Nanoporous metal organic framework materials for hydrogen storage

Hydrogen is expected to play an important role in future transportation as a promising alternative clean energy source to carbon-based fuels. One of the key challenges to commercialize hydrogen energy is to develop appropriate onboard hydrogen storage systems, capable of charging and discharging large quantities of hydrogen with fast enough kinetics to meet commercial requirements. Metal organic framework (MOF) is a new type of inorganic and organic hybrid nanoporous particulate materials. Its diverse networks can enhance hydrogen storage through tuning the structure and property of MOFs. The MOF materials so far developed adsorb hydrogen through weak dispersion interactions, which allow significant quantity of hydrogen to be stored at cryogenic temperatures with fast kinetics. Novel MOFs are being developed to strengthen the interactions between hydrogen and MOFs in order to store hydrogen under ambient conditions. This review surveys the development of such candidate materials, their performance and future research needs. (C) 2009 Chinese Society of Particuology and Institute of Process Engineering, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Optimisation and scaling of interfacial GeO2 layers for high-k gate stacks on germanium and extraction of dielectric constant of GeO2

Germanium is an attractive channel material for MOSFETs because of its higher mobility than silicon. In this paper, GeO2 has been investigated as an interfacial layer for high-kappa gate stacks on germanium. Thermally grown GeO2 layers have been prepared at 550 degrees C to minimise GeO volatilisation. GeO2 growth has been performed in both pure O-2 ambient and O-2 diluted with N-2. GeO2 thickness has been scaled down to approximately 3 nm. MOS capacitors have been fabricated using different GeO2 thicknesses with a standard high-kappa dielectric on top. Electrical properties and thermal stability have been tested up to at least 350 degrees C. The K value of GeO2 was experimentally determined to be 4.5. Interface state densities (D-it) of less than 10(12) CM-2 eV(-1) have been extracted for all devices using the conductance method.

Interstitial Nitrogen in Diamond – Optical and EPR Studies

Nitrogen is one of the most common impurities in diamond. On a substitutional site it acts as a deep donor, approximately 1.7 eV below the conduction band. Irradiation of nitrogen containing diamond and subsequent annealing creates the nitrogen vacancy centre, which has recently attracted much attention for quantum information processing application. Another possible product of irradiation and annealing of nitrogen containing diamond is interstitial nitrogen. Presumably, a mobile carbon interstitial migrates to a substitutional nitrogen to produce an interstitial nitrogen complex which may or may not be mobile. The configuration(s) of interstitial nitrogen related defects (e.g. bond centred, [001]-split) are not known. An infra-red (IR) absorption peak at 1450 cm-1 labelled H1a has been associated with an nitrogen interstitial complex. [1] Theoretical modelling suggested that this IR local mode is due to a bond centred nitrogen interstitial [2]. However, more recent modelling [3] suggests that this defect is mobile at temperatures were H1a is stable and instead assign H1a to two nitrogen atoms occupying a single lattice site in a [001]-split configuration. To date no electron paramagnetic resonance (EPR) spectra have been conclusively associated with an interstitial nitrogen defect.

In this study we present data from new EPR and optical absorption studies in combination with uniaxial stress of nitrogen interstitial related defects in electron irradiated and annealed nitrogen doped diamond. These measurements yield symmetry information about the defects allowing us to determine which of the proposed models are possible. EPR spectra of nitrogen interstitial related defects in samples isotopically enriched with 15N are reported and we show that these explain the lack of previous EPR data for these defects. Correlations between the IR absorbance and the integrated intensity of the new EPR defects are studied for varying irradiation doses and annealing temperatures.

Evaluation of a substructured soft Real-time Hybrid Test for performing Seismic analysis of complex structural systems

The hybrid test method is a relatively recently developed dynamic testing technique that uses numerical modelling combined with simultaneous physical testing. The concept of substructuring allows the critical or highly nonlinear part of the structure that is difficult to numerically model with accuracy to be physically tested whilst the remainder of the structure, that has a more predictable response, is numerically modelled. In this paper, a substructured soft-real time hybrid test is evaluated as an accurate means of performing seismic tests of complex structures. The structure analysed is a three-storey, two-by-one bay concentrically braced frame (CBF) steel structure subjected to seismic excitation. A ground storey braced frame substructure whose response is critical to the overall response of the structure is tested, whilst the remainder of the structure is numerically modelled. OpenSees is used for numerical modelling and OpenFresco is used for the communication between the test equipment and numerical model. A novel approach using OpenFresco to define the complex numerical substructure of an X-braced frame within a hybrid test is also presented. The results of the hybrid tests are compared to purely numerical models using OpenSees and a simulated test using a combination of OpenSees and OpenFresco. The comparative results indicate that the test method provides an accurate and cost effective procedure for performing
full scale seismic tests of complex structural systems.

Catalysis of CO electrooxidation at Pt, Ru, and PtRu alloy. An in situ FTIR study

A comparative study of CO electrooxidation on different catalysts using in situ FTIR spectroscopy is presented. As electrode materials, polycrystalline Pt and Ru and a PtRu (50:50) alloy are used. The latter is one of the well-known active alloys for CO oxidation. The potential dependence of the band frequencies for the CO stretch indicates the formation of relatively compact islands at pure Pt and Ru, and a loose adlayer structure at the alloy. This loose structure has a positive effect on the rate of oxidative desorption. CO submonolayer coverages are obtained by integrating the absorption bands for CO produced upon oxidation of adsorbed CO. The band intensities measured at Pt, Ru, and PtRu indicate an influence of the substrate on the absorption coefficient of the CO stretch. It is shown that for a correct description of the catalyst properties toward CO electrooxidation, it must be distinguished between bulk and adsorbed CO. In contrast to the statement of most of the recent papers that a PtRu alloy (50:50) is the material with the highest activity for CO oxidation, it is demonstrated and rationalized in the present paper that for bulk CO oxidation pure Ru is the best catalyst. © 1999 American Chemical Society.

Process efficiency in polymer extrusion: Correlation between the energy demand and melt thermal stability

Thermal stability is of major importance in polymer extrusion, where product quality is dependent upon the level of melt homogeneity achieved by the extruder screw. Extrusion is an energy intensive process and optimisation of process energy usage while maintaining melt stability is necessary in order to produce good quality product at low unit cost. Optimisation of process energy usage is timely as world energy prices have increased rapidly over the last few years. In the first part of this study, a general discussion was made on the efficiency of an extruder. Then, an attempt was made to explore correlations between melt thermal stability and energy demand in polymer extrusion under different process settings and screw geometries. A commodity grade of polystyrene was extruded using a highly instrumented single screw extruder, equipped with energy consumption and melt temperature field measurement. Moreover, the melt viscosity of the experimental material was observed by using an off-line rheometer. Results showed that specific energy demand of the extruder (i.e. energy for processing of unit mass of polymer) decreased with increasing throughput whilst fluctuation in energy demand also reduced. However, the relationship between melt temperature and extruder throughput was found to be complex, with temperature varying with radial position across the melt flow. Moreover, the melt thermal stability deteriorated as throughput was increased, meaning that a greater efficiency was achieved at the detriment of melt consistency. Extruder screw design also had a significant effect on the relationship between energy consumption and melt consistency. Overall, the relationship between the process energy demand and thermal stability seemed to be negatively correlated and also it was shown to be highly complex in nature. Moreover, the level of process understanding achieved here can help to inform selection of equipment and setting of operating conditions to optimise both energy and thermal efficiencies in parallel. 

Effect of Different Types of Processing and Storage on the Polyacetylene Profile of Carrots and Parsnips.

Polyacetylenes of the falcarinol type such as falcarinol and falcarindiol naturally occur in plants of the Apiaceae family, mainly carrots and parsnips. In extracts of newly harvested carrots and parsnips, their levels vary between 20 and 300 mg/kg fresh weight and depend on agronomic factors, in particular the cultivar type. With increasing evidence of their in vitro bioactivity, the retention of these heat-sensitive compounds is desirable during handling, processing, and storage of carrots and parsnips. Quantification of these compounds is usually performed using reverse-phase chromatography coupled with mass spectrometry or other detection methods after appropriate solvent extraction. During minimal processing most losses occur during peeling of the carrots due to the higher distribution of polyacetylenes in the vegetable skin. Heat processing results in reduction of polyacetylene levels, whereas in the case of non-thermal processing, it is mainly dependent on the method employed. The levels of polyacetylenes are rather stable during short-term storage. There are some general guidelines to ensure higher retention of polyacetylene.

On the halogenation of N(1),N(2)-di-t-Boc-5-hydroxy-piperazic acid esters and the conformational preferences of their 5-halo-piperazic acid products. The importance of A1,3 rotameric-strain in determining N(2)-acyl piperazic acid ring conformation

In this Letter, an unambiguous synthetic strategy is reported for the preparation of enantiomerically purecis-5-halo-piperazic acid derivatives in single diastereoisomer form. Contrary to the recent report by Shin and co-workers (Chem. Lett. 2001, 1172), in which it is claimed that the Ph₃P and N-chlorosuccinimide (NCS)-mediated chlorination of (3R,5S)-trans-N(1),N(2)-di-t-Boc-5-hydroxy-piperazic acid derivative 1proceeds with retention of configuration at C(5) to give 2, we now show that this and related Ph₃P-mediated halogenations all occur with S_N2 inversion at the alcohol center, as is customary for such reactions. Specifically, we demonstrate that the (3R,5S)-trans-5-Cl-piperazic acid derivative 2 claimed by Shin and co-workers (Chem. Lett. 2001, 1172) is in actual fact the chlorinated (3S,5R)-enantiomer 6, which must have been prepared from the cis-(3S,5S)-alcohol 3, a molecule whose synthesis is not formally described in the Shin paper. We further show here that the cis-(3R,5R)-5-Cl-Piz 13 claimed by Shin and co-workers inChem. Lett. 2001, 1172, is also (3S,5R)-trans-5-Cl-Piz 6. Authentic 13 has now been synthesized by us, for the very first time, here. Since Lindsley and Kennedy have recently utilized the now invalid Shin and co-workers’ retentive Ph₃P/NCS chlorination procedure on 1 in their synthetic approach to piperazimycin A (Tetrahedron Lett. 2010, 51, 2493), it follows that their claimed 5-Cl-Piz-containing dipeptide 25 probably has the alternate structure 26, where the 5-Cl-Piz residue has a 3,5-cis-configuration. The aforementioned stereochemical misassignments appear to have come from a mix-up of starting materials by Shin and co-workers (Chem. Lett. 2001, 1172), and an under-appreciation of the various steric and conformational effects that operate in N(2)-acylated piperazic acid systems, most especially rotameric A^1,3-strain. The latter has now been unambiguously delineated and defined here under the banner of the A^1,3-rotamer effect.

Extreme learning machines for virtual metrology and etch rate prediction

Virtual metrology (VM) aims to predict metrology values using sensor data from production equipment and physical metrology values of preceding samples. VM is a promising technology for the semiconductor manufacturing industry as it can reduce the frequency of in-line metrology operations and provide supportive information for other operations such as fault detection, predictive maintenance and run-to-run control. Methods with minimal user intervention are required to perform VM in a real-time industrial process. In this paper we propose extreme learning machines (ELM) as a competitive alternative to popular methods like lasso and ridge regression for developing VM models. In addition, we propose a new way to choose the hidden layer weights of ELMs that leads to an improvement in its prediction performance.

Sandwich nanoarchitecture of LiV3O8/graphene multilayer nanomembranes via layer-by-layer self-assembly for long-cycle-life lithium-ion battery cathodes

A lack of suitable high-performance cathode materials has become the major barrier to their applications in future advanced communication equipment and electric vehicle power systems. In this paper, we have developed a layer-by-layer self-assembly approach for fabricating a novel sandwich nanoarchitecture of multilayered LiV₃O₈ nanoparticle/graphene nanosheet (M-nLVO/GN) hybrid electrodes for potential use in high performance lithium ion batteries by using a porous Ni foam as a substrate. The prepared sandwich nanoarchitecture of M-nLVO/GN hybrid electrodes exhibited high performance as a cathode material for lithium-ion batteries, such as high reversible specific capacity (235 mA h g^-1 at a current density of 0.3 A g^-1), high coulombic efficiency (over 98%), fast rate capability (up to a current density of 10 A g^-1), and superior capacity retention during cycling (90% capacity retention with a current density of 0.3 A g^-1 after 300 cycles). Very significantly, this novel insight into the design and synthesis of sandwich nanoarchitecture would extend their application to various electrochemical energy storage devices, such as fuel cells and supercapacitors.

Awareness and attitudes towards the emerging use of nanotechnology in the agri-food sector

Nanotechnology has relevance to applications in all areas of agri-food including agriculture, aquaculture, production, processing, packaging, safety and nutrition. Scientific literature indicates uncertainties in food safety aspects about using nanomaterials due to potential health risks. To date the agri-food industry's awareness and attitude towards nanotechnology have not been addressed. We surveyed the awareness and attitudes of agri-food organisations on the island of Ireland (IoI) with regards to nanotechnology. A total of 14 agri-food stakeholders were interviewed and 88 agri-food stakeholders responded to an on-line questionnaire. The findings indicate that the current awareness of nanotechnology applications in the agri-food sector on the IoI is low and respondents are neither positive nor negative towards agri-food applications of nanotechnology. Safer food, reduced waste and increased product shelf life were considered to be the most important benefits to the agri-food industry. Knowledge of practical examples of agri-food applications is limited however opportunities were identified in precision farming techniques, innovative packaging, functional ingredients and nutrition of foods, processing equipment, and safety testing. Perceived impediments to nanotechnology adoption were potential unknown human health and environmental impacts, consumer acceptance and media framing. The need for a risk assessment framework, research into long term health and environmental effects, and better engagement between scientists, government bodies, the agri-food industry and the public were identified as important.

Comparative functional responses predict the invasiveness and ecological impacts of alien herbivorous snails.

Understanding determinants of the invasiveness and ecological impacts of alien species is amongst the most sought-after and urgent research questions in ecology. Several studies have shown the value of comparing the functional responses (FRs) of alien and native predators towards native prey, however, the technique is under-explored with herbivorous alien species and as a predictor of invasiveness as distinct from ecological impact. Here, in China, we conducted a mesocosm experiment to compare the FRs among three herbivorous snail species: the golden apple snail, Pomacea canaliculata, a highly invasive and high impact alien listed in “100 of the World's Worst Invasive Alien Species”; Planorbarius corneus, a non-invasive, low impact alien; and the Chinese native snail, Bellamya aeruginosa, when feeding on four locally occurring plant species. Further, by using a numerical response equation, we modelled the population dynamics of the snail consumers. For standard FR parameters, we found that the invasive and damaging alien snail had the highest “attack rates” a, shortest “handling times” h and also the highest estimated maximum feeding rates, 1/hT, whereas the native species had the lowest attack rates, longest handling times and lowest maximum feeding rates. The non-invasive, low impact alien species had consistently intermediate FR parameters. The invasive alien species had higher population growth potential than the native snail species, whilst that of the non-invasive alien species was intermediate. Thus, while the comparative FR approach has been proposed as a reliable method for predicting the ecological impacts of invasive predators, our results further suggest that comparative FRs could extend to predict the invasiveness and ecological impacts of alien herbivores and should be explored in other taxa and trophic groups to determine the general utility of the approach.

Chalcogenide thin films for solar cells: growth and properties

Thin film solar cells have in recent years gained market quota against traditional silicon photovoltaic panels. These developments were in a large part due to CdTe solar panels on whose development started earlier than their competitors. Panels based on Cu(In,Ga)Se2 (CIGS), despite being more efficient in a laboratory and industrial scale than the CdTe ones, still need a growth technology cheaper and easier to apply in industry. Although usually presented as a good candidate to make cheap panels, CIGS uses rare and expensive materials as In and Ga. The price evolution of these materials might jeopardize CIGS future. This thesis presents three different studies. The first is the study of different processes for the incorporation of Ga in a hybrid CIGS growth system. This system is based on sputtering and thermal evaporation. This technology is, in principle, easier to be applied in the industry and solar cells with efficiencies around to 7% were fully made in Aveiro. In the second part of this thesis, a new material to replace CIGS in thin film solar cells is studied. The growth conditions and fundamental properties of Cu2ZnSnSe4 (CZTSe) were studied in depth. Suitable conditions of temperature and pressure for the growth of this material are reported. Its band gap energy was estimated at 1.05 eV and the Raman scattering peaks were identified. Solar cells made with this material showed efficiencies lower than 0.1%. Finally, preliminary work regarding the incorporation of selenium in Cu2ZnSnS4 (CZTS) thin films was carried out. The structural and morphological properties of thin films of Cu2ZnSn(S,Se)4 have been studied and the results show that the incorporation of selenium is higher in films with precursors rather with already formed Cu2SnS3 or Cu2ZnSnS4 thin films. A solar cell with 0.9 % of efficiency was prepared.

Development of polymeric materials to inhibit bacterial quorum sensing

Bacterial infections are an increasing problem for human health. In fact, an increasing number of infections are caused by bacteria that are resistant to most antibiotics and their combinations. Therefore, the scientific community is currently searching for new solutions to fight bacteria and infectious diseases, without promoting antimicrobial resistance. One of the most promising strategies is the disruption or attenuation of bacterial Quorum Sensing (QS), a refined system that bacteria use to communicate. In a QS event, bacteria produce and release specific small chemicals, signal molecules - autoinducers (AIs) - into the environment. At the same time that bacterial population grows, the concentration of AIs in the bacterial environment increases. When a threshold concentration of AIs is reached, bacterial cells respond to it by altering their gene expression profile. AIs regulate gene expression as a function of cell population density. Phenotypes mediated by QS (QSphenotypes) include virulence factors, toxin production, antibiotic resistance and biofilm formation. In this work, two polymeric materials (linear polymers and molecularly imprinted nanoparticles) were developed and their ability to attenuate QS was evaluated. Both types of polymers should to be able to adsorb bacterial signal molecules, limiting their availability in the extracellular environment, with expected disruption of QS. Linear polymers were composed by one of two monomers (itaconic acid and methacrylic acid), which are known to possess strong interactions with the bacterial signal molecules. Molecularly imprinted polymer nanoparticles (MIP NPs) are particles with recognition capabilities for the analyte of interest. This ability is attained by including the target analyte at the synthesis stage. Vibrio fischeri and Aeromonas hydrophila were used as model species for the study. Both the linear polymers and MIP NPs, tested free in solutions and coated to surfaces, showed ability to disrupt QS by decreasing bioluminescence of V. fischeri and biofilm formation of A. hydrophila. No significant effect on bacterial growth was detected. The cytotoxicity of the two types of polymers to a fibroblast-like cell line (Vero cells) was also tested in order to evaluate their safety. The results showed that both the linear polymers and MIP NPs were not cytotoxic in the testing conditions. In conclusion, the results reported in this thesis, show that the polymers developed are a promising strategy to disrupt QS and reduce bacterial infection and resistance. In addition, due to their low toxicity, solubility and easy integration by surface coating, the polymers have potential for applications in scenarios where bacterial infection is a problem: medicine, pharmaceutical, food industry and in agriculture or aquaculture.

Logistics and the waste sector: a London case study

London has traditionally exported most of its waste to former mineral workings in surrounding counties for landfill. Many of these sites are being filled and opportunities for new sites are limited. Virtually all waste reprocessing and recycling facilities, with the exception of textile sorting and some facilities for glass and organic waste composting, are outside London. The Mayor of London's Vision for Waste in London is that by 2020, municipal waste should not compromise London’s future as a sustainable city. This will involve managing waste better, so that its impact on the local and global environment and on London communities, economy and health is minimised. The majority of waste and recyclable materials in London are currently collected and transported for recovery, disposal or reprocessing by road in large vehicles. Environmental costs include, adding to congestion, noise, energy usage, air pollution, and accidents. The Mayor is keen to increase recycling and reuse of waste materials in London, and to ensure that as more of London's waste is diverted away from landfill sites to recycling facilities. Several projects and initiatives have been established and these are reviewed in the paper.