Metal Oxide Nanofiber Catalysis
- Author(s): Noon, Daniel Patrick
- Advisor(s): Senkan, Selim M
- et al.
The synthesis of solids with finely turned nanostructures that offer superior catalytic performance is a major challenge in heterogeneous catalysis for gas phase reactions. Industrial catalysts are almost universally composed of quasi-spherical nanoparticles, or powders plagued with particle agglomeration, migration and sintering problems that lead to deactivation. In this work, quasi-cylindrical nanofibers are electrospun and extensively utilized for the oxidative coupling of methane (OCM), as well as for propylene epoxidation and the catalytic partial oxidation (CPO) of methane.
Electrospun nanofibers of metal oxides may be tuned to have high surface areas but typically possess no internal porosity, reducing diffusion limitations that would lengthen the exposure of target intermediate oxidation products to unselective catalysis. Additionally, experiments and density functional theory (DFT) studies have previously shown that pentagonal Ag nanowires exhibit higher selectivity than conventional particles in ethylene epoxidation since their surfaces are terminated mainly by the (100) surface facet rather than the lowest energy (111) facet that dominates particles. Hence, nanofibers may elevate catalytic performance in broad range of partial oxidation reaction schemes.
Research into the oxidative coupling of methane, or, the catalytic conversion of methane to ethane and ethylene by molecular oxygen, almost exclusively utilized powders and failed to result in viable catalyst despite four decades of intense, global efforts. Accordingly, the use of catalytic nanofibers provides a potentially fruitful path towards a solution. Here, nanofiber fabrics of La2O3-CeO2 were electrospun and used in fixed bed OCM reactors to achieve 70% selectivity and 16% yield for C2+ hydrocarbons at a CH4/O2 feed ratio of 7 and remarkably low feed temperature of 470 ?C. Powders of La2O3-CeO2 documented in the literature exhibit similar selectivity and yield, but with the feed at 715 ?C. The electrospun fabrics used in this research were found to have dense nanofibers of diameters typically within the 20 – 200 nm range and, accordingly, surface areas of 10 – 20 m2/g as well as thinner fibers tending towards both higher C2+ selectivity and CH4 conversion.
While performing reaction engineering studies using the aforementioned fabrics, it was found that designing reactors comprising dual catalytic La2O3-CeO2 fabric beds with inter-stage O2 injection and cooling pushes yields to 21%. Moreover, a novel in-situ microprobe sampling technique for acquiring spatial temperature and concentration profiles within these OCM reactors was developed, providing a means to formulate and validate detailed chemical kinetic mechanisms. This has led to the discovery of prompt H2 formation in OCM, a feature previously unidentified that may break ground in mechanism refinement. Additionally, spatial concentration and temperature profiles were acquired in fixed bed reactors comprising La2O3-CeO2 fabrics doped with varying levels of Ir and fed CH4/O2 mixtures to gain insight into the transition from OCM to the catalytic partial oxidation of methane. It was found that, in general, OCM and CPO appear to occur both in parallel and sequentially in a fixed bed, evidenced by the temporary rise and subsequent destruction of C2+ hydrocarbons when the catalyst is doped with 0.05 wt% Ir. Clearly, this sampling technique has broad applicability in catalysis research over a limitless number of reactions for the acquisition of comprehensive data sets potentially useful for formulating and refining detailed chemical kinetic mechanisms (DCKM), thus furthering a fundamental understanding of the catalysis and advancing faster towards the development of higher performing materials.