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Context <p>Chalcopyrite is the most abundant copper sulfide mineral and is becoming increasingly important for meeting the growing demand for copper. However, its slow dissolution during the leaching process remains a technological challenge, in which the key step is the oxidation of chalcopyrite. The initial stages of chalcopyrite oxidation by Fe<sup>3</sup>⁺(aq) were investigated on the sulfur-terminated (001) and (112) surfaces. Adsorption of the [Fe(OH)<sub>3</sub>(H<sub>2</sub>O)<sub>2</sub>] complex is stronger on the (001)-S surface (−18.8&#xa0;kcal&#xa0;mol⁻<sup>1</sup>) than on (112)-S (−13.4&#xa0;kcal&#xa0;mol⁻<sup>1</sup>), forming bidentate bonds that promote electron transfer from the surface to the oxidizing agent. The subsequent redox step proceeds through a hydrogen-transfer mechanism, in which water undergoes homolytic dissociation to yield Fe<sup>2</sup>⁺–OH<sub>2</sub> and an ∙OH radical that attacks surface sulfur atoms, forming S–OH species. This process is both thermodynamically and kinetically favorable on (001)-S (Δ<i>E</i> = −6&#xa0;kcal&#xa0;mol⁻<sup>1</sup>; <i>E</i><sub><i>a</i></sub> = 11&#xa0;kcal&#xa0;mol⁻<sup>1</sup>) but strongly hindered on (112)-S (<i>E</i><sub><i>a</i></sub> ≈ 80&#xa0;kcal&#xa0;mol⁻<sup>1</sup>). The high stabilization of reaction products on (112)-S likely promotes surface passivation, which may explain the kinetic limitations observed experimentally during chalcopyrite leaching. Comparatively, although O<sub>2</sub> is a stronger oxidant, its low solubility in aqueous media limits its effectiveness relative to Fe<sup>3</sup>⁺.</p> Methods <p>Density functional theory (DFT) calculations were performed under periodic boundary conditions using the PW91 exchange–correlation functional and plane-wave basis sets and Vanderbilt ultrasoft pseudopotentials. A Hubbard U correction of 2&#xa0;eV was applied to surface Fe atoms. Calculations were carried out using the Quantum ESPRESSO 6.2.1 package. Activation barriers were computed using the nudged elastic band method, and atomic charges were obtained through Löwdin population analysis.</p> Graphical Abstract <p></p>

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The role of Fe(III) and water in the oxidation of chalcopyrite

  • 期刊论文

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  • 发表日期：

    2026年5月7日

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  • Selma Fabiana Bazan,
  • Hélio Anderson Duarte,
  • Guilherme Ferreira de Lima

摘要

Context

Chalcopyrite is the most abundant copper sulfide mineral and is becoming increasingly important for meeting the growing demand for copper. However, its slow dissolution during the leaching process remains a technological challenge, in which the key step is the oxidation of chalcopyrite. The initial stages of chalcopyrite oxidation by Fe3⁺(aq) were investigated on the sulfur-terminated (001) and (112) surfaces. Adsorption of the [Fe(OH)3(H2O)2] complex is stronger on the (001)-S surface (−18.8 kcal mol⁻1) than on (112)-S (−13.4 kcal mol⁻1), forming bidentate bonds that promote electron transfer from the surface to the oxidizing agent. The subsequent redox step proceeds through a hydrogen-transfer mechanism, in which water undergoes homolytic dissociation to yield Fe2⁺–OH2 and an ∙OH radical that attacks surface sulfur atoms, forming S–OH species. This process is both thermodynamically and kinetically favorable on (001)-S (ΔE = −6 kcal mol⁻1; Ea = 11 kcal mol⁻1) but strongly hindered on (112)-S (Ea ≈ 80 kcal mol⁻1). The high stabilization of reaction products on (112)-S likely promotes surface passivation, which may explain the kinetic limitations observed experimentally during chalcopyrite leaching. Comparatively, although O2 is a stronger oxidant, its low solubility in aqueous media limits its effectiveness relative to Fe3⁺.

Methods

Density functional theory (DFT) calculations were performed under periodic boundary conditions using the PW91 exchange–correlation functional and plane-wave basis sets and Vanderbilt ultrasoft pseudopotentials. A Hubbard U correction of 2 eV was applied to surface Fe atoms. Calculations were carried out using the Quantum ESPRESSO 6.2.1 package. Activation barriers were computed using the nudged elastic band method, and atomic charges were obtained through Löwdin population analysis.

Graphical Abstract