Multifunctional
Fe3O4@Nb2O5@Co@Re catalysts
with metal loadings in the range of 2–7
wt % were prepared via a multistep process. Magnetic nanoparticles
prepared by coprecipitation were covered with a niobia shell precipitated
from an ammonium niobate–oxalate complex in the presence of
hexadecyltrimethylammonium bromide. The deposition of cobalt was performed
using a deposition/precipitation procedure. Finally, rhenium has been
deposited following three different routes: (i) impregnation, (ii)
deposition and precipitation of rhenium chloride (ImC and PP, respectively),
and (iii) impregnation with ammonium perrhenate (ImA). The characterization
of these catalysts was achieved by X-ray diffraction, Raman, H2 and NH3 temperature-programmed desorption, X-ray
photoelectron spectroscopy, and transmission electron microscopy showing
the influence of the preparation procedure, reduction, and Re/Co cooperation
on the degree of dispersion and reduction. ImC and ImA routes led
to more reduced catalysts, and the decrease in cobalt content corresponded
to more reduced rhenium. An inverse relation between the acidity and
the degree of reduction has been found. The screening of these catalysts
in the fragmentation of the lignin confirmed the role of the structural
characteristics and solvent. ImC catalysts exhibited better catalytic
activity, especially for low metal loadings [2%Co@3%Re, 85% yield
of LF, 15.5% yield of LR in tetrahydrofuran (THF), and 14.5% yield
of insoluble LR in THF]. Although the extent was smaller, the PP catalysts
allowed a more advanced fragmentation of the lignin to fragments with
molecular weights between 200 and 400 Da. The catalysts were totally
recovered by application of a magnetic field and recycled six times
without any loss of activity or selectivity.