Hypercoordinated organotin compounds containing sulfur and chlorine. Molcular structures of [(Ph3P)2N]+[S(SnR2Cl)2Cl]- (R=Me, t-Bu)

The reaction of diorganotin sulfides, cyclo-(R₂SnS)_n (R=Me, n-Bu; n=3; R=t-Bu; n=2) with the corresponding diorganotin dichlorides, R₂SnCl₂, provided the tetraorganodistannathianes, (R₂ClSn)₂S (1, R=Me; 2, R=n-Bu; 3, R=t-Bu). ¹H-, ¹³C-, and ¹¹⁹Sn-NMR studies indicate that these compounds are kinetically labile and in equilibrium with the starting materials. Addition of equimolar amounts of [(Ph₃P)₂N]Cl to the reaction mixtures gave the chloride complexes [(Ph₃P)₂N]⁺[S(SnR₂Cl)₂Cl]⁻ (4, R=Me; 5, R=n-Bu; 6, R=t-Bu). Single-crystal X-ray diffraction studies revealed the tin atoms in both 4 and 6 to adopt distorted trigonal bipyramidal configurations with the chlorine atoms occupying the axial positions.

Photocatalytic degradation of dye effluent by titanium dioxide pillar pellets in aqueous solution

Photocatalytic oxidation (PCO) process is an effective way to deal with organic pollutants in wastewater which could be difficult to be degraded by conventional biological treatment methods. Normally the TiO2 powder in nanometre size range was directly used as photocatalyst for dye degradation in wastewater. However the titanium dioxide powder was arduous to be recovered from the solution after treatment. In this application, a new form of TiO2 (i.e. pillar pellets ranging from 2.5 to 5.3 mm long and with a diameter of 3.7 mm) was used and investigated for photocatalytic degradation of textile dye effluent. A test system was built with a flat plate reactor (FPR) and UV light source (blacklight and solar simulator as light source respectively) for investigating the effectiveness of the new form of TiO2. It was found that the photocatalytic process under this configuration could efficiently remove colours from textile dyeing effluent. Comparing with the TiO2 powder, the pellet was very easy to recovered from the treated solution and can be reused in multiple times without the significant change on the photocatalytic property. The results also showed that to achieve the same photocatalytic performance, the FPR area by pellets was about 91% smaller than required by TiO2 powder. At least TiO2 pellet could be used as an alternative form of photocatalyst in applications for textile effluent treatment process, also other wastewater treatment processes.

Photocatalytic reduction of carbon dioxide

Carbon dioxide reforming happens all the time in nature by photosynthesis of plants. It thus provides a great challenge to equal or surpass this photosynthesis in an artificial system. This paper presents a literature review of using semi-conductor to assist photocatalytic reduction of carbon dioxide under UV irradiation. It analyses some key factors influencing the reaction rates which have been studied worldwide in respective areas. Special interest is taken in recommending possible improvements for the heterogeneous photocatalysis involving gas-solid interfaces, particularly in relation to the influencing factors affecting product concentrations and the reduction rate.

Photocatalytic production of methane and hydrogen through reduction of carbon dioxide with water using titania pellets

This paper presents an experimental study on employing a pellet form of catalyst in photo-reduction of carbon dioxide with water. Water was first absorbed into titania pellets. Highly purified carbon dioxide gas was then discharged into a reactor containing the wet pellets, which were then illuminated continuously for 65 hours using UVC lamps. Analysing the products accumulated in the reactor confirmed that methane and hydrogen were produced through photo-reduction of carbon dioxide with water. No other hydrocarbons were detected. Increasing the temperature in the reactor has showed little change on the amount of methane produced.

Photocatalytic reduction of carbon dioxide into gaseous hydrocarbon using TiO2 pellets

It has been shown that CO₂ could be transformed into hydrocarbons when it is in contact with water vapour and catalysts under UV irradiation. This paper presents an experimental set-up to study the process employing a new approach of heterogeneous photocatalysis using pellet form of catalyst instead of immobilized catalysts on solid substrates. In the experiment, CO₂ mixed with water vapour in saturation state was discharged into a quartz reactor containing porous TiO₂ pellets and illuminated by various UV lamps of different wavelengths for 48 h continuously. The gaseous products extracted were identified using gas chromatography. The results confirmed that CO₂ could be reformed in the presence of water vapour and TiO₂ pellets into CH₄ under continuous UV irradiation at room conditions. It showed that when UVC (253.7 nm) light was used, total yield of methane was approximately 200 ppm which was a fairly good reduction yield as compared to those obtained from the processes using immobilized catalysts through thin-film technique and anchoring method. CO and H₂ were also detected. Switching from UVC to UVA (365 nm) resulted in significant decrease in the product yields. The pellet form of catalyst has been found to be attractive for use in further research on photocatalytic reduction of CO₂.

Carbon dioxide levels and ventilation strategies in 'green' office buildings

Energy efficient office buildings are intended to provide a comfortable and healthy environment for their occupants as well as reducing the energy consumption of the building. They are often designed as "showcase" buildings illustrating the potential for savings through some innovative design technology. But do such buildings actually deliver the desired energy savings and satisfactory comfort conditions for occupants? Measurements of a "green" University campus building in Victoria, Australia, designed with an innovative fabric energy storage system, demonstrate that the ventilation system is not providing acceptable indoor air quality conditions. The design strategies used to reduce energy consumption have had negative consequences on the air quality of the building. Insufficient fresh air is being drawn into the building leading to an excessive build up of carbon dioxide. It is recommended that monitoring systems need to use a wider range of measurements than temperature alone to guarantee good quality indoor air and working conditions and that commissioning of buildings should include adequate monitoring of the operational performance of the building. Designers need to be made aware of the potential consequences of their decisions when attempting innovative energy-efficient designs.

End-Permian catastrophe by a bolide impact: evidence of a gigantic release of sulfur from the mantle

Our studies in southern China have revealed a remarkable sulfur and strontium isotope excursion at the end of the Permian, along with a coincident concentration of impact- metamorphosed grains and kaolinite and a significant decrease in manganese, phosphorous, calcium, and microfossils (foraminifera). These data suggest that an asteroid or a comet hit the ocean at the end of Permian time and caused a rapid and massive release of sulfur from the mantle to the ocean-atmosphere system, leading to significant oxygen consumption, acid rain, and the most severe biotic crisis in the history of life on Earth.

Manganese dioxide allylic and benzylic oxidation reactions in ionic liquids

Ionic liquids 1-butyl-3-methylimidazolium tetrafluoroborate [bmIm][BF₄] and 1-butyl-3-methylimidazolium hexafluorophosphate [bmIm][PF₆] were evaluated as reaction media for allylic and benzylic oxidation reactions using manganese dioxide. The use of ionic liquids as an extractant in the reaction work-up was also investigated. Procedures for recycling of the [bmIm][PF₆] ionic liquids used in these MnO₂ oxidation reactions were also developed.

Gas chromatography-chemical ionization-mass spectrometric fatty acid analysis of a commercial supercritical carbon dioxide lipid extract from New Zealand green-lipped mussel (Perna canaliculus)

Supercritical fluid extracts of New Zealand green-lipped mussels (NZGLM) have been suggested to have therapeutic properties related to their oil components. The large number of minor FA in NZGLM extract was characterized by a GC-CIMS/MS method that excels at identification of double-bond positions in FAME. The extract contained five major lipid classes: sterol esters, TAG, FFA, sterols, and polar lipids. The total FA content of the lipid extract was 0.664 g/mL. Fifty-three unsaturated FA (UFA) were fully identified, of which 37 were PUFA, and a further 21 UFA were detected for which concentrations were too low for assignment of double-bond positions. There were 17 saturated FA, with 14∶0, 16∶0, and 18∶0 present in the greatest concentration. The 10 n−3 PUFA detected included 20∶5n−3 and 22∶6n−3, the two main n−3 FA; n−3 PUFA at low concentrations were 18∶3, 18∶4, 20∶3, 20∶4, 21∶5, 22∶5, 24∶6, and 28∶8. There were 43 UFA from the n−4, n−5, n−6, n−7, n−8, n−9, n−10, n−11 families, with 16∶2n−4, 16∶1n−5, 18∶1n−5, 18∶2n−6, 20∶4n−6, 16∶1n−7, 20∶1n−7, 16∶1n−9, 18∶1n−9, and 20∶1n−9 being the most abundant. In general, we estimated that FAME concentrations greater than 0.05% (w/w) were sufficient to assign double-bond positions. In total, 91 FA were detected in an extract of the NZGLM, whereas previous studies of fresh flesh from the NZGLM had reported identification of 42 FA. These data demonstrate a remarkable diversity of NZGLM FA.