Abstract:Iron-catalyzed oxidation reactions have been increasingly investigated in the past two decades and have seen a major increase in research activity. This review article demonstrates the vigorous research activities in the field based on examples from the most recent literature. Catalyst systems are discussed that are active in the oxygenation of alkanes and alkenes to obtain alcohols, ketones or epoxides. Iron-catalyzed oxidation of alcohols to the corresponding carbonyl units are also included. Enantioselectiv… Show more
“…Iron-based catalysts or co-catalysts are well-introduced and famous species for catalyzing oxidation reactions in organic chemistry. ,, Iron and other transition metals mainly catalyze oxidation through the redox property. ,− Iron oxide is one of the famous species and effective catalysts for the oxidation reactions of organic compounds such as alcohols, , alkenes, , asphaltenes, ,, and crude oils. , In addition, iron oxides can be easily applied in industry because of their relatively low cost. Therefore, in this work, we focus on iron oxide (Fe 2 O 3 ).…”
Oil-dispersed
α-Fe2O3 nanocatalysts
were prepared by coating α-Fe2O3 nanoparticles
with oleic acid (OA). Mössbauer spectroscopy, X-ray diffraction,
and field emission scanning electron microscopy were used to characterize
α-Fe2O3 and α-Fe2O3@OA. Their impact on the oxidation process of heavy oil was
evaluated using a porous medium thermo-effect cell and thermogravimetry–infrared
spectroscopy coupled with isoconversional kinetic analysis. Compared
with α-Fe2O3, α-Fe2O3@OA more efficiently catalyzed the combustion of heavy oil
due to its good dispersion in heavy oil. α-Fe2O3 was found to be transformed into smaller size magnetite (Fe3O4), maghemite (γ-Fe2O3), and α-Fe2O3 during heavy oil combustion.
Fe2O3@OA reduced the activation energy from
a maximum of 537 to 246 kJ/mol, which considerably facilitates fuel
formation and makes an easier transition from fuel formation to its
combustion in the high-temperature oxidation (HTO) stage, thus shifting
HTO into lower temperatures. These enhanced performances in the heavy
oil combustion by α-Fe2O3@OA could be
favorable for improving the efficiency of the in situ combustion (ISC)
technique in oilfields.
“…Iron-based catalysts or co-catalysts are well-introduced and famous species for catalyzing oxidation reactions in organic chemistry. ,, Iron and other transition metals mainly catalyze oxidation through the redox property. ,− Iron oxide is one of the famous species and effective catalysts for the oxidation reactions of organic compounds such as alcohols, , alkenes, , asphaltenes, ,, and crude oils. , In addition, iron oxides can be easily applied in industry because of their relatively low cost. Therefore, in this work, we focus on iron oxide (Fe 2 O 3 ).…”
Oil-dispersed
α-Fe2O3 nanocatalysts
were prepared by coating α-Fe2O3 nanoparticles
with oleic acid (OA). Mössbauer spectroscopy, X-ray diffraction,
and field emission scanning electron microscopy were used to characterize
α-Fe2O3 and α-Fe2O3@OA. Their impact on the oxidation process of heavy oil was
evaluated using a porous medium thermo-effect cell and thermogravimetry–infrared
spectroscopy coupled with isoconversional kinetic analysis. Compared
with α-Fe2O3, α-Fe2O3@OA more efficiently catalyzed the combustion of heavy oil
due to its good dispersion in heavy oil. α-Fe2O3 was found to be transformed into smaller size magnetite (Fe3O4), maghemite (γ-Fe2O3), and α-Fe2O3 during heavy oil combustion.
Fe2O3@OA reduced the activation energy from
a maximum of 537 to 246 kJ/mol, which considerably facilitates fuel
formation and makes an easier transition from fuel formation to its
combustion in the high-temperature oxidation (HTO) stage, thus shifting
HTO into lower temperatures. These enhanced performances in the heavy
oil combustion by α-Fe2O3@OA could be
favorable for improving the efficiency of the in situ combustion (ISC)
technique in oilfields.
“…These results revealed that the anionic ligand of iron had a crucial effect on the alcohol oxidation. In the case of [NO 3 – ] and [Cl – ], we suspected that in situ generation of NO x and hypochlorous acid was responsible for the menthol oxidation . Nevertheless, this finding suggested that the FeBr 3 /H 2 O 2 system was less likely to involve the high-valent iron species for the alcohol oxidation (entries 9 and 10).…”
In 2003, Martı ́n et al. reported a green alcohol oxidation with FeBr 3 (cat.)/H 2 O 2 and proposed a high-valent iron species (HIS) responsible for the alcohol oxidation. Reinvestigating this FeBr 3 (cat.)/H 2 O 2 method led us to propose a different mechanism that involves a reactive brominating species (RBS) for the oxidation of alcohols. The evidence to support this RBS-based mechanism includes (1) our recent findings of in situ-generated RBS from the related FeBr 2 /H 2 O 2 or CeBr 3 /H 2 O 2 systems, (2) our results of a series of controlled experiments, and ( 3) some related RBS-based precedents (NBS, NBA, or Br 2 ) showing similar high oxidation selectivity of secondary over primary alcohols. These studies enable us to discover that a RBS from CeBr 3 /H 2 O 2 is much more efficient for the oxidation of secondary and benzylic alcohols, which represents a new green protocol for selective oxidation of alcohols to carbonyls.
“…The alternative of employing iron-based catalysts and hydrogen peroxide as oxidant is gaining importance for the liquid phase oxidation of glycerol under mild conditions (base-free, ambient temperature, and atmospheric pressure). , Crotti and Farnetti performed the glycerol oxidation in an acetonitrile/water mixture using homogeneous iron complexes associated to the tridentate ligand bis(2-pyridinylmethyl)amine (BPA) as catalyst. They reported that high selectivity toward DHA or formic acid could be achieved by tuning operating conditions.…”
Section: Clean Catalytic
Oxidation Of Alcoholsmentioning
There has been a growing interest in the last decades in technologies that transform biomass-derived feedstock into renewable chemicals. A group of target molecules derived from biomass as key intermediates between raw materials and final products have been designed as "platform chemicals". Sustainable processes involve the use of renewable feedstock, but also pursue low energy consumption, the use of less hazardous materials, and diminished generation of waste. This review aims to present recent advances on environmentally friendly catalytic oxidation routes for transforming three platform chemicals, ethanol, glycerol, and 5-hydroxymethylfurfural, to value added intermediates and final products using air or oxygen as oxidants and water without additives (base-free) as solvent, and preferably under moderate operating conditions. Works carried out under continuous flow have been particularly reviewed.
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