Electronic Metal–Support Interactions and the Production of Hydrogen Through the Water-Gas Shift Reaction and Ethanol Steam Reforming: Fundamental Studies with Well-Defined Model Catalysts

The electronic properties of Ni and Pt nanoparticles deposited on CeO₂(111) have been examined using core and valence photoemission. The results of valence photoemission point to a new type of metal–support interaction which produces large electronic perturbations for small Ni and Pt particles in contact with ceria. The Ni/CeO₂(111) and Pt/CeO₂(111) systems exhibited a density of metal d states near the Fermi level that was much smaller than that expected for bulk metallic Ni or Pt. The electronic perturbations induced by ceria on Ni made this metal a very poor catalyst for CO methanation, but transformed Ni into an excellent catalyst for the production of hydrogen through the water-gas shift and the steam reforming of ethanol. Furthermore, the large electronic perturbations seen for small Pt particles in contact with ceria significantly enhanced the ability of the admetal to adsorb and dissociate water made it a highly active catalyst for the water-gas shift. The behaviour seen for the Ni/CeO₂(111) and Pt/CeO₂(111) systems illustrates the positive effects derived from electronic metal–support interactions and points to a promising approach for improving or optimizing the performance of metal/oxide catalysts.     

Co–Ni Catalysts Derived from Hydrotalcite-Like Materials for Hydrogen Production by Ethanol Steam Reforming

A series of Co–Ni catalysts, prepared from hydrotalcite (HT)-like materials by co-precipitation, has been studied for the hydrogen production by ethanol steam reforming. The total metal loading was fixed at 40% and the Co–Ni composition was varied (40–0, 30–10, 20–20, 10–30 and 0–40). The catalysts were characterized using X-ray diffraction, N₂ physisorption, H₂ chemisorption, temperature-programmed reduction, scanning transmission electron microscope and energy dispersive spectroscopy. The results demonstrated that the particle size and reducibility of the Co–Ni catalysts are influenced by the degree of formation of a HT-like structure, increasing with Co content. All the catalysts were active and stable at 575 °C during the course of ethanol steam reforming with a molar ratio of H₂O:ethanol = 3:1. The activity decreased in the order 30Co–10Ni > 40Co ~ 20Ni–20Co ~ 10Co–30Ni > 40Ni. The 40Ni catalyst displayed the strongest resistance to deactivation, while all the Co-containing catalysts exhibited much higher activity than the 40Ni catalyst. The hydrogen selectivities were high and similar among the catalysts, the highest yield of hydrogen was found over the 30Co–10Ni catalyst. In general, the best catalytic performance is obtained with the 30Co–10Ni catalyst, in which Co and Ni are intimately mixed and dispersed in the HT-derived support, as indicated by the STEM micrograph and complementary mapping of Co, Ni, Al, Mg and O.     

Ethanol Steam Reforming for Hydrogen Production over Bimetallic Pt–Ni/Al2O3

Ethanol steam reforming was studied at 673–823 K over Pt–Ni/δ-Al₂O₃. Results indicate that bimetallic catalyst is resistant to coke deposition at steam-to-carbon ratios as low as 1.5 and higher ratios are beneficial for both ethanol conversion and hydrogen formation. About 773 K is the optimum since high H₂ production rates are accompanied by low CO and CH₄ production rates. A power-function rate expression obtained on the basis of intrinsic rates at 673 K gives reaction orders of 1.25 (±0.05) and −0.215 (±0.015) for ethanol and steam, respectively; the apparent activation energy is calculated as 39.3 (±2) kJ mol⁻¹ between 673 and 723 K.     

Kinetics of Oxidative Steam Reforming of Ethanol Over Bimetallic Catalysts Supported on CeO2–SiO2: A Comparative Study

Topics in Catalysis - The catalytic activity of M(Ag, Ru, Pt)–Ni/CeO2–SiO2 catalysts prepared by wet impregnation at different M loadings (0–3 wt%) for oxidative steam...     

Oxidative Steam Reforming of Ethanol over Ni–Cu/SiO2, Rh/Al2O3 and Ir/CeO2: Effect of Metal and Support on Reaction Mechanism

The effect of metal and support on ethanol oxidative steam reforming (OSR) has been investigated over a series of stable and active catalytic systems with noble (Rh or Ir) and non noble metal (Ni–Cu) supported over neutral (SiO₂), amphoteric (Al₂O₃) or redox (CeO₂) supports. Ethanol decomposition and oxidative steam reforming was investigated by in situ diffuse reflectance infrared spectroscopy under temperature-programmed desorption and surface reaction conditions. Different mechanisms were established for these systems, from the initial steps of ethanol activation to the final equilibration of the decomposition products CO, CO₂, H₂ and H₂O. Various intermediates such as formates, acetates and/or carbonates were found to play different roles depending on the catalyst composition. The stability and activity of the investigated systems were finally assigned to specific features of these mechanisms.     

Role of Pt in the Activity and Stability of PtNi/CeO2–Al2O3 Catalysts in Ethanol Steam Reforming for H2 Production

Hydrogen production from ethanol reforming was investigated on bimetallic PtNi catalysts supported on CeO₂/Al₂O₃. Pt content was varied from 0.5 to 2.5 %. Physico-chemical characterization of the as-prepared and H₂-reduced catalysts by TPR, XRD and XPS showed that Pt phase interacted with the Ni and Ce species present at the surface of the catalysts. This interaction leads to an enhancement of the reducibility of both Ni and Ce species. Loadings of Pt higher than 1.0 wt% improved the activity and stability of the Ni/CeO₂–Al₂O₃ catalyst in ethanol steam reforming, in terms of lower formation of coke, C₂ secondary products and a constant production of CO₂ and H₂. The amount and type of carbon deposited on the catalyst was analyzed by TG–TPO while the changes in crystalline phases after reaction were studied by XRD. It was found that for Pt contents higher than 1 wt% in the catalysts, a better contact between Pt and Ce species is achieved. This Pt–Ce interaction facilitates the dispersion of small particles of Pt and thereby improves the reducibility of both Ce and Ni components at low temperatures. In this type of catalysts, the cooperative effect between Pt⁰, Ni⁰ and reduced Ce phases leads to an improvement in the stability of the catalysts: Ni provides activity in C–C bond breakage, Pt particles enhance the hydrogenation of coke precursors (C_xH_y) formed in the reaction, and Ce increases the availability of oxygen at the surface and thereby further enhances the gasification of carbon precursors.     

Application of Mesoporous Metal Oxide Immobilized Gold–Palladium Nanoalloys as Catalysts for Ethanol Oxidation

Gold–palladium nanoalloys (AuPd) were synthesized by a dendrimer templating method and the as-prepared nanoalloys were immobilized on several reducible mesoporous metal oxides (MMOs). The MMOs of MnO₂, Co₃O₄ and CeO₂ exhibited low catalytic activity in gas-phase oxidation of ethanol. Upon immobilization of the AuPd nanoalloys the activity increased significantly, with high acetaldehyde selectivity at 120 °C. However, this activity increase from pure MMOs to AuPd/MMOs was accompanied by decrease in selectivity to acetaldehyde. One other interesting observation lies on the amount of gold in the nanoalloy. Increasing the ratio of Au:Pd in the nanoalloy from 1:1 to 10:1 lowered the activity by a factor of six but had a positive effect on selectivity. From this, we postulate dissociation absorption of molecular oxygen to the reactive oxides occurs more effectively on the Pd metal surface. With higher Au loading, the acetaldehyde selectivity remained above 90% even at higher reaction temperatures of 160 °C. This led to a postulation of quick desorption of acetaldehyde from the Au surface more than it does on the Pd surface.

Graphical Abstract

Open image in new window

     

Silica-Supported Au–Ni Catalysts for the Dehydrogenation of Propane

Abstract  

Inspired by previous studies on model systems, a series of silica-supported Au–Ni catalysts were prepared and tested for the conversion of propane in the presence of hydrogen. The Au–Ni/SiO₂ catalysts were prepared by successive impregnation, i.e. Ni was deposited first followed by Au. TEM/EDX results confirmed the presence of bimetallic Au–Ni nanoparticles. The dehydrogenation of propane to propylene was observed on the Au–Ni bimetallic catalysts, whereas only hydrogenolysis products were observed on the monometallic Ni catalyst. The selectivity to propylene was found to increase monotonically with the Au loading. The results are in good agreement with the results on model catalysts.     

Potassium-Doped Ni–MgO–ZrO2 Catalysts for Dry Reforming of Methane to Synthesis Gas

Ni/K–MgO–ZrO₂ catalysts for dry reforming of methane, with a range of Mg/Zr ratios and each containing about 10 wt% Ni, were prepared via Ni nitrate impregnation on MgO–ZrO₂ supports synthesized by co-precipitation using K₂CO₃. It was found that a proportion of the potassium of the precipitant remained in the samples and improved the stability of the catalysts in the reaction. It was also shown that reduction of the catalysts at 1,023 K without calcination in air is necessary for stable and high activity; calcination in air at 1,073 K gives a deterioration of the catalytic properties, leading to rapid deactivation during the reaction. The order of the CH₄ conversions of the reduced catalysts after 14 h on stream was as follows: Ni/K–Mg₅Zr₂ ~ Ni/K–Mg ≥ Ni/K–Mg₂Zr₅ ? Ni/K–Zr. A catalyst with 0.95 wt% K on MgO–ZrO₂ with a Mg:Zr mole ratio of 5:2 showed the best resistance to deactivation. Experiments in a microbalance system showed that there was only negligible coke deposition on the surface of this sample. This behaviour was attributed to the presence of Ni nanoparticles with a diameter of less than 10 nm located on a MgO/NiO solid solution shell doped by K ions; this in turn covers a core of tetragonal ZrO₂ and/or a MgO/ZrO₂ solid solution. This conclusion was supported by EDS/TEM, XPS, XRD and H₂ chemisorption measurements.     

Ni–Nb-Based Mixed Oxides Precursors for the Dry Reforming of Methane

Perovskite-related mixed-oxides based on La Ni Nb and La Sr Ni Nb were synthesized by the auto combustion method to use as precursors materials for the catalytic reforming of methane at 700 ºC, atmospheric pressure, CH₄:CO₂ = 1:1. LaNiO₃ and LaNbO₄ were used as reference. XRD analysis show that the synthesis method produce a new series of precursor family formed by a mixture of oxides where Ni crystallized as part of a perovskite and Ruddlesden–Popper structure while Nb formed lanthanum orthoniobate LaNbO₄, a scheelite-type structure alternating with oxide layers, with phase distribution depending on niobium content. For Nb (x ≤ 0.3) Ni crystallizes as LaNiO₃ perovskite-type oxide while for Nb (x ≥ 0.7) it forms mainly the orthoniobate phase LaNbO₄ a scheelite-type structure. At higher calcined temperatures (~1100 °C) La₂Ni_0.8Nb_0.2O₄ was formed with a Ruddlesden–Popper structure consisting of three perovskite type layers along the c-axis alternating with a layer of the rock salt type phase. TEM analysis showed the presence of cubic particles with sizes varying between 5 and 60 nm depending on the extent of substitution of Ni by Nb. Reduction of the perovskite-related precursor oxides produced a series of Ni⁰/La₂O₃–NbOx oxides with high metallic dispersion which favors the activity and stability of the catalysts. Introduction of doping quantities of Sr into LaNi_0.8Nb_0.2O_3±λ structure produced a mixture of oxides with Sr dissolved in the lanthanum orthoniobate LaNbO₄ scheelite-type structure due to the similarity of ionic radii of La and Sr. Under the reaction conditions conversions near the thermodynamic equilibrium were attained which remains for long periods of time assessing the stability of the synthesized catalysts.     

Structure and Composition of Au–Cu and Pd–Cu Bimetallic Catalysts Affecting Acetylene Reactivity

Au–Cu and Pd–Cu bimetallic model catalysts were prepared on native SiO₂/Si(100) substrate under ultra high vacuum (UHV) by employing buffer layer assisted growth procedure with amorphous solid water as the buffer material. The effect of the bimetallic nanoclusters (NCs) surface composition and morphology on their chemical reactivity has been studied with acetylene decomposition and conversion to ethylene and benzene as the chemical probe. It was found that among the Au–Cu NCs compositions, Au_0.5Cu₃ NCs revealed outstanding catalytic selectivity towards ethylene formation. These NCs were further characterized by employing TEM, XPS and HAADF-STEM coupled EDX analysis. With CO molecule as a probe, CO temperature programmed desorption has been used to investigate the distribution of gold on the top-most surface of the supported clusters. Surface segregation at high relative elemental fraction of gold leads to a decreased activity of the Au–Cu NCs towards ethylene formation. In contrast to the Au–Cu NCs, the Pd–Cu bimetallic system reveals reduced sensitivity to the relative elemental composition with respect to selectivity of the acetylene transformation toward ethylene formation. On the other hand, remarkable activity towards benzene formation has been observed at elemental composition of Cu₃Pd, at comparable rates to those for ethylene formation on clean Pd NCs.     

Bimetallic Au–Cu, Ag–Cu/CrAl3O6 Catalysts for Methanol Synthesis

The influence of silver and gold addition on the activity and physicochemical properties of supported Cu/CrAl₃O₆ catalysts was the aim of this work. The reduction of CrAl₃O₆ support shows only one reduction stage attributed to Cr (VI) species reduction originating from previously oxidized binary oxide. Supported copper catalysts reduce in one or two stages depending on copper concentration representing the reduction of copper oxide—CuO, copper oxide chemically combined with Cr(III) oxide as copper chromite—CuCr₂O₄ and Cr(VI) species originating from surface chromate ions CrO₄ ^2?. Additionally, the introduction of silver into supported copper catalysts Cu/CrAl₃O₆ can led to the appearance of silver chromate phase. XRD investigations of support CrAl₃O₆ alone, supported copper and gold and silver promoted copper supported catalysts calcined at 400, 700 and 900 °C indicated the presence of highly amorphous alumina γ-Al₂O₃ like structure network in which some of cationic locations of aluminum were occupied by chromium atoms and small quantities of α-Cr₂O₃ phase. Additionally, for copper, silver–copper, and gold–copper supported catalysts the following oxide phases were distinguished: monometallic oxides CuO, Ag₂O, binary oxides CuAl₂O₄, Ag₂CrO₄, CuCr₂O₄ and even ternary oxide CuAlCrO₄. In the case of gold promoted copper supported catalysts metallic gold phase was detected. Activity tests carried out for these catalysts show that the most active was 20 wt.% Cu/CrAl₃O₆ catalyst. Promotion of copper catalysts by silver improves the activity in methanol synthesis, what can be assigned to silver chromate formation. The analogical gold chromate like formation was not confirmed.     

Waste-free Soft Reactive Grinding Synthesis of High-Surface-Area Copper–Manganese Spinel Oxide Catalysts Highly Effective for Methanol Steam Reforming

Cu–Mn spinel oxides with a high specific surface area were prepared by a simple and waste-free soft reactive grinding (SRG) technique involving the use of clean precursor salts as the starting materials. The samples were characterized by means of N₂ adsorption, X-ray diffraction (XRD), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and temperature-programmed reduction (H₂-TPR). The results show that the catalysts obtained from the SRG route exhibited much higher catalytic activity in methanol steam reforming as compared to their wet-chemically synthesized counterparts prepared by conventional coprecipitation. The superior performance of the SRG-derived Cu–Mn materials was attributed to the favorable formation of Cu_1.5Mn_1.5O₄ spinel phase leading to the creation of much smaller copper nanoparticles with enhanced stability in the working catalyst.