Reforming of bioethanol over Ni/Al2O3 and Ni/CeZrO2/Al2O3 catalysts in supercritical water for hydrogen production

Bioethanol was reformed in supercritical water (SCW) at 500 °C and 25 MPa on Ni/Al₂O₃ and Ni/CeZrO₂/Al₂O₃ catalysts to produce high-pressure hydrogen. The results were compared with non-catalytic reactions. Under supercritical water and in a non-catalytic environment, ethanol was reformed to H₂, CO₂ and CH₄ with small amounts of CO and C2 gas and liquid products. The presence of either Ni/Al₂O₃ or Ni/CeZrO₂/Al₂O₃ promoted reactions of ethanol reforming, dehydrogenation and decomposition. Acetaldehyde produced from the decomposition of ethanol was completely decomposed into CH₄ and CO, which underwent a further water-gas shift reaction in SCW. This led to great increases in ethanol conversion and H₂ yield on the catalysts of more than 3-4 times than that of the non-catalytic condition. For the catalytic operation, adding small amounts of oxygen at oxygen to ethanol molar ratio of 0.06 into the feed improved ethanol conversion, at the expense of some H₂ oxidized to water, resulting in a slightly lower H₂ yield. The ceria-zirconia promoted catalyst was more active than the unpromoted catalyst. On the promoted catalyst, complete ethanol conversion was achieved and no coke formation was found. The ceria-zirconia promoter has important roles in improving the decomposition of acetaldehyde, the enhancement of the water-gas shift as well as the methanation reactions to give an extremely low CO yield and a tremendously high H₂/CO ratio. The SCW environment for ethanol reforming caused the transformation of gamma-alumina towards the corundum phase of the alumina support in the Ni/Al₂O₃ catalyst, but this transformation was slowed down by the presence of the ceria-zirconia promoter.     

Mesoporous zirconia-modified clays supported nickel catalysts for CO and CO2 methanation

The Ni catalysts supported on a new structure with zirconia nanoparticles highly dispersed on the partly damaged clay layers has been prepared by the incipient wetness impregnation method and the new structure of the support has been prepared in one pot by the hydrothermal treatment of the mixture of the clay suspension and the ZrO(NO₃)₂ solution. The catalytic performances for the CO and CO₂ methanation on the catalysts have been investigated at a temperature range from 300 °C to 500 °C at atmospheric pressure. The catalysts and supports have been characterized by X-ray diffraction (XRD), transmittance electron microscopy (TEM), H₂ temperature-programmed reduction (H₂-TPR), nitrogen adsorption–desorption, and thermogravimetry and differential thermal analysis (TG-DTA). It is found that the zirconia-modified clays have the typical bimodal pore size distribution. Most of the pores with the sizes smaller than 10 nm are resulted from the zirconia pillared clays and the mesopores with the sizes larger than 10 nm and the macropores with the sizes larger than 50 nm are resulted from the partly damaged clay layers. The bimodal pore structure is beneficial to the dispersion of Ni on the layers of the zirconia-modified clays and the increase in Ni loading. The zirconia nanoparticles are highly dispersed on the partly damaged clay layers. Nickel oxide in cubic phase is the only Ni species that can be detected by XRD. The nickel oxide nanoparticles with the sizes of 12 nanometers or more are well dispersed on the zirconia-modified clay layers, which are observed to be buried in the stack layers of zirconia. The presence of nickel oxide in six different forms could be perceived on the new structure. Five of them except the Ni species that forms the spinel phase with Al in clays can be reduced to the active Ni species for the CO and CO₂ methanation. But the activity of the Ni species is different, which is associated with the chemical environment at which the Ni species is located. The catalyst with the higher zirconia content, which also has the larger specific surface area and pore volume, exhibits the better catalytic performance for the CO or CO₂ methanation. Zirconia in the catalyst is responsible for the dispersion of the Ni species, and it prevents the metallic Ni nanoparticles from sintering during the process of the reaction. In addition, it is also responsible for the reduction of the inactive carbon deposition. The catalyst with 15 wt.% zirconia content has the highest CO conversion of about 100% and the highest methane selectivity of about 93% at 450 °C for CO methanation, and the catalyst with 20% zirconia content has the CO₂ conversion of about 80% and the highest methane selectivity of about 99% for CO₂ methanation at 350 °C. The catalyst with 15 wt.% zirconia possesses promising stability and no distinct deactivation could be perceived after reaction for 40 h. This new catalyst has great potential to be used in the conversion of the blast furnace gas (BFG) and the coke oven gas (COG) to methane.     

Fuel cell grade hydrogen production via methanol steam reforming over CuO/ZnO/Al2O3 nanocatalyst with various oxide ratios synthesized via urea-nitrates combustion method

Hydrogen production via steam reforming of methanol has been studied over a series of CuO/ZnO/Al₂O₃ catalysts synthesized by the combustion method using urea as fuel. Furthermore, the effect of alumina loading on the properties of the catalyst has been investigated. XRD analysis illustrated the crystallinity of the Cu and Zn oxides decreases by enhancing alumina loading. BET showed the surface area improvement and FESEM images revealed lower size distribution by increasing the amount of alumina. EDX results gave approximately the same metal oxide compositions of primary gel for the surface of the nanocatalysts. Catalytic performance tests showed the well practicability of catalysts synthesized by the combustion method for steam reforming of methanol process. Alumina addition to the CuO/ZnO catalyst caused the higher methanol conversion and the lower CO generation. Among different compositions the sample with molar component of CuO/ZnO/Al₂O₃ = 4/4/2.5 showed the best performance which without CO generation at 240 °C its methanol conversion decreased from 90 to 60% after 90 h.     

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.     

Stabilized zirconia-based sensor utilizing SnO2-based sensing electrode with an integrated Cr2O3 catalyst layer for sensitive and selective detection of hydrogen

A highly selective hydrogen (H₂) sensor has been successfully developed by using an yttria-stabilized zirconia (YSZ)-based mixed-potential-type sensor utilizing SnO₂ (+30 wt.% YSZ) sensing electrode (SE) with an intermediate Al₂O₃ barrier layer which was coated with a catalyst layer of Cr₂O₃. The sensor utilizing SnO₂ (+30 wt.% YSZ)-SE was found to be capable of detecting H₂ and propene (C₃H₆) sensitively at 550 °C. In order to enhance the selectivity towards H₂, a selective C₃H₆ oxidation catalyst was employed to minimize unwanted responses caused by interfering gases. Among the examined metal oxides, Cr₂O₃ facilitated the selective oxidation of C₃H₆. However, the addition or lamination of Cr₂O₃ to SnO₂ (+30 wt.% YSZ)-SE was found to diminish the sensing responses to all examined gases. Therefore, an intermediate layer of Al₂O₃ was sandwiched between the SE layer and the catalyst layer to prevent the penetration of Cr₂O₃ particles into the SE layer. The sensor using SnO₂ (+30 wt.% YSZ)-SE coated with a catalyst layer of Cr₂O₃ as well as an intermediate layer of Al₂O₃ exhibited a sensitive response toward H₂, with only minor responses toward other examined gases at 550 °C under humid conditions (21 vol.% O₂ and 1.35 vol.% H₂O in N₂ balance). A linear relationship was observed between sensitivity and H₂ concentration in the range of 20–800 ppm on a logarithmic scale. The results of sensing performance evaluation and polarization curve measurements indicate that the sensing mechanism is based on the mixed-potential model.     

Hydroprocessing of Jatropha oil over NiMoCe/Al2O3 catalyst

The non-sulfided NiMoCe/Al₂O₃ catalyst was developed to produce green diesel from the hydroprocessing of Jatropha oil. The NiMoCe/Al₂O₃ catalysts were prepared by impregnation and characterized by N₂-BET, SEM, XRD and TPD-H_ads techniques. The straight chain alkanes ranging from C15 to C18 were the main components in product oil. The maximum yield of C15-C18 alkanes of 80%, selectivity of 90% and conversion of 89% were obtained at 370 °C, 3.5 MPa and 0.9 h⁻¹. Influence of reaction temperature (280–400 °C) and reaction time (10–163 h) on the composition of product oil were discussed. The experimental results demonstrated that a suitable amount of metal Ce doping on the NiMo/Al₂O₃ catalyst presented stable catalytic performance and enhanced Jatropha oil conversion as well as C15-C18 fraction selectivity.     

La0.6Sr0.4Co0.8Ni0.2O3−δ hollow fiber membrane reactor: Integrated oxygen separation – CO2 reforming of methane reaction for hydrogen production

An integrated reactor system which combines oxygen permeable La_0.6Sr_0.4Co_0.8Ni_0.2O_3−δ (LSCN) perovskite ceramic hollow fiber membrane with Ni based catalyst has been successfully developed to produce hydrogen through oxy-CO₂ reforming of methane (OCRM). Dense La_0.6Sr_0.4Co_0.8Ni_0.2O_3−δ hollow fiber membrane was prepared using phase inversion-sintering method. OCRM reaction was tested from 650 °C to 800 °C with a quartz reactor packed with 0.5 g Ni/Al₂O₃ catalyst around the LSCN hollow fiber membrane. CH₄ and CO₂ were used as reactants and air as the oxygen source was fed through the bore side of the hollow fiber membrane. In order to gauge the effectiveness of this membrane reactor system, air flow was closed at 800 °C and dry reforming of methane (DRM) was tested for comparison. The results show that the oxygen fluxes of LSCN membrane swept by helium are nearly 3 times less than those swept by OCRM reactants. With increasing temperature and oxygen supply, methane conversion in the OCRM reactor reaches 100%, but CO₂ conversion decreases from 87% to 72% due to the competition reaction with POM. CO selectivity is as high as nearly 100% at reaction temperatures of 700 °C–800 °C while H₂ selectivity reaches a maximum of 88% at 700 °C. At 800 °C, when air supply was closed and DRM was conducted for comparison, CO selectivity decreased to 91%, resulting in carbon deposition which was around 4 times more than those obtained under OCRM reaction and H₂/CO ratio decreased from 0.93 to 0.74, showing better carbon resistance and higher H₂ selectivity of the Ni-based catalyst over the integrated oxygen separation-OCRM reaction across the LSCN hollow fiber membrane reactor.     

Methanation of CO2 over alumina supported nickel or cobalt catalysts: Effects of the coordination between metal and support on formation of the reaction intermediates

This study focused on the potential coordination between nickel or cobalt and alumina in Ni/Al₂O₃ and Co/Al₂O₃ catalysts and the impacts on their catalytic performances in methanation of CO₂. The results exhibited that Co/Al₂O₃ catalyst was far more active than Ni/Al₂O₃ catalyst, due to the varied reaction intermediates formed in methanation. The DRIFTS results of methanation of CO₂ exhibited that, over bare alumina, bicarbonate, formate and carbonate were the main intermediate species, which could be formed at even 80 °C. Over unsupported Ni catalyst, the formaldehyde species (H₂CO*) and CO* species were dominated. Over the Ni/Al₂O₃ catalyst, however, the reaction intermediates formed were determined by alumina and accumulated on surface of the catalysts. The coordination effects between nickel and alumina in Ni/Al₂O₃ were thus not remarkable in terms of enhancing catalytic activity when compared to that in Co/Al₂O₃ catalyst. Over unsupported Co catalyst and the bare alumina, the reaction intermediates formed were roughly similar. Nevertheless, the combination of Co and alumina in Co/Al₂O₃ catalyst could effectively facilitate the conversion of bicarbonate, formate and carbonate species. CO₂ could be activated over metallic cobalt sites, which could migrate and integrate with the hydroxyl group in alumina to form bicarbonate and further to formate and CO* species, and be further hydrogenated over cobalt sites to CH₄. Such a coordination between alumina and cobalt species promoted the catalytic performances.     

Nanocrystallites-forming hierarchical porous Ni/Al2O3–TiO2 catalyst for dehydrogenation of organic chemical hydrides

Dehydrogenation of organic chemical hydrides has been improved by reconstructing the catalyst in the form of hierarchical porous structure nanocatalyst, in which the economical Ni was adopted as catalytic component and nano Al₂O₃–TiO₂ hybrid composite as support. The Al₂O₃–TiO₂ composite was prepared by spontaneous self-assembly of nano Al₂O₃ and TiO₂ aggregates by hydrolysis of tetra-n-butyl-titanate under continuous agitation. The multi-scaled distribution of Al₂O₃–TiO₂ aggregates with hierarchy could be observed in dynamic light scattering spectrometer. The aggregates are comprised of nano-sized γ-Al₂O₃ and anatase TiO₂ crystallites with sizes of about 5 and 7 nm, respectively. The surface modulation by TiO₂ could be verified in FTIR Spectra. The migration of Ti species and crystallite growth were hindered by the Al₂O₃ skeleton and the hierarchical porous structure was sustained during the thermal related process. The multi-scaled distributed pores were confirmed by both TEM analysis and N₂ adsorption results. The results of dehydrogenation experiments showed that the hierarchical porous structure nano Ni/Al₂O₃–TiO₂ exhibited superior catalytic performance to Ni/Al₂O₃ with the optimum conversion of 99.9% at 400 °C, while the catalyst of Ni/Al₂O₃ exhibited only 16.5% under the same condition.     

Evaluation of Ni/Y2O3/Al2O3 catalysts for hydrogen production by autothermal reforming of methane

Ni/xY₂O₃–Al₂O₃ (x = 5, 10, 15, 20 wt%) catalysts were prepared by sequential impregnation synthesis. The catalytic performance for the autothermal reforming of methane was evaluated and compared with Ni/γ-Al₂O₃ catalyst. The physicochemical properties of catalysts were characterized by X-ray diffraction (XRD), Transmission electron microscope (TEM), X-Ray Photoelectron Spectrometer (XPS), Thermo Gravimetric Analyzer (TGA) and H₂-temperature programmed reduction techniques (TPR). The decrease of nickel particle size and the change of reducibility were found with Y modification. The CH₄ conversion increased with elevating levels of Y₂O₃ from 5% to 10%, then decreased with Y content from 10% to 20%. Ni/xY₂O₃–Al₂O₃ catalysts maintained high activity after 24 h on stream, while Ni/Al₂O₃ had a significant deactivation. The characterization of spent catalysts indicated that the addition of Y retarded Ni sintering and decreased the amount of coke.     

Effect of N2O-mediated calcination on nickel species and the catalytic activity of nickel catalysts supported on γ-Al2O3 in the steam reforming of glycerol

The steam reforming of glycerol over supported nickel catalysts is a promising and cost-effective method for producing hydrogen. The activity of nickel catalysts supported on γ-Al₂O₃ is low, primarily due to the formation of inactive nickel species during high temperature calcination in air. In order to address this problem, a Ni/γ-Al₂O₃ catalyst was prepared by calcination at 700 °C in a nitrous oxide (N₂O) environment. The N₂O calcined catalyst showed an enhanced activity for the steam reforming of glycerol. A variety of characterization techniques (XRD, TPR, XPS and H₂ Chemisorption) confirmed that the high temperature N₂O calcination resulted in a significant decrease in the levels of nickel aluminate. The N₂O calcination also led to an enhancement in the amount of NiO as well as nickel ions present on the surface of the catalyst. Interestingly, compared to an air calcined catalyst, the N₂O calcined catalyst contained larger nickel particles after reduction but the N₂O calcined catalyst had a much larger nickel surface area and dispersion, which resulted in higher glycerol conversion and hydrogen yield.     

Oxidative steam reforming of methanol over CuO/ZnO/CeO2/ZrO2/Al2O3 catalysts

The composition (CuO/ZnO/Al₂O₃ = 30/60/10) of a commercial catalyst G66B was used as a reference for designing CuO/ZnO/CeO₂/ZrO₂/Al₂O₃ catalysts for the oxidative (or combined) steam reforming of methanol (OSRM). The effects of Al₂O₃, CeO₂ and ZrO₂ on the OSRM reaction were clearly identified. CeO₂, ZrO₂ and Al₂O₃ all promoted the dispersions of CuO and ZnO in CuO/ZnO/CeO₂/ZrO₂/Al₂O₃ catalysts. Aluminum oxide lowered the reducibility of the catalyst, and weakened the OSRM reaction. Cerium oxide increased the reducibility of the catalyst, but weakened the reaction. Zirconium oxide improved the reducibility of the catalyst, and promoted the reaction. A lower CuO/ZnO ratio of the catalyst was associated with greater promotion of ZrO₂. The critical CuO/ZnO ratio for the promotion of ZrO₂ was approximately 0.75–0.8. Introducing of ZrO₂ into CuO/ZnO/Al₂O₃ also improved the stability of the catalyst. Although Al₂O₃ inhibited the OSRM reaction, a certain amount of it was required to ensure the stability and the mechanical strength of the catalysts.     

Methanol steam reforming in an Al2O3 supported thin Pd-layer membrane reactor over Cu/ZnO/Al2O3 catalyst

In this experimental study, a membrane reactor housing a composite membrane constituted by a thin Pd-layer supported onto Al₂O₃ is utilized to perform methanol steam reforming reaction to produce high-grade hydrogen for PEM fuel cell applications. The influence of various parameters such as temperature, from 280 to 330 °C, and pressure, from 1.5 to 2.5 bar, is analyzed. A commercial Cu/Zn-based catalyst is packed in the annulus of the membrane reactor and the experimental tests are performed at space velocity equal to 18,500 h⁻¹ and H₂O:CH₃OH feed molar ratio equal to 2.5:1. Results in terms of methanol conversion, hydrogen recovery, hydrogen yield and products selectivities are given. As a best result of this work, 85% of methanol conversion and a highly pure hydrogen stream permeated through the membrane with a CO content lower than 10 ppm were reached at 330 °C and 2.5 bar. Furthermore, a comparison between the experimental results obtained in this work and literature data is proposed and discussed.     

Photocatalytic hydrogen production from aqueous methanol solution with CuO/Al2O3/TiO2 nanocomposite

The photocatalytic hydrogen production from aqueous methanol solution was investigated with ZnO/TiO₂, SnO/TiO₂, CuO/TiO₂, Al₂O₃/TiO₂ and CuO/Al₂O₃/TiO₂ nanocomposites. A mechanical mixing method, followed by the solid-state reaction at elevated temperature, was used for the preparation of nanocomposite photocatalyst. Among these nanocomposite photocatalysts, the maximal photocatalytic hydrogen production was observed with CuO/Al₂O₃/TiO₂ nanocomposites. A variety of components of CuO/Al₂O₃/TiO₂ photocatalysts were tested for the enhancement of H₂ formation. The optimal component was 0.2 wt% CuO/0.3 wt% Al₂O₃/TiO₂. The activity exhibited approximately tenfold enhancement at the optimum loading, compared with that with pure P-25 TiO₂. Nano-sized TiO₂ photocatalytic hydrogen technology has great potential for low-cost, environmentally friendly solar-hydrogen production to support the future hydrogen economy.     

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.     

Effect of nickel content and preparation method on the performance of Ni-Al2O3 towards the applications in solid oxide fuel cells

Ni-Al₂O₃ composites with varying contents of nickel are synthesized via a glycine nitrate process (GNP) and an impregnation process (IMP). Their potential application as an anode functional layer for internal methane CO₂ reforming in a solid oxide fuel cell is investigated. H₂-TPR results show that the chemical interaction between NiO and Al₂O₃ decreases as the nickel content increases. Catalytic tests demonstrate that 15 wt.% Ni-Al₂O₃ catalysts exhibit the best catalytic activity for methane CO₂ reforming. However, the carbon formation rates over Ni-Al₂O₃ prepared via GNP are lower than those over Ni-Al₂O₃ prepared via IMP using the same amounts of nickel, with the exception of the 1 wt.% Ni-Al₂O₃ catalyst. Raman spectroscopy and O₂-TPO results indicate that the degree of graphitization and the amount of carbon deposited on the 15 wt.% Ni-Al₂O₃ catalyst synthesized via GNP are lower than those of the catalyst prepared via IMP following a 60 h stability test. A cell with a 15 wt.% Ni-Al₂O₃ catalyst layer prepared via GNP is fabricated that delivers a peak power density of 1006 mW cm⁻² at 850 °C when operating on methane-CO₂ gas mixtures, which is comparable to that observed when operating on hydrogen fuel.     

Effects of modifying Ni/Al2O3 catalyst with cobalt on the reforming of CH4 with CO2 and cracking of CH4 reactions

Alumina supported nickel (Ni/Al₂O₃), nickel–cobalt (Ni–Co/Al₂O₃) and cobalt (Co/Al₂O₃) catalysts containing 15% metal were synthesized, characterized and tested for the reforming of CH₄ with CO₂ and CH₄ cracking reactions. In the Ni–Co/Al₂O₃ catalysts Ni–Co alloys were detected and the surface metal sites decreased with decrease in Ni:Co ratio. Turnover frequencies of CH₄ were determined for both reactions. The initial turnover frequencies of reforming (TOF_DRM) for Ni–Co/Al₂O₃ were greater than that for Ni/Al₂O₃, which suggested a higher activity of alloy sites. The initial turnover frequencies for cracking (TOF_CRK) did not follow this trend. The highest average TOF_DRM, H₂:CO ratio and TOF_CRK were observed for a catalyst containing a Ni:Co ratio of 3:1. This catalyst also had the maximum carbon deposited during reforming and produced the maximum reactive carbon during cracking. It appeared that carbon was an intermediate product of reforming and the best catalyst was able to most effectively crack CH₄ and oxidize carbon to CO by CO₂.     

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.     

Carbon dioxide reforming of methane to synthesis gas over Ni/Si3N4 catalysts

Silicon nitride supported nickel catalyst prepared by impregnation using nickel nitrate solution was employed for the carbon dioxide reforming of methane. The catalyst was tested at 800 °C under atmospheric pressure. The influences of Ni loading and calcination temperature on the catalytic performance were investigated. It was found that the nickel loading and calcination temperature strongly influenced the catalytic performance. Over the 7 wt. % Ni/Si₃N₄ catalyst calcined at 400 °C, the conversions of CH₄ and CO₂ can achieve 95% and 91%, respectively. Appropriate interaction between the metal and the basic support makes the catalyst more resistant to sintering and coking, and thus an excellent stability.     

Mesocellular-foam-silica-supported Ni catalyst: Effect of pore size on H2 production from cellulose pyrolysis

Supported nickel metal can be used as a tar-cracking catalyst in the thermal processing of large organics to give H₂. Though porous supports offer the opportunity to disperse a relatively large amount of nickel, catalytic sites within small pores may be inaccessible to large tar molecules. To investigate this, we prepared nickel catalysts supported on γ-Al₂O₃ and on SBA-15- and mesocellular-foam-(MCF)-type silicas and studied their catalytic activities in the pyrolytic decomposition of cellulose (RT → 800 °C, ∂T/∂t = 40 °C/min). A thermogravimetric analyser-mass spectrometer (TG-MS) was used to study the influence of the Ni catalyst and support materials on the H₂ yield and selectivity. The silica-MCF-supported Ni catalyst decreased char residue and enhanced H₂ yield, producing 1.6 and 3.5× the H₂ yield obtained using SBA-15-supported Ni and γ-Al₂O₃-supported Ni, respectively. MCF, with ultra-large pores (d ∼ 15−50 nm), was thus identified as the most beneficial catalyst support for this application.