A sensing mechanism for the detection of carbon nanotubes using selective photoluminescent probes based on ionic complexes with organic dyes

The multifunctional properties of carbon nanotubes (CNTs) make them a powerful platform for unprecedented innovations in a variety of practical applications. As a result of the surging growth of nanotechnology, nanotubes present a potential problem as an environmental pollutant, and as such, an efficient method for their rapid detection must be established. Here, we propose a novel type of ionic sensor complex for detecting CNTs – an organic dye that responds sensitively and selectively to CNTs with a photoluminescent signal. The complexes are formed through Coulomb attractions between dye molecules with uncompensated charges and CNTs covered with an ionic surfactant in water. We demonstrate that the photoluminescent excitation of the dye can be transferred to the nanotubes, resulting in selective and strong amplification (up to a factor of 6) of the light emission from the excitonic levels of CNTs in the near-infrared spectral range, as experimentally observed via excitation-emission photoluminescence (PL) mapping. The chirality of the nanotubes and the type of ionic surfactant used to disperse the nanotubes both strongly affect the amplification; thus, the complexation provides sensing selectivity towards specific CNTs. Additionally, neither similar uncharged dyes nor CNTs covered with neutral surfactant form such complexes. As model organic molecules, we use a family of polymethine dyes with an easily tailorable molecular structure and, consequently, tunable absorbance and PL characteristics. This provides us with a versatile tool for the controllable photonic and electronic engineering of an efficient probe for CNT detection.

Low-emission vehicle adoption in a UK local authority fleet:economic barriers and air quality benefits

Local air quality was one of the main stimulants for low carbon vehicle development during the 1990s. Issues of national fuel security and global air quality (climate change) have added pressure for their development, stimulating schemes to facilitate their deployment in the UK. In this case study, Coventry City Council aimed to adopt an in-house fleet of electric and hybrid-electric vehicles to replace business mileage paid for in employee's private vehicles. This study made comparisons between the proposed vehicle technologies, in terms of costs and air quality, over projected scenarios of typical use. The study found that under 2009 conditions, the electric and hybrid fleet could not compete on cost with the current business model because of untested assumptions, but certain emissions were significantly reduced >50%. Climate change gas emissions were most drastically reduced where electric vehicles were adopted because the electricity supply was generated by renewable energy sources. The study identified the key cost barriers and benefits to adoption of low-emission vehicles in current conditions in the Coventry fleet. Low-emission vehicles achieved significant air pollution-associated health cost and atmospheric emission reductions per vehicle, and widespread adoption in cities could deliver significant change. © The Author 2011. Published by Oxford University Press. All rights reserved.

Applying consumer responsibility principle in evaluating environmental load of carbon emissions

There is a need for a proper indicator in order to assess the environmental impact of international trade, therefore using the carbon footprint as an indicator can be relevant and useful. The aim of this study is to show from a methodological perspective how the carbon footprint, combined with input- output models can be used for analysing the impacts of international trade on the sustainable use of national resources in a country. The use of the input-output approach has the essential advantage of being able to track the transformation of goods through the economy. The study examines the environmental impact of consumption related to international trade, using the consumer responsibility principle. In this study the use of the carbon footprint and input-output methodology is shown on the example of the Hungarian consumption and the impact of international trade. Moving from a production- based approach in climate policy to a consumption-perspective principle and allocation, would also help to increase the efficiency of emission reduction targets and the evaluation of the ecological impacts of international trade.

Carbon emissions locked - in trade

In recent years there has been a growing concern about the emission trade balance of countries. It is due to the fact that countries with an open economy are active players in the international trade, though trade is not only a major factor in forging a country’s economic structure anymore, but it does contribute to the movement of embodied emissions beyond the country borders. This issue is especially relevant from the carbon accounting policy’s point of view, as it is known that the production-based principle is in effect now in the Kyoto agreement. The study aims at revealing the interdependence of countries on international trade and its environmental impacts, and how the carbon accounting method plays a crucial role in evaluating a country’s environmental performance and its role in the climate mitigation processes. The input-output models are used in the methodology, as they provide an appropriate framework for this kind of environmental accounting; the analysis shows an international comparison of four European countries (Germany, the United Kingdom, the Netherlands, and Hungary) with extended trading activities and carbon emissions. Moving from the production-based approach in the climate policy, to the consumptionperspective principle and allocation [15], it would also help increasing the efficiency of emission reduction targets and the evaluation of the sustainability dimension and its impacts of international trade. The results of the study have shown that there is an importance of distinction between the two emission allocation approaches, both from global and local level point of view.

Applying consumer responsibility principle in evaluating environmental load of carbon emissions

There is a need for a proper indicator in order to assess the environmental impact of international trade, therefore using the carbon footprint as an indicator can be relevant and useful. The aim of this study is to show from a methodological perspective how the carbon footprint, combined with input- output models can be used for analysing the impacts of international trade on the sustainable use of national resources in a country. The use of the input-output approach has the essential advantage of being able to track the transformation of goods through the economy. The study examines the environmental impact of consumption related to international trade, using the consumer responsibility principle. In this study the use of the carbon footprint and input-output methodology is shown on the example of the Hungarian consumption and the impact of international trade. Moving from a production- based approach in climate policy to a consumption-perspective principle and allocation, would also help to increase the efficiency of emission reduction targets and the evaluation of the ecological impacts of international trade.

Emissziós jogok közgazdasági relevanciája és számviteli leképezése (Economic relevancy and accounting mapping of emission rights)

A cikk bemutatja, hogy az emissziós jogok mérleg- és beszámoló-képességi kritériumai milyen leképezést tesznek lehetővé a jelenleg érvényes Nemzetközi Pénzügyi Beszámolási Standardokban (IFRS, International Financial Reporting Standards). A vizsgálat fókuszában az üzemeltető áll, aki az Európai Unió kibocsátás-kereskedelmi rendszerének hatálya alá tartozik, azaz ipari tevékenysége folytán szén-dioxiddal szennyezi a Föld légterét. Az üzemeltető mint az emissziós jog tulajdonosa jelenik meg. A cikk megvizsgálja mindazokat a folyamatokat, melynek eredményeképpen birtokolhatja ezeket az egységeket, valamint azt, hogy az IFRS-ek milyen lehetőséget nyújtanak a különböző forrásból származó jogosultságok értékelésére. / === / The author presents that accounting and report ability criteria of the emission rights what mapping allows in the current International Financial Standards. The study focuses on the operator, who is the subject of the European Union Emissions Trading Scheme, whose industrial activities pollute with carbon dioxide to the earth’s atmosphere. The operator, as the owner of emission rights is displayed. This article examines those processes, which resulted in these units may be owned, and that what possibility is provided by IFRSs to evaluate rights from different sources.

Carbon pricing: theory and practice

Carbon pricing policy is a fundamental humanly devised theoretical and practical cornerstone in the fight against climate change. It involves short term and long term policies, theoretical and practical considerations. A quantitative global stabilisation target range for the stock of greenhouse gases in the atmosphere is needed, because it is an important and useful foundation in the shaping of a comprehensive climate pricing policy. A global stabilisation target range is obviously a long term policy to control climate change and events ensuing excessive increase in temperature. Setting long term objectives in the fight against climate change are substantial in avoiding catastrophic consequences therefore short term policies, which aim advances in emission reductions, have to be consistent with the pre-defined long term stabilisation goals. Short term policy reaction means using price-driven instruments like taxes and tradable quotas. These instruments allow broad flexibility in the parameters of emission reduction, and provide opportunities and incentives wherewith the cost of mitigation and abatement can be kept down. Taxes and tradable quotas give the flexibility in how, where and when emission reduction can be accomplished thereby reaching agreements between states and companies may result an appropriate and environment-conscious emission scheme, that can fit into the long term objectives.

A villamos erőművek szén-dioxid-kibocsátásának modellezése reálopciók segítségével = Modelling of the carbon dioxide emissions of a power plant, using real options

A szerző egy, a szennyezőanyag-kibocsátás európai kereskedelmi rendszerében megfelelésre kötelezett gázturbinás erőmű szén-dioxid-kibocsátását modellezi négy termékre (völgy- és csúcsidőszaki áramár, gázár, kibocsátási kvóta) vonatkozó reálopciós modell segítségével. A profitmaximalizáló erőmű csak abban az esetben termel és szennyez, ha a megtermelt áramon realizálható fedezete pozitív. A jövőbeli időszak összesített szén-dioxid-kibocsátása megfeleltethető európai típusú bináris különbözetopciók összegének. A modell keretein belül a szén-dioxid-kibocsátás várható értékét és sűrűségfüggvényét becsülhetjük, az utóbbi segítségével a szén-dioxid-kibocsátási pozíció kockáztatott értékét határozhatjuk meg, amely az erőmű számára előírt megfelelési kötelezettség teljesítésének adott konfidenciaszint melletti költségét jelenti. A sztochasztikus modellben az alaptermékek geometriai Ornstein-Uhlenbeck-folyamatot követnek. Ezt illesztette a szerző a német energiatőzsdéről származó publikus piaci adatokra. A szimulációs modellre támaszkodva megvizsgálta, hogy a különböző technológiai és piaci tényezők ceteris paribus megváltozása milyen hatással van a megfelelés költségére, a kockáztatott értékére. ______ The carbon-dioxide emissions of an EU Emissions Trading System participant, gas-fuelled power generator are modelled by using real options for four underlying instruments (peak and off-peak electricity, gas, emission quota). This profit-maximizing power plant operates and emits pollution only if its profit (spread) on energy produced is positive. The future emissions can be estimated by a sum of European binary-spread options. Based on the real-option model, the expected value of emissions and its probability-density function can be deducted. Also calculable is the Value at Risk of emission quota position, which gives the cost of compliance at a given confidence level. To model the prices of the four underlying instruments, the geometric Ornstein-Uhlenbeck process is supposed and matched to public available price data from EEX. Based on the simulation model, the effects of various technological and market factors are analysed for the emissions level and the cost of compliance.

Controlled growth of carbon nanotubes for high performance nanoelectronics

Unique electrical and mechanical properties of single-walled carbon nanotubes (SWNTs) have made them one of the most promising candidates for next-generation nanoelectronics. Efficient utilization of the exceptional properties of SWNTs requires controlling their growth direction (e.g., vertical, horizontal) and morphologies (e.g., straight, junction, coiled). ^ In this dissertation, the catalytic effect on the branching of SWNTs, Y-shaped SWNTs (Y-SWNTs), was investigated. The formation of Y-shaped branches was found to be dependent on the composition of the catalysts. Easier carbide formers have a strong tendency to attach to the sidewall of SWNTs and thus enhance the degree of branching. Y-SWNTs based field-effect transistors (FETs) were fabricated and modulated by the metallic branch of the Y-SWNTs, exhibiting ambipolar characteristics at room temperature. A subthreshold swing of 700 mV/decade and an on/off ratio of 105 with a low off-state current of 10-13 A were obtained. The transport phenomena associated with Y- and cross-junction configurations reveals that the conduction mechanism in the SWNT junctions is governed by thermionic emission at T > 100 K and by tunneling at T < 100 K. ^ Furthermore, horizontally aligned SWNTs were synthesized by the controlled modification of external fields and forces. High performance carbon nanotube FETs and logic circuit were demonstrated utilizing the aligned SWNTs. It is found that the hysteresis in CNTFETs can be eliminated by removing absorbed water molecules on the CNT/SiO2 interface by vacuum annealing, hydrophobic surface treatment, and surface passivation. SWNT “serpentines” were synthesized by utilization of the interaction between drag force from gas flow and Van der Waals force with substrates. The curvature of bent SWNTs could be tailored by adjusting the gas flow rate, and changing the gas flow direction with respect to the step-edges on a single-crystal quartz substrate. Resistivity of bent SWNTs was observed to increase with curvature, which can be attributed to local deformations and possible chirality shift at curved part. ^ Our results show the successful synthesis of SWNTs having controllable morphologies and directionality. The capability of tailoring the electrical properties of SWNTs makes it possible to build an all-nanotube device by integrating SWNTs, having different functionalities, into complex circuits. ^

Robust and high current cold electron source based on carbon nanotube field emitters and electron multiplier microchannel plate

The aim of this research was to demonstrate a high current and stable field emission (FE) source based on carbon nanotubes (CNTs) and electron multiplier microchannel plate (MCP) and design efficient field emitters. In recent years various CNT based FE devices have been demonstrated including field emission displays, x-ray source and many more. However to use CNTs as source in high powered microwave (HPM) devices higher and stable current in the range of few milli-amperes to amperes is required. To achieve such high current we developed a novel technique of introducing a MCP between CNT cathode and anode. MCP is an array of electron multipliers; it operates by avalanche multiplication of secondary electrons, which are generated when electrons strike channel walls of MCP. FE current from CNTs is enhanced due to avalanche multiplication of secondary electrons and in addition MCP also protects CNTs from irreversible damage during vacuum arcing. Conventional MCP is not suitable for this purpose due to the lower secondary emission properties of their materials. To achieve higher and stable currents we have designed and fabricated a unique ceramic MCP consisting of high SEY materials. The MCP was fabricated utilizing optimum design parameters, which include channel dimensions and material properties obtained from charged particle optics (CPO) simulation. Child Langmuir law, which gives the optimum current density from an electron source, was taken into account during the system design and experiments. Each MCP channel consisted of MgO coated CNTs which was chosen from various material systems due to its very high SEY. With MCP inserted between CNT cathode and anode stable and higher emission current was achieved. It was ∼25 times higher than without MCP. A brighter emission image was also evidenced due to enhanced emission current. The obtained results are a significant technological advance and this research holds promise for electron source in new generation lightweight, efficient and compact microwave devices for telecommunications in satellites or space applications. As part of this work novel emitters consisting of multistage geometry with improved FE properties were was also developed.

Carbon nanotube based systems for high energy efficient applications

In the current age of fast-depleting conventional energy sources, top priority is given to exploring non-conventional energy sources, designing highly efficient energy storage systems and converting existing machines/instruments/devices into energy-efficient ones. ‘Energy efficiency’ is one of the important challenges for today’s scientific and research community, worldwide. In line with this demand, the current research was focused on developing two highly energy-efficient devices – field emitters and Li-ion batteries, using beneficial properties of carbon nanotubes (CNT). Interface-engineered, directly grown CNTs were used as cathode in field emitters, while similar structure was applied as anode in Li-ion batteries. Interface engineering was found to offer minimum resistance to electron flow and strong bonding with the substrate. Both field emitters and Li-ion battery anodes were benefitted from these advantages, demonstrating high energy efficiency. Field emitter, developed during this research, could be characterized by low turn-on field, high emission current, very high field enhancement factor and extremely good stability during long-run. Further, application of 3-dimensional design to these field emitters resulted in achieving one of the highest emission current densities reported so far. The 3-D field emitter registered 27 times increase in current density, as compared to their 2-D counterparts. These achievements were further followed by adding new functionalities, transparency and flexibility, to field emitters, keeping in view of current demand for flexible displays. A CNT-graphene hybrid structure showed appreciable emission, along with very good transparency and flexibility. Li-ion battery anodes, prepared using the interface-engineered CNTs, have offered 140% increment in capacity, as compared to conventional graphite anodes. Further, it has shown very good rate capability and an exceptional ‘zero capacity degradation’ during long cycle operation. Enhanced safety and charge transfer mechanism of this novel anode structure could be explained from structural characterization. In an attempt to progress further, CNTs were coated with ultrathin alumina by atomic layer deposition technique. These alumina-coated CNT anodes offered much higher capacity and an exceptional rate capability, with very low capacity degradation in higher current densities. These highly energy efficient CNT based anodes are expected to enhance capacities of future Li-ion batteries.

Carbon nanostructure based electrodes for high efficiency dye sensitized solar cell

Synthesis and functionalization of large-area graphene and its structural, electrical and electrochemical properties has been investigated. First, the graphene films, grown by thermal chemical vapor deposition (CVD), contain three to five atomic layers of graphene, as confirmed by Raman spectroscopy and high-resolution transmission electron microscopy. Furthermore, the graphene film is treated with CF4 reactive-ion plasma to dope fluorine ions into graphene lattice as confirmed by X-ray photoelectron spectroscopy (XPS) and UV-photoemission spectroscopy (UPS). Electrochemical characterization reveals that the catalytic activity of graphene for iodine reduction enhanced with increasing plasma treatment time, which is attributed to increase in catalytic sites of graphene for charge transfer. The fluorinated graphene is characterized as a counter-electrode (CE) in a dye-sensitized solar cell (DSSC) which shows ~ 2.56% photon to electron conversion efficiency with ~11 mAcm−2 current density. Second, the large scale graphene film is covalently functionalized with HNO3 for high efficiency electro-catalytic electrode for DSSC. The XPS and UPS confirm the covalent attachment of C-OH, C(O)OH and NO3- moieties with carbon atoms through sp2-sp3 hybridization and Fermi level shift of graphene occurs under different doping concentrations, respectively. Finally, CoS-implanted graphene (G-CoS) film was prepared using CVD followed by SILAR method. The G-CoS electro-catalytic electrodes are characterized in a DSSC CE and is found to be highly electro-catalytic towards iodine reduction with low charge transfer resistance (Rct ~5.05 Ωcm 2) and high exchange current density (J0~2.50 mAcm -2). The improved performance compared to the pristine graphene is attributed to the increased number of active catalytic sites of G-CoS and highly conducting path of graphene. We also studied the synthesis and characterization of graphene-carbon nanotube (CNT) hybrid film consisting of graphene supported by vertical CNTs on a Si substrate. The hybrid film is inverted and transferred to flexible substrates for its application in flexible electronics, demonstrating a distinguishable variation of electrical conductivity for both tension and compression. Furthermore, both turn-on field and total emission current was found to depend strongly on the bending radius of the film and were found to vary in ranges of 0.8 - 3.1 V/μm and 4.2 - 0.4 mA, respectively.

Clean hydrogen production and carbon dioxide capture methods

Fossil fuels constitute a significant fraction of the world's energy demand. The burning of fossil fuels emits huge amounts of carbon dioxide into the atmosphere. Therefore, the limited availability of fossil fuel resources and the environmental impact of their use require a change to alternative energy sources or carriers (such as hydrogen) in the foreseeable future. The development of methods to mitigate carbon dioxide emission into the atmosphere is equally important. Hence, extensive research has been carried out on the development of cost-effective technologies for carbon dioxide capture and techniques to establish hydrogen economy. Hydrogen is a clean energy fuel with a very high specific energy content of about 120MJ/kg and an energy density of 10Wh/kg. However, its potential is limited by the lack of environment-friendly production methods and a suitable storage medium. Conventional hydrogen production methods such as Steam-methane-reformation and Coal-gasification were modified by the inclusion of NaOH. The modified methods are thermodynamically more favorable and can be regarded as near-zero emission production routes. Further, suitable catalysts were employed to accelerate the proposed NaOH-assisted reactions and a relation between reaction yield and catalyst size has been established. A 1:1:1 molar mixture of LiAlH 4, NaNH2 and MgH2 were investigated as a potential hydrogen storage medium. The hydrogen desorption mechanism was explored using in-situ XRD and Raman Spectroscopy. Mesoporous metal oxides were assessed for CO2 capture at both power and non-power sectors. A 96.96% of mesoporous MgO (325 mesh size, surface area = 95.08 ± 1.5 m2/g) was converted to MgCO 3 at 350°C and 10 bars CO2. But the absorption capacity of 1h ball milled zinc oxide was low, 0.198 gCO2 /gZnO at 75°C and 10 bars CO2. Interestingly, 57% mass conversion of Fe and Fe 3O4 mixture to FeCO3 was observed at 200°C and 10 bars CO2. MgO, ZnO and Fe3O4 could be completely regenerated at 550°C, 250°C and 350°C respectively. Furthermore, the possible retrofit of MgO and a mixture of Fe and Fe3O 4 to a 300 MWe coal-fired power plant and iron making industry were also evaluated.

Effects of Land Use on Sources and Ages of Inorganic and Organic Carbon in Temperate Headwater Streams

The amounts, sources and relative ages of inorganic and organic carbon pools were assessed in eight headwater streams draining watersheds dominated by either forest, pasture, cropland or urban development in the lower Chesapeake Bay region (Virginia, USA). Streams were sampled at baseflow conditions six different times over 1 year. The sources and ages of the carbon pools were characterized by isotopic (δ13C and ∆14C) analyses and excitation emission matrix fluorescence with parallel factor analysis (EEM–PARAFAC). The findings from this study showed that human land use may alter aquatic carbon cycling in three primary ways. First, human land use affects the sources and ages of DIC by controlling different rates of weathering and erosion. Relative to dissolved inorganic carbon (DIC) in forested streams which originated primarily from respiration of young, 14C-enriched organic matter (OM; δ13C = −22.2 ± 3 ‰; ∆14C = 69 ± 14 ‰), DIC in urbanized streams was influenced more by sedimentary carbonate weathering (δ13C = −12.4 ± 1 ‰; ∆14C = −270 ± 37 ‰) and one of pasture streams showed a greater influence from young soil carbonates (δ13C = −5.7 ± 2.5 ‰; ∆14C = 69 ‰). Second, human land use alters the proportions of terrestrial versus autochthonous/microbial sources of stream water OM. Fluorescence properties of dissolved OM (DOM) and the C:N of particulate OM (POM) suggested that streams draining human-altered watersheds contained greater relative contributions of DOM and POM from autochthonous/microbial sources than forested streams. Third, human land uses can mobilize geologically aged inorganic carbon and enable its participation in contemporary carbon cycling. Aged DOM (∆14C = −248 to −202 ‰, equivalent14C ages of 1,811–2,284 years BP) and POM (∆14C = −90 to −88 ‰, 14C ages of 669–887 years BP) were observed exclusively in urbanized streams, presumably a result of autotrophic fixation of aged DIC (−297 to −244 ‰, 14C age = 2,251–2,833 years BP) from sedimentary shell dissolution and perhaps also watershed export of fossil fuel carbon. This study demonstrates that human land use may have significant impacts on the amounts, sources, ages and cycling of carbon in headwater streams and their associated watersheds.

Effects of engine cooling water temperature on performance and emission characteristics of a CI engine operated with biofuel blend

The temperature of the coolant is known to have significant influence on engine performance and emissions. Whereas existing literature describes the effects of coolant temperature in engines using fossil derived fuels, very few studies have investigated these effects when biofuel is used. In this study, Jatropha oil was blended separately with ethanol and butanol. It was found that the 80% jatropha oil + 20% butanol blend was the most suitable alternative, as its properties were closest to that of fossil diesel. The coolant temperature was varied between 50°C and 95°C. The combustion process enhanced for both diesel and biofuel blend, when the coolant temperature was increased. The carbon dioxide emissions for both diesel and biofuel blend were observed to increase with temperature. The carbon monoxide, oxygen and lambda values were observed to decrease with temperature. When the engine was operated using diesel, nitrogen oxides emissions correlated in an opposite manner to smoke opacity; however, nitrogen oxides emissions and smoke opacity correlated in an identical manner for biofuel blend. Brake specific fuel consumption was observed to decrease as the temperature was increased and was higher on average when the biofuel was used. The study concludes that both biofuel blend and fossil diesel produced identical correlations between coolant temperature and engine performance. The trends of nitrogen oxides and smoke emissions with cooling temperatures were not identical to fossil diesel when biofuel blend was used in the engine.