Role of cobalt on γ-Al2O3 based NO x storage catalyst

Co/Pt/Ba/γ-Al₂O₃, Co/Ba/γ-Al₂O₃, Pt/Ba/γ-Al₂O₃, Co/Pt/γ-Al₂O₃, Ba/γ-Al₂O₃, Pt/γ-Al₂O₃, and Co/γ-Al₂O₃ type catalysts were prepared by a conventional impregnation method, and their NO _x storage capacities were evaluated by colorimetric assay. Co-containing catalysts had a higher NO _x storage capacity than that of Co-free counterparts. The role of each component, especially Co, for the catalysts prepared was investigated by using in-situ FTIR. The high NO _x storage for Co-containing catalysts including Co/Ba/γ-Al₂O₃ and Co/Pt/Ba/γ-Al₂O₃ is mainly due to the formation of Co₃O₄ on the catalyst surface identified by XAFS.     

Deactivation and coke formation on palladium and platinum catalysts in vegetable oil hydrogenation

Deactivation of palladium and platinum catalysts due to coke formation was studied during hydrogenation of methyl esters of sunflower oil. The supported metal catalysts were prepared by impregnating γ-alumina with either palladium or platinum salts, and by impregnating α-alumina with palladium salt. The catalysts were reused for several batch experiments. The Pd/γ-Al₂O₃ catalyst lost more than 50% of its initial activity after four batch experiments, while the other catalysts did not deactivate. Samples of used catalysts were cleaned from remaining oil by repeated extractions with methanol, and the amount of coke formed on the catalysts was studied by temperature-programmed oxidation. The deactivation of the catalyst is a function of both the metal and the support. The amount of coke increased on the Pd/γ-Al₂O₃ catalyst with repeated use, but the amount of coke remained approximately constant for the Pt/γ-Al₂O₃ catalyst. Virtually no coke was detected on the Pd/α-Al₂O₃ catalyst. The formation of coke on Pd/α-Al₂O₃ may be slower than on the Pd/γ-Al₂O₃ owing to the carrier’s smaller surface area and less acidic character. The absence of deactivation for the Pt/γ-Al₂O₃ catalyst may be explained by slower formation of coke precursors on platinum compared to palladium.     

Pt–Ni/γ-Al2O3 catalyst for the preferential CO oxidation in the hydrogen stream

The preferential CO oxidation (PROX) in the presence of excess hydrogen was studied over Pt–Ni/γ-Al₂O₃. CO chemisorption, X-ray diffraction, transmission electron microscopy, energy dispersive X-ray spectroscopy and temperature-programmed reduction were conducted to characterize active catalysts. The co-impregnated Pt–Ni/γ-Al₂O₃ was superior to Pt/Ni/γ-Al₂O₃ and Ni/Pt/γ-Al₂O₃ prepared by a sequential impregnation of each component on alumina support. The PROX activity was affected by the reductive pretreatment condition. The pre-reduction was essential for the low-temperature PROX activity. As the reduction temperature increased above 423 K, the CO₂ selectivity decreased and the atomic percent of Ni in the bimetallic phase of Pt–Ni increased. This catalyst exhibited the high CO conversion even in the presence of 2% H₂O and 20% CO₂ over a wide reaction temperature. The bimetallic phase of Pt–Ni seems to give rise to high catalytic activity for the PROX in H₂-rich stream.     

Role of Support in Lean DeNOx Catalysis

FTIR and pulse thermal analysis were applied to investigate catalysts containing Pt (1 wt%)/Ba (17 wt%) supported on -Al₂O₃, SiO₂ and ZrO₂. The aim was to learn how the support material affects the thermal stability of barium carbonate and its activity in the reaction to bulk Ba(NO₃)₂. The lower thermal stability of BaCO₃ in alumina supported samples was found to influence the formation of barium nitrate during the NO _x storage process. Quantification of Ba(NO₃)₂ formed during NO _x storage indicated that for alumina supported catalysts only ca. 30% of barium present in the sample is involved in the storage process. The low thermal stability found for alumina supported barium nitrite excludes its role in the formation of barium nitrate during interaction of NO _x with the catalyst at 300 °C. The studies indicate that -Al₂O₃ plays a major role in influencing the thermal stability of BaCO₃ and Ba(NO₃)₂. This finding seems to be relevant for the higher activity of -Al₂O₃-supported catalysts in NO _x storage reduction reactions.     

Deterioration Mode of Barium-Containing NOx Storage Catalyst

Barium-containing NO _x storage catalyst showed serious deactivation under thermal exposure at high temperatures. To elucidate the thermal deterioration of the NO _x storage catalyst, four types of model catalyst, Pt/Al₂O₃, Ba/Al₂O₃, Pt–Ba/Al₂O₃, and a physical mixture of Pt/Al₂O₃ + Ba/Al₂O₃ were prepared and their physicochemical properties such as BET, NO TPD, TGA/DSC, XRD, and XPS were evaluated while the thermal aging temperature was increased from 550 to 1050°C. The fresh Pt–Ba/Al₂O₃ showed a sorption capacity of 3.35 wt%/g-cat. but the aged one revealed a reduced capacity of 2.28 wt%/g-cat. corresponding to 68% of the fresh one. It was found that this reduced sorption capacity was directly related to the deterioration of the NO _x storage catalyst by thermal aging. The Ba on Ba/Al₂O₃ and Pt–Ba/Al₂O₃ catalysts began to interact with alumina to form Ba–Al solid alloy above 600°C and then transformed into stable BaAl₂O₄ having a spinel structure. However, no phase transition was observed in the Pt/Al₂O₃ catalyst having no barium component, even after aging at 1050°C.     

Hydrodesulfurization of dibenzothiophene over supported and unsupported molybdenum carbide catalysts

A series of γ-Al₂O₃ supported molybdenum carbides [carbided Mo/γ-Al₂O₃ (MCS), Co-Mo/γ-Al₂O₃ (CMCS), and Ni-Mo/γ-Al₂O₃ (NMCS)] and unsupported molybdenum carbide (MCUS) were prepared by the temperature-programmed carburization of their corresponding molybdenum nitrides with 20 % CH₄/H₂. XRD and SEM studies show that unsupported molybdenum carbide catalyst possesses a typical crystalline Mo₂C (FCC structure), while supported molybdenum carbide catalysts possess highly dispersed surface molybdenum carbide species on an alumina oxide support. The results of dibenzothiophene (DBT) hydrodesulfurization over molybdenum carbide catalysts show that the reactivity is strongly dependent on the type of catalyst. Supported molybdenum carbide catalysts possess a higher reactivity than the unsupported molybdenum carbide catalyst. In addition, Co or Ni promoted, supported molybdenum carbide catalyst possesses a higher reactivity than the unpromoted, supported molybdenum carbide catalyst. The reactivity, which is also dependent on the reaction conditions, increases with increasing reaction temperature and pressure and contact time. The CO uptakes of the molybdenum carbide catalysts correlate well with overall activity (total rate) for DBT hydrodesulfurization. The major reaction product is biphenyl, with cyclohexylbenzene next in abundance regardless of the type of catalysts and reaction conditions. It was also found that the molybdenum carbide catalysts exhibit stable initial reactivity due to the stable and weak acidic characteristics of these catalysts.     

Methane conversion over nanostructured Pt/γAl2O3 catalysts in dielectric-barrier discharge

Spherical nanostructured γ-Al₂O₃ granules were prepared by combining the modified Yoldas process and oil-drop method, followed by the Pt impregnation inside mesopores of the granules by incipient wetness method. Prepared Pt/γ-Al₂O₃ catalysts were reduced by novel method using plasma, which was named plasma assisted reduction (PAR), and then used for methane conversion in dielectric-barrier discharge (DBD). The effect of Pt loading, calcination temperature on methane conversion, and selectivities and yields of products were investigated. Prepared Pt/γ-Al₂O₃ catalysts were successfully reduced by PAR. The main products of methane conversion were the light alkanes such as C₂H₆, C₃H₈ and C₄H₁₀ when the catalytic plasma reaction was carried out with Pt/γ-Al₂O₃ catalyst. Methane conversion was in the range of 38–40% depending on Pt loading and calcination temperature. The highest yield of C₂H₆ was 12.7% with 1 wt% Pt/γ-Al₂O₃ catalysts after calcinations at 500 ‡C.     

Correlating Low-temperature Hydrogenation Activity of Co/Pt(111) Bimetallic Surfaces to Supported Co/Pt/γ-Al2O3 Catalysts

The low-temperature self-hydrogenation (disproportionation) of cyclohexene was used as a probe reaction to correlate the reactivity of Co/Pt(111) bimetallic surfaces with supported Co/Pt/γ-Al₂O₃ catalysts. Temperature-programmed desorption (TPD) experiments show that cyclohexene undergoes self-hydrogenation on the ~1 ML Co/Pt(111) surface at ~219 K, which does not occur on either pure Pt(111) or a thick Co film on Pt(111). Supported catalysts with a 1:1 atomic ratio of Co:Pt were synthesized on a high surface area γ-Al₂O₃ to verify the bimetallic effect on the self-hydrogenation of cyclohexene. EXAFS experiments confirmed the presence of Co–Pt bonds in the catalyst. Using FTIR in a batch reactor configuration, the bimetallic catalyst showed a higher activity toward the self-hydrogenation of cyclohexene at room temperature than either Pt/γ-Al₂O₃ or Co/γ-Al₂O₃ catalysts. The comparison of Co/Pt(111) and Co/Pt/γ-Al₂O₃ provided an excellent example of correlating the self-hydrogenation activity of cyclohexene on bimetallic model surfaces and supported catalysts.     

H2/CO2 separation characteristics of γ-Al2O3 membrane by aging stage in sol-gel process

γ-AlO(OH) sol solution was prepared by aluminum isopropoxide as an initial material. γ-Al₂O₃ membrane on the α-Al₂O₃ support was continuously made through coating and thermal treatment from the α-AlO(OH) sol. Previous work [Yoo et al., 1997] has shown that the aging stage in the sol preparation process mainly affects the characterization of γ-Al₂O₃ particles as well as γ-AlO(OH) sol. Based on this fact, the γ-Al₂O₃ membrane was prepared with two aging conditions in the present study. The separation characteristics experiment of the H₂/CO₂ mixture was performed on these membranes. As a result of the study, the mechanism of gas transport on the two membranes was proved as Knudsen diffusion. The ideal separation factor was reached at the value of the calculated Knudsen separation factor; however, permeability increased and selectivity decreased selectivity according to the aging.     

A planar catalytic combustion sensor using nano-crystalline F-doped SnO2 as a supporting material for hydrogen detection

A planar catlytic combustion gas sensor based on Pd/Pt catalyst supported on F-doped SnO₂ nano-crystalline materials has been designed and fabricated for hydrogen detection. The sensor consists of platinum heaters on an alumina plate coated with a catalytic layer and compensating layer. This sensor exhibited better performance than that of the sensors employing sensing material of Pd/Pt catalyst on γ-Al₂O₃ and of Pd/Pt catalyst on nano-crystalline SnO₂. The detection limit of the sensor at 370 °C is in the concentration range of 0.5–5% (v/v), with an excellent linearity of signal voltage to the hydrogen gas concentration.     

Effect of Ba Addition on Catalytic Activity of Pt and Rh Catalysts Loaded on γ-Alumina

The catalytic activity of Pt catalyst loaded on -alumina was improved by Ba addition in simulated automotive exhaust gases. On the other hand, the result of Rh catalyst was the opposite. From the results of the partial reaction orders in C₃H₆–O₂ reaction and TPR, it was concluded that the Ba addition to Pt catalyst suppressed the hydrocarbon chemisorption on the Pt catalyst and therefore allowed the catalytic reaction to proceed smoothly. On the other hand, Ba addition to Rh catalyst caused such a strong oxygen adsorption on Rh that rejected the hydrocarbon adsorption and suppressed the reaction.     

Partial oxidation of methane over nickel catalysts supported on various aluminas

Partial oxidation of methane (POM) was systematically investigated in a fixed bed reactor over 12 wt% Ni catalysts supported on α-A1₂O₃, γ-A1₂O₃ and θ-A1₂O₃ which were prepared at different conditions. Results indicate that the catalytic activity toward POM strongly depends on the BET surface area of the support. All the Ni/ θ-Al₂O₃ catalysts showed high activity toward POM due to the less formation of inactive NiAl₂O₄ species, the existence of NiO, species and stable θ-Al₂O₃ phase. Although Ni/γ-Al₂O₃ showed the highest activity toward POM, long-time stability cannot be expected as a result of the deterioration of the support at higher temperature, which is revealed from BET results. From the reaction and characterization results, it is inferred that the optimal conditions for the preparation of θ-Al₂O₃ are 1,173 K and 12 h.     

Vapour phase dehydrogenation of cyclohexanol over alumina-supported Pt-Co bimetallic catalysts

Pt/γ- Al₂O₃, Co/γ- Al₂O₃ and Pt- Co/γ- Al₂O₃ with different Pt : Co atomic ratios have been prepared with a total metal content of 10 wt% and characterised by hydrogen chemisorption. The activities of the prereduced catalysts were studied for the reaction of cyclohexanol at 523 K and WHSV of 4.82 and 7.7 h^-1. The Pt-Co/γ-Al₂O₃ catalyst with 1 : 1 Pt : Co atomic ratio shows typical high metal dispersion and cyclohexanone selectivity. This revised version was published online in July 2006 with corrections to the Cover Date.     

Transesterification of Rapeseed Oil for Synthesizing Biodiesel by K/KOH/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> as Heterogeneous Base Catalyst

The heterogeneous base catalyst, γ-Al₂O₃ loaded with KOH and K (K/KOH/γ-Al₂O₃) was first prepared and used in the transesterification of rapeseed oil with methanol to produce biodiesel. The prepared catalyst was characterized by X-ray diffraction, scanning electron microscopy, Brunauer–Emmett–Teller method, infrared spectroscopy and X-ray photoelectron spectroscopy. It was found that when γ-Al₂O₃ is loaded with KOH and K, the Al–O–K species is produced, resulting in an increase in the catalytic activity. The impacts of catalyst preparation conditions on the catalytic activities of K/KOH/γ-Al₂O₃ were investigated. The results demonstrate that the catalyst K/KOH/γ-Al₂O₃ has high catalytic activity when the added amounts of KOH and K are 20 and 7.5 wt% respectively. The transesterification of rapeseed oil to biodiesel with the prepared heterogeneous base catalyst was optimized. It was found that the yield of biodiesel can reach as high as 84.52% after 1 h reaction at 60°C, with a 9:1 molar ratio of methanol to oil, a catalyst amount of 4 wt%, and a stirring rate of 270 g.     

Operando X-ray Absorption Spectroscopy Study of Pt/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> During the Total Oxidation of C<Subscript>3</Subscript>H<Subscript>6</Subscript>

Operando X-ray absorption fine structure (XAFS) investigations were performed on Pt/γ-Al₂O₃ during the total oxidation of C₃H₆ in reducing and oxidizing atmospheres. Study of the Pt valance state and catalytic conversion behavior as a function of temperature revealed that both the creation of metallic Pt sites and the activation of adsorbed species on Pt are important for the functioning of the catalytic reaction at low temperature.     

The functionalities of Pt/γ-Al2O3 catalysts in simultaneous HDS and HDA reactions

A Pt/γ-Al₂O₃ catalyst was tested in simultaneous hydrodesulfurization (HDS) of dibenzothiophene and hydrodearomatization (HDA) of naphthalene reactions. Samples of it were subjected to different pretreatments: reduction, reduction–sulfidation, sulfidation with pure H₂S and non-activation. The reduced catalyst presented the best performance, even comparable to that of Co(Ni)Mo catalysts. All catalyst samples were selective to the HDS reaction over HDA, and to the direct desulfurization pathway of dibenzothiophene HDS over the hydrogenation reaction pathway of HDS. The effect of H₂S partial pressure on the functionalities of the reduced Pt/γ-Al₂O₃ catalyst was studied. The results showed that an increase in H₂S partial pressure does not cause poisoning, but an inhibition effect, without changing the catalyst selectivity. Accordingly, the activity trends were ascribed to adsorption differences between the different reactive molecules over the same catalytic active site. TPR characterization along with a thermodynamics analysis showed that the active phase of reduced Pt/γ-Al₂O₃ is constituted by Pt⁰ particles. However, presulfidation of the catalyst leads to a mixture of PtS and Pt⁰ which has a negative effect on the catalytic performance without changing catalyst functionalities.     

XPS evidence for molybdenum nitride formation in ZSM-5

Microwave plasma-assisted catalytic reduction of SO₂ by CO was studied over four catalysts. The activities of the four catalysts under microwave plasma decreased in the order of CoO/γ-Al₂O₃>>SnO₂> copper wires > iron wires, which was consistent with the results under conventional heating. By comparing the activity of CoO/γ-Al₂O₃ catalyst in the microwave plasma mode with that in the conventional mode, it is demonstrated that the temperature at which the full SO₂ conversion was obtained in the microwave plasma mode was about 200 °C lower than that under the conventional heating mode. Moreover, an increase of space velocity had little effect on SO₂ conversion and sulfur selectivity under microwave plasma; while under conventional heating mode, both SO₂ conversion and sulfur selectivity significantly decreased with an increase of space velocity.     

Hydrogen production by steam reforming of LNG over Ni/Al2O3-ZrO2 catalysts: Effect of ZrO2 and preparation method of Al2O3-ZrO2

An Al₂O₃-ZrO₂ support was prepared by grafting a zirconium precursor onto the surface of commercial γ-Al₂O₃. A physical mixture of Al₂O₃-ZrO₂ was also prepared for the purpose of comparison. Ni/Al₂O₃-ZrO₂ catalysts were then prepared by an impregnation method, and were applied to the hydrogen production by steam reforming of liquefied natural gas (LNG). The effect ZrO₂ and preparation method of Al₂O₃-ZrO₂ on the performance of supported nickel catalysts in the steam reforming of LNG was investigated. The Al₂O₃-ZrO₂ prepared by a grafting method was more efficient as a support for nickel catalyst than the physical mixture of Al₂O₃-ZrO₂ in the hydrogen production by steam reforming of LNG. The well-developed tetragonal phase of ZrO₂ and the high dispersion of ZrO₂ on the surface of γ-Al₂O₃ were responsible for the enhanced catalytic performance of Ni/Al₂O₃-ZrO₂ prepared by way of a grafting method.     

Reduction of NO by H2 and CO on PdO-MoO3/γ-Al2O3 of low molybdena loading

The activity and selectivity in the catalytic reduction of NO by a mixture of CO and H₂ of three PdO-MoO₃/-Al₂O₃ catalysts are compared in the presence of varying amounts of oxygen at reaction temperatures from 100 to 550°C. The catalysts were prepared by different methods and contain about 2% Mo and 2% Pd. Results are compared with those for PdO/-Al₂O₃, PdO-MoO₃/-Al₂O₃ containing 2% Pd and 20% Mo, and a commercial Pt-Rh catalyst. The PdO-MoO₃/-Al₂O₃ catalysts are more active for the selective reduction of NO to N₂ and N₂O than PdO/-Al₂O₃ under slightly oxidizing conditions at temperatures from 300 to 550°C. At these reaction conditions, the fresh PdO-MoO₃/-Al₂O₃ catalysts are comparable with a commercial Pt-Rh catalyst. The improved activity of PdO-MoO₃/-Al₂O₃ relative to PdO/-Al₂O₃ is believed to be due to the interaction between Pd and Mo. The effect of O₂ on the activity and selectivity of these catalysts is different in the reduction of NO by H₂, by CO, and by a mixture of H₂ and CO. The results using the mixture of reductants cannot be inferred from the results with the single reductants.     

Characterization of supported Pd-Cu bimetallic catalysts by SEM, EDXS, AES and catalytic selectivity measurements

Pd-Cu/γ-Al₂O₃ bimetallic catalysts were prepared according to different impregnation sequences of γ-Al₂O₃ and characterized by XRD, SEM, EDXS and AES. The catalysts were tested for the selective hydrogenation of aqueous nitrate solutions to nitrogen. The reaction selectivity was found to be dependent on the catalyst preparation procedures, which affect the spatial distribution of metallic copper and palladium phases. A catalyst prepared by impregnating γ -Al₂O₃ with copper followed by palladium gives higher selectivity to nitrogen than a catalyst prepared by impregnating the support with palladium followed by copper. The AES examination shows that in the catalyst exhibiting a higher nitrogen production yield, a reaction zone for the liquid-phase nitrate reduction is located in the interior of particles and covered by a layer of Pd atoms. This revised version was published online in July 2006 with corrections to the Cover Date.