Sulfidation of Zero-valent Iron Nanoparticles for Environmental Remediation

<p>The ability of nano-sized zero-valent iron (nZVI) to remove environmental contaminants, from heavy metals to polyhalogenated hydrocarbons, has been well established. However, the reactivity of nZVI towards contaminants is hampered due to competing for side reactions with oxygen and water. Sulfidemodified nZVI (S-nZVI) has become a viable option as S-nZVI has been shown to reduce organic compounds such as trichloroethylene faster than nZVI while also maintaining an increased resistance to oxidation by water. The Fulton group has established that nZVI supported on a naturally occurring microsilicate (Microsilica600, or “misi”), from a Rotorua geothermal deposit, is capable of removing nitrates from water. This material, or nZVI@misi, minimises the potential bioaccumulation path that nZVI has, and is easier to handle than unsupported nZVI. This research investigated the effect of sulfidation of nZVI@misi (or S-nZVI@misi) on the reactivity towards the degradation of a variety of different potential contaminants. S-nZVI@misi was synthesised using sodium thiosulfate for sulfidation. Increasing the concentration of the reagent and sulfidation time from 3 hours to 24 hours resulted in high percentages of sulfur-to-iron (S/Fe) for each material. This increase in S/Fe had a significant impact on the removal of cadmium and chromium as with higher the percentage of S/Fe, the faster the removal of these species occurred. Compared to pristine nZVI@misi, S-nZVI@misi was significantly faster at removing both cadmium and chromium. However, sulfidation of nZVI@misi proved to reduce the rate of 4-nitrophenol reduction and prevent nitrate reduction from occurring. Experimental analysis also showed that cadmium removal was faster with S-nZVI supported by FeOOH-coated microsilica, compared to material supported by un-coated microsilica. Therefore, we have synthesised supported S-nZVI that quickly removes cadmium and chromium from solution compared to standard supported nZVI.</p>

Sulfidation of Zero-valent Iron Nanoparticles for Environmental Remediation

<p>The ability of nano-sized zero-valent iron (nZVI) to remove environmental contaminants, from heavy metals to polyhalogenated hydrocarbons, has been well established. However, the reactivity of nZVI towards contaminants is hampered due to competing for side reactions with oxygen and water. Sulfidemodified nZVI (S-nZVI) has become a viable option as S-nZVI has been shown to reduce organic compounds such as trichloroethylene faster than nZVI while also maintaining an increased resistance to oxidation by water. The Fulton group has established that nZVI supported on a naturally occurring microsilicate (Microsilica600, or “misi”), from a Rotorua geothermal deposit, is capable of removing nitrates from water. This material, or nZVI@misi, minimises the potential bioaccumulation path that nZVI has, and is easier to handle than unsupported nZVI. This research investigated the effect of sulfidation of nZVI@misi (or S-nZVI@misi) on the reactivity towards the degradation of a variety of different potential contaminants. S-nZVI@misi was synthesised using sodium thiosulfate for sulfidation. Increasing the concentration of the reagent and sulfidation time from 3 hours to 24 hours resulted in high percentages of sulfur-to-iron (S/Fe) for each material. This increase in S/Fe had a significant impact on the removal of cadmium and chromium as with higher the percentage of S/Fe, the faster the removal of these species occurred. Compared to pristine nZVI@misi, S-nZVI@misi was significantly faster at removing both cadmium and chromium. However, sulfidation of nZVI@misi proved to reduce the rate of 4-nitrophenol reduction and prevent nitrate reduction from occurring. Experimental analysis also showed that cadmium removal was faster with S-nZVI supported by FeOOH-coated microsilica, compared to material supported by un-coated microsilica. Therefore, we have synthesised supported S-nZVI that quickly removes cadmium and chromium from solution compared to standard supported nZVI.</p>

A hydrophobic FeMn@Si catalyst increases olefins from syngas by suppressing C1 by-products

Although considerable efforts have been made in the selective conversion of syngas [carbon monoxide (CO) and hydrogen] to olefins through Fischer-Tropsch synthesis (FTS), ~50% of the converted CO is transformed into the undesired one-carbon molecule (C1) by-products [carbon dioxide (CO2) and methane (CH4)]. In this study, a core-shell FeMn@Si catalyst with excellent hydrophobicity was designed to hinder the formation of CO2 and CH4. The hydrophobic shell protected the iron carbide core from oxidation by water generated during FTS and shortened the retention of water on the catalyst surface, restraining the side reactions related to water. Furthermore, the electron transfer from manganese to iron atoms boosted olefin production and inhibited CH4 formation. The multifunctional catalyst could suppress the total selectivity of CO2 and CH4 to less than 22.5% with an olefin yield of up to 36.6% at a CO conversion of 56.1%.

Evoked Methane Photocatalytic Conversion to C2 Oxygenates over Ceria with Oxygen Vacancy

Direct conversion of methane to its oxygenate derivatives remains highly attractive while challenging owing to the intrinsic chemical inertness of CH4. Photocatalysis arises as a promising green strategy which could stimulate water splitting to produce oxidative radicals for methane C–H activation and subsequent C–C coupling. However, synthesis of a photocatalyst with an appropriate capability of methane oxidation by water remains a challenge using an effective and viable approach. Herein, ceria nanoparticles with abundant oxygen vacancies prepared by calcinating commercial CeO2 powder at high temperatures in argon are reported to capably produce ethanol and aldehyde from CH4 photocatalytic oxidation under ambient conditions. Although high-temperature calcinations lead to lower light adsorptions and increased band gaps to some extent, deficient CeO2 nanoparticles with oxygen vacancies and surface CeIII species are formed, which are crucial for methane photocatalytic conversion. The ceria catalyst as-calcinated at 1100 °C had the highest oxygen vacancy concentration and CeIII content, achieving an ethanol production rate of 11.4 µmol·gcat−1·h−1 with a selectivity of 91.5%. Additional experimental results suggested that the product aldehyde was from the oxidation of ethanol during the photocatalytic conversion of CH4.

Solar Thermochemical Hydrogen Production via Terbium Oxide Based Redox Reactions

The computational thermodynamic modeling of the terbium oxide based two-step solar thermochemical water splitting (Tb-WS) cycle is reported. The 1st step of the Tb-WS cycle involves thermal reduction of TbO2into Tb and O2, whereas the 2nd step corresponds to the production of H2through Tb oxidation by water splitting reaction. Equilibrium compositions associated with the thermal reduction and water splitting steps were determined via HSC simulations. Influence of oxygen partial pressure in the inert gas on thermal reduction of TbO2and effect of water splitting temperature (TL) on Gibbs free energy related to the H2production step were examined in detail. The cycle (ηcycle) and solar-to-fuel energy conversion (ηsolar-to-fuel) efficiency of the Tb-WS cycle were determined by performing the second-law thermodynamic analysis. Results obtained indicate thatηcycleandηsolar-to-fuelincrease with the decrease in oxygen partial pressure in the inert flushing gas and thermal reduction temperature (TH). It was also realized that the recuperation of the heat released by the water splitting reactor and quench unit further enhances the solar reactor efficiency. AtTH=2280 K, by applying 60% heat recuperation, maximumηcycleof 39.0% andηsolar-to-fuelof 47.1% for the Tb-WS cycle can be attained.

Confinement dependence of electro-catalysts for hydrogen evolution from water splitting

Density functional theory is utilized to articulate a particular generic deconstruction of the electrode/electro-catalyst assembly for the cathode process during water splitting. A computational model was designed to determine how alloying elements control the fraction of H2 released during zirconium oxidation by water relative to the amount of hydrogen picked up by the corroding alloy. This model is utilized to determine the efficiencies of transition metals decorated with hydroxide interfaces in facilitating the electro-catalytic hydrogen evolution reaction. A computational strategy is developed to select an electro-catalyst for hydrogen evolution (HE), where the choice of a transition metal catalyst is guided by the confining environment. The latter may be recast into a nominal pressure experienced by the evolving H2 molecule. We arrived at a novel perspective on the uniqueness of oxide supported atomic Pt as a HE catalyst under ambient conditions.