Potassium promoted Ru/meso-macroporous SiO2 catalyst for the preferential oxidation of CO in H2-rich gases

A series of potassium promoted Ru/meso-macroporous SiO₂ catalysts were prepared and used for the preferential oxidation of CO (CO-PROX) in H₂-rich gases. The catalysts were characterized by using techniques of TEM, SEM TPR, XPS, and N₂ adsorption/desorption. The catalytic activity of Ru/meso-macroporous SiO₂ was markedly improved by the introduction of potassium. The catalyst of K-5 wt.% Ru/meso-macroporous SiO₂ with molar ratio of K:Ru = 5:7 exhibited relatively high activity and selectivity for CO-PROX. Nanoparticles of ruthenium species can be highly dispersed on the meso-macroporous SiO₂ support by the simple impregnation method. The addition of potassium weakened the interaction between metallic Ru and the silica support. Lowering the reduction temperature of ruthenium ions could keep ruthenium in the state of metallic Ru, and it was proposed that potassium acted as an electron donating agent. The electron donating effect of potassium improved the low temperature activity for CO oxidation and increased the selectivity of O₂ for CO oxidation, thus K-modified Ru/meso-macroporous SiO₂ catalyst showed obviously a wide temperature window for CO elimination from H₂-rich gases, meanwhile the related mechanism was discussed.     

Promotion of CO2 methanation activity and CH4 selectivity at low temperatures over Ru/CeO2/Al2O3 catalysts

The effect of CeO₂ loading amount of Ru/CeO₂/Al₂O₃ on CO₂ methanation activity and CH₄ selectivity was studied. The CO₂ reaction rate was increased by adding CeO₂ to Ru/Al₂O₃, and the order of CO₂ reaction rate at 250 °C is Ru/30%CeO₂/Al₂O₃ > Ru/60%CeO₂/Al₂O₃ > Ru/CeO₂ > Ru/Al₂O₃. With a decrease in CeO₂ loading of Ru/CeO₂/Al₂O₃ from 98% to 30%, partial reduction of CeO₂ surface was promoted and the specific surface area was enlarged. Furthermore, it was observed using FTIR technique that intermediates of CO₂ methanation, such as formate and carbonate species, reacted with H₂ faster over Ru/30%CeO₂/Al₂O₃ and Ru/CeO₂ than over Ru/Al₂O₃. These could result in the high CO₂ reaction rate over CeO₂-containing catalysts. As for the selectivity to CH₄, Ru/30%CeO₂/Al₂O₃ exhibited high CH₄ selectivity compared with Ru/CeO₂, due to prompt CO conversion into CH₄ over Ru/30%CeO₂/Al₂O₃.     

CO2 methanation over ordered mesoporous NiRu-doped CaO-Al2O3 nanocomposites with enhanced catalytic performance

The ordered mesoporous NiRu-doped CaO-Al₂O₃ nanocomposites were synthesized via a facile evaporation-induced self-assembly method for CO₂ methanation. Metallic Ni and Ru species retained the single-component heterostructure rather than NiRu alloy over the 600 °C-reduced catalysts. Owing to the synergistic effect of bimetallic Ni–Ru as well as the improved H₂ and CO₂ chemisorption capacities after the addition of Ru and CaO promoters, the ordered mesoporous 10N1R2C-OMA catalyst exhibited enhanced catalytic activity and selectivity, which achieved the maximum CO₂ conversion of 83.8% and CH₄ selectivity of 100% at 380 °C, 0.1 MPa, 30000 mL g^?1 h^?1. In a 550 °C-109 h-lifetime test, the ordered mesoporous 10N1R2C-OMA catalyst showed high stability and superior anti-sintering property due to the confinement effect of the ordered mesostructure.     

Selective CO oxidation in H2 streams on CuO/CexZr1−xO2 catalysts: Correlation between activity and low temperature reducibility

Catalysts synthesized by incorporating CuO (7 wt.% of Cu) on six commercial Ce_xZr_1−xO₂ mixed oxides (x = 1, 0.8, 0.68, 0.5, 0.15, 0) have been prepared by conventional wetness impregnation method. These catalysts have been screened for CO oxidation in hydrogen streams (CO-PROX) and characterized by means of XRD, BET, Raman, XPS and H₂-TPR experiments. Activity towards CO oxidation in hydrogen streams has been discussed and correlated with the properties of the catalysts. XRD and Raman analysis of the supports show an increase of oxygen defect as Zr content increase. Below 150 °C the catalysts reducibility measured by H₂-TPR correlates with ceria content in the support, although an increase of Zr content in the support increases considerably the reduction degree of ceria in the 0–600 °C interval. Activity towards CO oxidation in hydrogen streams also correlates with Ce/Cu molar ratio and low temperature reducibility of copper species. Most of the catalysts give complete CO conversion with high selectivity operating with λ = 2. The most active catalysts is CuO supported on pure ceria, which is able to oxidize completely CO in the interval 96–164 °C, with maximum selectivity of 90%. On the other hand, the operation window becomes narrower as Zr content in the supports increases.     

CNT-based catalysts for H2 production by ethanol reforming

Hydrogen production by steam reforming of ethanol (SRE) was studied using steam-to-ethanol ratio of 3:1, between the temperature range of 150–450 °C over metal and metal oxide nanoparticle catalysts (Ni, Co, Pt and Rh) supported on carbon nanotubes (CNTs) and compared to a commercial catalyst (Ni/Al₂O₃). The aim was to find out the suitability of CNTs supports with metal nanoparticles for the SRE reactions at low temperatures. The idea to develop CNT-based catalysts that have high selectivity for H₂ is one of the driving forces for this study. The catalytic performance was evaluated in terms of ethanol conversion, product gas composition, hydrogen yield and selectivity to hydrogen. The Co/CNT and Ni/CNT catalysts were found to have the highest activity and selectivity towards hydrogen formation among the catalysts studied. Almost complete ethanol conversion is achieved over the Ni/CNT catalyst at 400 °C. The highest hydrogen yield of 2.5 is, however, obtained over the Co/CNT catalyst at 450 °C. The formation of CO and CH₄ was very low over the Co/CNT catalyst compared to all the other tested catalysts. The Pt and Rh CNT-based catalysts were found to have low activity and selectivity in the SRE reaction. Hydrogen production via steam reforming of ethanol at low temperatures using especially Co/CNT catalyst has thus potential in the future in e.g. the fuel cell applications.     

Preferential oxidation of CO in a H2-rich stream over multi-walled carbon nanotubes confined Ru catalysts

Multi-walled carbon nanotubes (MWNTs) confined Ru catalysts were prepared by a modified procedure using ultrasonication-aided capillarity action to deposit Ru nanoparticles onto MWNTs inner surface. The structure properties of MWNTs supports and Ru catalysts were extensively characterized by XRD, TGA, H₂-TPR, XPS, TEM, FTIR and Raman spectra. The catalytic performance in the preferential oxidation of CO in a H₂-rich stream was examined in detail with respect to the influences of Ru loading, MWNTs diameter, various pretreatment conditions, and the presence of CO₂ and H₂O in the feed stream. In contrast with Ru catalysts supported on MWNTs external surface and other carbon materials, the superior activity was observed for the MWNTs-confined Ru catalyst, which was discussed intensively in terms of the confinement effect of carbon nanotubes. The optimized catalyst of 5 wt.% Ru confined in MWNTs with diameter of 8–15 nm can achieve the complete CO conversion in the wider temperature range and the favorable stability at 80 °C under the simulated reformatted gas mixture, which proves a promising catalyst for preferential CO oxidation in H₂-rich stream.     

CO removal via selective methanation over the catalysts Ni/ZrO2 prepared with reduction by the wet H2-rich gas

The wet H₂-rich gas was used as reducing gas instead of the H₂/N₂ gas in the reduction step of the catalyst preparation. It is found that the selectivity for CO methanation over the catalysts 0.4Ni/ZrO₂ so-obtained was decreased in comparison to the case of the H₂/N₂ gas used as reducing gas. Even though, the samples with the different feed atomic ratios of Ni/Zr prepared by the impregnation method and the co-precipitation method, respectively, were evaluated with the wet H₂-rich gas both as reducing gas and as reactant gas. The catalysts Ni/ZrO₂-CP prepared by the co-precipitation method exhibited a high catalytic activity for CO removal at a lowered reaction temperature with increasing the Ni loading. Over the catalyst 3.0Ni/ZrO₂-CP, CO in the reactant gas could be removed to below 10 ppm at reaction temperatures of 220–260 °C with the selectivity higher than 50%. And the selectivity was kept at 100% during the 100 h test at 220 °C. The catalysts were characterized by XRD, XPS, XRF and the adsorption isotherm measurement. In addition, effect of water vapor in reactant gas was studied over the catalysts 0.4Ni/ZrO₂ with the wet H₂-rich gas and the dry H₂-rich gas as reactant gas, respectively, in the case of the H₂/N₂ gas fixed as reducing gas. It is seen that presence of water vapor in the reactant gas retarded methanation reactions of CO and CO₂ on the catalysts.     

Flowerlike microspheres catalyst NiO/La2O3 for ethanol-H2 production

Catalysts of nano-sized nickel oxide particles based on flowerlike lanthanum oxide microspheres with high disperse were prepared to achieve simultaneous dehydrogenation of ethanol and water molecules on multi-active sites. XRD, SEM, 77K N₂ adsorption were used to analyze and observe the catalysts’ structure, morphology and porosity. Catalytic parameters with respect to yield of H₂, activity, selectivity towards gaseous products and stability with time-on-stream and time-on-off-stream were all determined. This special morphology NiO/La₂O₃ catalyst represented more than 1000 h time-on-stream stability test and 500 h time-on-off-stream stability test for hydrogen fuel production from ethanol steam reforming at 300 °C without any deactivation. During the 1000 h time-on-stream stability test, ethanol–water mixtures could be converted into H₂, CO, and CH₄ with average selectivity values of 57.0, 20.1, 19.6 and little CO₂ of 3.2 mol%, respectively, and average ethanol conversion values of 96.7 mol%, with H₂ yield of 1.61 mol H₂/mol C₂H₅OH. During the 500 h time-on-off-stream stability test, ethanol–water mixtures could be converted into H₂, CO, CH₄ and CO₂ with average selectivity values of 65.1, 17.3, 15.1 and 2.5 mol%, respectively, and average ethanol conversion values of 80.0 mol%. For the ethanol-H₂ and petrolic hybrid vehicle (EH–HV), the combustion value is the most important factor. So, it was very suitable for the EH–HV application that the low temperature ethanol steam reforming products’ distribution was with high H₂, CO, CH₄ and very low CO₂ selectivity over the special NiO/La₂O₃ flowerlike microspheres.     

Comparative study of CuO supported on CeO2, Ce0.8Zr0.2O2 and Ce0.8Al0.2O2 based catalysts in the CO-PROX reaction

CuO supported on CeO_2, Ce_0.8Zr_0.2O₂ and Ce_0.8Al_0.2O₂ based catalysts (6%wt Cu) were synthesized and tested in the preferential oxidation of CO in a H₂-rich stream (CO-PROX). Nanocrystalline supports, CeO₂ and solid solutions of modified CeO₂ with zirconium and aluminum were prepared by a freeze-drying method. CuO was supported by incipient wetness impregnation and calcination at 400 °C. All catalysts exhibit high activity in the CO-PROX reaction and selectivity to CO₂ at low reaction temperature, being the catalyst supported on CeO₂ the more active and stable. The influence of the presence of CO₂ and H₂O was also studied.     

Effect of ruthenium addition on molybdenum catalysts for syngas production via catalytic partial oxidation of methane in a monolithic reactor

Hydrogen is mainly produced from hydrocarbon resources. Natural gas, mostly composed of methane, is widely used for hydrogen production. As a valuable feedstock for ‘Fischer–Tropsch’ (FT) process and ‘Gas to Liquids’ (GTL) technology, syngas production from catalytic partial oxidation of methane (CPOM) is gaining prominence especially owing to its more desirable H₂/CO ratio; relatively less energy consumption, and lower investment, compared to steam reforming processes (SMR), the leading technology.In the present study, effect of ruthenium (Ru) addition on molybdenum (Mo) catalysts for syngas production from methane (CH₄) via partial oxidation in a monolithic reactor was investigated. Mo based catalysts supported on Nickel (Ni) and Cobalt (Co) metal oxides and Ni-Co bimetallic oxides and their Ru added versions were developed, characterized, and tested for performance in a monolithic type reactor system. Catalyst activity was investigated in terms of H₂ and CO selectivity, CH₄ conversion; and CO₂ emission and it is concluded that addition of Ru over the structure led to increase in catalytic activity and reduction in carbon deposition over the catalyst surface.     

Catalytic behaviour of Mn2.94M0.06O4-δ (M=Pt,Ru and Pd) catalysts for low temperature water gas shift (WGS) and CO oxidation

Noble metal (Pt, Ru and Pd) substituted Mn₃O₄ catalysts have been synthesized in this work by a sonochemical route. The catalysts were characterised by XRD, XPS, TEM, H₂-TPR and BET surface area analyser and the activity of these catalysts was tested towards low temperature water gas shift reaction (WGS) and CO oxidation reaction. It was observed that these catalysts have the tetragonal crystalline structure of Mn₃O₄ and the average particle size was found in the range of 12 nm–22 nm. H₂-TPR results show that the strong metal support interaction between substituted metal and Mn₃O₄ leads to high reducibility and makes these catalysts active for WGS and CO oxidation. Pt substituted Mn₃O₄ showed higher activity towards WGS compared to other synthesized catalysts and 99.9% conversion was observed at 260 °C without methane formation. The activation energy of Mn_2.94Pt_0.06O_4-δ was found to be 59 ± 0.6 kJ/mol. DRIFTS analysis was carried out to propose the reaction mechanism for water gas shift and CO oxidation. Redox mechanism was hypothesized for WGS and used to correlate the experimental data over Pt substituted Mn₃O₄. Similarly, kinetic parameters were estimated based on Langmuir-Hinshelwood mechanism for CO oxidation over Pd substituted Mn₃O₄ which showed better activity compare to other synthesized catalysts and 99.9% conversion was observed at 175 °C. The activation energy was calculated from Arrhenius plot which was found to be 30 ± 0.4 kJ/mol.     

Effect of different activated carbon support on CH4CO2 reforming over Co-based catalysts

CH₄CO₂ reforming to syngas was investigated over three different activated carbon catalysts. To better understand the influence of the supports on the catalytic properties, catalysts were analyzed by some characterization methods, such as nitrogen adsorption–desorption isotherms, XRD, H₂-TPR, NH₃-TPD, CO₂-TPD, FTIR, TEM and EDX. The results showed that the catalyst with AC₂ as the support provided the best catalytic activity. The CH₄ conversion and CO₂ conversion were 92% and 98% at 900 °C, respectively; best selectivity with the H₂/CO ratio was close to 1 among the three supports used. It also showed a better stability at 900 °C. H₂-TPR analysis showed that Co species in Co/AC₂ catalyst were strong interaction with the support. It was observed that active metals were well dispersed on the AC₂ support by the TEM. In addition, the ratio of CH₄/CO₂ also had great influence on the CH₄ and CO₂ conversion.     

Catalysts for H2 production using the ethanol steam reforming (a review)

This review aims to provide an overview of the main catalytic studies of H₂ production by ethanol steam reforming (ESR). The reaction is endothermic and produces H₂, CO₂, CH₄, CO and coke. The conversion and H₂ selectivity of these products depended greatly of the physicochemical properties of the catalysts, active metal, promoters, temperature, long-term reaction, water/ethanol ratio, space velocity, contact time, and presence of O₂. Initial total conversion has been reported in all catalysts evaluated between 300 and 850 °C. The noble catalysts with high selectivity to H₂ (more than 80%) were: Rh, Ru, Pd and Ir and non-noble metal catalysts were: Ni, Co and Cu. The support materials include CeO₂, ZnO, MgO, Al₂O₃, zeolites-Y, TiO₂, SiO₂, La₂O₂CO₃, CeO₂–ZrO₂ and hydrotalcites. The impregnation method produced the best noble metal catalysts in terms of selectivity and conversion. The decrease of coke was related with the presence of basic sites on the support.     

Preparation of high surface area Ni/MgAl2O4 nanocatalysts for CO selective methanation

Methanation of carbon monoxide in the H₂-rich gas stream was performed on a series of the Ni/MgAl₂O₄ catalysts in a fixed bed micro-reactor. The catalysts were synthesized using wetness impregnation method and the prepared samples were characterized by XRD, BET, SEM, TEM, H₂-TPR, CO chemisorption and CO-TPD techniques. The catalyst carrier was prepared by a novel sol-gel method using nitrate salts precursors and propylene oxide as a gelation agent. MgAl₂O₄ as catalyst carrier possessed a high BET area of 340 m² g^?1 with high pore volume (0.563 cc g^?1) and small pore size (6.56 nm). The catalysts also showed high BET area, which decreased with the increase in Ni content. These catalysts exhibited mesoporous structure with average nickel crystal size smaller than 20 nm. The catalyst with Ni content of 25 wt% exhibited the maximum CO conversion and CH₄ selectivity and can be considered as a catalyst with high catalytic potential for the selective methanation of carbon monoxide.     

Effect of Ce on 5 wt% Ni/ZSM-5 catalysts in the CO2 reforming of CH4 reaction

The aim of this study is to investigate the promotional effect of Ce on Ni/ZSM-5 catalysts in the CO₂ reforming of CH₄ reaction. The evaluation of the catalytic performances of the composite catalysts was conducted in a fixed-bed reactor at atmospheric pressure. The influencing factors, including temperature, Ni and Ce loadings, molar feed ratio of CO₂/CH₄, and time-on-stream (TOS), were investigated. The characteristics of the catalysts were checked with Brunauer-Emmett-Teller (BET) analysis, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The reduction and the basic properties of the composite catalysts were elucidated by temperature-programmed reduction by H₂ (H₂-TPR) and temperature-programmed desorption of CO₂ (CO₂-TPD), respectively. The reactivity of deposited carbon was studied by sequential temperature-programmed surface reaction of CH₄ (CH₄-TPSR) and temperature-programmed oxidation using CO₂ and O₂ (CO₂-TPO and O₂-TPO). Results indicate that higher CH₄ conversion, H₂ selectivity, and desired H₂/CO ratio for 5 wt% Ni & 5 wt% Ce/ZSM-5 could be achieved with CO₂/CH₄ feed ratio close to unity over the temperature range of 500–900 °C. Moreover, the addition of Ce could not only promote CH₄ decomposition for H₂ production but also the gasification of deposited carbon with CO₂. The dispersion of Ni particles could be improved with Ce presence as well. A partial reduction of CeO₂ to CeAlO₃ was observed from XPS spectra over 5 wt% Ni & 5 wt% Ce/ZSM-5 after H₂ reduction and 24 h CO₂–CH₄ reforming reaction. Benefiting from the introduction of 5 wt% Ce, the calculated apparent activation energies of CH₄ and CO₂ over the temperature range of 700–900 °C could be reduced by 30% and 40%, respectively.     

Electrooxidation of H2/CO on carbon-supported PtRu-MoOx nanoparticles for polymer electrolyte fuel cells

Ternary PtRu-MoO_x catalysts with various Mo compositions have been investigated as anode electrocatalytic materials for a polymer electrolyte fuel cell fed with H₂/CO mixtures. Electrocatalysts have been prepared using a highly reproducible two step method, which allowed good control over the composition and particle size. All the prepared catalysts record a total metal loading close to 30 wt%, and a Mo load of 0, 1 and 3 wt%, supported on carbon Vulcan XC-72R, keeping the Pt/Ru atomic ratio constant. The incorporation of different amounts of Mo over the PtRu system does not modify structural characteristics such as particle size and crystal phases. However, the surface composition depends largely on the amount of Mo. An increase in the Mo loading to 3 wt% resulted in a decrease of the Pt surface area. The in situ FTIR technique has been used to investigate the CO oxidation process. The extent of CO poisoning was found to be lower for the trimetallic catalysts than for the binary catalyst at a potential below 0.25 V. The fuel cell performance was evaluated at 80 °C in a PEMFC fed with H₂/CO (10 ppm). Polarization curves for the catalysts show that activity depends heavily on composition, with catalysts with a small amount of Mo (1 wt%) displaying the highest CO tolerance. An increase in Mo loading (3 wt%) decreases activity of the PtRuMo, although it also reduces CO poisoning. The presence of Mo⁵⁺ species must be crucial for reducing the saturation coverage of irreversibly adsorbed CO on Pt surface atoms at very low potentials. However, the surface metal ratio of Pt/Mo (wt%) must be higher than 4, in order to keep the enough surface bare platinum sites, which are required for the dissociative adsorption of molecular H₂.     

Preferential oxidation of CO in H2 stream on Au/CeO2–TiO2 catalysts

A series of Au catalysts supported on CeO₂–TiO₂ with various CeO₂ contents were prepared. CeO₂–TiO₂ was prepared by incipient-wetness impregnation with aqueous solution of Ce(NO₃)₃ on TiO₂. Gold catalysts were prepared by deposition–precipitation method at pH 7 and 65 °C. The catalysts were characterized by XRD, TEM and XPS. The preferential oxidation of CO in hydrogen stream was carried out in a fixed bed reactor. The catalyst mainly had metallic gold species and small amount of oxidic Au species. The average gold particle size was 2.5 nm. Adding suitable amount of CeO₂ on Au/TiO₂ catalyst could enhance CO oxidation and suppress H₂ oxidation at high reaction temperature (>50 °C). Additives such as La₂O₃, Co₃O₄ and CuO were added to Au/CeO₂–TiO₂ catalyst and tested for the preferential oxidation of CO in hydrogen stream. The addition of CuO on Au/CeO₂–TiO₂ catalyst increased the CO conversion and CO selectivity effectively. Au/CuO–CeO₂–TiO₂ with molar ratio of Cu:Ce:Ti = 0.5:1:9 demonstrated very high CO conversion when the temperature was higher than 65 °C and the CO selectivity also improved substantially. Thus the additive CuO along with the promoter and amorphous oxide ceria and titania not only enhances the electronic interaction, but also stabilizes the nanosize gold particles and thereby enhancing the catalytic activity for PROX reaction to a greater extent.     

Co@Ru nanoparticle with core–shell structure supported over γ-Al2O3 for Fischer–Tropsch synthesis

Co@Ru/γ-Al₂O₃ core–shell structure catalysts with Co/Ru different weight ratios are successfully prepared via surface displacement reaction. This novel route including reduction of Co core by NaBH₄ on the surface of γ-Al₂O₃ and then substitution of Co species with Ru species, the resultant of reduction of RuCl₃ precursor with N₂H₄. These catalysts are characterized with techniques X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX), high resolution transmission electron microscopy (HRTEM), N₂ adsorption/desorption (BET), temperature programmed reduction (TPR), X-ray photoelectron spectroscopy (XPS) and Fourier transform infra-red (FTIR) of CO adsorbed. The characterization results confirm a uniform dispersion of Co@Ru nanoparticles with core–shell structure over γ-Al₂O₃. The core–shell Co@Ru/γ-Al₂O₃ catalysts show the remarkable catalytic activity towards Fischer–Tropsch synthesis (FTS) in comparison with Co/γ-Al₂O₃, which is related to special core–shell structure. These catalysts exhibited excellent abilities in the cases of increasing formation of long-chain hydrocarbons and suppressing selectivity to lighter hydrocarbons.     

Lowering risk of methanation of carbon support in Ru/carbon catalysts for CO methanation by adding lanthanum

Two series of Ru/C catalysts doped with lanthanum ions are prepared and studied in CO methanation in the H₂-rich gas. The samples are characterized by N₂ physisorption, TG-MS studies, XRD, XPS, TEM/STEM and CO chemisorption. Two graphitized carbons differing in surface area (115 and 80.6 m²/g) are used as supports. The average sizes of ruthenium crystallites deposited on their surfaces are 4.33 and 5.95 nm, respectively. The addition of the proper amount of La to the Ru/carbon catalysts leads to an above 20% increase in the catalytic activity along with stable CH₄ selectivity higher than 99% at all temperatures. Simultaneously, lanthanum acts as the inhibitor of methanation of the carbon support under conditions of high temperature and hydrogen atmosphere. Such positive effects are achieved at a very low concentration of La in the prepared samples, a maximum 0.04 La/Ru (molar ratio). 0.01 mmol La introduced to the Ru/C system leads to 98% CO conversion at 270 °C.     

Effect of preparation method on the performance of the Ni/Al2O3 catalysts for aqueous-phase reforming of ethanol: Part II-characterization

In the first part of this paper [1], we have discussed the effect of preparation method on the performance of Ni/Al₂O₃ catalysts for aqueous-phase reforming of ethanol (EtOH). One catalyst was synthesized using a sol–gel method (SG). The other was synthesized by adding nickel nitrate to a solution combustion synthesized alumina support (SCS). Based on the product distribution, we proposed the reaction pathway as a mixture of dehydrogenation of EtOH to acetaldehyde followed by C–C bond breaking to produce CO and CH₄ and oxidation of acetaldehyde to acetic acid followed by decarbonylation to CO₂ and CH₄. CH₄ (C₂H₆ and C₃H₈ also) can form via Fischer–Tropsch reactions of CO/CO₂ with H₂. The CH₄ (C₂H₆ and C₃H₈) reacts to form hydrogen and carbon monoxide through steam reforming, while CO converts to CO₂ mostly through the water-gas shift reaction (WGSR). The SG catalysts showed poorer WGSR activity than the SCS catalysts. The difference of the metal particle size distribution governed by preparation method appeared to be the key factor of controlling catalytic efficiency, but some contradictory results could not be explained.