RESUMO
Iron oxide nanostructured catalysts have emerged as potential candidates for efficient energy conversion and electrochemical energy storage devices. However, synthesis and design of nanomaterial plays a key role in its performance and efficiency. Herein, we describe a one-pot solution combustion synthesis (SCS) of α-Fe2O3 with glycine as a fuel, and a subsequent reduction step to produce iron-containing catalysts (i.e., Fe3O4, Fe-Fe3O4, and Fe0). The synthesized iron-based nanoparticles were investigated for methyl orange (MO) degradation through Microwave (MW) energy under continuous flow conditions. Fe-Fe3O4 showed higher MO degradation efficiency than α-Fe2O3, Fe3O4 and Fe0 at low absorbed MW power (i.e. 5-80 W). The enhanced degradation efficiency is associated to the combination of higher availability of electron density and higher heating effect under MW energy. Investigation of dielectric properties showed relative dielectric loss of Fe3O4, Fe-Fe3O4, and Fe0 as 3847, 2010, and 1952, respectively. The calculated average local temperature by the comparative analysis of MW treatment with conventional thermal (CT) treatment showed a marked thermal effect of MW-initiated MO degradation. This work highlights the potential of microwave-driven water depollution under continuous-flow processing conditions and demonstrates the positive impact that earth-abundant Fe catalyst synthesized by green SCS method can have over the treatment of wastewater.
Assuntos
Águas Residuárias , Poluentes Químicos da Água , Catálise , Ferro , Micro-OndasRESUMO
With mounting concerns over climate change, the utilisation or conversion of carbon dioxide into sustainable, synthetic hydrocarbons fuels, most notably for transportation purposes, continues to attract worldwide interest. This is particularly true in the search for sustainable or renewable aviation fuels. These offer considerable potential since, instead of consuming fossil crude oil, the fuels are produced from carbon dioxide using sustainable renewable hydrogen and energy. We report here a synthetic protocol to the fixation of carbon dioxide by converting it directly into aviation jet fuel using novel, inexpensive iron-based catalysts. We prepare the Fe-Mn-K catalyst by the so-called Organic Combustion Method, and the catalyst shows a carbon dioxide conversion through hydrogenation to hydrocarbons in the aviation jet fuel range of 38.2%, with a yield of 17.2%, and a selectivity of 47.8%, and with an attendant low carbon monoxide (5.6%) and methane selectivity (10.4%). The conversion reaction also produces light olefins ethylene, propylene, and butenes, totalling a yield of 8.7%, which are important raw materials for the petrochemical industry and are presently also only obtained from fossil crude oil. As this carbon dioxide is extracted from air, and re-emitted from jet fuels when combusted in flight, the overall effect is a carbon-neutral fuel. This contrasts with jet fuels produced from hydrocarbon fossil sources where the combustion process unlocks the fossil carbon and places it into the atmosphere, in longevity, as aerial carbon - carbon dioxide.
RESUMO
Hydrogen as an energy carrier promises a sustainable energy revolution. However, one of the greatest challenges for any future hydrogen economy is the necessity for large scale hydrogen production not involving concurrent CO2 production. The high intrinsic hydrogen content of liquid-range alkane hydrocarbons (including diesel) offers a potential route to CO2 -free hydrogen production through their catalytic deep dehydrogenation. We report here a means of rapidly liberating high-purity hydrogen by microwave-promoted catalytic dehydrogenation of liquid alkanes using Fe and Ni particles supported on silicon carbide. A H2 production selectivity from all evolved gases of some 98 %, is achieved with less than a fraction of a percent of adventitious CO and CO2 . The major co-product is solid, elemental carbon.
RESUMO
A series of MoO3/H-ZSM-5 (Si/Al = 25) catalysts were prepared via calcination at a lower-than-usual temperature (400 °C) and subsequently evaluated in the methanol-to-hydrocarbon reaction at that same temperature. The catalytic properties of those catalysts were compared with the sample prepared at the more conventional, higher temperature of 500 °C. For the lower temperature preparations, molybdenum oxide was preferentially dispersed over the zeolite external surface, while only the higher loading level of MoO3 (7.5 wt% or higher) led to observable inner migration of the Mo species into the zeolite channels, with concomitant partial loss of the zeolite Brønsted acidity. On the MoO3 modified samples, the early-period gas yield, especially for valuable propylene and C4 products, was noticeably accelerated, and is gradually converted into an enhanced liquid aromatic formation. The 7.5 wt% MoO3/H-ZSM-5 sample prepared at 400 °C thereby achieved a balance between the zeolite surface dispersion of Mo species, their inner channel migration and the corresponding effect on the intrinsic Brønsted acidity of the acidic zeolite. That loading level also possessed the highest product selectivity (after 5 h reaction) to benzene, toluene and xylenes, as well as higher early-time valuable gas product yields in time-on-stream experiments. However, MoO3 loading levels of 7.5 wt% and above also resulted in earlier catalyst deactivation by enhanced coke accumulation at, or near, the zeolite channel openings. Our research illustrates that the careful adoption of moderate/lower temperature dispersion processes for zeolite catalyst modification gives considerable potential for tailoring and optimizing the system's catalytic performance.
RESUMO
We report investigations with the dispersion-corrected B3LYP density functional method on mechanisms and energetics for reactions of group I metal phenoxides with halobenzenes as models for polyether formation. Calculated barriers for ether formation from para-substituted fluorobenzenes are well correlated with the electron-donating or -withdrawing properties of the substituent at the para position. These trends have also been explained with the distortion/interaction energy theory model which show that the major component of the activation energy is the energy required to distort the arylfluoride reactant into the geometry that it adopts at the transition state. Resonance-stabilized aryl anion intermediates (Meisenheimer complexes) are predicted to be energetically disfavored in reactions involving fluorobenzenes with a single electron-withdrawing group at the para position of the arene, but are formed when the fluorobenzenes are very electron-deficient, or when chelating substituents at the ortho position of the aryl ring are capable of binding with the metal cation, or both. Our results suggest that the presence of the metal cation does not increase the rate of reaction, but plays an important role in these reactions by binding the fluoride or nitrite leaving group and facilitating displacement. We have found that the barrier to reaction decreases as the size of the metal cation increases among a series of group I metal phenoxides due to the fact that the phenoxide becomes less distorted in the transition state as the size of the metal increases.