Evidence is accumulating that sorption of organic chemicals to soils and sediments can be described by “dual-mode sorption”:  absorption in amorphous organic matter (AOM) and adsorption to carbonaceous materials such as black carbon (BC), coal, and kerogen, collectively termed “carbonaceous geosorbents” (CG). Median BC contents as a fraction of total organic carbon are 9% for sediments (number of sediments, n ≈ 300) and 4% for soils (n = 90). Adsorption of organic compounds to CG is nonlinear and generally exceeds absorption in AOM by a factor of 10−100. Sorption to CG is particularly extensive for organic compounds that can attain a more planar molecular configuration. The CG adsorption domain probably consists of surface sites and nanopores. In this review it is shown that nonlinear sorption to CG can completely dominate total sorption at low aqueous concentrations (<10-6 of maximum solid solubility). Therefore, the presence of CG can explain (i) sorption to soils and sediments being up to 2 orders of m...

Extensive sorption of organic compounds to black carbon, coal, and kerogen in sediments and soils: mechanisms and consequences for distribution, bioaccumulation, and biodegradation

Graphene oxide and reduced graphene oxide studied by the XRD, TEM and electron spectroscopy methods

Over the last two decades, our understanding of soot formation has evolved from an empirical, phenomenological description to an age of quantitative modeling for at least small fuel compounds. In this paper, we review the current state of knowledge of the fundamental sooting processes, including the chemistry of soot precursors, particle nucleation and mass/size growth. The discussion shows that though much progress has been made, critical gaps remain in many areas of our knowledge. We propose the roles of certain aromatic radicals resulting from localized π electron structures in particle nucleation and subsequent mass growth. The existence of these free radicals provides a rational explanation for the strong binding forces needed for forming initial clusters of polycyclic aromatic hydrocarbons. They may also explain a range of currently unexplained sooting phenomena, including the large amount of aliphatics observed in nascent soot formed in laminar premixed flames and the mass growth of soot in the absence of gas-phase H atoms. While the above suggestions are inspired, to an extent, by recent theoretical findings from the materials research community, this paper also demonstrates that the knowledge garnered through our longstanding interest in soot formation may well be carried over to flame synthesis of functional nanomaterials for clean and renewable energy applications. In particular, work on flame-synthesized thin films of nanocrystalline titania illustrates how our combustion knowledge might be useful for developing advanced yet inexpensive thin-film solar cells and chemical sensors for detecting gaseous air pollutants.

Formation of nascent soot and other condensed-phase materials in flames

Solution combustion is an exciting phenomenon, which involves propagation of self-sustained exothermic reactions along an aqueous or sol–gel media. This process allows for the synthesis of a variety of nanoscale materials, including oxides, metals, alloys, and sulfides. This Review focuses on the analysis of new approaches and results in the field of solution combustion synthesis (SCS) obtained during recent years. Thermodynamics and kinetics of reactive solutions used in different chemical routes are considered, and the role of process parameters is discussed, emphasizing the chemical mechanisms that are responsible for rapid self-sustained combustion reactions. The basic principles for controlling the composition, structure, and nanostructure of SCS products, and routes to regulate the size and morphology of the nanoscale materials are also reviewed. Recently developed systems that lead to the formation of novel materials and unique structures (e.g., thin films and two-dimensional crystals) with unusual...

Jean-François Brilhac

Papers

The oxidation of soot: a review of experiments, mechanisms and models

Oxidation of carbon by NOx, with particular reference to NO2 and N2O

Kinetics of the oxidation of carbon black by NO2: Influence of the presence of water and oxygen

Oxidation mechanism of carbon black by NO2: Effect of water vapour

Pyrolysis of coal and woody biomass under N2 and CO2 atmospheres using a drop tube furnace - experimental study and kinetic modeling