Direct selective oxidation of hydrocarbons to oxygenates by O2 is challenging. Catalysts are limited by the low activity and narrow application scope, and the main focus is on active C−H bonds at benzylic positions. In this work, stable, lead‐free, Cs3Bi2Br9 halide perovskites are integrated within the pore channels of mesoporous SBA‐15 silica and demonstrate their photocatalytic potentials for C−H bond activation. The composite photocatalysts can effectively oxidize hydrocarbons (C5 to C16 including aromatic and aliphatic alkanes) with a conversion rate up to 32900 μmol gcat−1 h−1 and excellent selectivity (>99 %) towards aldehydes and ketones under visible‐light irradiation. Isotopic labeling, in situ spectroscopic studies, and DFT calculations reveal that well‐dispersed small perovskite nanoparticles (2–5 nm) possess enhanced electron–hole separation and a close contact with hydrocarbons that facilitates C(sp3)−H bond activation by photoinduced charges.
A novel hydrodeoxygenation catalytic system, Ni2P/SBA-15,
has been synthesized by temperature-programmed reduction of a nickel
phosphate precursor impregnated in the mesostructured silica support.
The formation of this active phase was verified by X-ray diffraction,
whereas the study by transmission electron microscopy revealed that
the catalyst is mainly constituted of nickel phosphide particles of
relatively uniform size dispersed within the SBA-15 channels. Both
Ni2P/SBA-15 and a reference Ni/SBA-15 catalyst were tested
for the hydrodeoxygenation of methyl oleate (C17H33–COO–CH3) in a fixed-bed continuous flow
reactor. This compound was used as a convenient surrogate of triglyceride
molecules present in vegetable oils that following catalytic hydrotreating
yields n-alkanes as the main products. In the whole
range of pressure studied (3–40 bar) and for temperatures higher
than 290 °C, both systems achieve more than 80% ester conversion
at 20 h–1 WHSV, although the Ni/SBA-15 catalyst
presents a slightly higher activity. Overall, higher pressure and
lower temperature and space velocity favors the formation of C18 hydrocarbon, which is the preferred product in terms of
carbon atom economy. Nevertheless, under all the assayed conditions,
the n-C18/n-C17 ratio was remarkably higher for Ni2P/SBA-15 than for
Ni/SBA-15 catalysts. On the basis of these results, it can be concluded
that both deoxygenation and decarboxylation occur simultaneously over
the Ni2P catalyst, whereas decarboxylation and cracking
are the prevailing processes over the Ni catalyst. Owing to these
high yields of long-chain paraffins, Ni2P/SBA-15 can be
considered as a very promising catalyst for the production of green
diesel.
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