Christelle Yacou

Structural and functional investigation of graphene oxide-Fe3O4 nanocomposites for the heterogeneous Fenton-like reaction.

Graphene oxide–iron oxide (GO–Fe3O4) nanocomposites were synthesised by co-precipitating iron salts onto GO sheets in basic solution. The results showed that formation of two distinct structures was dependent upon the GO loading. The first structure corresponds to a low GO loading up to 10 wt%, associated with the beneficial intercalation of GO within Fe3O4 nanoparticles and resulting in higher surface area up to 409 m2 g−1. High GO loading beyond 10 wt% led to the aggregation of Fe3O4 nanoparticles and the undesirable stacking of GO sheets. The presence of strong interfacial interactions (Fe-O-C bonds) between both components at low GO loading lead to 20% higher degradation of Acid Orange 7 than the Fe3O4 nanoparticles in heterogeneous Fenton-like reaction. This behaviour was attributed to synergistic structural and functional effect of the combined GO and Fe3O4 nanoparticles.

The sacrificial role of graphene oxide in stabilising a Fenton-like catalyst GO–Fe3O4

Owing to the electron donor-acceptor properties of GO, the active sites ([triple bond, length as m-dash]Fe(2+)) of Fe3O4 are not oxidised ([triple bond, length as m-dash]Fe(3+)) in the heterogeneous Fenton-like reaction. GO plays a sacrificial role via the oxidation of (C[double bond, length as m-dash]C) carbon domains, and transferring electrons to Fe3O4. Therefore, GO-Fe3O4 confers superior catalytic efficiency, recyclability and longevity, otherwise not available in Fe3O4.

Performance and Long Term Stability of Mesoporous Silica Membranes for Desalination

This work shows the preparation of silica membranes by a two-step sol-gel method using tetraethyl orthosilicate in ethanolic solution by employing nitric acid and ammonia as co-catalysts. The sols prepared in pH 6 resulted in the lowest concentration of silanol (Si–OH) species to improve hydrostability and the optimized conditions for film coating. The membrane was tested to desalinate 0.3–15 wt % synthetic sodium chloride (NaCl) solutions at a feed temperature of 22 °C followed by long term membrane performance of up to 250 h in 3.5 wt % NaCl solution. Results show that the water flux (and salt rejection) decrease with increasing salt concentration delivering an average value of 9.5 kg m–2 h–1 (99.6%) and 1.55 kg m–2 h–1 (89.2%) from the 0.3 and 15 wt % saline feed solutions, respectively. Furthermore, the permeate salt concentration was measured to be less than 600 ppm for testing conditions up to 5 wt % saline feed solutions, achieving below the recommended standard for potable water. Long term stability shows that the membrane performance in water flux was stable for up to 150 h, and slightly reduced from thereon, possibly due to the blockage of large hydrated ions in the micropore constrictions of the silica matrix. However, the integrity of the silica matrix was not affected by the long term testing as excellent salt rejection of >99% was maintained for over 250 h.

Tailoring the oxidation state of cobalt through halide functionality in sol-gel silica.

The functionality or oxidation state of cobalt within a silica matrix can be tailored through the use of cationic surfactants and their halide counter ions during the sol-gel synthesis. Simply by adding surfactant we could significantly increase the amount of cobalt existing as Co3O4 within the silica from 44% to 77%, without varying the cobalt precursor concentration. However, once the surfactant to cobalt ratio exceeded 1, further addition resulted in an inhibitory mechanism whereby the altered pyrolysis of the surfactant decreased Co3O4 production. These findings have significant implications for the production of cobalt/silica composites where maximizing the functional Co3O4 phase remains the goal for a broad range of catalytic, sensing and materials applications.

Influence of surfactant alkyl length in functionalizing sol–gel derived microporous cobalt oxide silica

The size or alkyl chain length of cationic surfactants can be used to tailor both the pore morphology and the functionality or oxidation state of cobalt in silica materials. This work shows for the first time that these two mechanisms are interconnected. Cobalt oxide silica materials, with the same cobalt loading (Co : Si = 1 : 4), were prepared using an acid catalysed sol–gel method where the cobalt/surfactant ratio was systematically varied. The alkyl chain length of the cationic surfactant was also varied from 2 to 12 by using tetraethyl (C2-AB) ammonium bromide, and triethyl hexyl (C6-AB) and dodecyl trimethyl (C12-AB) ammonium bromides as the templating agents. Initial addition of C2-AB, C6-AB or C12-AB enhanced the oxidation of cobalt to cobalt (II,III) oxide in the xerogels. However, as more surfactant is added the enhancement effect is reversed and the cobalt (II,III) oxide content of the sample begins to decline. The point at which this transition occurs is a function of the alkyl chain length of the surfactant, with a longer chain indicating an earlier transition. Pore morphology was influenced in a similar fashion with the longer alkyl chain C12-AB surfactant undergoing an earlier transition (i.e. at lower concentrations) towards mesoporosity, than either of the smaller C2-AB and C6-AB surfactants. In both mechanisms it was the increased propensity of the C12-AB surfactant to aggregate (given its larger size and lower solubility) that was the controlling factor.

Graphene oxide with zinc partially substituted magnetite (GO–Fe1−xZnxOy) for the UV-assisted heterogeneous Fenton-like reaction

A series of graphene oxide (GO) and zinc partially substituted magnetite GO–Fe1−xZnxOy (0 ≤ x ≤ 0.285) catalysts were synthesised through a precipitation-oxidation method. The rate constants for the degradation of acid orange seven (AO7) proceeded at a significant faster rate under UV-irradiation (up to 670%) than the conventional heterogeneous Fenton-like reaction. The resultant catalysts were mesoporous, so there was no mass transfer limitation for AO7 to access active sites in the catalysts. Further, maximum increases of rate constant up to 220% occurred as the zinc molar concentration increased from x = 0 to x = 0.159. GO enhanced to incorporation of zinc into the combined metal oxide, whilst zinc limited crystal growth, thus forming smaller crystallite sizes. These features proved to be essential for the improved catalytic activity of the resultant catalysts. The optimised zinc molar value at x = 0.159 delivered the best catalytic activity.

Molecular weight cut-off and structural analysis of vacuum-assisted titania membranes for water processing

This work investigates the structural formation and analyses of titania membranes (TM) prepared using different vacuum exposure times for molecular weight (MW) cut-off performance and oil/water separation. Titania membranes were synthesized via a sol-gel method and coated on macroporous alumina tubes followed by exposure to a vacuum between 30 and 1200 s and then calcined at 400 °C. X-ray diffraction and nitrogen adsorption analyses showed that the crystallite size and particle size of titania increased as a function of vacuum time. All the TM membranes were mesoporous with an average pore diameter of ~3.6 nm with an anatase crystal morphology. Water, glucose, sucrose, and polyvinylpyrrolidone with 40 and 360 kDa (PVP-40 kDa and PVP-360 kDa) were used as feed solutions for MW cut-off and hexadecane solution for oil filtration investigation. The TM membranes were not able to separate glucose and sucrose, thus indicating the membrane pore sizes are larger than the kinetic diameter of sucrose of 0.9 nm, irrespective of vacuum exposure time. They also showed only moderate rejection (20%) of the smaller PVP-40 kDa, however, all the membranes were able to obtain an excellent rejection of near 100% for the larger PVP-360 kDa molecule. Furthermore, the TM membranes were tested for the separation of oil emulsions with a high concentration of oil (3000 ppm), reaching high oil rejections of more than 90% of oil. In general, the water fluxes increased with the vacuum exposure time indicating a pore structural tailoring effect. It is therefore proposed that a mechanism of pore size tailoring was formed by an interconnected network of Ti–O–Ti nanoparticles with inter-particle voids, which increased as TiO2 nanoparticle size increased as a function of vacuum exposure time, and thus reduced the water transport resistance through the TM membranes.

Physico-chemical properties of zinc partially substituted magnetite nanoparticles

In this work, a series of zinc partially substituted magnetite nanoparticles (Fe3-xZnxO4, 0 ≤ x ≤ 0.4), were synthesised through a facile precipitation-oxidation method. The partial substitution of zinc into the magnetite (Fe3O4) structure was confirmed by the collective findings of nitrogen sorption, XRD and TG-DTG analysis. It was found that the partial substitution of zinc slightly changed the textural properties of the resultant Fe3-xZnxO4 nanoparticles. From the XRD analysis, there was no visible formation of secondary phase or impurity peaks in the nanoparticles. These findings indicated the partial substitution of zinc into the Fe3O4 crystal structure with a good dispersion within the Fe3O4 matrix.