Robust Hydrogen Production via Pickering Interfacial Catalytic Photoreforming of n-Octanol-Water Biphasic System

Pickering emulsion offers a promising platform for conducting interfacial reactions between immiscible reagents; it is particularly suitable for hydrogen production by photoreforming of non-water soluble biomass liquid and water. Herein, Pt-promoted (001)-facet-dominated anatase TiO2 nanosheets were synthesized by a hydrothermal route associated with microfluidic technology for high activity and metal dispersion, and selective surface modification was carried out for preparing Janus particles. Photoreforming hydrogen production through n-octanol and water that formed O/W microemulsion with an average diameter of 540 µm was achieved to obtain amphiphilic catalyst. The as-prepared 2D Janus-type catalysts exhibited remarkably stable emulsification performance as well as photocatalytic activity. This finding indicates that triethoxyfluorosilane had negligible impact on the catalytic performance, yet provided a remarkable benefit to large specific surface area at microemulsion interface, thereby enhancing the H2 yield up to 2003 μmol/g. The cyclic experiments indicate that the decrease in cyclic performance was more likely to be caused by the coalescence of the microemulsion rather than the decrease in catalytic activity, and the microemulsion could be easily recovered by simply hand shaking to more than 96% of the initial performance.

Influence of Preparation Conditions on the Catalytic Performance of Mo/H-ZSM-5 for Methane Dehydroaromatization

Methane, the main component of natural gas, is an interesting source of chemicals and clean liquid fuels, and a promising alternative raw material to oil. Among the possible direct routes for methane conversion, its aromatization under non-oxidative conditions has received increasing attention, despite the low conversions obtained due to thermodynamic limitations, because of its high selectivity to benzene. Mo/H-ZSM-5, the first bifunctional zeolite-catalyst proposed for this reaction, is still considered as one of the most adequate and has been widely studied. Although the mono- or bifunctional nature of the MDA mechanism is still under debate, it is generally accepted that the Mo species activate the C-H bond in methane, producing the intermediates. These will aromatize on the Brønsted acid sites of the zeolite, whose pore dimensions will provide the shape selectivity needed for converting methane into benzene. An additional role of the zeolite’s Brønsted acid sites is to promote the dispersion of the Mo oxide precursor. Here, we show the influence of the different preparation steps—metal incorporation, calcination and activation of the Mo/ZSM-5- on the metal dispersion and, therefore, on the activity and selectivity of the final catalyst. Metal dispersion is enhanced when the samples are calcined under dynamic conditions (DC) and activated in N2, and the benefits are larger when the metal has been incorporated by solid state reaction (SSR), as observed by FESEM-BSE and H2-TPR. This leads to catalysts with higher activity, increased aromatic selectivity and improved stability towards deactivation.

Ultrasound-Assisted Preparation of Mo/ZSM-5 Zeolite Catalyst for Non-Oxidative Methane Dehydroaromatization

The activity and selectivity of Mo/ZSM-5, benchmarking catalyst for the non-oxidative dehydroaromatization of methane, strongly depend on the cluster size, spatial distribution, and chemical environment of the Mo-based active sites. This study discloses the use of an ultrasound-assisted ion-exchange (US-IE) technique as an alternative Mo/ZSM-5 synthesis procedure in order to promote metal dispersion along the zeolite framework. For this purpose, a plate transducer (91.8 kHz) is employed to transmit the ultrasonic irradiation (US) into the ion-exchange reactor. The physico-chemical properties and catalytic activity of samples prepared under the said irradiation procedure and traditional impregnation (IWI) method are critically evaluated. Characterization results suggest that US neither affects the crystalline structure nor the particle size of the parent zeolite. However, US-IE promotes molybdenum species dispersion, avoids clustering at the external fresh zeolite surface and enhances molybdate species anchoring to the zeolite framework with respect to IWI. Despite the improved metal dispersion, the catalytic activity between catalysts synthesized by US-IE and IWI is comparable. This suggests that the sole initial dispersion enhancement does not suffice to boost the catalyst productivity and further actions such ZSM-5 support and catalyst pre-conditioning are required. Nevertheless, the successful implementation of US-IE and the resulting metal dispersion enhancement pave the way toward the application of this technique to the synthesis of other dispersed catalysts and materials of interest.

Influence of the Reduction Temperature and the Nature of the Support on the Performance of Zirconia and Alumina-Supported Pt Catalysts for n-Dodecane Hydroisomerization

Catalysts based on zirconia- and alumina-supported tungsten oxides (15 wt % W) with a small loading of platinum (0.3 wt % Pt) were selected to study the influence of the reduction temperature and the nature of the support on the hydroisomerization of n-dodecane. The reduction temperature has a major influence on metal dispersion, which impacts the catalytic activity. In addition, alumina and zirconia supports show different catalytic properties (mainly acid site strength and surface area), which play an important role in the conversion. The NH3-TPD profiles indicate that the acidity in alumina-based catalysts is clearly higher than that in their zirconia counterparts; this acidity can be attributed to a stronger interaction of the WOx species with alumina. The PtW/Al catalyst was found to exhibit the best catalytic performance for the hydroisomerization of n-dodecane based on its higher acidity, which was ascribed to its larger surface area relative to that of its zirconia counterparts. The selectivity for different hydrocarbons (C7–10, C11 and i-C12) was very similar for all the catalysts studied, with branched C12 hydrocarbons being the main products obtained (~80%). The temperature of 350 °C was clearly the best reduction temperature for all the catalysts studied in a trickled-bed-mode reactor.