Propylene oxide (PO) is a versatile
chemical intermediate, and
by volume it is among the top 50 chemicals produced in the world.
The catalytic conversion of propylene to PO by molecular oxygen with
minimum waste production is of high significance from an academic
as well as an industrial point of view. We have developed a new synthesis
strategy to prepare 2–5 nm metallic silver nanoparticles (AgNPs)
supported on tungsten oxide (WO3) nanorods with diameters
between 30 and 40 nm, in the presence of cationic surfactant (cetyltrimethylammonium
bromide: CTAB), capping agent (polyvinylpyrrolidone: PVP), and hydrazine.
The synergy between the surface AgNPs and WO3 nanorods
facilitates the dissociation of molecular oxygen on the metallic Ag
surface to produce silver oxide, which then transfers its oxygen to
the propylene to form PO selectively. The catalyst exhibits a PO production
rate of 6.1 × 10–2 mol gcat
–1 h–1, which is almost comparable
with the industrial ethylene-to-ethylene oxide production rate.
Cationic surfactant cetyltrimethylammonium chloride-mediated hydrothermal preparation of CuCr 2 O 4 spinel nanoparticles has been reported. This CuCr 2 O 4 spinel nanoparticle catalyst has been characterized by XRD, XPS, SEM, TEM, TGA, and ICP-AES. Characterization results showed the formation of CuCr 2 O 4 spinel nanoparticles with sizes between 25 and 50 nm. It was found that the catalyst can selectively convert aniline to azoxybenzene with H 2 O 2 as oxidant. The effect of different reaction parameters like reaction temperature, H 2 O 2 to aniline molar ratio, reaction time, and so forth have been studied in detail. An aniline conversion of 78% with azoxybenzene selectivity of 92% can be achieved over this catalyst at 70 °C. The catalyst did not show any leaching up to five reuses, showing the true heterogeneity of the catalyst. However, significant H 2 O 2 decomposition occurs on the catalyst necessitating its usage in five-fold excess.
Three-dimensional (3D) raspberry-like CuCr2O4 spinel nanoparticles were prepared hydrothermally in the presence of cationic surfactant, cetyltrimethylammonium bromide (CTAB). Detailed characterization of the material was carried out by X-ray diffraction (XRD), inductively coupled plasma-atomic emission spectroscopy (ICP-AES), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, and thermogravimetric analysis (TGA). XRD revealed the formation of CuCr2O4 spinel phase, and SEM showed the formation of a 3D raspberry-like structure, composed of 20-50 nm nanoparticles. The raspberry-like particles exhibited excellent catalytic behavior for the hydroxylation of benzene to phenol with H2O2. The influence of reaction parameters were investigated in detail. A benzene conversion of 68.5% with 95% phenol selectivity was achieved at 80 °C. The catalyst did not show any leaching up to 10 reuses, showing the true heterogeneity of the catalyst. However, significant H2O2 decomposition occurs on the catalyst necessitating its use in 5-fold excess.
The well-known cumene
process via an explosive cumene hydroperoxide
intermediate in liquid phase currently employed for phenol production
is energy-intensive and not environmentally friendly. Therefore, there
is a demand for an alternative single-step gas-phase catalysis process.
According to the conventional catalysis concept, selective oxidation
reactions are promoted by redox catalysts and not by acid–base
catalysts. In general, alkali and alkaline earth metal ions cannot
activate each of benzene, O2, and N2O when they
adsorb separately. However, we observed an unprecedented catalysis
of single alkali and alkaline earth metal ion sites incorporated into
zeolite pores for the selective oxidation of benzene to phenol with
N2O and O2 + NH3, thereby providing
a single-site catalytic platform with high selectivity. Among alkali
and alkaline earth metal ions, single Cs+ and Rb+ sites with ion diameters of >300 pm in the pores of β-zeolites
exhibited remarkable selectivity for benzene C–H activation
to phenol catalysis in a concerted reaction pathway.
Heterogeneous catalysts comprising silver nanoparticles supported on nanostructured tungsten oxide were applied for room temperature oxidative coupling of aniline to azoxybenzene, an important chemical intermediate and a chemical of industrial interest.
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