Best Available Techniques (BAT) and coal fired power stations: Can the energy gap be plugged without increasing emissions?

At present, there is much anxiety regarding the security of energy supplies; for example, the UK and other European States are set to become increasingly dependant upon imports of natural gas from states with which political relations are often strained. These uncertainties are felt acutely by the electricity generating sector, which is facing major challenges regarding the choice of fuel mix in the years ahead. Nuclear energy may provide an alternative; however, in the UK, progress in replacing the first generation reactors is exceedingly slow. A number of operators are looking to coal as a means of plugging the energy gap. However, in the light of ever more stringent legal controls on emissions, this step cannot be taken without the adoption of sophisticated pollution abatement technology. This article examines the role which legal concepts such as Best Available Techniques (BAT) must play in bringing about these changes.

Temperature- and Pressure-induced Proton Transfer in the 1:1 Adduct Formed between Squaric Acid and 4,4 '-Bipyridine

We have applied a combination of spectroscopic and diffraction methods to study the adduct formed between squaric acid and bypridine, which has been postulated to exhibit proton transfer associated with a single-crystal to single-crystal phase transition at ca. 450 K. A combination of X-ray single-crystal and very-high flux powder neutron diffraction data confirmed that a proton does transfer from the acid to the base in the high-temperature form. Powder X-ray diffraction measurements demonstrated that the transition was reversible but that a significant kinetic energy barrier must be overcome to revert to the original structure. Computational modeling is consistent with these results. Modeling also revealed that, while the proton transfer event would be strongly discouraged in the gas phase, it occurs in the solid state due to the increase in charge state of the molecular ions and their arrangement inside the lattice. The color change is attributed to a narrowing of the squaric acid to bipyridine charge-transfer energy gap. Finally, evidence for the possible existence of two further phases at high pressure is also presented.

Consequences of N,C,N '- and C,N,N '-coordination modes on electronic and photophysical properties of cyclometalated aryl ruthenium(II) complexes

The effects of isoelectronic replacement of a neutral nitrogen donor atom by an anionic carbon atom in terpyridine ruthenium(II) complexes on the electronic and photophysical properties of the resulting N,C,N'- and C,N,N'-cyclometalated aryl ruthenium(II) complexes were investigated. To this end, a series of complexes was prepared either with ligands containing exclusively nitrogen donor atoms, that is, [Ru(R-1-tpy)(R-2-tpy)](2+) (R-1, R-2 = H, CO2Et), or bearing either one N,C,N'- or C,N,N'-cyclometalated ligand and one tpy ligand, that is, [Ru(R-1-(NCN)-C-Lambda-N-Lambda)(R-2-tpy)](+) and [Ru(R-1-(CNN)-N-Lambda-N-Lambda)(R-2-tpy)](+), respectively. Single-crystal X-ray structure determinations showed that cyclometalation does not significantly alter the overall geometry of the complexes but does change the bond lengths around the ruthenium(II) center, especially the nitrogen-to-ruthenium bond length trans to the carbanion. Substitution of either of the ligands with electron-withdrawing ester functionalities fine-tuned the electronic properties and resulted in the presence of an IR probe. Using trends obtained from redox potentials, emission energies, IR spectroelectrochemical responses, and the character of the lowest unoccupied molecular orbitals from DFT studies, it is shown that the first reduction process and luminescence are associated with the ester-substituted C,N,N'-cyclometalated ligand in [Ru(EtO2C-(CNN)-N-Lambda-N-Lambda)(tpy)](+). Cyclometalation in an N,C,N'-bonding motif changed the energetic order of the ruthenium d(zx), d(yz), and d(xy) orbitals. The red-shifted absorption in the N,C,N'-cyclometalated complexes is assigned to MLCT transitions to the tpy ligand. The red shift observed upon introduction of the ester moiety is associated with an increase in intensity of low-energy transitions, rather than a red shift of the main transition. Cyclometalation in the C,N,N'-binding motif also red-shifts the absorption, but the corresponding transition is associated with both ligand types. Luminescence of the cyclometalated complexes is relatively independent of the mode of cyclometalation, obeying the energy gap law within each individual series.

Investigation of ultra wideband multi-channel dichroic beamsplitters from 0.3 to 52µm

The development of a set of multi-channel dichroics which includes a 6 channel dichroic operating over the wavelength region from 0.3 to 52µm is described. In order to achieve the optimum performance, the optical constants of PbTe, Ge and CdTe coatings in the strongly absorptive region have been determined by use of a new iterative method using normal incidence reflectance measurement of the multilayer together with initial values of energy gap Eg and infinite refractive index n for the semiconductor model. The design and manufacture of the dichroics is discussed and the final results are presented.

The power of NMR. Part 1: the beginnings

Nuclear mnagnetic resonance (NMR) spectroscopy involves the excitation of nuclei by electromagnetic radiation in the radio-frequency range of the electromagnetic spectrum. For a nucleus to absorb energy from radiowaves in this way, it must hve the quantum mechanical property of spin. A spinning nucleus, such as that of the hydrogen atom, will dopt one f only two possible states when placed in a magnetic field. (In NMR, the hydrogen nucleus is often referred to as a proton, and is given the abbreviation 1H.) Az the strength of the magnetic field is increased, there is a proportional increase in the energy 'gap' between these two states. We can predic the resonant frequency at which any spinning nucleus will absorb energy from radio-frequency radiation as it jumps from the lower energy state to the upper state.

Solvent-dependent modulation of metal–metal electronic interactions in a dinuclear cyanoruthenate complex: a detailed electrochemical, spectroscopic and computational study

The dinuclear complex [{Ru(CN)4}2(μ-bppz)]4− shows a strongly solvent-dependent metal–metal electronic interaction which allows the mixed-valence state to be switched from class 2 to class 3 by changing solvent from water to CH2Cl2. In CH2Cl2 the separation between the successive Ru(II)/Ru(III) redox couples is 350 mVand the IVCT band (from the UV/Vis/NIR spectroelectrochemistry) is characteristic of a borderline class II/III or class III mixed valence state. In water, the redox separation is only 110 mVand the much broader IVCT transition is characteristic of a class II mixed-valence state. This is consistent with the observation that raising and lowering the energy of the d(π) orbitals in CH2Cl2 or water, respectively, will decrease or increase the energy gap to the LUMO of the bppz bridging ligand, which provides the delocalisation pathway via electron-transfer. IR spectroelectrochemistry could only be carried out successfully in CH2Cl2 and revealed class III mixed-valence behaviour on the fast IR timescale. In contrast to this, time-resolved IR spectroscopy showed that the MLCTexcited state, which is formulated as RuIII(bppz˙−)RuII and can therefore be considered as a mixed-valence Ru(II)/Ru(III) complex with an intermediate bridging radical anion ligand, is localised on the IR timescale with spectroscopically distinct Ru(II) and Ru(III) termini. This is because the necessary electron-transfer via the bppz ligand is more difficult because of the additional electron on bppz˙− which raises the orbital through which electron exchange occurs in energy. DFT calculations reproduce the electronic spectra of the complex in all three Ru(II)/Ru(II), Ru(II)/Ru(III) and Ru(III)/Ru(III) calculations in both water and CH2Cl2 well as long as an explicit allowance is made for the presence of water molecules hydrogen-bonded to the cyanides in the model used. They also reproduce the excited-state IR spectra of both [Ru(CN)4(μ-bppz)]2– and [{Ru(CN)4}2(μ-bppz)]4− very well in both solvents. The reorganization of the water solvent shell indicates a possible dynamical reason for the longer life time of the triplet state in water compared to CH2Cl2.

Influencing energy efficient occupant behavior through improved building and control design

There is growing pressure on the construction industry to deliver energy efficient, sustainable buildings but there is evidence to suggest that, in practice, designs regularly fail to achieve the anticipated levels of in-use energy consumption. One of the key factors behind this discrepancy is the behavior of the building occupants. This paper explores how insights from experimental psychology could potentially be used to reduce the gap between the predicted and actual energy performance of buildings. It demonstrates why traditional methods to engage with the occupants are not always successful and proposes a model for a more holistic approach to this issue. The paper concludes that achieving energy efficiency in buildings is not solely a technological issue and that the construction industry needs to adopt a more user-centred approach.

Post-occupancy evaluation studies in recently refurbished office building: energy performance and employees' satisfaction

Existing buildings contribute greatly to global energy use and greenhouse gas emissions. In the UK, about 18% of carbon emissions are generated by non-domestic buildings; sustainable building refurbishment can play an important role in reducing carbon emissions. This paper looks at the performance of a recently refurbished 5-storey office building in London, in terms of energy consumption as well as occupants’ satisfaction. Pre- and post-occupancy evaluation studies were conducted using online questionnaire surveys and energy consumption evaluation. Results from pre-occupancy and post-occupancy evaluation studies showed that employees, in general, were more satisfied with their work environment at the refurbished building than with that of their previous office. Employees’ self-reported productivity improved after the move to Elms House. These surveys showed a positive relationship between employees’ satisfaction with their work environment and their self-reported productivity, well-being and enjoyment at work. The factor that contributed to increasing employee satisfaction the most was: better use of interior space. Although the refurbishment was a success in terms of reducing energy consumption per m2, the performance gap was almost 3 times greater than that estimated. Unregulated loads, problems with building control, ineffective use of space and occupants’ behaviour are argued to be reasons for this gap.

Post-occupancy studies of an office environment: Energy performance and occupants’ satisfaction

It is generally accepted that the physical workplace environment affects employees’ satisfaction and, consequently, their perceived productivity and well-being. This study investigated whether employee “satisfaction” variables can predict perceived productivity, well-being and enjoyment at work, and if so, to what extent. The study also explored whether limiting employees’ control over their environment could save energy without compromising employees’ satisfaction and perceived productivity. Preoccupancy and post-occupancy evaluation studies were conducted, in terms of both energy consumption and employee perceptions, to make comparisons between a company’s old and current headquarters buildings, both located in the same area of London. The results showed that employees were more satisfied with their work environment at their new HQ, in general, than with that of their previous office. Also, employees’ self-reported productivity, well-being and enjoyment at work improved after the move. It was revealed that the combination of employees’ level of satisfaction with “interior use of space” and “physical conditions” was the best predictor of their perceived productivity, while satisfaction with “indoor facilities” was not a good predictor. In terms of energy performance, although the new HQ’s energy consumption per m2 was significantly less than that of the previous building, there was still a gap between the refurbishment design target and the actual performance of the building. The findings suggest that this gap could be due to a number of factors, including an ineffective use of interior space, and occupants’ behaviour.

Band gap control via tuning of inversion degree in CdIn2S4 spinel

Based on theoretical arguments we propose a possible route for controlling the band-gap in the promising photovoltaic material CdIn2S4. Our ab initio calculations show that the experimental degree of inversion in this spinel (fraction of tetrahedral sites occupied by In) corresponds approximately to the equilibrium value given by the minimum of the theoretical inversion free energy at a typical synthesis temperature. Modification of this temperature, or of the cooling rate after synthesis, is then expected to change the inversion degree, which in turn sensitively tunes the electronic band-gap of the solid, as shown here by Heyd-Scuseria-Ernzerhof screened hybrid functional calculations.

Effect of building gap to improve pedestrian comfort levels and ventilation

Rapid rates of urbanization have resulted into increased concerns of urban environment. Amongst them, wind and thermal comfort levels for pedestrians have attracted research interest. In this regards, urban wind environment is seen as a crucial components that can lead to improved thermal comfort levels for pedestrian population. High rise building in modern urban setting causes high levels of turbulence that renders discomfort to pedestrians. Additionally, a higher frequency of high ris e buildings at a particular region acts as a shield against the wind flow to the lower buildings beyond them resulting into higher levels of discomfort to users or residents. Studies conducted on developing wind flow models using Computational Fluid Dynami cs (CFD) simulations have revealed improvement in interval to height ratios can results into improved wind flow within the simulation grid. However, high value and demand for land in urban areas renders expansion to be an impractical solution. Nonetheless, innovative utilization of architectural concepts can be imagined to improve the pedestrian comfort levels through improved wind permeability. This paper assesses the possibility of through-building gaps being a solution to improve pedestrian comfort levels.

Spin polarization, orbital occupation and band gap opening in vanadium dioxide: the effect of screened Hartree–Fock exchange

The metal–insulator transition of VO2 so far has evaded an accurate description by density functional theory. The screened hybrid functional of Heyd, Scuseria and Ernzerhof leads to reasonable solutions for both the low-temperature monoclinic and high-temperature rutile phases only if spin polarization is excluded from the calculations. We explore whether a satisfactory agreement with experiment can be achieved by tuning the fraction of Hartree Fock exchange (a) in the density functional. It is found that two branches of locally stable solutions exist for the rutile phase for 12:5% 6 a 6 20%. One is metallic and has the correct stability as compared to the monoclinic phase, the other is insulating with lower energy than the metallic branch. We discuss these observations based on the V 3d orbital occupations and conclude that a ¼ 10% is the best possible choice for spin-polarized VO2 calculations.

Promoting behaviour change through personalized energy feedback in offices

A body of research suggests that the provision of energy feedback information to building users can elicit significant energy reductions through behaviour change. However, most studies have focused on energy use in homes and the assessment of interventions and technologies, to the neglect of the non-domestic context and broader issues arising from the introduction of feedback technologies. To address this gap, a non-domestic case study explores the delivery of personalized energy feedback to office workers through a novel system utilizing wireless technologies. The research demonstrates advantages of monitoring occupancy and quantifying energy use from specific behaviours as a basis for effective energy feedback; this is particularly important where there are highly disaggregated forms of energy use and a range of locations for that activity to take place. Quantitative and qualitative data show that personalized feedback can help individuals identify energy reduction opportunities. However, the analysis also highlights important contextual barriers and issues that need to be addressed when utilizing feedback technologies in the workplace. If neglected, these issues may limit the effective take-up of feedback interventions.