Tuning the valence of the cerium center in (Na)phthalocyaninato and porphyrinato cerium double-deckers by changing the nature of the tetrapyrrole ligands

A series of 7 cerium double-decker complexes with various tetrapyrrole ligands including porphyrinates, phthalocyaninates, and 2,3-naphthalocyaninates have been prepared by previously described methodologies and characterized with elemental analysis and a range of spectroscopic methods. The molecular structures of two heteroleptic \[(na)phthalocyaninato](porphyrinato) complexes have also been determined by X-ray diffraction analysis which exhibit a slightly distorted square antiprismatic geometry with two domed ligands. Having a range of tetrapyrrole ligands with very different electronic properties, these compounds have been systematically investigated for the effects of ligands on the valence of the cerium center. On the basis of the spectroscopic (UV−vis, near-IR, IR, and Raman), electrochemical, and structural data of these compounds and compared with those of the other rare earth(III) counterparts reported earlier, it has been found that the cerium center adopts an intermediate valence in these complexes. It assumes a virtually trivalent state in cerium bis(tetra-tert-butylnaphthalocyaninate) as a result of the two electron rich naphthalocyaninato ligands, which facilitate the delocalization of electron from the ligands to the metal center. For the rest of the cerium double-deckers, the cerium center is predominantly tetravalent. The valences (3.59−3.68) have been quantified according to their LIII-edge X-ray absorption near-edge structure (XANES) profiles.

Public acceptance of carbon dioxide capture and storage in a proposed demonstration area

With the rising levels of CO2 in the atmosphere, low-emission technologies with carbon dioxide capture and storage (CCS) provide one option for transforming the global energy infrastructure into a more environmentally, climate sustainable system. However, like many technology innovations, there is a social risk to the acceptance of CCS. This article presents the findings of an engagement process using facilitated workshops conducted in two communities in rural Queensland, Australia, where a demonstration project for IGCC with CCS has been announced. The findings demonstrate that workshop participants were concerned about climate change and wanted leadership from government and industry to address the issue. After the workshops, participants reported increased knowledge and more positive attitudes towards CCS, expressing support for the demonstration project to continue in their local area. The process developed is one that could be utilized around the world to successfully engage communities on the low carbon emission technology options.

Corrosion studies on the plasma-sprayed nanostructured titanium dioxide coating

Purpose: The purpose of this paper is to report the resistance of plasma-sprayed titanium dioxide (TiO2) nanostructured coatings in a corrosive environment.----- Design/methodology/approach: Weight loss studies are performed according to ASTM G31 specifications in 3.5?wt% NaCl. Electrochemical polarization resistance measurements are made according to ASTM G59-91 specifications. Corrosion resistance in a humid and corrosive environment is determined by exposing the samples in a salt spray chamber for 100?h. Microstructural studies are carried out using an atomic force microscope and scanning electron microscope.----- Findings: The nanostructured TiO2 coatings offer good resistance to corrosion, as shown by the results of immersion, electrochemical and salt spray studies. The corrosion resistance of the coating is dictated primarily by the geometry of splat lamellae, density of unmelted nanoparticles, magnitude of porosity and surface homogeneity.----- Practical implications: The TiO2 nanostructured coatings show promising potential for use as abrasion, wear-resistant and thermal barrier coatings for service in harsh environments.----- Originality/value: The paper relates the corrosion resistance of nanostructured TiO2 coatings to their structure and surface morphology.

Carbon dioxide emissions from diesel and compressed natural gas buses during acceleration

Motor vehicle emission factors are generally derived from driving tests mimicking steady state conditions or transient drive cycles. However, neither of these test conditions completely represents real world driving conditions. In particular, they fail to determine emissions generated during the accelerating phase – a condition in which urban buses spend much of their time. In this study we analyse and compare the results of time-dependant emission measurements conducted on diesel and compressed natural gas (CNG) buses during an urban driving cycle on a chassis dynamometer and we derive power-law expressions relating carbon dioxide (CO2) emission factors to the instantaneous speed while accelerating from rest. Emissions during acceleration are compared with that during steady speed operation. These results have important implications for emission modelling particularly under congested traffic conditions.

Effect of thermal treatment on adsorption-desorption of ammonia and sulfur dioxide on palygorskite : change of surface acid-alkali properties

Thermally activated Palygorskite (Pg) has been found to be a good adsorbent material for ammonia (NH3) and sulfur dioxide (SO2). This research investigated the effect of thermal treatment on pore structure and surface acid-alkali properties of Pg through the adsorption-desorption of NH3 and SO2. The results showed that, up to 200 °C, the adsorption of NH3 on Pg was significantly higher than SO2. This was due to NH3 being adsorbed in the internal surface of Pg and forming hydrogen bonds (H-bonds) with coordinated water. The increase in thermal treatment temp. from 150 to 550 °C, showed a gradual decrease in the no. of surface acid sites, while the no. of surface alk. sites increased from 200 to 400 °C. The change of surface acidity-alk. sites is due to the collapse of internal channels of Pg and desorption of different types of hydroxyls assocd. with the Pg structure.

Indoor and outdoor nitrogen dioxide concentration in residential houses in Australia

As part of a larger indoor environmental study, residential indoor and outdoor levels of nitrogen dioxide (NO2) were measured for 14 houses in a suburb of Brisbane, Queensland, Australia. Passive samplers were used for 48-h sampling periods during the winter of 1999. The average indoor and outdoor NO2 levels were 13.8 ± 6.3 and 16.7 ± 4.2 ppb, respectively. The indoor/outdoor NO2 concentration ratio ranged from 0.4 to 2.3, with a median value of 0.82. The results of statistic analyses indicated that there was no significant correlation between indoor and outdoor NO2 concentrations, or between indoor and fixed site NO2 monitoring station concentrations. However, there was a significant correlation between outdoor and fixed site NO2 monitoring station concentrations. There was also a significant correlation between indoor NO2 concentration and indoor submicrometre (0.007–0.808 μm) aerosol particle number concentrations. The results in this study indicated indoor NO2 levels are significantly affected by indoor NO2 sources, such as a gas stove and cigarette smoking. It implies that the outdoor or fixed site monitoring concentration alone is a poor predictor of indoor NO2 concentration.

Investigation of phenol degradation : True reaction kinetics on fixed film titanium dioxide photocatalyst

This study of photocatalytic oxidation of phenol over titanium dioxide films presents a method for the evaluation of true reaction kinetics. A flat plate reactor was designed for the specific purpose of investigating the influence of various reaction parameters, specifically photocatalytic film thickness, solution flow rate (1–8 l min−1), phenol concentration (20, 40 and 80 ppm), and irradiation intensity (70.6, 57.9, 37.1and 20.4 W m−2), in order to further understand their impact on the reaction kinetics. Special attention was given to the mass transfer phenomena and the influence of film thickness. The kinetics of phenol degradation were investigated with different irradiation levels and initial pollutant concentration. Photocatalytic degradation experiments were performed to evaluate the influence of mass transfer on the reaction and, in addition, the benzoic acid method was applied for the evaluation of mass transfer coefficient. For this study the reactor was modelled as a batch-recycle reactor. A system of equations that accounts for irradiation, mass transfer and reaction rate was developed to describe the photocatalytic process, to fit the experimental data and to obtain kinetic parameters. The rate of phenol photocatalytic oxidation was described by a Langmuir–Hinshelwood type law that included competitive adsorption and degradation of phenol and its by-products. The by-products were modelled through their additive effect on the solution total organic carbon.

Photocatalytic reduction of carbon dioxide to formic acid, formaldehyde, and methanol using dye-sensitized TiO2 film

A bifunctionalized TiO2 film containing a dye-sensitized zone and a catalysis zone is designed for visible-light photocatalytic reduction of CO2 to chemicals continuously. Charge separation can be accomplished with electron transferring to catalysis zone and positive charge transforming to anode. Highly efficient conversion of CO2 to formic acid, formaldehyde, and methanol is achieved through the transferring electrons on conduction bands (CB) of TiO2. Reduction of CO2 and O2 evolution take place in separated solutions on different catalysts. The separated solution carried out in this photo-reactor system can avoid CO2 reduction products being oxidized by anode. The yields of reduction products were enhanced remarkably by external electrical power. This study provides not only a new photocatalytic system but also a potential of renewable energy source via carbon dioxide.

Enhancing photoactivity of TiO2(B)/anatase core-shell nanofibers by selectively doping cerium ions into the TiO2(B) Core

Cerium ions (Ce3+) can beselectively doped into the TiO2(B) core of TiO2(B)/anatase core–shell nanofibers by means of a simple one-pot hydrothermal treatment of a starting material of hydrogen trititanate (H2Ti3O7) nanofibers. These Ce3+ ions (≈0.202 nm) are located on the (110) lattice planes of the TiO2(B) core in tunnels (width≈0.297 nm). The introduction of Ce3+ ions reduces the defects of the TiO2(B) core by inhibiting the faster growth of (110) lattice planes. More importantly, the redox potential of the Ce3+/Ce4+ couple (E0(Ce3+/Ce4+)=1.715 V versus the normal hydrogen electrode) is more negative than the valence band of TiO2(B). Therefore, once the Ce3+-doped nanofibers are irradiated by UV light, the doped Ce3+ ions in close vicinity to the interface between the TiO2(B) core and anatase nanoshell can efficiently trap the photogenerated holes. This facilitates the migration of holes from the anatase shell and leaves more photogenerated electrons in the anatase nanoshell, which results in a highly efficient separation of photogenerated charges in the anatase nanoshell. Hence, this enhanced charge-separation mechanism accelerates dye degradation and alcohol oxidation processes. The one-pot treatment doping strategy is also used to selectively dope other metal ions with variable oxidation states such as Co2+/3+ and Cu+/2+ ions. The doping substantially improves the photocatalytic activity of the mixed-phase nanofibers. In contrast, the doping of ions with an invariable oxidation state, such as Zn2+, Ca2+, or Mg2+, does not enhance the photoactivity of the mixed-phase nanofibers as the ions could not trap the photogenerated holes.

Challenges facing carbon dioxide labelling of construction materials

In the absence of a benchmarking mechanism specifically designed for local requirements and characteristics, a carbon dioxide footprint assessment and labelling scheme for construction materials is urgently needed to promote carbon dioxide reduction in the construction industry. This paper reports on a recent interview survey of 18 senior industry practitioners in Hong Kong to elicit their knowledge and opinions concerning the potential of such a carbon dioxide labelling scheme. The results of this research indicate the following. A well-designed carbon dioxide label could stimulate demand for low carbon dioxide construction materials. The assessment of carbon dioxide emissions should be extended to different stages of material lifecycles. The benchmarks for low carbon dioxide construction materials should be based on international standards but without sacrificing local integrity. Administration and monitoring of the carbon dioxide labelling scheme could be entrusted to an impartial and independent certification body. The implementation of any carbon dioxide labelling schemes should be on a voluntary basis. Cost, functionality, quality and durability are unlikely to be replaced by environmental considerations in the absence of any compelling incentives or penalties. There are difficulties in developing and operating a suitable scheme, particularly in view of the large data demands involved, reluctance in using low carbon dioxide materials and limited environmental awareness.