Redox Properties of Plant Biomass-Derived Black Carbon (Biochar)

TLDR

Soils and sediments worldwide contain thermally altered organic matter (chars) that possess electroactive quinoid groups and polycondensed aromatic sheets, yet their redox properties across different pyrolysis conditions have not been systematically studied. The study aims to characterize the redox behavior of chars derived from various feedstocks and pyrolysis temperatures, and to evaluate their potential use in environmental engineering applications requiring controlled electron transfer. Mediated electrochemical analysis shows that chars are redox‑active, reversibly accepting and donating up to 2 mmol e⁻ g⁻¹, with intermediate to high heat‑treatment temperatures (400–700 °C) yielding the highest capacities, driven by phenolic moieties at low HTT, quinone groups at intermediate HTT, and quinones or condensed aromatics at high HTT, and suggesting that electroactive char components may also contribute to humic substance redox properties.

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".