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A DFT study of the adsorption of O2 and [Fe(H2O)2(OH)3] on the (001) and (112) surfaces of chalcopyrite

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Abstract

The oxidation of chalcopyrite, CuFeS2, is still not well understood and relevant in the context of the hydrometallurgical extraction of copper. Herein, we used DFT calculations within the periodic boundary conditions formalism to study the adsorption of O2 and [Fe(H2O)2(OH)3] molecules on the (001) and (112) surfaces of CuFeS2. The O2 molecule adsorbs strongly by a dissociative pathway at sulfur atoms on the (001) surface with an adsorption energy of − 76.5 kcal mol−1. The surface is chemically modified forming SO2 groups, in which the S–O bond length is calculated to be 1.47 and 1.54 Å. PDOS and Löwdin charges analyses indicate the oxidation of the sulfur atoms on the surface. We tested different adsorption modes of [Fe(H2O)2(OH)3], and a bidantade coordination with the Oads–Fesur and Feads–Ssur bond lengths of 2.02 and 2.47 Å is the most favorable with an adsorption energy of − 18.8 kcal mol−1 on the (001) surface. Adsorptions of each species are also observed on the (112) surface, but they are weaker than those observed on the (001) surface.

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Additional figures and all optimized coordinates are available in the Supplementary Information and further information can be requested directly from the corresponding author.

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Funding

This work was supported by the Brazilian agencies Conselho Nacional para o Desenvolvimento Científico e Tecnológico — CNPq (INCT-Acqua), Coordenação de Aperfeiçoamento de Pessoal de Ensino Superior — CAPES, and Fundação de Amparo à Pesquisa do Estado de Minas Gerais — FAPEMIG (APQ-00519–21 and RenovaMin, RED-00102–16).

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  1. Grupo de Pesquisa Em Química Inorgânica Teórica, Departamento de Química – ICEx, Universidade Federal de Minas Gerais, Av. Antônio Carlos, 6627, Pampulha, Belo Horizonte, MG, 31270–901, Brazil

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

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  1. Selma Fabiana Bazan
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  2. Hélio Anderson Duarte
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  3. Guilherme Ferreira de Lima
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GFL and HAD coordinate the project and supervise the SFB Ph.D. SFB carried out all the calculations and drafted the first figures and tables. All the authors contributed to writing and revising the manuscript.

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Correspondence to Guilherme Ferreira de Lima.

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This paper belongs to Topical Collection XXI - Brazilian Symposium of Theoretical Chemistry (SBQT2021).

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Bazan, S.F., Duarte, H.A. & de Lima, G.F. A DFT study of the adsorption of O2 and [Fe(H2O)2(OH)3] on the (001) and (112) surfaces of chalcopyrite. J Mol Model 28, 257 (2022). https://doi.org/10.1007/s00894-022-05263-z

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