ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCorrection: Initiation of Methyl Methacrylate Polymerization by the Nonvolatile Products of a Methyl Methacrylate PlasmaCharles Paul, Alexis Bell, and David SoongCite this: Macromolecules 1986, 19, 2, 502Publication Date (Print):February 1, 1986Publication History Published online29 December 2003Published inissue 1 February 1986https://pubs.acs.org/doi/10.1021/ma00156a600https://doi.org/10.1021/ma00156a600research-articleACS PublicationsRequest reuse permissionsArticle Views31Altmetric-Citations-LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts
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Density functional theory calculations are used to study the energetics of the electrochemical oxygen evolution reaction (OER) of water and the reverse oxygen reduction reaction (ORR) on metal-porphyrin-like centers incorporated into graphene layers or single-walled carbon nanotubes (SWCNTs). The objective is to explore the reductions in computational thermodynamic overpotential that can be achieved relative to catalysis on metal oxide surfaces (OER) or platinum (ORR) by varying the metal center and axial ligand. This permits a degree of simultaneous control over the free energy gap between the lowest energy OH and highest energy OOH intermediates, and the position of the oxo (O) intermediate in this gap. Optimal choice of metal toward the right of the first transition series largely controls the gap. Given a suitable metal such as Fe, the overpotential for OER can be tuned over a range greater than 0.35 V by choice of the axial ligand. For OER occurring within the SWCNTs, a minimum predicted overpotential of 0.35 V is found, very close to the gap-imposed limit of 0.30 V for this system. Similarly, the overpotential of ORR can be tuned over a range more than 0.30 V by selection of the axial ligand. While the calculations necessarily have limited accuracy, the principles should provide a transferable path toward overpotential optimization for the OER and ORR.
Abstract Globally, soils store two to three times as much carbon as currently resides in the atmosphere, and it is critical to understand how soil greenhouse gas (GHG) emissions and uptake will respond to ongoing climate change. In particular, the soil‐to‐atmosphere CO 2 flux, commonly though imprecisely termed soil respiration ( R S ), is one of the largest carbon fluxes in the Earth system. An increasing number of high‐frequency R S measurements (typically, from an automated system with hourly sampling) have been made over the last two decades; an increasing number of methane measurements are being made with such systems as well. Such high frequency data are an invaluable resource for understanding GHG fluxes, but lack a central database or repository. Here we describe the lightweight, open‐source COSORE (COntinuous SOil REspiration) database and software, that focuses on automated, continuous and long‐term GHG flux datasets, and is intended to serve as a community resource for earth sciences, climate change syntheses and model evaluation. Contributed datasets are mapped to a single, consistent standard, with metadata on contributors, geographic location, measurement conditions and ancillary data. The design emphasizes the importance of reproducibility, scientific transparency and open access to data. While being oriented towards continuously measured R S , the database design accommodates other soil‐atmosphere measurements (e.g. ecosystem respiration, chamber‐measured net ecosystem exchange, methane fluxes) as well as experimental treatments (heterotrophic only, etc.). We give brief examples of the types of analyses possible using this new community resource and describe its accompanying R software package.
Two Ni2+-containing metal–organic frameworks, Ni2(dobdc) and Ni2(dobpdc), are shown to be active for the oligomerization of propene in the gas phase. The metal–organic frameworks exhibit activity comparable to Ni2+-exchanged aluminosilicates but maintain high selectivity for linear oligomers. Thus, these frameworks should enable the high yielding synthesis of linear propene oligomers for use in detergent and diesel fuel applications.
The development of a descriptor or descriptors that can relate the activity of catalysts to their physical properties is a major objective of catalysis research. In this study, we have found that the apparent activation energy for propene oxidation to acrolein over scheelite-structured, multicomponent, mixed metal oxides (Bi3FeMo2O12, Bi2Mo2.5W0.5O12, and Bi1-x/3V1-xMoxO4, where 0 ≤ x ≤ 1) correlates with the band gap of the catalyst measured at reaction temperature. We show through theoretical analysis of the energy components comprising the activation energy why the band-gap energy is the primary component dependent on catalyst composition and, hence, why one should expect the activation energy for propene oxidation to correlate with the band-gap energy. We also demonstrate that the change in band-gap energy with composition arises from the interplay between the sizes and energies of the V 3d, Fe 3d, Mo 4d, and W 5d orbitals, which give rise to the lowest unoccupied crystal orbitals. Both the utility of the band-gap energy as a descriptor for catalytic activity and the role of orbital overlap in determining the band gap are likely to be general features in mixed metal oxide oxidation catalysts, enabling the rational design of catalysts with greater activity for oxidation reactions.
Abstract In this study, we demonstrate that while the energy density and lubricity of the C 15 and C 16 products of furan condensation of biomass‐derived aldehydes with 2‐methylfuran are consistent with requirements for diesel, these products do not meet specifications for cetane number and pour point due to their aromatic furan rings. However, a novel class of products that fully meet or exceed most specifications for diesel can be produced by converting the furan rings in these compounds to cyclic ether moieties. Full hydrodeoxygenation of furan condensation products to alkanes would require 55–60 % higher hydrogen demand, starting from biomass, compared to the products of furan ring saturation, providing an additional incentive to support the saturated products. We also report here on a tunable class of catalysts that contain Pd nanoparticles supported on ionic liquid‐modified SiO 2 that can achieve complete saturation of the furan rings in yields of 95 % without opening these rings.
Abstract The role of coastal mangrove wetlands in sequestering atmospheric carbon dioxide (CO 2 ) and mitigating climate change has received increasing attention in recent years. While recent studies have shown that methane (CH 4 ) emissions can potentially offset the carbon burial rates in low‐salinity coastal wetlands, there is hitherto a paucity of direct and year‐round measurements of ecosystem‐scale CH 4 flux (F CH4 ) from mangrove ecosystems. In this study, we examined the temporal variations and biophysical drivers of ecosystem‐scale F CH4 in a subtropical estuarine mangrove wetland based on 3 years of eddy covariance measurements. Our results showed that daily mangrove F CH4 reached a peak of over 0.1 g CH 4 ‐C m −2 day −1 during the summertime owing to a combination of high temperature and low salinity, while the wintertime F CH4 was negligible. In this mangrove, the mean annual CH 4 emission was 11.7 ± 0.4 g CH 4 ‐C m –2 year −1 while the annual net ecosystem CO 2 exchange ranged between −891 and −690 g CO 2 ‐C m −2 year −1 , indicating a net cooling effect on climate over decadal to centurial timescales. Meanwhile, we showed that mangrove F CH4 could offset the negative radiative forcing caused by CO 2 uptake by 52% and 24% over a time horizon of 20 and 100 years, respectively, based on the corresponding sustained‐flux global warming potentials. Moreover, we found that 87% and 69% of the total variance of daily F CH4 could be explained by the random forest machine learning algorithm and traditional linear regression model, respectively, with soil temperature and salinity being the most dominant controls. This study was the first of its kind to characterize ecosystem‐scale F CH4 in a mangrove wetland with long‐term eddy covariance measurements. Our findings implied that future environmental changes such as climate warming and increasing river discharge might increase CH 4 emissions and hence reduce the net radiative cooling effect of estuarine mangrove forests.
Abstract The Front Cover highlights the work of Prof. Alexis T. Bell and co‐workers at the University of California at Berkeley. The Cover picture shows the value of using silica‐supported alkyl sulfonic acid catalysts for the sustainable production of diesel fuel from biomass. The Full Paper itself is available at 10.1002/cssc.201300931
Methane emissions from natural wetlands tend to increase with temperature and therefore may lead to a positive feedback under future climate change. However, their temperature response includes confounding factors and appears to differ on different time scales. Observed methane emissions depend strongly on temperature on a seasonal basis, but if the annual mean emissions are compared between sites, there is only a small temperature effect. We hypothesize that microbial dynamics are a major driver of the seasonal cycle and that they can explain this apparent discrepancy. We introduce a relatively simple model of methanogenic growth and dormancy into a wetland methane scheme that is used in an Earth system model. We show that this addition is sufficient to reproduce the observed seasonal dynamics of methane emissions in fully saturated wetland sites, at the same time as reproducing the annual mean emissions. We find that a more complex scheme used in recent Earth system models does not add predictive power. The sites used span a range of climatic conditions, with the majority in high latitudes. The difference in apparent temperature sensitivity seasonally versus spatially cannot be recreated by the non‐microbial schemes tested. We therefore conclude that microbial dynamics are a strong candidate to be driving the seasonal cycle of wetland methane emissions. We quantify longer‐term temperature sensitivity using this scheme and show that it gives approximately a 12% increase in emissions per degree of warming globally. This is in addition to any hydrological changes, which could also impact future methane emissions.
Read moreThis is the AmeriFlux Management Project (AMP) created FLUXNET-1F version of the carbon flux data for the site US-Tw1 Twitchell Wetland West Pond. This is the FLUXNET version of the carbon flux data for the site US-Tw1 Twitchell Wetland West Pond produced by applying the standard ONEFlux (1F) software. Site Description - The Twitchell Wetland site is a 7.4-acre restored wetland on Twitchell Island, that is managed by the California Department of Water Resources (DWR) and the U.S. Geological Survey (USGS). In the fall of 1997, the site was permanently flooded to a depth of approximately 25 cm. The wetland was almost completely covered by cattails and tules by the third growing season. A flux tower equipped to analyze energy, H2O, CO2, and CH4 fluxes was installed on May 17, 2012.
Read moreThis is the FLUXNET-CH4 version of the carbon flux data for the site US-Tw5 East Pond Wetland.
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