Formation of dibenzofuran, dibenzo-p-dioxin and their hydroxylated derivatives from catechol
Literature Information
Mohammednoor Altarawneh, Bogdan Z. Dlugogorski
We present, in this study, mechanistic and kinetic accounts of the formation of dibenzofuran (DF), dibenzo-p-dioxin (DD) and their hydroxylated derivatives (OHs-DF/OHs-DD) from the catechol (CT) molecule, as a model compound for phenolic constituents in biomass. Self-condensation of two CT molecules produces predominantly a DD molecule via open- and closed-shell corridors. Coupling modes involving the o-semiquinone radical and the CT molecule (o-SQ/CT) generate two direct structural blocks for the formation of OHs-DF/OHs-DD structures, ether-type intermediates and di-keto moieties. The calculated reaction rate constants indicate that the fate of ether-type intermediates is to make hydroxylated diphenyl ethers rather than to undergo cyclisation reactions leading to the formation of preDF structures. Unimolecular loss of a H or OH moiety from a pivotal carbon in these hydroxylated diphenyl ethers then produces hydroxylated and non-hydroxylated DD molecules. Formation of OHs-DF initiated by o(C)–o(C) cross-linkages involving o-SQ/o-SQ and o-SQ/CT reactions incurs very similar reaction and activation enthalpies encountered in the formation of chlorinated DFs from chlorophenols.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.











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