The influence of carbon surface oxygen groups on Dubinin–Astakhov equation parameters calculated from CO2 adsorption isotherm

We present the results of a systematic study of the influence of carbon surface oxidation on Dubinin–Astakhov isotherm parameters obtained from the fitting of CO2 adsorption data. Using GCMC simulations of adsorption on realistic VPC models differing in porosity and containing the most frequently occurring carbon surface functionalities (carboxyls, hydroxyls and carbonyls) and their mixtures, it is concluded that the maximum adsorption calculated from the DA model is not strongly affected by the presence of oxygen groups. Unfortunately, the same cannot be said of the remaining two parameters of this model i.e. the heterogeneity parameter (n) and the characteristic energy of adsorption (E0). Since from the latter the pore diameters of carbons are usually calculated, by inverse-type relationships, it is concluded that they are questionable for carbons containing surface oxides, especially carboxyls.

Imaging the structure of activated carbon using aberration corrected TEM

The precise atomic structure of activated carbon is unknown, despite its commercial importance. Here we show that the structure of a commercial activated carbon can be imaged directly using aberration corrected transmission electron microscopy. Images are presented both of the as-produced carbon and of the carbon following heat- treatment at 2000°C. In the 2000°C carbon clear evidence is found for the presence of pentagonal rings, suggesting that the carbons have a fullerene-related structure.

The role of closed ecological systems in carbon cycle modelling

Acquiring a mechanistic understanding of the role of the biotic feedbacks on the links between atmospheric CO2 concentrations and temperature is essential for trustworthy climate predictions. Currently, computer based simulations are the only available tool to estimate the global impact of the biotic feedbacks on future atmospheric CO2 and temperatures. Here we propose an alternative and complementary approaches by using materially closed and energetically open analogue/physical models of the carbon cycle. We argue that there is potential in using a materially closed approach to improve our understanding of the magnitude and sign of many biotic feedbacks, and that recent technological advance make this feasible. We also suggest how such systems could be designed and discuss the advantages and limitations of establishing physical models of the global carbon cycle.

An investigation of the impact of time of generation on carbon savings from PV systems in Great Britain

PV only generates electricity during daylight hours and primarily generates over summer. In the UK, the carbon intensity of grid electricity is higher during the daytime and over winter. This work investigates whether the grid electricity displaced by PV is high or low carbon compared to the annual mean carbon intensity using carbon factors at higher temporal resolutions (half-hourly and daily). UK policy for carbon reporting requires savings to be calculated using the annual mean carbon intensity of grid electricity. This work offers an insight into whether this technique is appropriate. Using half hourly data on the generating plant supplying the grid from November 2008 to May 2010, carbon factors for grid electricity at half-hourly and daily resolution have been derived using technology specific generation emission factors. Applying these factors to generation data from PV systems installed on schools, it is possible to assess the variation in the carbon savings from displacing grid electricity with PV generation using carbon factors with different time resolutions. The data has been analyzed for a period of 363 to 370 days and so cannot account for inter-year variations in the relationship between PV generation and carbon intensity of the electricity grid. This analysis suggests that PV displaces more carbon intensive electricity using half-hourly carbon factors than using daily factors but less compared with annual ones. A similar methodology could provide useful insights on other variable renewable and demand-side technologies and in other countries where PV performance and grid behavior are different.

Unsaturated σ-hydrocarbyl transition-metal complexes. Part 4. Crystal and molecular structure of trans-chlorobis(diethylphenylphosphine)-(phenylethynyl)platinum(II) and comments on the relative trans influence of various carbon ligands

The molecular structure of trans-[PtCl(CCPh)(PEt2Ph)2] has been determined by X-ray diffraction methods. The crystals are monoclinic, space group P21, with a= 12.359(3), b= 13.015(3), c= 9.031(2)Å, β= 101.65(2)°, and Z= 2. The structure has been solved by the heavy-atom method and refined by full-matrix least squares to R 0.046 for 1 877 diffractometric intensity data. The crystals contain discrete molecules in which the platinum coordination is square planar. The phenylethynyl group is non-linear, with a Pt–CC angle of 163(2)°. Selected bond lengths are Pt–Cl 2.407(5) and Pt–C 1.98(2)Å. The structural trans influences of CCPh, CHCH2, and CH2SiMe3 ligands in platinum(II) complexes are compared; there is only a small dependence on hybridization at the ligating carbon atom.

Prediction of moisture, calorific value, ash and carbon content of two dedicated bioenergy crops using near-infrared spectroscopy

The potential of near infrared spectroscopy in conjunction with partial least squares regression to predict Miscanthus xgiganteus and short rotation coppice willow quality indices was examined. Moisture, calorific value, ash and carbon content were predicted with a root mean square error of cross validation of 0.90% (R2 = 0.99), 0.13 MJ/kg (R2 = 0.99), 0.42% (R2 = 0.58), and 0.57% (R2 = 0.88), respectively. The moisture and calorific value prediction models had excellent accuracy while the carbon and ash models were fair and poor, respectively. The results indicate that near infrared spectroscopy has the potential to predict quality indices of dedicated energy crops, however the models must be further validated on a wider range of samples prior to implementation. The utilization of such models would assist in the optimal use of the feedstock based on its biomass properties.

Case study on the whole life carbon cycle in buildings

Global temperatures are expected to rise by between 1.1 and 6.4oC this century, depending, to a large extent, on the amount of carbon we emit to the atmosphere from now onwards. This warming is expected to have very negative effects on many peoples and ecosystems and, therefore, minimising our carbon emissions is a priority. Buildings are estimated to be responsible for around 50% of carbon emissions in the UK. Potential reductions involve both operational emissions, produced during use, and embodied emissions, produced during manufacture of materials and components, and during construction, refurbishments and demolition. To date the major effort has focused on reducing the, apparently, larger operational element, which is more readily quantifiable and reduction measures are relatively straightforward to identify and implement. Various studies have compared the magnitude of embodied and operational emissions, but have shown considerable variation in the relative values. This illustrates the difficulties in quantifying embodied, as it requires a detailed knowledge of the processes involved in the different life cycle phases, and requires the use of consistent system boundaries. However, other studies have established the interaction between operational and embodied, which demonstrates the importance of considering both elements together in order to maximise potential reductions. This is borne out in statements from both the Intergovernmental Panel on Climate Change and The Low Carbon Construction Innovation and Growth Team of the UK Government. In terms of meeting the 2020 and 2050 timeframes for carbon reductions it appears to be equally, if not more, important to consider early embodied carbon reductions, rather than just future operational reductions. Future decarbonisation of energy supply and more efficient lighting and M&E equipment installed in future refits is likely to significantly reduce operational emissions, lending further weight to this argument. A method of discounting to evaluate the present value of future carbon emissions would allow more realistic comparisons to be made on the relative importance of the embodied and operational elements. This paper describes the results of case studies on carbon emissions over the whole lifecycle of three buildings in the UK, compares four available software packages for determining embodied carbon and suggests a method of carbon discounting to obtain present values for future emissions. These form the initial stages of a research project aimed at producing information on embodied carbon for different types of building, components and forms of construction, in a simplified form, which can be readily used by building designers in optimising building design in terms of minimising overall carbon emissions. Keywords: Embodied carbon; carbon emission; building; operational carbon.

Protecting degraded rainforests: enhancement of forest carbon stocks under REDD+

The likely Reducing Emissions from Deforestation and Degradation (REDD+) mechanism includes strategies for the enhancement of forest carbon stocks. Recent concerns have been expressed that such enhancement, or restoration, of forest carbon could be counterproductive to biodiversity conservation, because forests are managed as “carbon farms” with the application of intensive silvicultural management that could homogenize diverse degraded rainforests. Restoration increases regeneration rates in degraded forest compared to naturally regenerating forest, and thus could yield significant financial returns for carbon sequestered. Here, we argue that such forest restoration projects are, in fact, likely to provide a number of benefits to biodiversity conservation including the retention of biodiversity, the prevention of forest conversion to agriculture, and employment opportunities for poor local communities. As with other forms of forest-based carbon offsets, there are possible moral hazard and leakage problems with restoration. However, due to the multiple benefits, we urge that enhancement of forest carbon stocks be detailed as a major component in the future negotiations of REDD+.

Governing the clean development mechanism: global rhetoric versus local realities in carbon sequestration projects

Global agreements have proliferated in the past ten years. One of these is the Kyoto Protocol, which contains provisions for emissions reductions by trading carbon through the Clean Development Mechanism (CDM). The CDM is a market-based instrument that allows companies in Annex I countries to offset their greenhouse gas emissions through energy and tree offset projects in the global South. I set out to examine the governance challenges posed by the institutional design of carbon sequestration projects under the CDM. I examine three global narratives associated with the design of CDM forest projects, specifically North – South knowledge politics, green developmentalism, and community participation, and subsequently assess how these narratives match with local practices in two projects in Latin America. Findings suggest that governance problems are operating at multiple levels and that the rhetoric of global carbon actors often asserts these schemes in one light, while the rhetoric of those who are immediately involved locally may be different. I also stress the alarmist’s discourse that blames local people for the problems of environmental change. The case studies illustrate the need for vertical communication and interaction and nested governance arrangements as well as horizontal arrangements. I conclude that the global framing of forests as offsets requires better integration of local relationships to forests and their management and more effective institutions at multiple levels to link the very local to the very large scale when dealing with carbon sequestration in the CDM.

The influence of the carbon surface chemical composition on Dubinin-Astakhov equation parameters calculated from SF(6) adsorption data-grand canonical Monte Carlo simulation

Using grand canonical Monte Carlo simulation we show, for the first time, the influence of the carbon porosity and surface oxidation on the parameters of the Dubinin-Astakhov (DA) adsorption isotherm equation. We conclude that upon carbon surface oxidation, the adsorption decreases for all carbons studied. Moreover, the parameters of the DA model depend on the number of surface oxygen groups. That is why in the case of carbons containing surface polar groups, SF(6) adsorption isotherm data cannot be used for characterization of the porosity.

Simple model of adsorption on external surface of carbon nanotubes: a new analytical approach basing on molecular simulation data

Nitrogen adsorption on carbon nanotubes is wide- ly studied because nitrogen adsorption isotherm measurement is a standard method applied for porosity characterization. A further reason is that carbon nanotubes are potential adsorbents for separation of nitrogen from oxygen in air. The study presented here describes the results of GCMC simulations of nitrogen (three site model) adsorption on single and multi walled closed nanotubes. The results obtained are described by a new adsorption isotherm model proposed in this study. The model can be treated as the tube analogue of the GAB isotherm taking into account the lateral adsorbate-adsorbate interactions. We show that the model describes the simulated data satisfactorily. Next this new approach is applied for a description of experimental data measured on different commercially available (and characterized using HRTEM) carbon nanotubes. We show that generally a quite good fit is observed and therefore it is suggested that the observed mechanism of adsorption in the studied materials is mainly determined by adsorption on tubes separated at large distances, so the tubes behave almost independently.