequent precursor addition (Co(acac)₂) and calcination, resulting in catalysts containing ca. 3–10 wt.% Co. Samples were also prepared where the last calcination step was omitted, i.e. uncalcined catalysts. Calcination at 450 °C decreased the reducibility of the Co(acac)₂/Al₂O₃ catalysts due to formation of a cobalt oxide phase strongly interacting with the support and aluminate type surface species. The reducibility increased with metal loading on both calcined and uncalcined catalysts; however the reducibility of the calcined catalysts remained lower than of the uncalcined ones. The dispersion was found to be lower on the calcined catalysts. The cobalt particle sizes on the calcined samples was ca. 8 nm and on the uncalcined 4–5 nm, for cobalt loadings of ca. 6–10 wt.%. Catalytic activity was tested by gas phase hydrogenation of toluene in temperature programmed mode (30–150 °C).     

Cobalt Catalyst Doped with Cerium and Barium Obtained by Co-Precipitation Method for Ammonia Synthesis Process

Abstract  

Unsupported cobalt catalysts promoted with barium (symbol Co/Ba), cerium (Co/Ce) or both (Co/Ce/Ba) were synthesized and tested in ammonia synthesis at 6.3 MPa. The Ba-free Co and Co/Ce oxide forms of the catalysts were prepared by precipitation/co-precipitation and a subsequent calcination at 500 °C. The Co and Co/Ce powders were impregnated with an aqueous solution of barium nitrite. Nitrogen physisorption and H₂ chemisorption measurements revealed that cerium and barium play the role of structural promoters, which hinder the sintering of cobalt oxide during calcination and stabilize the surface of cobalt under reduction conditions. It seems that barium also modifies the surface of the active phase, i.e., cobalt. The kinetic studies of NH₃ synthesis have shown that the co-promoted material (Co/Ce/Ba) is about 2–3 times more active than the system doped with barium (Co/Ba) and more than ten times as active as that with Ce. At 400 °C and at low conversion (1% NH₃), the ammonia synthesis rate (TOF) over Co/Ce/Ba proved to be almost 60% as high as that obtained for the commercial iron catalyst (KMI, H. Tops?e) commonly used in ammonia plants all over the world. Moreover, at the same temperature and a high ammonia concentration (8%) the co-promoted cobalt catalyst is over two times more active than the fused iron catalyst. Another asset of the cobalt catalyst is its high thermal stability.     

Synthesis of 2-Methylpyrazine Over Highly Dispersed Copper Catalysts

Abstract  

A series of CuCoAl catalysts were synthesized by co-precipitation and impregnation methods, tested in synthesis of 2-methylpyrazine (2-MP) and characterized by X-ray diffraction, N₂ adsorption, thermo-gravimetry analysis, H₂-temperature-programmed reduction, dissociative N₂O adsorption and temperature-programmed oxidation. The precursors prepared by co-precipitation method shows a well-crystallized hydrotalcite. The study proves that the calcination temperature of hydrotalcite has a significant effect on the catalyst surface area, crystallite size and copper dispersion. In comparison with catalyst prepared by impregnation, the catalyst prepared by co-precipitation method calcined at 500 °C exhibits higher specific surface area, higher copper dispersion and the better reducibility. Consequently, CuCoAl catalyst derived from hydrotalcite is more active and selective for synthesis of 2-MP. Moreover, it shows the better stability due to the good resistance to coke formation.     

Effect of calcination atmosphere and temperature on γ-Al2O3 supported cobalt Fischer-Tropsch catalysts

The effect of calcination temperature and atmosphere on the properties of γ-Al₂O₃ supported cobalt Fischer-Tropsch catalysts has been investigated. One common precursor for all the catalysts was prepared by incipient wetness impregnation of γ-Al₂O₃ with an aqueous solution of cobalt nitrate hexahydrate. It was subjected to four different calcination atmospheres (air/50% steam: 30 mL/min, air: 30 mL/min, air: 50 mL/min, N₂: 30 mL/min) and eight different calcination temperatures (range: 473–723 K), making the total number of samples 32. Both the post calcination nitrogen content and the cobalt dispersion were measured. The results demonstrated that in order to maximise the cobalt dispersion, it is necessary to use low calcination temperatures and remove the precursor decomposition products (NO, NO₂, H₂O) efficiently. The Fischer-Tropsch synthesis performance of two catalysts calcined at the same temperature, but at different air flow rates was evaluated. No significant effect of the air flow rate was found on the turnover frequency or C₅₊ selectivity, but a high flow rate resulted in 30% higher activity per gram catalyst.     

Nitrous Oxide Decomposition Over MCO3–Co3O4 (M = Ca, Sr, Ba) Catalysts

In this paper, nitrous oxide decomposition over a series of MCO₃–Co₃O₄ (M = Ca, Sr, Ba) catalysts having M/Co ratios of 0.1–0.4 has been studied. The various catalysts were characterized using thermal (TGA, DTA), XRD, IR and N₂ sorption techniques. N₂O decomposition activity was found to be dependent on the type of the alkaline earth cation, the M/Co ratio, cobalt oxide crystallites sizes, and the calcination temperature.     

Carbon-supported cobalt catalyst for ammonia synthesis: Effect of preparation procedure

Supported cobalt catalysts were synthesised, characterised (by H₂ TPD, XRD, TEM), and tested in ammonia synthesis at 9.0 MPa (400–470 °C; H₂:N₂ = 3:1). Partly graphitised carbon of high surface area (840 m²/g), cobalt nitrate, and barium nitrate were used as a support, a precursor of the active phase, and a promoter precursor, respectively. Both cobalt dispersion in the Ba-doped catalyst and, to a greater extent, catalytic properties of the promoted Co surfaces (TOF) proved to be dependent on the unpromoted material pretreatment (reduction in H₂, subsequent calcination in air). The kinetic studies of NH₃ synthesis have shown explicitly that Ba-promoted cobalt on carbon is very active and less inhibited by the ammonia product than the commercial magnetite-based material.     

Silica-Supported Cobalt Catalysts for Fischer–Tropsch Synthesis: Effects of Calcination Temperature and Support Surface Area on Cobalt Silicate Formation

Cobalt silicate formation reduces the activity of the catalyst in Fischer–Tropsch synthesis (FTS). In this article, the effects of calcination temperature and support surface area on the formation of cobalt silicate are explored. FTS catalysts were prepared by incipient wetness impregnation of cobalt nitrate precursor into various silica supports. Deionized water was used as preparation medium. The properties of catalysts were characterized at different stages using FTIR, XRD and BET techniques. FTIR-ATR analysis of the synthesized catalyst samples before and after 48 h reaction identified cobalt species formed during the impregnation/calcination stage and after the reduction/reaction stage. It was found that in the reduction/reaction stage, metal-support interaction (MSI) added to the formation of irreducible cobalt silicate phase. Co/silica catalysts with lower surface area (300 m²/g) exhibited higher C₅₊ selectivity which can be attributed to less MSI and higher reducibility and dispersion. The prepared catalysts with different drying and calcination temperatures were also compared. Catalysts dried and calcined at lower temperatures exhibited higher activity and lower cobalt silicate formation. The catalyst sample calcined at 573 K showed the highest CO conversion and the lowest CH₄ selectivity.     

CO Hydrogenation: Exploring Iridium as a Promoter for Supported Cobalt Catalysts by TPR-EXAFS/XANES and Reaction Testing

Abstract  

The price of iridium currently trends at about half the cost of platinum, the latter being a typical reduction promoter for Co/Al₂O₃ Fischer–Tropsch (FT) synthesis catalysts in gas-to-liquids (GTL) technology. In the current contribution, both fixed-bed catalytic FT and TPR-EXAFS/XANES experiments were carried out over 0.1% iridium-doped 25% Co/Al₂O₃ catalysts in order to (1) assess the effectiveness of Ir as a promoter of cobalt oxide reduction and (2) evaluate the effectiveness of the incipient wetness impregnation (IWI) technique for adding the Ir precursor by comparing a catalyst prepared by IWI to one prepared by atomic layer deposition (ALD). Ir was demonstrated to be an effective promoter for facilitating the second step of cobalt oxide reduction, CoO to Co⁰, and the IWI method was found to be superior to ALD.     

Novel aspects of the physical chemistry of Co/SiO2 Fischer–Tropsch catalyst preparations: Cobalt oxide-induced silica migration during calcination of cobalt nitrate-impregnated high surface area silica

Co/SiO₂ catalysts were prepared by aqueous cobalt nitrate impregnations of silicas with different surface areas to study the effect of the support surface area on the reactions occurring during impregnation and calcination and to define the stage and mode of metal–support interactions. TPR analyses of samples calcined in dry air showed the presence of various quantities of cobalt silicate species, while cobalt silicate formation was not discernible by other analytical techniques. Our conclusion, confirmed in our later studies, is that cobalt silicate does not form during impregnation or calcination, but is created during the reduction in the TPR instrument. Because of these and other ambiguities of the TPR analyses, in our continuing studies we preferred alternative analytical approaches.These studies on the calcination stage resulted in the following unusual findings: (1) X-ray photoelectron spectroscopy revealed drastic decreases in the surface cobalt concentration after calcination of high surface silicas impregnated with cobalt nitrate solutions. (2) Infrared spectroscopy indicated much less than expected Co₃O₄ formation upon calcination if high surface area silica was the support. (3) A method was devised to calculate the surface areas of individual components in mixtures. The calculations indicated about 20% surface area losses for the silica in calcined catalysts. (4) Scanning electron micrographs of a calcined catalyst on high surface area silica support showed smaller-sized decorations around the larger silica particles. Energy-dispersive X-ray analysis of the decorations showed Si as major, and Co as a minor component. Pure Co₃O₄ phases were not found by EDX analyses of these decorations. These four seemingly unrelated findings are attributed to a common cause: silica migration and weak bond formation between CoO and SiO₂. The extent of surface area losses (i.e. the extent of silica migration) is about an order of magnitude greater in CoO_x–SiO₂ catalysts than in analogously treated SiO₂. The migration of silica must have occurred in a relatively short time period during the thermal decomposition of cobalt nitrate, while simultaneous migration and oxidation of CoO to Co₃O₄ aggregates also occurred. The CoO species intercepted by SiO₂ were unable to oxidize, resulting in reduced quantity of Co₃O₄ formation. The extensive migration of silica is attributed to strong attraction between SiO₂ and CoO species, inducing the removal of silicic acid or silica molecules from the silica surface.     

Plasma catalytic methane conversion over sol–gel derived Ru/TiO2 catalyst in a dielectric-barrier discharge reactor

Plasma catalytic methane conversion was carried out in the presence of sol–gel derived Ru/TiO₂ catalysts within a dielectric-barrier discharge (DBD) reactor. Plasma-assisted reduction (PAR) was applied to reduce the prepared Ru/TiO₂ catalysts in DBD reactor, and most of the catalysts were successively reduced by PAR within 15 min. The highest methane conversion was obtained when 5 wt% Ru/TiO₂ catalysts were used after calcination at 400 °C. The selectivities of light alkanes (C₂H₆, C₃H₈, C₄H₁₀) were highly increased when Ru/TiO₂ catalysts were used in DBD reactor.     

Effect of promotion with ruthenium on the structure and catalytic performance of mesoporous silica (smaller and larger pore) supported cobalt Fischer–Tropsch catalysts

The effects of promotion with ruthenium on the structure of cobalt catalysts and their performance in Fischer–Tropsch synthesis were studied using MCM-41 and SBA-15 as catalytic supports. The catalysts were characterized by N₂ physisorption, H₂-temperature programmed reduction, in situ magnetic measurements, X-ray diffraction and X-ray photoelectron spectroscopy. It was found that monometallic cobalt catalysts supported by smaller pore mesoporous silicas (d_p = 3–4 nm) had much lower activity in Fischer–Tropsch synthesis than their larger pore counterparts (d_p = 5–6 nm). Promotion with ruthenium of smaller pore cobalt catalysts led to a considerable increase in Fischer–Tropsch reaction rate, while the effect of the promotion with ruthenium was less significant with the catalysts supported by larger pore silicas.Characterizations of smaller pore cobalt catalysts revealed strong impact of ruthenium promotion on the repartition of cobalt between reducible Co₃O₄ phase and barely reducible amorphous cobalt silicate in the calcined catalyst precursors. Smaller pore monometallic cobalt catalysts showed high fraction of barely reducible cobalt silicate. Promotion with ruthenium led to a significant increase in the fraction of reducible Co₃O₄ and in decrease in the amount of cobalt silicate. In both calcined monometallic and Ru-promoted cobalt catalysts supported by larger pore silicas, easy reducible Co₃O₄ was the dominant phase. Promotion with ruthenium of larger pore catalysts had smaller influence on cobalt dispersion, fraction of reducible cobalt phases and thus on catalytic performance.     

Co-based catalysts from Co/Fe/Al layered double hydroxides for preparation of carbon nanotubes

Carbon nanotubes have been prepared via catalytic chemical vapor deposition of acetylene on a series of catalysts derived from Co/Fe/Al layered double hydroxides (LDHs). The catalytically active cobalt particles were obtained by calcination of LDHs containing cobalt (II) ions followed by reduction. The obtained products were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, high-resolution electron microscopy and Raman spectroscopy. The content of Co in the precursors had a distinct effect on the growth of carbon nanotubes. Increasing Co content enhanced the carbon yield, due to good dispersion of a large number of active Co species. This indicated that the agglomeration of metallic Co particles did not take place even at high Co content. Higher Co content led to the formation of carbon nanotubes with smaller diameters and less structural disorder.     

A study of the influence of the synthesis conditions upon the catalytic properties of Co/SiO2 or Co/Al2O3 catalysts used for ethanol steam reforming

Oxides of cobalt supported on various supports such as SiO₂ and Al₂O₃ have been prepared by using incipient wetness technique (IMP), the sol–gel (SG) route and the combination of the two methods (ISG). The solids formed, after calcination of the corresponding precursors, were characterised by X-ray diffraction, BET area measurements, metal dispersion, and by X-ray photoelectron spectroscopy. Using metal loading of 8%, a high catalytic activity was demonstrated for ethanol steam reforming. Products distribution of the reaction has been found to be dependent on the nature of the support and of the preparation method of the catalysts.     

Comparative Study on Catalytic Performances for Low-temperature CO Oxidation of Cu–Ce–O and Cu–Co–Ce–O Catalysts

Two series of Cu–Ce–O and Cu–Co–Ce–O catalysts were prepared by co-precipitation method. The prepared catalysts were characterized by XRD, IR, TPR, XPS, BET and ICP-AES. The catalytic activities of the catalysts for low-temperature CO oxidation were evaluated through a microreactor-GC system. TPR results indicate that the addition of cobalt to the Cu–Ce–O can increase the dispersion of copper oxide, and the interaction between cobalt and copper can enhance the reducibility of each other. XPS analysis show that Ce⁴⁺, Cu²⁺, along with Co₃O₄, are present on the surface of Cu_0.4Co_0.6Ce₄ catalyst. The Co/Cu atomic ratio and the calcination temperature have significant effect on the activities of the catalysts. Compared with Cu₁Ce₄ catalyst, the Cu_0.4Co_0.6Ce₄ catalyst has better activity and thermal stability.     

Co/TiO2-SiO2催化剂上肉桂醛选择性加氢制备肉桂醇

采用等体积浸渍法制备了系列Co/TiO₂-SiO₂催化剂,用于肉桂醛选择性加氢制备肉桂醇反应体系。系统考察了钴含量、焙烧温度、还原温度、稀土助剂等参数变化对钴催化剂选择性加氢性能的影响。结果表明,钴催化剂的活性和选择性与其表面钴的晶粒度有一定关系,较大尺寸的钴物种对肉桂醛加氢有利。当Co含量为15%、焙烧温度和还原温度均为823 K时,催化剂表现出良好的加氢性能。稀土助剂La和Ce的引入能改善Co /TiO₂-SiO₂催化剂表面活性组分钴的分散度,提高了钴催化剂的加氢性能。     

The influence of precursors on Rh/SBA-15 catalysts for N2O decomposition

Series of Rh/SBA-15 catalysts were prepared by impregnation and grafting method applying different Rh precursors. The catalytic behaviors of N₂O decomposition over these catalysts were tested in an automated eight flow reactor system. The catalysts were characterized by X-ray fluorescence spectroscopy (XRF), X-ray diffraction (XRD), N₂ adsorption/desorption, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) techniques. The results showed that the dispersion of Rh species on the catalysts is closely related to the molecular size and the hydrophobic property of the precursors comparing to the hydrophilic support, better dispersion results were found in catalysts by impregnation of smaller precursors, while by grafting better dispersion resulted from big precursor. On the other hand, the activities of the catalysts match well with the Rh dispersion status. Rh/SBA-15-CDCR starting from [(CO)₂RhCl]₂ showed good dispersion and gave the best N₂O decomposition activity.     

Novel Synthesis Techniques for Preparation of Co/CeO2 as Ethanol Steam Reforming Catalysts

Novel synthesis methods such as solvothermal decomposition, colloidal crystal templating, and reverse microemulsion have been used to prepare CeO₂-supported Co catalysts. These catalysts have shown much better catalytic performance than the catalysts prepared using conventional incipient wetness impregnation for Ethanol Steam Reforming. The improvement can be attributed to a better cobalt dispersion and a better Co–CeO₂ interaction for the catalysts prepared using these novel methods.     

Highly active and selective CoCu/ZnO catalysts prepared by mild oxalic acid co-precipitation method in dimethyl oxalate hydrogenation

Novel CoCu/ZnO catalysts prepared by oxalic acid co-precipitation method have been systematically characterized focusing on the effect of calcination temperature on the structural evolution of the catalysts and the catalytic performance in dimethyl oxalate hydrogenation. The calcination temperature plays an important role in determining the physicochemical features of cobalt species and dispersion of copper species in the CoCu/ZnO catalysts. 100% dimethyl oxalate conversion and 93% selectivity to ethylene glycol could be obtained over the CoCu/ZnO catalyst calcined at 450 °C. High dispersion of Co species interacting with crystalline Cu contributed to the excellent catalytic performance.     

Catalytic Methane Combustion over Co<Subscript>3</Subscript>O<Subscript>4</Subscript>/CeO<Subscript>2</Subscript> Composite Oxides Prepared by Modified Citrate Sol–Gel Method

Abstract  

Co–Ce–O composite oxides with high surface areas were firstly prepared by a modified citrate sol–gel method with N₂ thermal treatment prior to calcination in air. The prepared Co–Ce–O catalysts have higher Brunauer–Emmett–Teller surface areas than those prepared by conventional calcination in air, and thus exhibit more effective catalytic activities. Adding CeO₂ into Co₃O₄ can not only increase the activity of Co₃O₄ but also greatly enhance its thermal stability. When the bulk atomic ratio of Co/Ce is 3/1, Co–Ce–O composite oxide possesses the best activity and stability for the methane combustion.     

Fischer–Tropsch synthesis using Co/SiO2 catalysts prepared from mixed precursors and addition effect of noble metals

Fischer–Tropsch synthesis in Co/SiO₂ catalysts, which were prepared by mixed impregnation of cobalt (II) nitrate and cobalt (II) acetate, was studied under mild reaction conditions (Total pressure=1 MPa, H₂/CO=2, T=513 K). X-ray diffraction indicated that highly dispersed cobalt metal was the main active sites on the catalyst prepared by the same method. It was considered that the metallic crystallines, which were readily reduced from cobalt nitrate, promoted the reduction of Co²⁺ to metallic a state in cobalt acetate by H₂ spillover mechanism during the catalyst reduction process. The reduced cobalt, from cobalt acetate, was highly dispersed one and remarkably enhanced the catalytic activity. The addition of a small amount of Ru to this type of catalyst remarkably increased the catalytic activity and the reduction degree. Its turn over frequency (TOF) increased but the selectivity of CH₄ was unchanged. However, when Pt or Pd were added into catalysts, they exhibited a higher selectivity of CH₄. Although Pt and Pd hardly exerted an effect on cobalt reduction degree, they promoted cobalt dispersion and decreased the value of TOF. Characterization of these bimetallic catalysts suggested that a different contact between Co and Ru, Pt or Pd existed. Ru was enriched on the metallic cobalt surface but, Pt or Pd dispersed well in the form of Pt–Co or Pd–Co alloy.