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To the extent that this char is representative of environmental black carbons, our results indicate that it is imperative to consider steric effects in adsorption of molecules the size of trichlorobenzene or larger

Characterization of aromatic compound sorptive interactions with black carbon (charcoal) assisted by graphite as a model.

ENVIRONMENTAL SCIENCE & TECHNOLOGY, no. 7 (2005): 2033-2041

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摘要

Molecular interactions controlling the sorption of pollutants to environmental black carbons (soot, charcoal) are not well-resolved. Sorption of a series of aromatic compounds was studied to wood charcoal and nonporous graphite powder as a model adsorbent. Issues of concern were the possible involvement of pi-pi electron donor-acceptor (E...更多

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简介
  • Environmental black carbon (BC) refers to products of incomplete combustion of fossil fuels and biomass that enter the environment [1, 2].
  • Molecular interactions controlling the sorption of organic compounds to BC particles are incompletely understood.
  • How aromatic compounds interact with the graphene planes and edge functionality is not clear.
  • Since most of the surface area of BCs exists in pores <2 nm wide, accessibility of pollutants to the pore network is likely to depend on molecular size; steric factors have not yet been systematically considered in structure-activity relationships.
  • The present study was designed to explore the possibility of π-π electron donor-acceptor (π-π EDA) interactions between the graphene surface and adsorbates of sufficient π-acceptor or π-donor strength.
  • It was further designed to assess steric effects on sorption
重点内容
  • Environmental black carbon (BC) refers to products of incomplete combustion of fossil fuels and biomass that enter the environment [1, 2]
  • BC particles tend to sorb hydrophobic organic compounds more strongly on an organic carbon basis than macromolecular forms of natural organic matter [35] and may play an important role in the fate of pollutants in soils and aquatic sediments depending on their abundance in a given locale
  • The magnitude of enhancement follows the order expected on the basis of the combined π-electron-withdrawing ability of the substituents: TNT > DNT > MNT ∼ BNTL. These results indicate that specific π-π electron donor-acceptor (EDA) interactions may occur between the π-acceptors and the graphite surface
  • Possible reasons include (a) competitive adsorption by water molecules near functionalized edges of char; (b) reduced polarizability of char graphene sheets due to their finite size or the presence of electron-withdrawing edge functionality; and (c) poorer adsorbate contact with the surface owing to the disoriented structure or the curvature in sheets induced by the presence of functional groups or non-hexogonal rings [8, 38]
  • To the extent that this char is representative of environmental black carbons, our results indicate that it is imperative to consider steric effects in adsorption of molecules the size of trichlorobenzene or larger
  • Further elemental analysis (Galbraith Laboratories, Knoxville, TN) gave C (100.1%), H (<0.5%), and O (<0.5%)
  • 2040 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 39, NO. 7, 2005 we propose that π-π electron donor-acceptor (π-π EDA) interactions exist between π-acceptors and graphene units in charcoal
结果
  • Adsorption isotherms on graphite were fit to the Freundlich model: q ) KFCWn [1].
  • Where q and Cw are the equilibrium sorbed and solution concentrations, respectively; KF is the Freundlich affinity coefficient; and n is the Freundlich linearity index.
结论
  • Similar sorption intensity on a surface-area basis between charcoal and graphite (Figure 6) and the generally consistent results for the test compounds when steric effects are taken into account suggest that the graphite surface is a reasonable model for the charcoal surface.
  • The fact that chargraphite partition coefficients for nonbulky solutes are mostly greater than 1, despite a lower hydrophobic driving force for char, indicates an opposing enhancement mechanism for char, possibly pore-filling in micropores.
  • It may reflect the uncertainty in the N2 surface area.
  • The weaker sorption of 1,3,5-TCB than 1,2,4-TCB is due to presence in the former of substituents on both sides of the c2 axis of benzene, limiting the accessible pore volume relative to 1,2,4TCB
总结
  • Introduction:

    Environmental black carbon (BC) refers to products of incomplete combustion of fossil fuels and biomass that enter the environment [1, 2].
  • Molecular interactions controlling the sorption of organic compounds to BC particles are incompletely understood.
  • How aromatic compounds interact with the graphene planes and edge functionality is not clear.
  • Since most of the surface area of BCs exists in pores <2 nm wide, accessibility of pollutants to the pore network is likely to depend on molecular size; steric factors have not yet been systematically considered in structure-activity relationships.
  • The present study was designed to explore the possibility of π-π electron donor-acceptor (π-π EDA) interactions between the graphene surface and adsorbates of sufficient π-acceptor or π-donor strength.
  • It was further designed to assess steric effects on sorption
  • Results:

    Adsorption isotherms on graphite were fit to the Freundlich model: q ) KFCWn [1].
  • Where q and Cw are the equilibrium sorbed and solution concentrations, respectively; KF is the Freundlich affinity coefficient; and n is the Freundlich linearity index.
  • Conclusion:

    Similar sorption intensity on a surface-area basis between charcoal and graphite (Figure 6) and the generally consistent results for the test compounds when steric effects are taken into account suggest that the graphite surface is a reasonable model for the charcoal surface.
  • The fact that chargraphite partition coefficients for nonbulky solutes are mostly greater than 1, despite a lower hydrophobic driving force for char, indicates an opposing enhancement mechanism for char, possibly pore-filling in micropores.
  • It may reflect the uncertainty in the N2 surface area.
  • The weaker sorption of 1,3,5-TCB than 1,2,4-TCB is due to presence in the former of substituents on both sides of the c2 axis of benzene, limiting the accessible pore volume relative to 1,2,4TCB
表格
  • Table1: Data for Solutes: Graphite-Water Freundlich Model Coefficients (KF and n)a, Hexadecane-Water (KHW,i), and Benzene-Water (KBW,i) Partition Coefficients compound
Download tables as Excel
基金
  • This project was funded by a grant (99-35107-7816) from the NRICGP (CSREES, U.S Department of Agriculture). Supporting Information Available
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