Improved dark ambient degradation of organic pollutants by cerium strontium cobalt perovskite.

This work investigates the effect of cerium substation into strontium cobalt perovskites (CeSrCoO) for the oxidative degradation of Orange II (OII) in dark ambient conditions without the aid of any external stimulants such as light, heating or chemical additives. The OII degradation rate by CeSrCoO reached 65% in the first hour, whilst for the blank sample without cerium (SrCoO) took over 2 hr to reach the same level of OII degradation. Hence, the cerium substitution improved the catalytic activity of the perovskite material, mainly associated with the Ce0.1Sr0.9CoO3 perovskite phase. Upon contacting CeSrCoO, the -NN- azo bonds of the OII molecules broke down resulting in electron donation and the formation of by-products. The electrons are injected into the CeSrCoO and resulted in a redox pair of Co3+/Co2+, establishing a bridge for the electron transfer between OII and the catalysts. Concomitantly, the electrons also formed reactive species (·OH) responsible for OII degradation as evidenced by radical trapping experiment. Reactive species were formed via the reaction between O2 and donated electrons from OII with the aid of cobalt redox pair. As the prepared materials dispensed with the need for light irradiation and additional oxidants, it opens a window of environmental applications for treating contaminated wastewaters.

2D/3D Assemblies of Amine-Functionalized Graphene Silica (Templated) Aerogel for Enhanced CO2 Sorption.

This work investigates the one-pot facile synthesis of novel 2D/3D assemblies containing graphene silica (templated) aerogel sorbents for CO2 capture, a greenhouse gas of major global concern. In this synthesis, 3D silica (templated) aerogels were formed along the planes of 2D graphene sheets, resulting in 2D/3D assemblies of flake-like shapes. The templates were burnt off from the 2D/3D assembly, leaving a mesoporous cavity which increased with the carbon chain length used in the synthesis method. As such, morphological features related to surface area and total pore volume increased significantly by over 80% as compared to blank (no template) samples and reached maximum values of 734 m2 g-1 and 0.42 cm3 g-1, respectively. The increase in total pore volume allowed for higher content of impregnated amine into the 2D/3D assembly followed by a freeze-drying method. The CO2 sorption capacity of the amine-functionalized 2D/3D assemblies reached high values at 4.9 mmol g-1 (mass over weight ratio), equivalent to 11.67 mmol cm-3 (mass over total pore volume ratio). The amine-functionalized 2D/3D assemblies were stable over 10 cycles of CO2 sorption and desorption. Further, heat of sorption results were generally low, with the lowest value reaching 59 kJ mol-1. These results are desirable for the deployment of 2D/3D assemblies as sorbents to capture CO2.

Enhanced CO2 sorption efficiency in amine-functionalised 2D/3D graphene/silica hybrid sorbents.

Owing to the geometrical features of 2D graphene intercalated into 3D mesoporous silica, CO2 sorption increased by 51% and the heat of sorption reduced by up to 27% as compared to a pure 3D mesoporous silica sorbent without graphene. The superior performance of the amine-functionalised 2D/3D hybrid sorbent was attributed to the enhanced porosity and graphene physisorption at the expense of amine chemisorption.

Environmental mineralization of caffeine micro-pollutant by Fe-MFI zeolites.

Environmentally emerging micro-pollutant, caffeine, was mineralized (i.e., full degradation) by the isomorphic incorporation of Fe into silicalite-1 (mordenite framework inverted (MFI) structure zeolite) through a microwave synthesis method. The Fe incorporation conferred mesopore formation that facilitated caffeine access and transport to the MFI zeolite structure. Increasing the Fe content favored the formation of Fe(O)4 sites within the MFI structure. The catalytic activity for the degradation of caffeine increased as a function of Fe(O)4 sites via a Fenton-like heterogeneous reaction, otherwise not attainable using Fe-free pure MFI zeolites. Caffeine degradation reached 96% (TOC based) for zeolites containing 2.33% of Fe.

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.

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.

Nanoscale assembly of lanthanum silica with dense and porous interfacial structures.

This work reports on the nanoscale assembly of hybrid lanthanum oxide and silica structures, which form patterns of interfacial dense and porous networks. It was found that increasing the molar ratio of lanthanum nitrate to tetraethyl orthosilicate (TEOS) in an acid catalysed sol-gel process alters the expected microporous metal oxide silica structure to a predominantly mesoporous structure above a critical lanthanum concentration. This change manifests itself by the formation of a lanthanum silicate phase, which results from the reaction of lanthanum oxide nanoparticles with the silica matrix. This process converts the microporous silica into the denser silicate phase. Above a lanthanum to silica ratio of 0.15, the combination of growth and microporous silica consumption results in the formation of nanoscale hybrid lanthanum oxides, with the inter-nano-domain spacing forming mesoporous volume. As the size of these nano-domains increases with concentration, so does the mesoporous volume. The absence of lanthanum hydroxide (La(OH)3) suggests the formation of La2O3 surrounded by lanthanum silicate.

Modulation of microporous/mesoporous structures in self-templated cobalt-silica.

Finite control of pore size distributions is a highly desired attribute when producing porous materials. While many methodologies strive to produce such materials through one-pot strategies, oftentimes the pore structure requires post-treatment modification. In this study, modulation of pore size in cobalt-silica systems was investigated by a novel, non-destructive, self-templated method. These systems were produced from two cobalt-containing silica starting materials which differed by extent of condensation. These starting materials, sol (SG') and xerogel (XG'), were mixed with pure silica sol to produce materials containing 5-40 mol% Co. The resultant SG-series materials exhibited typical attributes for cobalt-silica systems: mesoporous characteristics developed at high cobalt concentrations, coinciding with Co3O4 formation; whereas, in the XG-series materials, these mesoporous characteristics were extensively suppressed. Based on an examination of the resultant materials a mechanism describing the pore size formation and modulation of the two systems was proposed. Pore size modulation in the XG-series was caused, in part, by the cobalt source acting as an autogenous template for the condensation of the silica network. These domains could be modified when wetted, allowing for the infiltration and subsequent condensation of silica oligomers into the pre-formed, mesoporous cages, leading to a reduction in the mesoporous content of the final product.

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 m(2) 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.