title: Redox properties of plant biomass-derived black carbon (biochar).
abstract: Soils and sediments worldwide contain appreciable amounts of thermally altered organic matter (chars). Chars contain electroactive quinoid functional groups and polycondensed aromatic sheets that were recently shown to be of biogeochemical and envirotechnical relevance. However, so far no systematic investigation of the redox properties of chars formed under different pyrolysis conditions has been performed. Here, using mediated electrochemical analysis, we show that chars made from different feedstock and over a range of pyrolysis conditions are redox-active and reversibly accept and donate up to 2 mmol electrons per gram of char. The analysis of two thermosequences revealed that chars produced at intermediate to high heat treatment temperatures (HTTs) (400-700 °C) show the highest capacities to accept and donate electrons. Combined electrochemical, elemental, and spectroscopic analyses of the thermosequence chars provide evidence that the pool of redox-active moieties is dominated by electron-donating, phenolic moieties in the low-HTT chars, by newly formed electron accepting quinone moieties in intermediate-HTT chars, and by electron accepting quinones and possibly condensed aromatics in the high-HTT chars. We propose to consider chars in environmental engineering applications that require controlled electron transfer reactions. Electroactive char components may also contribute to the redox properties of traditionally defined "humic substances".
authors.affiliation: Department of Environmental Systems Science, Institute of Biogeochemistry andPollutant Dynamics, Swiss Federal Institute of Technology (ETH) Zurich , 8092 Zurich, Switzerland.
authors.forename: Laura
authors.initials: L
authors.lastname: Klüpfel
authors.forename: Marco
authors.initials: M
authors.lastname: Keiluweit
authors.forename: Markus
authors.initials: M
authors.lastname: Kleber
authors.forename: Michael
authors.initials: M
authors.lastname: Sander
mesh_terms: D018533:Biomass; D002606:Charcoal / Q000737:chemistry*; D004563:Electrochemistry; D004583:Electrons; D006358:Hot Temperature; D010084:Oxidation-Reduction; D010944:Plants / Q000737:chemistry*; D006109:Poaceae / Q000737:chemistry; D014934:Wood / Q000737:chemistry
chemical_list: C540010:biochar; D002606:Charcoal