Ce1−xCuxO2−x/Al2O3/FeCrAl catalysts for catalytic combustion of methane

A series of the Ce_1−xCu_xO_2−x/Al₂O₃/FeCrAl catalysts (x = 0–1) were prepared. The structure of the catalysts was characterized using XRD, SEM and H₂-TPR. The catalytic activity of the catalysts for the combustion of methane was evaluated. The results indicated that in the Ce_1−xCu_xO_2−x/Al₂O₃/FeCrAl catalysts the surface phase structure were the Ce_1−xCu_xO_2−x solid solution, -Al₂O₃ and γ-Al₂O₃. The surface particle shape and size were different with the variety of the molar ratio of Ce to Cu in the Ce_1−xCu_xO_2−x solid solution. The Cu component of the Ce_1−xCu_xO_2−x/Al₂O₃/FeCrAl catalysts played an important role to the catalytic activity for the methane combustion. There were the stronger interaction among the Ce_1−xCu_xO_2−x solid solution and the Al₂O₃ washcoats and the FeCrAl support.     

Superior performance of Ir-substituted hexaaluminate catalysts for N2O decomposition

Novel Ir-substituted hexaaluminate catalysts were developed for the first time and used for catalytic decomposition of high concentration of N₂O. The catalysts were prepared by one-pot precipitation and characterized by X-ray diffraction (XRD), N₂-adsorption, scanning electronic microscopy (SEM) and temperature-programmed reduction (H₂-TPR). The XRD results showed that only a limited amount of iridium was incorporated into the hexaaluminate lattice by substituting Al³⁺ to form BaIr_xFe_1−xAl₁₁O₁₉ after being calcined at 1200 °C, while the other part of iridium existed as IrO₂ phase. The activity tests for high concentration (30%, v/v) of N₂O decomposition demonstrated that the BaIr_xFe_1−xAl₁₁O₁₉ hexaaluminates exhibited much higher activities and stabilities than the Ir/Al₂O₃-1200, and the pre-reduction with H₂ was essential for activating the catalysts. By comparing BaIr_xFe_1−xAl₁₁O₁₉ with BaIr_xAl_12−xO₁₉ (x = 0–0.8), it was found that iridium was the active component in the N₂O decomposition and the framework iridium was more active than the large IrO₂ particles. On the other hand, Fe facilitated the formation of hexaaluminate as well as the incorporation of iridium into the framework.     

Generating hydrogen-rich fuel-cell feeds from dimethyl ether (DME) using physical mixtures of a commercial Cu/Zn/Al2O3 catalyst and several solid–acid catalysts

Homogeneous physical mixtures containing a commercial Cu/ZnO/Al₂O₃ catalyst and a solid–acid catalyst were used to examine the acidity effects on dimethyl ether hydrolysis and their subsequent effects on dimethyl ether steam reforming (DME-SR). The acid catalysts used were zeolites Y [Si/Al = 2.5 and 15: denoted Y(Si/Al)], ZSM-5 [Si/Al = 15, 25, 40, and 140: denoted Z(Si/Al)] and other conventional catalyst supports (ZrO₂, and γ-Al₂O₃). The homogeneous physical mixtures contained equal amounts, by volume, of the solid–acid catalyst and the commercial Cu/ZnO/Al₂O₃ catalyst (BASF K3-110, denoted as K3). The steam reforming of dimethyl ether was carried out in an isothermal packed-bed reactor at ambient pressure.

The most promising physical mixtures for the low-temperature production of hydrogen from DME contained ZSM-5 as the solid–acid catalyst, with hydrogen yields exceeding 90% (T = 275 °C, S/C = 1.5, τ = 1.0 s and P = 0.78 atm) and hydrogen selectivities exceeding 94%, comparable to those observed for methanol steam reforming (MeOH-SR) over BASF K3-110, with values equaling 95% and 99%, respectively (T = 225 °C, S/C = 1.0, τ = 1.0 s and P = 0.78 atm). Large production rates of hydrogen were directly related to the type of acid catalyst used. The hydrogen production activity trend as a function of physical mixture was

     

NO reduction by CH4 in the presence of O2 over La2O3 supported on Al2O3

Dispersing La₂O₃ on δ- or γ-Al₂O₃ significantly enhances the rate of NO reduction by CH₄ in 1% O₂, compared to unsupported La₂O₃. Typically, no bend-over in activity occurs between 500° and 700°C, and the rate at 700°C is 60% higher than that with a Co/ZSM-5 catalyst. The final activity was dependent upon the La₂O₃ precursor used, the pretreatment, and the La₂O₃ loading. The most active family of catalysts consisted of La₂O₃ on γ-Al₂O₃ prepared with lanthanum acetate and calcined at 750°C for 10 h. A maximum in rate (mol/s/g) and specific activity (mol/s/m²) occurred between the addition of one and two theoretical monolayers of La₂O₃ on the γ-Al₂O₃ surface. The best catalyst, 40% La₂O₃/γ-Al₂O₃, had a turnover frequency at 700°C of 0.05 s⁻¹, based on NO chemisorption at 25°C, which was 15 times higher than that for Co/ZSM-5. These La₂O₃/Al₂O₃ catalysts exhibited stable activity under high conversion conditions as well as high CH₄ selectivity (CH₄ + NO vs. CH₄ + O₂). The addition of Sr to a 20% La₂O₃/γ-Al₂O₃ sample increased activity, and a maximum rate enhancement of 45% was obtained at a SrO loading of 5%. In contrast, addition of SO⁼₄ to the latter Sr-promoted La₂O₃/Al₂O₃ catalyst decreased activity although sulfate increased the activity of Sr-promoted La₂O₃. Dispersing La₂O₃ on SiO₂ produced catalysts with extremely low specific activities, and rates were even lower than with pure La₂O₃. This is presumably due to water sensitivity and silicate formation. The La₂O₃/Al₂O₃ catalysts are anticipated to show sufficient hydrothermal stability to allow their use in certain high-temperature applications.     

The homogeneity range and the microwave dielectric properties of the BaZn2Ti4O11 ceramics

Ceramics with a composition close to BaZn₂Ti₄O₁₁ were synthesized according to various substitutional mechanisms in order to verify an existence of a homogeneity range in the vicinity of this composition. Structural and microstructural investigations showed that the crystal structure of BaZn₂Ti₄O₁₁ was formed in the homogeneity range corresponding to the formula BaZn_2 − xTi₄O_11 − x (0 < x < 0.1). Densely sintered BaZn_2 − xTi₄O_11 − x (0 < x < 0.1) ceramics exhibited a dielectric constant around 30, τ_f = −30 ppm/K and high Q × f values, which increased from 68,000 GHz at x = 0 to 83,000 GHz at x = 0.05. Structurally, the deficiency of Zn in BaZn_2 − xTi₄O_11 − x (0 < x < 0.1) resulted in a slight decrease in the unit-cell volume. The influence of secondary phases in the BaZn₂Ti₄O₁₁-based materials on the microwave dielectric properties was also investigated. A presence of small amounts of ZnO, BaTiO₃, hollandite-type solid solutions (Ba_xZn_xTi_8 − xO₁₆) and BaTi₄O₉ caused a decrease in Q × f values.     

Lean reduction of NO by C3H6 over Ag/alumina derived from Al2O3, AlOOH and Al(OH)3

The effectiveness of Ag/Al₂O₃ catalyst depends greatly on the alumina source used for preparation. A series of alumina-supported catalysts derived from AlOOH, Al₂O₃, and Al(OH)₃ was studied by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet–visible (UV–vis) spectroscopy, diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, O₂, NO + O₂-temperature programmed desorption (TPD), H₂-temperature programmed reduction (TPR), thermal gravimetric analysis (TGA) and activity test, with a focus on the correlation between their redox properties and catalytic behavior towards C₃H₆-selective catalytic reduction (SCR) of NO reaction. The best SCR activity along with a moderated C₃H₆ conversion was achieved over Ag/Al₂O₃ (I) employing AlOOH source. The high density of Ag–O–Al species in Ag/Al₂O₃ (I) is deemed to be crucial for NO selective reduction into N₂. By contrast, a high C₃H₆ conversion simultaneously with a moderate N₂ yield was observed over Ag/Al₂O₃ (II) prepared from a γ-Al₂O₃ source. The larger particles of Ag_mO (m > 2) crystallites were believed to facilitate the propene oxidation therefore leading to a scarcity of reductant for SCR of NO. An amorphous Ag/Al₂O₃ (III) was obtained via employing a Al(OH)₃ source and 500 °C calcination exhibiting a poor SCR performance similar to that for Ag-free Al₂O₃ (I). A subsequent calcination of Ag/Al₂O₃ (III) at 800 °C led to the generation of Ag/Al₂O₃ (IV) catalyst yielding a significant enhancement in both N₂ yield and C₃H₆ conversion, which was attributed to the appearance of γ-phase structure and an increase in surface area. Further thermo treatment at 950 °C for the preparation of Ag/Al₂O₃ (V) accelerated the sintering of Ag clusters resulting in a severe unselective combustion, which competes with SCR of NO reaction. In view of the transient studies, the redox properties of the prepared catalysts were investigated showing an oxidation capability of Ag/Al₂O₃ (II and V) > Ag/Al₂O₃ (IV) > Ag/Al₂O₃ (I) > Ag/Al₂O₃ (III) and Al₂O₃ (I). The formation of nitrate species is an important step for the deNO_x process, which can be promoted by increasing O₂ feed concentration as evidenced by NO + O₂-TPD study for Ag/Al₂O₃ (I), achieving a better catalytic performance.     

Effect of glass additions on the sintering and microwave properties of composite dielectric ceramics based on BaO–Ln2O3–TiO2 (Ln = Nd, La)

Ten weight percent BBZS (Bi₂O₃, B₂O₃, ZnO and SiO₂) glass was added to x(Ba₄Nd_9.333Ti₁₈O₅₄) − (1 − x)(BaLa₄Ti₄O₁₅) (BNLT, 0 ≤ x ≤ 1) composite dielectric ceramics to lower their sintering temperature whilst retaining microwave properties useful for low temperature co-fired ceramic and antenna core technology. With the addition of 10 wt% BBZS glass, dense BNLT composite ceramics were produced at temperatures between 950 and 1140 °C, depending on composition (x), an average reduction of sintering temperature by 350 °C. X-ray diffraction, scanning and transmission electron microscopy and Raman spectroscopy studies revealed that there was limited inter-reaction between BLT/BNT and the BBZS glass. Microwave property measurement showed that the addition of BBZS glass to BNLT ceramics had a negligible effect on _r and τ_f, although deterioration in the measured quality factor (Qf) was observed. The optimised composition (xBNT − (1 − x)BLT)/0.1BBZS (x = 0.75) had _r  61, τ_f  38 ppm/°C and Qf  2305 GHz.     

Origin of transient species present on the surface of a PdO/γ-Al2O3 catalyst during the methane combustion reaction

Operando DRIFTS was applied to the study of the evolution of surface species formed on a Pd (2 wt.%)/γ-Al₂O₃ catalyst in various conditions. No differences were observed as a function of the initial oxidation state of palladium. Formates/carbonates species were identified at low temperature (<400 °C) and disappeared when CO₂ production started. These species come from the Pd-catalyzed interaction of CO with the alumina support, while CO₂ induces hydrogenocarbonates formation at low temperature (<300 °C). Their presence does not explain the inhibiting effect of CO₂ observed in CCM on Pd/γ-Al₂O₃ catalysts.     

Synthesis, characterization and catalytic activity for NO–CO reaction of Pd–(La, Sr)2MnO4 system

La_xSr_2−xMnO₄ (0 ≤ x ≤ 0.8) oxides were synthesized and single-phase K₂NiF₄-type oxides were obtained in the range of 0.1 ≤ x < 0.5. The catalytic activity of La_xSr_2−xMnO₄ for NO–CO reaction increased with increasing x in the range of solubility limit of La. La_0.5Sr_1.5MnO₄ showed the highest activity among La_xSr_2−xMnO₄ prepared in this study, but its activity was inferior to perovskite-type La_0.5Sr_0.5MnO₃. Among the Pd-loaded catalysts, however, Pd/La_0.8Sr_1.2MnO₄ showed the higher activity and the selectivity to N₂ than Pd/La_0.5Sr_0.5MnO₃ and Pd/γ-Al₂O₃. The excellent catalytic performance of Pd/La_0.2Sr_1.2MnO₄ could be ascribable to the formation of SrPd₃O₄ which was detected by XRD in the catalyst but not in the other two catalysts.     

η-Al2O3与γ-Al2O3在CS2催化水解反应中的性能比较

通过制备高纯度的前驱体湃铝石获得了η-Al₂O₃材料,采用XRD验证了η-Al₂O₃与γ-Al₂O₃在晶相结构上的差异,比较了两者的表面形貌、织构及酸碱性能,结果显示,η-Al₂O₃与γ-Al₂O₃的比表面积相当,但η-Al₂O₃具有更弱的弱碱位和较少的强碱位,并拥有丰富的中等强度酸性位。将η-Al₂O₃与γ-Al₂O₃作为催化剂应用于CS₂水解反应,结果表明,在(200~450) ℃测试温度范围内,η-Al₂O₃催化剂对CS₂的水解活性始终优于γ-Al₂O₃,两种催化剂上CS₂反应的浓度效应也明显不同,推测与它们的酸碱性质影响了对CS₂的吸附能力有关,导致两者催化CS₂水解反应遵循了不同的机制。     

Development of new catalysts for N2O-decomposition from adipic acid plant

Direct decomposition of N₂O was investigated using simulated and real industrial gas stream coming from an adipic acid plant. Two different kinds of catalysts were studied: (i) LaB_1−xB′_xO₃ and CaB_1−xCu_xO₃ (B = Mn, Fe and B′ = Cu, Ni) perovskites (PVKs) and (ii) supported PVKs (10 or 20 wt.%) on γ-Al₂O₃ and CeO₂–ZrO₂. The structural modifications induced by the composition of PVK samples affect the catalytic performances: mixed oxide formation in CaMn_0.7Cu_0.3O₃ samples allows to reach the highest values of N₂O conversion while the effect of PVK phases is more controversial. The importance of copper on catalytic activities is confirmed by the investigation on CaMn_1−xCu_xO₃ samples. The best results were obtained with a CaMn_0.6Cu_0.4O₃ catalyst calcined at 700 °C for 5 h, in which the presence of copper maximises the Ca₃CuMnO₆ phase formation. The increase in Cu-content produces a large segregation of CuO despite PVK formation. The best catalyst was tested using industrial gas stream, showing good stability also in the presence of H₂O and O₂ (8% v/v ) after 1400 h on-stream. To increase surface area, Cu-containing PVKs were deposed on γ-Al₂O₃ and CeO₂–ZrO₂, and this latter has been recognised as the best support. Indeed, the activity of the PVKs supported on ceria–zirconia is comparable to and even better than that of the bulk catalysts. A possible explanation regards the support contribution in terms of activity and/or promotion of O₂ mobility which enhances the overall activity of the catalyst.     

Sintering behavior and microwave dielectric properties of Bi2O3–ZnO–Nb2O5-based ceramics sintered under air and N2 atmosphere

The sintering behavior and dielectric properties of the monoclinic zirconolite-like structure compound Bi₂(Zn_1/3Nb_2/3)₂O₇ (BZN) and Bi₂(Zn_1/3Nb_2/3−xV_x)₂O₇ (BZNV, x = 0.001) sintered under air and N₂ atmosphere were investigated. The pure phase were obtained between 810 and 990 °C both for BZN and BZNV ceramics. The substitution of V₂O₅ and N₂ atmosphere accelerated the densification of ceramics slightly. The influences on microwave dielectric properties from different atmosphere were discussed in this work. The best microwave properties of BZN ceramics were obtained at 900 °C under N₂ atmosphere with _r = 76.1, Q = 850 and Q_f = 3260 GHz while the best properties of BZNV ceramics were got at 930 °C under air atmosphere with _r = 76.7, Q = 890 and Q_f = 3580 GHz. The temperature coefficient of resonant frequency τ_f was not obviously influenced by the different atmospheres. For BZN ceramics the τ_f was −79.8 ppm/°C while τ_f is −87.5 ppm/°C for BZNV ceramics.     

Quantification of the in situ DRIFT spectra of Pt/K/γ-A12O3 NOx adsorber catalysts

A method to quantify DRIFT spectral features associated with the in situ adsorption of gases on a NO_x adsorber catalyst, Pt/K/Al₂O₃, is described. To implement this method, the multicomponent catalyst is analysed with DRIFT and chemisorption to determine that under operating conditions the surface comprised a Pt phase, a pure γ-Al₂O₃ phase with associated hydroxyl groups at the surface, and an alkalized-Al₂O₃ phase where the surface –OH groups are replaced by –OK groups. Both DRIFTS and chemisorption experiments show that 93–97% of the potassium exists in this form. The phases have a fractional surface area of 1.1% for the 1.7 nm-sized Pt, 34% for pure Al₂O₃ and 65% for the alkalized-Al₂O₃. NO₂ and CO₂ chemisorption at 250 °C is implemented to determine the saturation uptake value, which is observed with DRIFTS at 250 °C. Pt/Al₂O₃ adsorbs 0.087 μmol CO₂/m²and 2.0 μmol NO₂/m², and Pt/K/Al₂O₃ adsorbs 2.0 μmol CO₂/m²and 6.4 μmol NO₂/m². This method can be implemented to quantitatively monitor the formation of carboxylates and nitrates on Pt/K/Al₂O₃ during both lean and rich periods of the NO_x adsorber catalyst cycle.     

Processing of hot pressed Al2O3–Cr2O3/Cr-carbide nanocomposite prepared by MOCVD in fluidized bed

Nanosized particles dispersed uniformly on Al₂O₃ particles were prepared from the decomposition of precursor Cr(CO)₆ by metal organic chemical vapor deposition (MOCVD) in a fluidized chamber. These nanosized particles consisted of Cr₂O₃, CrC_1−x, and C. A solid solution of Al₂O₃–Cr₂O₃ and an Al₂O₃–Cr₂O₃/Cr₃C₂ nanocomposite were formed when these fluidized powders were pre-sintered at 1000 and 1150 °C before hot-pressing at 1400 °C, respectively. In addition, an Al₂O₃–Cr₂O₃/Cr-carbide (Cr₃C₂ and Cr₇C₃) nanocomposite was formed when the particles were directly hot pressed at 1400 °C. The interface between Cr₃C₂ and Al₂O₃ is non-coherent, while the interface between Cr₇C₃ and Al₂O₃ is semi-coherent.     

Effects of alumina incorporation in coprecipitated NiO–Al2O3 catalysts

The effect of Al₂O₃ levels on the properties of NiO in coprecipitated NiO–Al₂O₃ samples were investigated, using samples with up to 60.7 wt.% Al₂O₃ that had been calcined in the range 300–700°C. Characterization techniques included BET surface area of fresh and reduced catalysts, X-ray diffraction analysis of structure and crystallite size, magnetic susceptibility measurements, oxidizing power, and reducibility in H₂. Only NiO was detected in samples with up to 4.1 wt.% Al₂O₃ for all sample calcination temperatures. Surface areas were similar for all fresh samples but decreased rapidly after calcination at high temperatures. The surface area loss was less for the higher Al₂O₃-containing samples. Nickel oxide crystallite sizes increased at higher calcination temperatures, but remained approximately the same for each Al₂O₃ level.

The NiO was nonstoichiometric (NiO_1+x), with x decreasing at higher calcination temperatures and increasing with small amounts of added Al₂O₃ through a maximum at about 3 wt.% Al₂O₃. However, this did not correlate well with microstrain in the NiO crystallites nor with reducibility, which decreased with Al₂O₃ addition. At higher levels of Al₂O₃ (13.6 wt.% and above), surface areas increased with higher Al₂O₃ loadings, but NiO crystallite sizes remained approximately the same, independent of both Al₂O₃ content and calcination temperature. X-ray diffraction patterns were very diffuse, and it was not possible to rule out the presence of pseudo-spinel combinations of NiO and Al₂O₃. Reducibility was more difficult than with low Al₂O₃ levels, and nonstoichiometry was low and independent of Al₂O₃ content.

Reducibilities of all samples calcined at 300°C correlated well with the final BET surface area of the reduced samples, indicating that more dispersed NiO crystallites are more difficult to reduce, a conclusion that supports a model for reduction proposed previously.     

Preparation and structural characterization of Co/Al2O3 catalysts for the ozonation of pyruvic acid

A series of Co/Al₂O₃ catalysts were prepared by the incipient wetness impregnation method using γ-Al₂O₃ support and (CH₃COO)₂Co·4H₂O solutions, followed by calcination at 500–800 °C. Characterization of catalysts was accomplished by several techniques such as thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), physisorption of nitrogen, mercury and helium-based pycnometries, Fourier transform-infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and pH of zero charge (PZC). Impregnation of support produced a moderate decrease of its surface area and pore volume and also led to minor changes of its PZC. Depending on preparation conditions (i.e., calcination atmosphere and temperature and metal loading), one or more of the following Co-containing compounds were identified: CoO, Co₃O₄ and CoAl₂O₄. The support and prepared Co/Al₂O₃ catalysts were tested to catalyze the ozonation of aqueous pyruvic acid at pH 2.5. Pyruvic acid was shown refractory towards single ozonation but the use of γ-Al₂O₃ and Co/Al₂O₃ catalysts resulted in 56–96% pyruvic acid conversion and 41–78% decrease in DOC after 2 h of ozonation of phosphate-buffered solutions. In the absence of the buffer, conversion rate was enhanced likely as a result of pH increase during the course of the process thus giving rise to the indirect way of ozonation through hydroxyl radicals. Acetic acid was found as the main by-product of pyruvic acid ozonation. Depending on the catalyst used, yield of acetic acid varied from 32 to 49%, values noticeably lower that that obtained from the control non-catalytic ozonation experiment (73%). Differences in catalytic activity amongst the various Co/Al₂O₃ catalysts investigated were attributed to the different Co active phases deposited on the γ-Al₂O₃ surface. The following sequence of increasing activity can be inferred from experimental results: CoO, CoAl₂O₄ and Co₃O₄. All the Co/Al₂O₃ catalysts prepared showed good stability as the percentage of cobalt leached out was rather low.     

Effect of the order of potassium introduction on the texture and activity of Mo/Al2O3 catalysts in water gas shift reaction

The effect of deposition and order of potassium introduction on the texture and activity of Mo/γ-Al₂O₃ catalysts in water gas shift (WGS) reaction was investigated. The samples were synthesised by incipient wetness impregnation of the carrier with aqueous solutions of the corresponding salts followed by drying and calcination after each deposition step. The prepared catalyst precursors were sulphided at 400°C for 2 h with 6% H₂S in H₂ before testing in WGS reaction in a glass flow apparatus at 400°C under atmospheric pressure.

The results show that potassium deposition alone on the bare γ-Al₂O₃ (sample K/Al₂O₃) decreases the specific surface after calcination by blocking the constrictions between the pores in the primary porous texture. In the WGS reaction conditions part of the pores are deblocked and a redistribution in the pore volumes occurs.

The deposition of the Mo (sample Mo/Al₂O₃) also results in a decrease in both specific surface and total pore volume with respect to the bare support. However after catalytic activity test no substantial changes in its texture were observed.

The addition of K to the Mo (sample KMo/Al₂O₃) leads to nonuniformity in distribution of molybdenum–oxygen entities due to partial migration of the MoO_x species to the external surface. The specific surface is not changed during the reaction test.

The deposition of Mo on K/Al₂O₃ contributes to the uniform distribution of oxomolybdenum species in the porous texture of the support. This uniformity is preserved to a high extent in the catalytic reaction as well. The activity in the synthesised samples in the WGS reaction decreases in the order MoK/Al₂O₃ > Mo/Al₂O₃ > KMo/Al₂O₃.     

Methane combustion over supported palladium catalysts I. Reactivity and active phase

The performance of Al₂O₃, ZrO₂ and ZrO₂ stabilized with SiO₂ (ZrO₂-s) supported palladium catalysts for the methane combustion was studied between 473 and 873 K. The nature of the surface species of palladium catalysts under reaction conditions were detected by FT-IR and microcalorimetry of CO adsorbed. The different behavior of palladium catalysts under reaction conditions is attributed to support effects associated to differences in thermal conductivity and oxygen mobility of supports. Prereduction of the catalysts enhances their activity. Under reaction conditions, the prereduced sample becomes partially oxidized by preferential adsorption/reaction of oxygen both on Pd (1 1 1) planes and on the sites that can multibondedly adsorb CO. The reconstruction of the metallic particles and the formation of PdO_x (0<x≤1) phase were directly observed by FT-IR and microcalorimetry of adsorbed CO. Combination of different characterization techniques with reaction results suggests that a mixed phase, Pd⁰/PdO_x, is the most active phase for methane combustion, and that a redox mechanism may occur on this phase.     

Quantified NOx adsorption on Pt/K/gamma-Al2O3 and the effects of CO2 and H2O

A multi-component NO_x-trap catalyst consisting of Pt and K supported on γ-Al₂O₃ was studied at 250 °C to determine the roles of the individual catalyst components, to identify the adsorbing species during the lean capture cycle, and to assess the effects of H₂O and CO₂ on NO_x storage. The Al₂O₃ support was shown to have NO_x trapping capability with and without Pt present (at 250 °C Pt/Al₂O₃ adsorbs 2.3 μmols NO_x/m²). NO_x is primarily trapped on Al₂O₃ in the form of nitrates with monodentate, chelating and bridged forms apparent in Diffuse Reflectance mid-Infrared Fourier Transform Spectroscopy (DRIFTS) analysis. The addition of K to the catalyst increases the adsorption capacity to 6.2 μmols NO_x/m², and the primary storage form on K is a free nitrate ion. Quantitative DRIFTS analysis shows that 12% of the nitrates on a Pt/K/Al₂O₃ catalyst are coordinated on the Al₂O₃ support at saturation.

When 5% CO₂ was included in a feed stream with 300 ppm NO and 12% O₂, the amount of K-based nitrate storage decreased by 45% after 1 h on stream due to the competition of adsorbed free nitrates with carboxylates for adsorption sites. When 5% H₂O was included in a feed stream with 300 ppm NO and 12% O₂, the amount of K-based nitrate storage decreased by only 16% after 1 h, but the Al₂O₃-based nitrates decreased by 92%. Interestingly, with both 5% CO₂ and 5% H₂O in the feed, the total storage only decreased by 11%, as the hydroxyl groups generated on Al₂O₃ destabilized the K–CO₂ bond; specifically, H₂O mitigates the NO_x storage capacity losses associated with carboxylate competition.     

Role of CeO2 in Ni/CeO2–Al2O3 catalysts for carbon dioxide reforming of methane

Ni catalysts supported on γ-Al₂O₃, CeO₂ and CeO₂–Al₂O₃ systems were tested for catalytic CO₂ reforming of methane into synthesis gas. Ni/CeO₂–Al₂O₃ catalysts showed much better catalytic performance than either CeO₂- or γ-Al₂O₃-supported Ni catalysts. CeO₂ as a support for Ni catalysts produced a strong metal–support interaction (SMSI), which reduced the catalytic activity and carbon deposition. However, CeO₂ had positive effect on catalytic activity, stability, and carbon suppression when used as a promoter in Ni/γ-Al₂O₃ catalysts for this reaction. A weight loading of 1–5 wt% CeO₂ was found to be the optimum. Ni catalysts with CeO₂ promoters reduced the chemical interaction between nickel and support, resulting in an increase in reducibility and stronger dispersion of nickel. The stability and less coking on CeO₂-promoted catalysts are attributed to the oxidative properties of CeO₂.