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.     

Co3O4/CeO2 composite oxides for methane emissions abatement: Relationship between Co3O4–CeO2 interaction and catalytic activity

Co₃O₄/CeO₂ composite oxides with different cobalt loading (5, 15, 30, 50, 70 wt.% as Co₃O₄) were prepared by co-precipitation method and investigated for the oxidation of methane under stoichiometric conditions. Pure oxides, Co₃O₄ and CeO₂ were used as reference. Characterization studies by X-ray diffraction (XRD), BET, temperature programmed reduction/oxidation (TPR/TPO) and X-ray photoelectron spectroscopy (XPS) were carried out.

An improvement of the catalytic activity and thermal stability of the composite oxides was observed with respect to pure Co₃O₄ in correspondence of Co₃O₄–CeO₂ containing 30% by weight of Co₃O₄. The combined effect of cobalt oxide and ceria, at this composition, strongly influences the morphological and redox properties of the composite oxides, by dispersing the Co₃O₄ phase and promoting the efficiency of the Co³⁺–Co²⁺ redox couple. The presence in the sample Co₃O₄(30 wt.%)–CeO₂ of a high relative amount of Ce³⁺/(Ce⁴⁺ + Ce³⁺) as detected by XPS confirms the enhanced oxygen mobility.

The catalysts stability under reaction conditions was investigated by XRD and XPS analysis of the used samples, paying particular attention to the Co₃O₄ phase decomposition. Methane oxidation tests were performed over fresh (as prepared) and thermal aged samples (after ageing at 750 °C for 7 h, in furnace). The resistance to water vapour poisoning was evaluated for pure Co₃O₄ and Co₃O₄(30 wt.%)–CeO₂, performing the tests in the presence of 5 vol.% H₂O. A methane oxidation test upon hydrothermal ageing (flowing at 600 °C for 16 h a mixture 5 vol.% H₂O + 5 vol.%O₂ in He) of the Co₃O₄(30 wt.%)–CeO₂ sample was also performed. All the results confirm the superiority of this composite oxide.     

Low-temperature H2-SCR of NO on a novel Pt/MgO-CeO2 catalyst

The selective catalytic reduction of NO by H₂ under strongly oxidizing conditions (H₂-SCR) in the low-temperature range of 100–200 °C has been studied over Pt supported on a series of metal oxides (e.g., La₂O₃, MgO, Y₂O₃, CaO, CeO₂, TiO₂, SiO₂ and MgO-CeO₂). The Pt/MgO and Pt/CeO₂ solids showed the best catalytic behavior with respect to N₂ yield and the widest temperature window of operation compared with the other single metal oxide-supported Pt solids. An optimum 50 wt% MgO-50wt% CeO₂ support composition and 0.3 wt% Pt loading (in the 0.1–2.0 wt% range) were found in terms of specific reaction rate of N₂ production (mols N₂/g_cat s). High NO conversions (70–95%) and N₂ selectivities (80–85%) were also obtained in the 100–200 °C range at a GHSV of 80,000 h⁻¹ with the lowest 0.1 wt% Pt loading and using a feed stream of 0.25 vol% NO, 1 vol% H₂, 5 vol% O₂ and He as balance gas. Addition of 5 vol% H₂O in the latter feed stream had a positive influence on the catalytic performance and practically no effect on the stability of the 0.1 wt% Pt/MgO-CeO₂ during 24 h on reaction stream. Moreover, the latter catalytic system exhibited a high stability in the presence of 25–40 ppm SO₂ in the feed stream following a given support pretreatment. N₂ selectivity values in the 80–85% range were obtained over the 0.1 wt% Pt/MgO-CeO₂ catalyst in the 100–200 °C range in the presence of water and SO₂ in the feed stream. The above-mentioned results led to the obtainment of patents for the commercial exploitation of Pt/MgO-CeO₂ catalyst towards a new NO_x control technology in the low-temperature range of 100–200 °C using H₂ as reducing agent. Temperature-programmed desorption (TPD) of NO, and transient titration of the adsorbed surface intermediate NO_x species with H₂ experiments, following reaction, have revealed important information towards the understanding of basic mechanistic issues of the present catalytic system (e.g., surface coverage, number and location of active NO_x intermediate species, NO_x spillover).     

On the mechanism of model diesel soot-O2 reaction catalysed by Pt-containing La-doped CeO2: A TAP study with isotopic O2

Pt supported on CeO₂ and 10 wt.% La³⁺-doped CeO₂ catalysts have been prepared, characterised and tested for soot oxidation by O₂ in TGA. The reaction mechanism has been studied in a TAP reactor with labelled O₂. Isotopic oxygen exchange between molecular O₂ and ‘O’ on the support/catalyst was observed and soot oxidation is being carried out by lattice oxygen. TAP studies further show that Pt improves O₂ adsorption and, therefore, 5 wt.% Pt-containing catalysts are more active for soot oxidation than the counterpart supports. In addition, CeO₂ doping by La³⁺ leads to an improved support, since La³⁺ stabilises the structure of CeO₂ when calcined at high temperature (1000 °C) and minimises sintering. In addition, La³⁺ improves the Ce⁴⁺/Ce³⁺ reduction as deduced from H₂-TPR experiments and favours oxygen mobility into the lattice. A synergetic effect of Pt and La³⁺ is observed, Pt-containing La³⁺-doped CeO₂ being the most active catalyst for soot oxidation by O₂ among the samples studied.     

The reactions of ethanol over M/CeO2 catalysts: Evidence of carbon–carbon bond dissociation at low temperatures over Rh/CeO2

The reactions of ethanol over Rh/CeO₂ have been investigated using the techniques of temperature programmed desorption (TPD) and FT-IR spectroscopy, in addition to steady state catalytic tests. A comparison with previous studies of ethanol adsorption over Pd/CeO₂ [J. Catal. 186 (1999) 279] and Pt/CeO₂ [J. Catal. 191 (2000) 30] catalysts is presented. The apparent activation energy for the reaction was 49, 40, and 43 kJ mol⁻¹ for Rh/CeO₂, Pd/CeO₂ and Pt/CeO_2, respectively, while the turnover number (TON) at 400 K was 5.9, 8.6 and 2.6, respectively. Surface compositions of catalysts were characterised by XPS. A decrease of the atomic O(1s)/Ce(3d) ratio of the CeO₂ support indicates its partial reduction upon addition of the noble metal. The extent of reduction per metal atom was in the following order: Pt>Pd>Rh. FT-IR and TPD studies have shown that dehydrogenation of ethanol to acetaldehyde occurred over Pd/CeO₂, Pt/CeO₂ and Rh/CeO₂. Moreover, Rh/CeO₂ readily dissociated the C–C bond of ethanol at room temperature to form adsorbed CO (IR bands at 1904–2091 cm⁻¹). This was corroborated by the low desorption temperature of CH₄ over Rh/CeO₂ (450 K) when compared to that of Pd/CeO₂ (550 K) or Pt/CeO₂ (585 K).     

Impact of support oxide and Ba loading on the NOx storage properties of Pt/Ba/support catalysts: CO2 and H2O effects

A series of 1 wt.%Pt/_xBa/Support (Support = Al₂O₃, SiO₂, Al₂O₃-5.5 wt.%SiO₂ and Ce_0.7Zr_0.3O₂, x = 5–30 wt.% BaO) catalysts was investigated regarding the influence of the support oxide on Ba properties for the rapid NO_x trapping (100 s). Catalysts were treated at 700 °C under wet oxidizing atmosphere. The nature of the support oxide and the Ba loading influenced the Pt–Ba proximity, the Ba dispersion and then the surface basicity of the catalysts estimated by CO₂-TPD. At high temperature (400 °C) in the absence of CO₂ and H₂O, the NO_x storage capacity increased with the catalyst basicity: Pt/20Ba/Si < Pt/20Ba/Al5.5Si < Pt/10Ba/Al < Pt/5Ba/CeZr < Pt/30Ba/Al5.5Si < Pt/20Ba/Al < Pt/10BaCeZr. Addition of CO₂ decreased catalyst performances. The inhibiting effect of CO₂ on the NO_x uptake increased generally with both the catalyst basicity and the storage temperature. Water negatively affected the NO_x storage capacity, this effect being higher on alumina containing catalysts than on ceria–zirconia samples. When both CO₂ and H₂O were present in the inlet gas, a cumulative effect was observed at low temperatures (200 °C and 300 °C) whereas mainly CO₂ was responsible for the loss of NO_x storage capacity at 400 °C. Finally, under realistic conditions (H₂O and CO₂) the Pt/20Ba/Al5.5Si catalyst showed the best performances for the rapid NO_x uptake in the 200–400 °C temperature range. It resulted mainly from: (i) enhanced dispersions of platinum and barium on the alumina–silica support, (ii) a high Pt–Ba proximity and (iii) a low basicity of the catalyst which limits the CO₂ competition for the storage sites.     

Catalytic performance of Co3O4/CeO2 and Co3O4/CeO2–ZrO2 composite oxides for methane combustion: Influence of catalyst pretreatment temperature and oxygen concentration in the reaction mixture

The influence of catalyst pre-treatment temperature (650 and 750 °C) and oxygen concentration (λ = 8 and 1) on the light-off temperature of methane combustion has been investigated over two composite oxides, Co₃O₄/CeO₂ and Co₃O₄/CeO₂–ZrO₂ containing 30 wt.% of Co₃O₄. The catalytic materials prepared by the co-precipitation method were calcined at 650 °C for 5 h (fresh samples); a portion of them was further treated at 750 °C for 7 h, in a furnace in static air (aged samples).

Tests of methane combustion were carried out on fresh and aged catalysts at two different WHSV values (12 000 and 60 000 mL g⁻¹ h⁻¹). The catalytic performance of Co₃O₄/CeO₂ and Co₃O₄/CeO₂–ZrO₂ were compared with those of two pure Co₃O₄ oxides, a sample obtained by the precipitation method and a commercial reference. Characterization studies by X-ray diffraction (XRD), BET and temperature-programmed reduction (TPR) show that the catalytic activity is related to the dispersion of crystalline phases, Co₃O₄/CeO₂ and Co₃O₄/CeO₂–ZrO₂ as well as to their reducibility. Particular attention was paid to the thermal stability of the Co₃O₄ phase in the temperature range of 750–800 °C, in both static (in a furnace) and dynamic conditions (continuous flow). The results indicate that the thermal stability of the phase Co₃O₄ heated up to 800 °C depends on the size of the cobalt oxide crystallites (fresh or aged samples) and on the oxygen content (excess λ = 8, stoichiometric λ = 1) in the reaction mixture. A stabilizing effect due to the presence of ceria or ceria–zirconia against Co₃O₄ decomposition into CoO was observed.

Moreover, the role of ceria and ceria–zirconia is to maintain a good combustion activity of the cobalt composite oxides by dispersing the active phase Co₃O₄ and by promoting the reduction at low temperature.     

Pt/MnOx–CeO2 catalysts for the complete oxidation of formaldehyde at ambient temperature

MnO_x–CeO₂ mixed oxides with a Mn/(Mn + Ce) molar ratios of 0–1 were prepared by a modified coprecipitation method and investigated for the complete oxidation of formaldehyde. The MnO_x–CeO₂ with Mn/(Mn + Ce) molar ratio of 0.5 exhibited the highest catalytic activity among the MnO_x–CeO₂ mixed oxides. Structure analysis by X-ray powder diffraction and temperature-programmed reduction of hydrogen revealed that the formation of MnO_x–CeO₂ solid solution greatly improved the low-temperature reducibility, resulting in a higher catalytic activity for the oxidation of formaldehyde. Promoting effect of Pt on the MnO_x–CeO₂ mixed oxide indicated that both the Pt precursors and the reduction temperature greatly affected the catalytic performance. Pt/MnO_x–CeO₂ catalyst prepared from chlorine-free precursor showed extremely high activity and stability after pretreatment with hydrogen at 473 K. 100% conversion of formaldehyde was achieved at ambient temperature and no deactivation was observed for 120 h time-on-stream. The promoting effect of Pt was ascribed to enhance the effective activation of oxygen molecule on the MnO_x–CeO₂ support.     

Potential rare-earth modified CeO2 catalysts for soot oxidation: Part III. Effect of dopant loading and calcination temperature on catalytic activity with O2 and NO + O2

CeO₂ and CeReO_x_y catalysts are prepared by the calcination at different temperatures (y = 500–1000 °C) and having a different composition (Re = La³⁺ or Pr^3+/4+_, 0–90 wt.%). The catalysts are characterised by XRD, H₂-TPR, Raman, and BET surface area. The soot oxidation is studied with O₂ and NO + O₂ in the tight and loose contact conditions, respectively. CeO₂ sinters between 800–900 °C due to a grain growth, leading to an increased crystallite size and a decreased BET surface area. La³⁺ or Pr^3+/4+ hinders the grain growth of CeO₂ and, thereby, improving the surface catalytic properties. Using O₂ as an oxidant, an improved soot oxidation is observed over CeLaO_x_y and CePrO_x_y in the whole dopant weight loading and calcination temperature range studied, compared with CeO₂. Using NO + O₂, the soot conversion decreased over CeLaO_x_y catalysts calcined below 800 °C compared with the soot oxidation over CeO₂_y. CePrO_x_y, on the other hand, showed a superior soot oxidation activity in the whole composition and calcination temperature range using NO + O₂. The improvement in the soot oxidation activity over the various catalysts with O₂ can be explained based on an improvement in the external surface area. The superior soot oxidation activity of CePrO_x_y with NO + O₂ is explained by the changes in the redox properties of the catalyst as well as surface area. CePrO_x_y, having 50 wt.% of dopant, is found to be the best catalyst due to synergism between cerium and praseodymium compared to pure components. NO into NO₂ oxidation activity, that determines soot oxidation activity, is improved over all CePrO_x catalysts.     

Non-steady activity during methane combustion over Pd/Al2O3 and the influences of Pt and CeO2 additives

Methane combustion over Pd/Al₂O₃ catalysts with and without added Pt and CeO₂ in both oxygen-rich and methane-rich mixtures at temperatures in the range 250–520°C has been investigated using a temperature-programmed reaction procedure with on-line gas analysis (FTIR). During the temperature loop under oxygen-rich conditions, there was an appreciable hysteresis in the activity of unmodified Pd/Al₂O₃, which was greatly enhanced over Pd–Pt/Al₂O₃. Over both catalysts the hysteresis was reversed under slightly methane-rich atmospheres, and as temperature was reduced, a sudden collapse or fluctuations in activity were shown respectively over Pd–Pt/Al₂O₃ and Pd/Al₂O₃. Such non-steady behaviour was almost eliminated over Pd/Al₂O₃–CeO₂. Under a very narrow range of conditions and over a Pd/Al₂O₃ packed bed, oscillation of methane combustion was observed.     

Thermal ageing of Pt on low-surface-area CeO2–ZrO2–La2O3 mixed oxides: Effect on the OSC performance

This work aims at exploring the thermal ageing mechanism of Pt on ceria-based mixed oxides and the corresponding effect on the oxygen storage capacity (OSC) performance of the support material. Pt was supported on low-surface-area CeO₂–ZrO₂–La₂O₃ mixed oxides (CK) by impregnation method and subsequently calcined in static air at 500, 700 and 900 °C, respectively. The evolutions of textural, microstructural and redox properties of catalysts after the thermal treatments were identified by means of X-ray diffraction (XRD), Raman, X-ray photoelectron spectroscopy (XPS), temperature programmed reduction (TPR) and high-resolution transmission electron microscope (HRTEM). The results reveal that, besides the sintering of Pt, encapsulation of metal by the mixed oxides occurs at the calcination temperature of 700 °C and above. The burial of Pt crystallites by support particles is proposed as a potential mechanism for the encapsulation. Further, the HRTEM images show that the distortion of the mixed oxides lattice and other crystal defects are distributed at the metal/oxides interface, probably indicating the interdiffusion/interaction between the metal and mixed oxide. In this way, encapsulation of Pt is capable to promote the formation of Ce³⁺ or oxygen vacancy on the surface and in the bulk of support. The OSC results show that the reducibility and oxygen release behavior of catalysts are related to both the metal dispersion and metal/oxides interface, and the latter seems to be more crucial for those supported on low-surface-area mixed oxides. Judging by the dynamic oxygen storage capacity (DOSC), oxygen storage capacity complete (OSCC) and oxygen releasing rate, the catalyst calcined at 700 °C shows the best OSC performance. This evident promotion of OSC performance is believed to benefit from the partial encapsulation of Pt species, which leads to the increment of Ce³⁺ or oxygen vacancies both on the surface and in the bulk of oxides despite a loss of chemisorption sites on the surface of metal particles.     

NO reduction by CH4 in the presence of excess O2 over Mn/sulfated zirconia catalysts

Selective catalytic reduction (SCR) of NO with methane in the presence of excess oxygen has been investigated over a series of Mn-loaded sulfated zirconia (SZ) catalysts. It was found that the Mn/SZ with a metal loading of 2–3 wt.% exhibited high activity for the NO reduction, and the maximum NO conversion over the Mn/SZ catalyst was higher than that over Mn/HZSM-5. NH₃–TPD results of the catalysts showed that the sulfation process of the supports resulted in the generation of strong acid sites, which is essential for the SCR of NO with methane. On the other hand, the N₂ adsorption and the H₂–TPR of the catalysts demonstrated that the presence of the SO₄²⁻ species promoted the dispersion of the metal species and made the Mn species less reducible. Such an increased dispersion of metal species suppressed the combustion reaction of CH₄ by O₂ and increased the selectivity towards NO. The Mn/SZ catalysts prepared by different methods exhibited similar activities in the SCR of NO with methane, indicating the importance of SO₄²⁻. The most attractive feature of the Mn/SZ catalysts was that they were more tolerant to water and SO₂ poisoning than Mn/HZSM-5 catalysts and exhibited higher reversibility after removal of SO₂.     

Hydrodesulfurization of model diesel using Pt/Al2O3 catalysts prepared by supercritical deposition

Pt/Al₂O₃ catalysts with Pt loadings ranging from 0.5 to 11 wt.% were synthesized by supercritical carbon dioxide (scCO₂) deposition method. Transmission electron microscopy (TEM) images showed that the synthesized catalysts contained small Pt nanoparticles (1–4 nm in diameter) with a narrow size distribution, no observable agglomeration, and uniformly dispersed on the alumina support. The catalysts were found to be active for hydrodesulfurization of dibenzothiophene (DBT) dissolved in n-hexadecane (n-HD) without sulfiding the metal phase. The reaction proceeded only via the direct hydrogenolysis route in the temperature range 310–400 °C and at atmospheric pressure. The activity increased with increasing the metal loading. Increasing [H₂]₀/[DBT]₀ by either increasing [H₂]₀ or decreasing [DBT]₀, increased the DBT conversion. At a fixed weight hourly space velocity and feed concentration, conversion did not increase with increasing temperature beyond 330 °C. The presence of toluene inhibited the catalyst activity presumably due to competitive adsorption between DBT and toluene. Under the operating conditions, the reaction was far from equilibrium.     

Catalytic performance of Ni/CeO2/Al2O3 modified with noble metals in steam gasification of biomass

In the steam gasification of biomass, the additive effect of noble metals such as Pt, Pd, Rh and Ru to the Ni/CeO₂/Al₂O₃ catalyst was investigated. Among these noble metals, the addition of Pt was most effective even when the loading amount of added Pt was as small as 0.01 wt.%. In addition, the catalyst characterization suggests the formation of the Pt–Ni alloy over the Pt/Ni/CeO₂/Al₂O₃.     

Coprecipitated iron-containing catalysts (Fe-Al2O3, Fe-Co-Al2O3, Fe-Ni-Al2O3) for methane decomposition at moderate temperatures: Part II. Evolution of the catalysts in reaction

Coprecipitated Fe-Al₂O₃, Fe-Co-Al₂O₃ and Fe-Ni-Al₂O₃ catalysts is shown to be very efficient in carbon deposition during methane decomposition at moderate temperatures (600–650 °C). The carbon capacity of the most efficient bimetallic catalysts containing 50–65 wt.% Fe, 5–10 wt.% Co (or Ni) and 25–40 wt.% Al₂O₃ is found to reach 145 g/g_cat. Most likely, their high efficiency is due to specific crystal structures of the metal particles and formation of optimum particle size distribution. According to the TEM data, catalytic filamentous carbon (CFC) is formed on them as multiwall carbon nanotubes (MWNTs). The phase composition of the catalysts during methane decomposition is studied using a complex of physicochemical methods (XRD, REDD, Mössbauer spectroscopy and EXAFS). Possible mechanisms of the catalyst deactivation are discussed.     

Isomerization of n-hexane over mono- and bimetallic Pd–Pt catalysts supported on ZrO2–Al2O3–WOx prepared by sol–gel

The catalytic performance of mono- and bimetallic Pd (0.6, 1.0 wt.%)–Pt (0.3 wt.%) catalysts supported on ZrO₂ (70, 85 wt.%)–Al₂O₃ (15, 0 wt.%)–WO_x (15 wt.%) prepared by sol–gel was studied in the hydroisomerization of n-hexane. The catalysts were characterized by N₂ physisorption, XRD, TPR, XPS, Raman, NMR, and FT-IR of adsorbed pyridine. The preparation of ZrW and ZrAlW mixed oxides by sol–gel favored the high dispersion of WO_x and the stabilization of zirconia in the tetragonal phase. The Al incorporation avoided the formation of monoclinic-WO₃ bulk phase. The catalysts increased their S_BET for about 15% promoted by Al₂O₃ addition. Various oxidation states of WO_x species coexist on the surface of the catalysts after calcination. The structure of the highly dispersed surface WO_x species is constituted mainly of isolated monotungstate and two-dimensional mono-oxotungstate species in tetrahedral coordination. The activity of Pd/ZrW catalysts in the hydroisomerization of n-hexane is promoted both with the addition of Al to the ZrW mixed oxide and the addition of Pt to Pd/ZrAlW catalysts. The improvement in the activity of Pd/ZrAlW catalysts is ascribed to a moderated acid strength and acidity, which can be correlated to the coexistence of W⁶⁺ and reduced-state WO_x species (either W⁴⁺ or W⁰). The addition of Pt to the Pd/ZrAlW catalyst does not modify significantly its acidic character. Selectivity results showed that the catalyst produced 2MP, 3MP and the high octane 2,3-dimethylbutane (2,3-DMB) and 2,2-dimethylbutane (2,2-DMB) isomers.     

A study of the behaviour of Pt supported on CeO2–ZrO2/Al2O3–BaO as NOx storage–reduction catalyst for the treatment of lean burn engine emissions

The behaviour of a Pt(1 wt.%) supported on CeO₂–ZrO₂(20 wt.%)/Al₂O₃(64 wt.%)–BaO(16 wt.%) as a novel NO_x storage–reduction catalyst is studied by reactivity tests and DRIFT experiments and compared with that of Pt(1%)–BaO(15 wt.%) on alumina. The former catalyst, designed as a hydrothermally stable sample, is composed of an alumina modified with Ba ions and an overlayer of ceria-zirconia. The results pointed out that during the calcination barium ions migrates over the surface of the catalyst which thus show a good NO_x storage–reduction behaviour comparable with that of Pt–BaO on alumina, although Ba ions result much better dispersed.     

Nano-structured CeO2 supported Cu-Pd bimetallic catalysts for the oxygen-assisted water–gas-shift reaction

The present work focuses on the development of novel Cu-Pd bimetallic catalysts supported on nano-sized high-surface-area CeO₂ for the oxygen-assisted water–gas-shift (OWGS) reaction. High-surface-area CeO₂ was synthesized by urea gelation (UG) and template-assisted (TA) methods. The UG method offered CeO₂ with a BET surface area of about 215 m²/g, significantly higher than that of commercially available CeO₂. Cu and Pd were supported on CeO₂ synthesized by the UG and TA methods and their catalytic performance in the OWGS reaction was investigated systematically. Catalysts with about 30 wt% Cu and 1 wt% Pd were found to exhibit a maximum CO conversion close to 100%. The effect of metal loading method and the influence of CeO₂ support on the catalytic performance were also investigated. The results indicated that Cu and Pd loaded by incipient wetness impregnation (IWI) exhibited better performance than that prepared by deposition–precipitation (DP) method. The difference in the catalytic activity was related to the lower Cu surface concentration, better Cu–Ce and Pd–Ce interactions and improved reducibility of Cu and Pd in the IWI catalyst as determined by the X-ray photoelectron spectroscopy (XPS) and temperature-programmed reduction (TPR) studies. A direct relation between BET surface area of the CeO₂ support and CO conversion was also observed. The Cu-Pd bimetallic catalysts supported on high-surface-area CeO₂ synthesized by UG method exhibited at least two-fold higher CO conversion than the commercial CeO₂ or that obtained by TA method. The catalyst retains about 100% CO conversion even under extremely high H₂ concentration.     

Total oxidation of propene and propane over gold–copper oxide on alumina catalysts: Comparison with Pt/Al2O3

Oxidation of propene and propane to CO₂ and H₂O has been studied over Au/Al₂O₃ and two different Au/CuO/Al₂O₃ (4 wt.% Au and 7.4 wt.% Au) catalysts and compared with the catalytic behaviour of Au/Co₃O₄/Al₂O₃ (4.1 wt.% Au) and Pt/Al₂O₃ (4.8 wt.% Pt) catalysts. The various characterization techniques employed (XRD, HRTEM, TPR and DR-UV–vis) revealed the presence of metallic gold, along with a highly dispersed CuO (6 wt.% CuO), or more crystalline CuO phase (12 wt.% CuO).

A higher CuO loading does not significantly influence the catalytic performance of the catalyst in propene oxidation, the gold loading appears to be more important. Moreover, it was found that 7.4Au/CuO/Al₂O₃ is almost as active as Pt/Al₂O₃, whereas Au/Co₃O₄/Al₂O₃ performs less than any of the CuO-containing gold-based catalysts.

The light-off temperature for C₃H₈ oxidation is significantly higher than for C₃H₆. For this reaction the particle size effect appears to prevail over the effect of gold loading. The most active catalysts are 4Au/CuO/Al₂O₃ (gold particles less than 3 nm) and 4Au/Co₃O₄/Al₂O₃ (gold particles less than 5 nm).     

The red–ox treatments influence on the structure and properties of M2O3–CeO2–ZrO2 (M=Y, La) solid solutions

The introduction of trivalent cation — Y³⁺ or La³⁺ — into the lattice of CeO₂–ZrO₂ solid solutions allows to stabilise a cubic structure at low ceria content (30 mol%). The reducibility of the samples has been compared in the experiments of temperature-programmed reduction (TPR). The introduction of lanthanum cations decreases the amount of hydrogen consumed during TPR, while the introduction of yttrium ones increases this value. At the same time, the value of temperature of the maximum speed of reduction (T_max) is independent on the trivalent dopant. The reducibility of these solid solutions did not change during repeated red–ox treatments at temperature below 1220 K. It is connected with the high thermostability of all systems in this temperature interval. TPR up to 1470 K causes a significant shift of T_max value to higher temperature and a slight decrease of hydrogen consumption in two to three cycles. It is suggested that this alterations are connected with the sharp decrease of the specific surface area of all samples and partially phase decomposition of CeO₂–ZrO₂ and Y₂O₃–CeO₂–ZrO₂ solid solutions. Raman characterisation of the oxygen sublattice of the fresh samples and of the samples after TPR has been carried out.