An investigation
of aerobic oxidation of 2-methoxy-4-methylphenol
to vanillin catalyzed by a number of cobalt salts, complexes, oxides,
and hydroxides in alkaline solutions is reported. A good yield of
vanillin (90%) was obtained when CoCl2 was used as the
catalyst, while a poor yield (6%) was obtained with Co3O4. Unexpectedly, however, the Co3O4 catalytic activity was restored after heating in an alcoholic solution
of NaOH for 24 h, producing a good yield of vanillin (85%). The recovered
catalytic activity of Co3O4 indicated a conversion
of inactivated heterogeneous particles to activated particles. In
addition, precipitates were generated when “homogeneous”
CoCl2 was employed as a catalyst, making us wonder about
the true nature of the catalyst in this reaction. A series of experiments
are described, including kinetic studies, filtration tests, centrifugation
tests, dynamic light scattering, transmission electron microscopy,
X-ray photoelectron spectroscopy, and powder X-ray diffraction, for
the investigation of the true catalyst under catalytic conditions.
The key observations led to the conclusion that the cobalt salts and
complexes act as precatalysts that transform to cobalt oxide/hydroxide
[CoO
x
(OH)
y
] nanoparticles, which is responsible for the benzylic C(sp3)–H oxyfunctionalization of 2-methoxy-4-methylphenol. Additionally,
the size of the particles is decisive for catalyst performance. The
nature of the active nanoparticles was also studied. With regard to
the identification of homogeneous or heterogeneous catalysis, this
study provides a complement to existing catalytic reaction types.
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