Inorganic nanofibers with tailored placement of nanocatalysts for hydrogen production via alkaline hydrolysis of glucose.

Monoaxial silica nanofibers containing iron species as well as coaxial nanofibers with a pure silica core and a silica shell containing high concentrations of iron nanocrystals were fabricated via electrospinning precursor solutions, followed by thermal treatment. Tetraethyl-orthosilicate (TEOS) and iron nitrate (Fe(NO(3))(3)) were used as the precursors for the silica and iron phases, respectively. Thermal treatments of as-spun precursor fibers were applied to generate nanocrystals of iron with various oxidation states (pure iron and hematite). Scanning electron microscopy (SEM), x-ray diffraction (XRD), and transmission electron microscopy (TEM) were used to probe the fiber morphology and crystal structures. The results indicated that the size, phase, and placement of iron nanocrystals can be tuned by varying the precursor concentration, thermal treatment conditions, and processing scheme. The resulting nanofiber/metal systems obtained via both monoaxial and coaxial electrospinning were applied as catalysts to the alkaline hydrolysis of glucose for the production of fuel gas. Differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and bulk weight change in a furnace with residual gas analysis (RGA) were used to evaluate the performance of the catalysts for various ratios of both Fe to Si, and catalyst to glucose, and the oxidation state of the iron nanocrystals. The product gas is composed of mostly H(2) (>96 mol%) and CH(4) with very low concentrations of CO(2) and CO. Due to the clear separation of reaction temperature for H(2) and CH(4) production, pure hydrogen can be obtained at low reaction temperatures. Our coaxial approach demonstrates that placing the iron species selectively near the fiber surface can lead to two to three fold reduction in catalytic consumption compared to the monoaxial fibers with uniform distribution of catalysts.