ZnO nanocones with high-index {101̅1} facets for enhanced energy conversion efficiency of dye-sensitized solar cells

ZnO is a promising photoanode material for dye-sensitized solar cells (DSCs) due to its high bulk electron mobility and because different geometrical structures can easily be tailored. Although various strategies have been taken to improve ZnO-based DSC efficiencies, their performances are still far lower than TiO2 counterparts, mainly because low conductivity Zn2+–dye complexes form on the ZnO surfaces. Here, cone-shaped ZnO nanocrystals with exposed reactive O-terminated {101̅1} facets were synthesized and applied in DSC devices. The devices were compared with DSCs made from more commonly used rod-shaped ZnO nanocrystals where {101̅0} facets are predominantly exposed. When cone-shaped ZnO nanocrystals were used, DSCs sensitized with C218, N719, and D205 dyes universally displayed better power conversion efficiency, with the highest photoconversion efficiency of 4.36% observed with the C218 dye. First-principles calculations indicated that the enhanced DSCs performance with ZnO nanocone photoanodes could be attributed to the strength of binding between the dye molecules and reactive O-terminated {101̅1} ZnO facets and that more effective use of dye molecules occurred due to a significantly less dye aggregation on these ZnO surfaces compared to other ZnO facets.

3D hierarchical rutile TiO2 and metal-free organic sensitizer producing dye-sensitized solar cells 8.6% conversion efficiency

Three-dimensional (3D) hierarchical nanoscale architectures comprised of building blocks, with specifically engineered morphologies, are expected to play important roles in the fabrication of 'next generation' microelectronic and optoelectronic devices due to their high surface-to-volume ratio as well as opto-electronic properties. Herein, a series of well-defined 3D hierarchical rutile TiO2 architectures (HRT) were successfully prepared using a facile hydrothermal method without any surfactant or template, simply by changing the concentration of hydrochloric acid used in the synthesis. The production of these materials provides, to the best of our knowledge, the first identified example of a ledgewise growth mechanism in a rutile TiO2 structure. Also for the first time, a Dye-sensitized Solar Cell (DSC) combining a HRT is reported in conjunction with a high-extinction-coefficient metal-free organic sensitizer (D149), achieving a conversion efficiency of 5.5%, which is superior to ones employing P25 (4.5%), comparable to state-of-the-art commercial transparent titania anatase paste (5.8%). Further to this, an overall conversion efficiency 8.6% was achieved when HRT was used as the light scattering layer, a considerable improvement over the commercial transparent/reflector titania anatase paste (7.6%), a significantly smaller gap in performance than has been seen previously.

Novel ruthenium bipyridyl dyes with s-donor ligands and their application in dye-sensitized solar cells

Two series of novel ruthenium bipyridyl dyes incorporating sulfur-donor bidentate ligands with general formula \[Ru(R-bpy)2C2N2S2] and \[Ru(R-bpy)2(S2COEt)]\[NO3] (where R =H, CO2Et, CO2H; C2N2S2 = cyanodithioimidocarbonate and S2COEt = ethyl xanthogenate) have been synthesized and characterized spectroscopically, electrochemically and computationally. The acid derivatives in both series (C2N2S2 3 and S2COEt 6) were used as a photosensitizer in a dye-sensitized solar cell (DSSC) and the incident photo-to-current conversion efficiency (IPCE), overall efficiency (_) and kinetics of the dye/TiO2 system were investigated. It was found that 6 gave a higher efficiency cell than 3 despite the latter dye’s more favorable electronic properties, such as greater absorption range, higher molar extinction coefficient and large degree of delocalization of the HOMO. The transient absorption spectroscopy studies revealed that the recombination kinetics of 3 were unexpectedly fast, which was attributed to the terminal CN on the ligand binding to the TiO2, as evidenced by an absorption study of R =H and CO2Et dyes sensitized on TiO2, and hence leading to a lower efficiency DSSC.

LCADesign : an integrated approach to automatic eco-efficiency assessment of commercial buildings

Buildings consume resources and energy, contribute to pollution of our air, water and soil, impact the health and well-being of populations and constitute an important part of the built environment in which we live. The ability to assess their design with a view to reducing that impact automatically from their 3D CAD representations enables building design professionals to make informed decisions on the environmental impact of building structures. Contemporary 3D object-oriented CAD files contain a wealth of building information. LCADesign has been designed as a fully integrated approach for automated eco-efficiency assessment of commercial buildings direct from 3D CAD. LCADesign accesses the 3D CAD detail through Industry Foundation Classes (IFCs) - the international standard file format for defining architectural and constructional CAD graphic data as 3D real-world objects - to permit construction professionals to interrogate these intelligent drawing objects for analysis of the performance of a design. The automated take-off provides quantities of all building components whose specific production processes, logistics and raw material inputs, where necessary, are identified to calculate a complete list of quantities for all products such as concrete, steel, timber, plastic etc and combines this information with the life cycle inventory database, to estimate key internationally recognised environmental indicators such as CML, EPS and Eco-indicator 99. This paper outlines the key modules of LCADesign and their role in delivering an automated eco-efficiency assessment for commercial buildings.

Beam steering with high front-to-back ratio and high directivity on small platforms using decoupled antenna pairs

Beam steering with high front-to-back ratio and high directivity on a small platform is proposed. Two closely spaced antenna pairs with eigenmode port decoupling are used as the basic radiating elements. Two orthogonal radiation patterns are obtained for each antenna pair. High front-to-back ratio and high directivity are achieved by combining the two orthogonal radiation patterns. With an infinite groundplane, a front-to-back ratio of 21 dB with a directivity of 9.8 dB can be achieved. Beam steering, at the expense of a slight decrease in directivity, is achieved by placing the two antenna pairs 0.5λ apart. The simulated half power beamwidth is 58°. A prototype was designed and the 2-D radiation patterns were measured. The prototype supports three directions of beam steering. The half power beamwidth was measured as 46°, 48°, and 50° for the three respective beam directions. The measured front-to-back ratio in azimuth plane is 8.5 dB, 8.0 dB and 7.6 dB, respectively.

Inhaled particle counts on bicycle commute routes of low and high proximity to motorised traffic

Frequent exposure to ultrafine particles (UFP) is associated with detrimental effects on cardiopulmonary function and health. UFP dose and therefore the associated health risk are a factor of exposure frequency, duration, and magnitude of (therefore also proximity to) a UFP emission source. Bicycle commuters using on-road routes during peak traffic times are sharing a microenvironment with high levels of motorised traffic, a major UFP emission source. Inhaled particle counts were measured along popular pre-identified bicycle commute route alterations of low (LOW) and high (HIGH) motorised traffic to the same inner-city destination at peak commute traffic times. During commute, real-time particle number concentration (PNC; mostly in the UFP range) and particle diameter (PD), heart and respiratory rate, geographical location, and meteorological variables were measured. To determine inhaled particle counts, ventilation rate was calculated from heart-rate-ventilation associations, produced from periodic exercise testing. Total mean PNC of LOW (compared to HIGH) was reduced (1.56 x e4 ± 0.38 x e4 versus 3.06 x e4 ± 0.53 x e4 ppcc; p = 0.012). Total estimated ventilation rate did not vary significantly between LOW and HIGH (43 ± 5 versus 46 ± 9 L•min; p = 0.136); however, due to total mean PNC, accumulated inhaled particle counts were 48% lower in LOW, compared to HIGH (7.6 x e8 ± 1.5 x e8 versus 14.6 x e8 ± 1.8 x e8; p = 0.003). For bicycle commuting at peak morning commute times, inhaled particle counts and therefore cardiopulmonary health risk may be substantially reduced by decreasing exposure to motorised traffic, which should be considered by both bicycle commuters and urban planners.

Ionic liquid pre-treatment and fractionation of sugarcane bagasse for the production of bioethanol

Pretretament is an essential and expensive processing step for the manufacturing of ethanol from lignocellulosic raw materials. Ionic liquids are a new class of solvents that have the potential to be used as pretreatment agents. The attractive characteristics of ionic liquid pretreatment of lignocellulosics such as thermal stability, dissolution properties, fractionation potential, cellulose decrystallisation capacity and saccharification impact are investigated in this thesis. Dissolution of bagasse with 1-butyl-3-methylimidazolium chloride ([C4mim]Cl) at high temperatures (110 �‹C to 160 �‹C) is investigated as a pretreatment process. Material balances are reported and used along with enzymatic saccharification data to identify optimum pretreatment conditions (150 �‹C for 90 min). At these conditions, the dissolved and reprecipitated material is enriched in cellulose, has a low crystallinity and the cellulose component is efficiently hydrolysed (93 %, 3 h, 15 FPU). At pretreatment temperatures < 150 �‹C, the undissolved material has only slightly lower crystallinity than the starting. At pretreatment temperatures . 150 �‹C, the undissolved material has low crystallinity and when combined with the dissolved material has a saccharification rate and extent similar to completely dissolved material (100 %, 3h, 15 FPU). Complete dissolution is not necessary to maximize saccharification efficiency at temperatures . 150 �‹C. Fermentation of [C4mim]Cl-pretreated, enzyme-saccharified bagasse to ethanol is successfully conducted (85 % molar glucose-to-ethanol conversion efficiency). As compared to standard dilute acid pretreatment, the optimised [C4mim]Cl pretreatment achieves substantially higher ethanol yields (79 % cf. 52 %) in less than half the processing time (pretreatment, saccharification, fermentation). Fractionation of bagasse partially dissolved in [C4mim]Cl to a polysaccharide rich and a lignin rich fraction is attempted using aqueous biphasic systems (ABSs) and single phase systems with preferential precipitation. ABSs of ILs and concentrated aqueous inorganic salt solutions are achievable (e.g. [C4mim]Cl with 200 g L-1 NaOH), albeit they exhibit a number of technical problems including phase convergence (which increases with increasing biomass loading) and deprotonation of imidazolium ILs (5 % - 8 % mol). Single phase fractionation systems comprising lignin solvents / cellulose antisolvents, viz. NaOH (2M) and acetone in water (1:1, volume basis), afford solids with, respectively, 40 % mass and 29 % mass less lignin than water precipitated solids. However, this delignification imparts little increase in saccharification rates and extents of these solids. An alternative single phase fractionation system is achieved simply by using water as an antisolvent. Regulating the water : IL ratio results in a solution that precipitates cellulose and maintains lignin in solution (0.5 water : IL mass ratio) in both [C4mim]Cl and 1-ethyl-3-methylimidazolium acetate ([C2mim]OAc)). This water based fractionation is applied in three IL pretreatments on bagasse ([C4mim]Cl, 1-ethyl-3-methyl imidazolium chloride ([C2mim]Cl) and [C2mim]OAc). Lignin removal of 10 %, 50 % and 60 % mass respectively is achieved although only 0.3 %, 1.5 % and 11.7 % is recoverable even after ample water addition (3.5 water : IL mass ratio) and acidification (pH . 1). In addition the recovered lignin fraction contains 70 % mass hemicelluloses. The delignified, cellulose-rich bagasse recovered from these three ILs is exposed to enzyme saccharification. The saccharification (24 h, 15 FPU) of the cellulose mass in starting bagasse, achieved by these pretreatments rank as: [C2mim]OAc (83 %)>>[C2mim]Cl (53 %)=[C4mim]Cl(53%). Mass balance determinations accounted for 97 % of starting bagasse mass for the [C4mim]Cl pretreatment , 81 % for [C2mim]Cl and 79 %for [C2mim]OAc. For all three IL treatments, the remaining bagasse mass (not accounted for by mass balance determinations) is mainly (more than half) lignin that is not recoverable from the liquid fraction. After pretreatment, 100 % mass of both ions of all three ILs were recovered in the liquid fraction. Compositional characteristics of [C2mim]OAc treated solids such as low lignin, low acetyl group content and preservation of arabinosyl groups are opposite to those of chloride IL treated solids. The former biomass characteristics resemble those imparted by aqueous alkali pretreatment while the latter resemble those of aqueous acid pretreatments. The 100 % mass recovery of cellulose in [C2mim]OAc as opposed to 53 % mass recovery in [C2mim]Cl further demonstrates this since the cellulose glycosidic bonds are protected under alkali conditions. The alkyl chain length decrease in the imidazolium cation of these ILs imparts higher rates of dissolution and losses, and increases the severity of the treatment without changing the chemistry involved.

Development of lightweight concrete with high resistance to water and chloride-ion penetration

This paper presents an experimental study to evaluate the influence of coarse lightweight aggregate (LWA), fine LWA and the quality of the paste matrix on water absorption and permeability, and resistance to chloride-ion penetration in concrete. The results indicate that incorporation of pre-soaked coarse LWA in concrete increases water sorptivity and permeability slightly compared to normal weight concrete (NWC) of similar water-to-cementitious materials ratio (w/cm). Furthermore, resistance of the sand lightweight concrete (LWC) to water permeability and chloride-ion penetration decreases with an increase in porosity of the coarse LWA. The use of fine LWA including a crushed fraction <1.18 mm reduced resistance of the all-LWC to water and chloride-ion penetration compared with the sand-LWC which has the same coarse LWA. Overall, the quality of the paste matrix was dominant in controlling the transport properties of the concrete, regardless of porosity of the aggregates used. With low w/cm and silica fume, low unit weight LWC (_1300 kg/m3) was produced with a higher resistance to water and chloride-ion penetration compared with NWC and LWC of higher unit weights.

Development of lightweight aggregate concrete with high resistance to water and chloride-ion penetration

This paper presents an experimental study to evaluate the effect of coarse and fine LWA in concrete on its water absorption and permeability, and resistance to chloride-ion penetration. In additions, LWC with lower unit weight of about 1300 kg/m3 but high resistance to water and chloride-ion penetration was developed and evaluated. The results indicate that the incorporation of coarse LWA in concrete increases water sorptivity and permeability slightly compared to NWC of similar w/c. The resistance of the sand-LWC to chloride-ion penetration depends on porosity of the coarse LWA. Fine LWA has more influence on the transport proper-ties of concrete than coarse LWA. Use of lightweight crushed sand <1.18 mm reduced the resistance of the LWC to water and chloride-ion penetration to some extent. With low w/cm and silica fume, low unit weight LWC (~1300 kg/m3) was produced with higher resistance to water and chloride ion penetration compared with concretes of higher unit weights.

The use of an electrostatic lens to enhance the efficiency of the electrospinning process

Electrospun scaffolds manufactured using conventional electrospinning configurations have an intrinsic thickness limitation, due to a charge build-up at the collector. To overcome this limitation, an electrostatic lens has been developed that, at the same relative rate of deposition, focuses the polymer jet onto a smaller area of the collector, resulting in the fabrication of thick scaffolds within a shorter period of time. We also observed that a longer deposition time (up to 13 h, without the intervention of the operator) could be achieved when the electrostatic lens was utilised, compared to 9–10 h with a conventional processing set-up and also showed that fibre fusion was less likely to occur in the modified method. This had a significant impact on the mechanical properties, as the scaffolds obtained with the conventional process had a higher elastic modulus and ultimate stress and strain at short times. However, as the thickness of the scaffolds produced by the conventional electrospinning process increased, a 3-fold decrease in the mechanical properties was observed. This was in contrast to the modified method, which showed a continual increase in mechanical properties, with the properties of the scaffold finally having similar mechanical properties to the scaffolds obtained via the conventional process at longer times. This “focusing” device thus enabled the fabrication of thicker 3-dimensional electrospun scaffolds (of thicknesses up to 3.5 mm), representing an important step towards the production of scaffolds for tissue engineering large defect sites in a multitude of tissues.

Reviewing in-vehicle systems to improve fuel efficiency and road safety

Road transport plays a significant role in various industries and mobility services around the globe and has a vital impact on our daily lives. However it also has serious impacts on both public health and the environment. In-vehicle feedback systems are a relatively new approach to encouraging driver behavior change for improving fuel efficiency and safety in automotive environments. While many studies claim that the adoption of eco-driving practices, such as eco-driving training programs and in-vehicle feedback to drivers, has the potential to improve fuel efficiency, limited research has integrated safety and eco-driving. Therefore, it is crucial to understand the human factors related theories and practices which will inform the design of an in-vehicle Human Machine Interface (HMI) that could provide real-time driver feedback and consequently improve both fuel efficiency and safety. This paper provides a comprehensive review of the current state of published literature on in-vehicle systems to identify and evaluate the impact of eco-driving and safety feedback systems. This paper also discusses how these factors may conflict with one another and have a negative effect on road safety, while also exploring possible eco-driving practices that could encourage more sustainable, environmentally-conscious and safe driving behavior. The review revealed a lack of comprehensive theoretical research integrating eco-driving and safe driving, and no current available HMI covering both aspects simultaneously. Furthermore, the review identified that some eco-driving in-vehicle systems may enhance fuel efficiency without compromising safety. The review has identified a range of concepts which can be developed to influence driver acceptance of safety and eco-driving systems within the area of HMI. This can promote new research aimed at enhancing our understanding of the relationship between eco-driving and safety from the human factors viewpoint. This provides a foundation for developing innovative, persuasive and acceptable in-vehicle HMI systems to improve fuel efficiency and road safety.

Enhanced electron lifetime of CdSe/CdS quantum dot (QD) sensitized solar cells using ZnSe core–shell structure with efficient regeneration of quantum Ddots

Research on development of efficient passivation materials for high performance and stable quantum dot sensitized solar cells (QDSCs) is highly important. While ZnS is one of the most widely used passivation material in QDSCs, an alternative material based on ZnSe which was deposited on CdS/CdSe/TiO2 photoanode to form a semi-core/shell structure has been found to be more efficient in terms of reducing electron recombination in QDSCs in this work. It has been found that the solar cell efficiency was improved from 1.86% for ZnSe0 (without coating) to 3.99% using 2 layers of ZnSe coating (ZnSe2) deposited by successive ionic layer adsorption and reaction (SILAR) method. The short circuit current density (Jsc) increased nearly 1-fold (from 7.25 mA/cm2 to13.4 mA/cm2), and the open circuit voltage (Voc) was enhanced by 100 mV using ZnSe2 passivation layer compared to ZnSe0. Studies on the light harvesting efficiency (ηLHE) and the absorbed photon-to-current conversion efficiency (APCE) have revealed that the ZnSe coating layer caused the enhanced ηLHE at wavelength beyond 500 nm and a significant increase of the APCE over the spectrum 400−550 nm. A nearly 100% APCE was obtained with ZnSe2, indicating the excellent charge injection and collection process in the device. The investigation on charge transport and recombination of the device has indicated that the enhanced electron collection efficiency and reduced electron recombination should be responsible for the improved Jsc and Voc of the QDSCs. The effective electron lifetime of the device with ZnSe2 was nearly 6 times higher than ZnSe0 while the electron diffusion coefficient was largely unaffected by the coating. Study on the regeneration of QDs after photoinduced excitation has indicated that the hole transport from QDs to the reduced species (S2−) in electrolyte was very efficient even when the QDs were coated with a thick ZnSe shell (three layers). For comparison, ZnS coated CdS/CdSe sensitized solar cell with optimum shell thickness was also fabricated, which generated a lower energy conversion efficiency (η = 3.43%) than the ZnSe based QDSC counterpart due to a lower Voc and FF. This study suggests that ZnSe may be a more efficient passivation layer than ZnS, which is attributed to the type II energy band alignment of the core (CdS/CdSe quantum dots) and passivation shell (ZnSe) structure, leading to more efficient electron−hole separation and slower electron recombination.