Bromination mechanisms of aromatic pollutants assume a chief contribution in the observed yields and pattern’s distribution of a wide array of dioxin-like toxicants. However, salient features of the governing pathways remain largely speculative. This study presents detail mechanistic insights into two commonly discussed routes; namely: surface-assisted conversion of HBr into Br₂ and direct bromine transfer from oxybromides into a benzene ring. Utilizing iron surfaces, as structural representative of the metallic content in electronic wastes, results from density functional theory calculations portray accessible reactions into the successive dissociative adsorption of HBr over the Fe(100) surface and the subsequent evolution of gas phase bromine molecules. Activation energies for HBr uptake by the plain iron surface reside in the range of 129–182 kJ/mol. Over an oxygen pre-covered surface, dissociative adsorption of HBr leading to bromine molecules requires significantly lower activation energies (45–78 kJ/mol). Likewise, bromination of a benzene ring into a monobromobenzene molecule over Fe(100)_O*Br* (i.e., an oxybromide) configuration ensues with an opening activation energy of ~ 165 kJ/mol. Adsorption of a phenyl radical over an iron-oxybromide forms a phenolate moiety that subsequently desorbs from the surface into a phenoxy radical. Reaction pathways presented herein shall be useful in the ongoing efforts to comprehend the formation and bromination routes of the notorious bromine-bearing pollutants in real scenarios, such as, these encountered in the open burning and primitive thermal recycling of electronic wastes.

Graphical abstract