Narrow Results

Transformation of methane, the most abundant and the least reactive compound of natural gas to valuable products is one of the most difficult chemical problems of great practical importance. In Nature, methane monooxygenase enzymes transform methane to methanol in water under physiological conditions. However, chemical analogs for such a transformation are unknown. Here, we show the mild and efficient aqueous oxidation of methane by hydrogen peroxide, an ecologically and biologically relevant oxidant catalyzed by supported μ-nitrido diiron phthalocyanine dimer, (FePc^tBu₄)₂N. This bio-inspired complex containing a stable Fe–N–Fe motif catalyzes the oxidation of methane to methanol which is further transformed to formaldehyde and formic acid as is demonstrated using ¹³CH₄ and ¹⁸O labelling. (FePc^tBu₄)₂N-H₂O₂ system shows a high activity in the oxidation of benzene to phenol which occurs via formation of benzene oxide and exhibits NIH shift typically accociated with biological oxidation. Mechanistic features of oxidation of methane and benzene as well as detected intermediate hydroperoxo- and high valent oxo diiron complexes support an O-atom transfer reaction mechanism relevant to bio-oxidation.

Carbon nanotubes (CNTs) were synthesized by a low-cost floating catalyst (FC) chemical vapor deposition (CVD) method in a horizontal reactor. It was found that iron (III) chloride (FeCl₃) is a high efficient FC precursor for methane CVD to grow CNTs. In this study, the effects of reaction temperature and flow ratio of methane to nitrogen (CH₄:N₂) on the morphology of the CNTs were investigated. The morphological analysis by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) revealed that increasing the reaction temperature and flow ratio of CH₄:N₂ grew CNTs of larger diameters. Energy dispersive X-ray (EDX) and thermogravimetric analysis (TGA) were employed to study the purity of the produced CNTs. As shown by the TGA, the highest yield of 74.19% was recorded for the CNTs grown at 1000°C and flow ratio CH₄:N₂ of 300:200.

Multi-walled carbon nanotubes (MWCNTs) were prepared by floating catalyst (FC) method, using methane as a carbon source and iron (III) chloride (FeCl₃) as a catalyst precursor, followed by purification with air oxidation and acid treatment. The as-grown and purified MWCNTs were characterized by transmission electron microscopy, scanning electron microscopy, energy dispersive spectroscopy, thermogravimetry analysis and Raman spectroscopy. The average inner and outer diameters of the MWCNTs were 25 and 39 nm, respectively. The purity and yield of the purified MWCNTs were more than 92% and 71% weight fraction, respectively.

Conversion of methane into high value added chemicals and clean fuels such as methanol under mild conditions is of great importance to the chemical industry. However, traditional thermal catalytic of methane always suffer from harsh reaction conditions and poor product selectivity. Here, we reported photoelectrocatalytic oxidation of methane over BiVO₄/Au/FeCo–LDH under simulated sunlight illumination with ambient‘ conditions. The results demonstrate that BiVO₄/Au/FeCo–LDH exhibits excellent photoelectrochemical properties and catalytic activity. The double-layer capacitance ($C_{dl}$) value of BiVO₄/Au/FeCo–LDH is estimated to be 3.00mF$\cdot$cm${}^{-2}$, indicating its considerable electrochemical active areas. The photocurrent density of BiVO₄/Au/FeCo–LDH reaches up to 1.46mA$\cdot$cm${}^{-2}$ in methane atmosphere. The methanol yield for photoelectrocatalytic oxidation of methane is 8.46 times that of pure BiVO₄, and the corresponding Faraday efficiency is 56.09%. Finally, the reaction mechanism of photoelectrocatalytic conversion of methane to methanol based on hydroxyl radical and methyl radical as intermediate products is proposed. Our finding is expected to provide new insight for the design of active and selective catalysts toward photoelectrocatalytic conversion of methane.

Owing to the growing concern for alternative sources of energy, the use of brewery spent grains as potential sources of energy (biogas) has been investigated. Brewery derived biowastes (spent grains) were collected from different breweries in southeast Nigeria. These wastes were digested anaerobically in IL laboratory scale digesters over a hydraulic retention time of 14 days (HRT 14) using cow rumen liquor as source of inoculums. An optimization study was carried out by varying some parameters as water dilution and nutrient supplements (wood ash, urea and poultry dropping). The spent grains gave biogas yield of 58-65% methane. Out of the four sets of spent grains used, feed to water ratio of 1:4w/v gave the best biogas yield for three while feed to water ratio of 1:6w/v gave the best yield for one. During nutrient supplementation, highest biogas yield was recorded for wood ash while urea supplements gave the least biogas yield. Increased carbon to nitrogen ratio was found to encourage biogas production. Wood ash increased carbon to nitrogen ratio while urea decreased it. These tests indicated that brewers spent grains can be utilized for biogas production when digested anaerobically and the sludge generated thereafter can provide high quality manure since nitrogen content of the stabilized bio-wastes increased at the end of the digestion as revealed by the proximate analysis.