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The effect of surface area and polarity ratio of ZnO support on the catalytic properties of CuO/ZnO catalyst for methanol steam reforming (MSR) are studied. The surface area of ZnO was varied changing the calcination temperature, and its polarity ratio was modified using different Zn precursors, zinc acetate and zinc nitrate. It was found that the copper dispersion and copper surface area increase with the surface area of the ZnO support, and the polarity ratio of ZnO strongly influences the reducibility of copper species. A higher polarity ratio promotes the reducibility, which is attributed to a strong interaction between copper and the more polar ZnO support. Interestingly, it was observed that the selectivity of CuO/ZnO catalysts (lower CO yield) increases with the polarity ratio of ZnO carriers. As another key result, CuO/ZnOAc375 catalyst has proven to be more selective (up to 90%) than a reference CuO/ZnO/Al2O3 sample (G66-MR, Süd Chemie).The activity of the best performing catalyst, CuO/ZnOAc-375, was assessed in a Pd-composite membrane reactor and in a conventional packed-bed reactor. A hydrogen recovery of ca. 75% and a hydrogen permeate purity of more than 90% was obtained. The Pd-based membrane reactor allowed to improve the methanol conversion, by partially suppressing the methanol steam reforming backward reaction, besides upgrading the reformate hydrogen purity for use in HT-PEMFC.2

The influence of the calcination atmosphere of ZnO precursor (Zn4(CO)3(OH)6·H2O) on the catalytic performance of a series of PdZn/ZnO catalysts was studied for production of H2 via low temperature (180 • C) direct methanol steam reforming (low temperature-MSR). The catalytic activity and selectivity of PdZn/ZnO were found to be strongly influenced by the calcination atmosphere of ZnO precursor and increased from oxidizing to reducing atmosphere, following the order (O2 < air < N2 < H2). As a result, a very active catalyst was obtained by simply supporting Pd on ZnO calcined in H2. Further evidence from XPS and TPR analysis indicated that calcination in reducing atmosphere gave rise to a significant increase in the concentration of oxygen vacancies on the surface of ZnO support. Thus, the superb performance of the best catalyst was attributed to the defect chemistry of ZnO support; mainly to the amount of oxygen vacancies present in the interface region, which act as additional active sites for water adsorption and subsequent activation. In addition, the formation of CO was drastically suppressed by replenishment of oxygen vacancies on ZnO support. Thus, it is clear that the abundance of specific active sites on PdZn/ZnO catalyst is strongly influenced by the preparation route of the ZnO support. Additionally, the PdZn alloy was discovered to be unstable under prolonged exposure to CO atmosphere and the stability test under methanol steam reforming conditions showed a 24% drop in conversion over 48 h testing period. This phenomena can have detrimental effect on the performance of this type of catalytic systems in continuous prolonged duty cycle time on-stream.

A simple urea-assisted hydrothermal synthesis method was used to tailor the physicochemical properties of ZnO materials. The role of Pluronic P123 block copolymer in the crystal growth, morphology and specific surface area of the as-prepared ZnO was studied. When Pluronic P123 is used, well-dispersed hierarchical microspheres, with a flower-like morphology, are obtained, but in its absence large spherical agglomerated clusters are formed. The polarity of the ZnO, measured as the ratio between plane (002) and plane (100), is also significantly higher for the Pluronic P123 sample. The influence of zinc salt precursors was also analysed. The use of zinc nitrate led to the formation of urchin-like ZnO structures, instead of the microflowers that result from zinc acetate salt. Despite having similar surface areas, the polarity of the zinc nitrate sample was much smaller. The decomposition of methylene blue corroborated the higher photocatalytic activity of the ZnO materials with a higher proportion of polar planes (higher polarity). The formation mechanism of the crystals is also suggested based on the observed gradual growth and assembly of the hydrozincite during the initial steps of the synthesis for the samples with and without Pluronic P123.

A novel nanoparticulate catalyst of copper (Cu) and ruthenium (Ru) was designed for low-temperature ammonia oxidation at near-stoichiometric mixtures using a bottom-up approach. A synergistic effect of the two metals was found. An optimum CuRu catalyst presents a reaction rate threefold higher than that for Ru and forty-fold higher than that for Cu. X-ray absorption spectroscopy suggests that in the most active catalyst Cu forms one or two monolayer thick patches on Ru and the catalysts are less active once 3D Cu islands form. The good performance of the tuned Cu/Ru catalyst is attributed to changes in the electronic structure, and thus the altered adsorption properties of the surface Cu sites.