Hierarchically Structured Porous Spinels via an Epoxide-Mediated Sol-Gel Process Accompanied by Polymerization-Induced Phase Separation.

Enhancing the activity and stability of catalysts is a major challenge in scientific research nowadays. Previous studies showed that the generation of an additional pore system can influence the catalytic performance of porous catalysts regarding activity, selectivity, and stability. This study focuses on the epoxide-mediated sol-gel synthesis of mixed metal oxides, NiAl2O4 and CoAl2O4, with a spinel phase structure, a hierarchical pore structure, and Ni and Co contents of 3 to 33 mol % with respect to the total metal content. The sol-gel process is accompanied by a polymerization-induced phase separation to introduce an additional pore system. The obtained mixed metal oxides were characterized with regard to pore morphology, surface area, and formation of the spinel phase. The Brunauer-Emmett-Teller surface area ranges from 74 to 138 m2·g-1 and 25 to 94 m2·g-1 for Ni and Co, respectively. Diameters of the phase separation-based macropores were between 500 and 2000 nm, and the mesopore diameters were 10 nm for the Ni-based system and between 20 and 25 nm for the cobalt spinels. Furthermore, Ni-Al spinels with 4, 5, and 6 mol % Ni were investigated in the dry reforming of CH4 (DRM) with CO2 to produce H2 and CO. CH4 conversions near the thermodynamic equilibrium were observed depending on the Ni content and reaction temperature. The Ni catalysts were further compared to a noble metal-containing catalyst based on a spinel system showing comparable CH4 conversion and carbon selectivity in the DRM.

Microimaging of transient concentration profiles of reactant and product molecules during catalytic conversion in nanoporous materials.

Microimaging by IR microscopy is applied to the recording of the evolution of the concentration profiles of reactant and product molecules during catalytic reaction, notably during the hydrogenation of benzene to cyclohexane by nickel dispersed within a nanoporous glass. Being defined as the ratio between the reaction rate in the presence of and without diffusion limitation, the effectiveness factors of catalytic reactions were previously determined by deliberately varying the extent of transport limitation by changing a suitably chosen system parameter, such as the particle size and by comparison of the respective reaction rates. With the novel options of microimaging, effectiveness factors become accessible in a single measurement by simply monitoring the distribution of the reactant molecules over the catalyst particles.

Nanoporous glass as a model system for a consistency check of the different techniques of diffusion measurement.

The remarkable differences in the guest diffusivities in nanoporous materials commonly found with the application of different measuring techniques are usually ascribed to the existence of a hierarchy of transport resistances in addition to the diffusional resistance of the pore system and their differing influence due to the differing diffusion path lengths covered by the different measuring techniques. We report diffusion measurements with nanoporous glasses where the existence of such resistances could be avoided. Molecular propagation over diffusion path lengths from hundreds of nanometers up to millimeters was thus found to be controlled by a uniform mechanism, appearing in coinciding results of microscopic and macroscopic diffusion measurement.