A DFT and cluster expansion study of (Fe,Ni)9S8 pentlandite and unravelling doping with Mn, Co, Cu and precious metals

IF 4.3 3区材料科学 Q2 MATERIALS SCIENCE, MULTIDISCIPLINARY

Materials Chemistry and Physics Pub Date : 2024-11-15 DOI:10.1016/j.matchemphys.2024.130146

Kgwajana B. Molala, Peace P. Mkhonto, Mofuti A. Mehlape, Phuti E. Ngoepe

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Abstract

This study used density functional theory (DFT) adopting the universal cluster expansion (UNCLE) technique to generate different structures for (Fe,Ni)₉S₈ pentlandite and doped with Mn, Co, Cu and precious metals (Ru, Rh, Pd, Os, Ir and Pt) on the Ni and Fe tetrahedral (T) sites. The cluster expansion (CE) depicted the Fe-rich Fe₅Ni₄S₈ structure with space-group of P4₂/nmc (tetragonal) as the most stable. The doped Fe₅Ni₄S₈ structure on the Fe(T) with Mn, Cu, Rh, Pd, Ir and Pt changed from tetragonal to cubic structures, while doping with Co, Ru and Os remained tetragonal. Doping on the Ni(T) with Co, the structure changed from tetragonal to cubic, while doping with Mn, Cu, Ru, Rh, Pd, Os, Ir and Pt the structure remained tetragonal. It was found that doping with Pd on the Fe(T) generated the most thermodynamically stable compound (Fe₃Pd₂Ni₄S₈) with heats of formation of −130.24 meV. The density of states (DOS) showed that the Pd and Pt were the most preferred substitution of Fe(T) in the pentlandite structure, while the Co preferred the Ni(T) sites. In addition doping with Mn on Fe(T) and Ru doped on Ni(T) induced magnetism to the structure. This study predicted various compositions of dopants on pentlandite and laid a foundation for prediction of new mineral-compounds using DFT-CE method.

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对(Fe,Ni)9S8戊兰特的 DFT 和聚类展开研究，以及对锰、钴、铜和贵金属掺杂的揭示

本研究利用密度泛函理论（DFT），采用通用聚类展开（UNCLE）技术，生成了(Fe,Ni)9S8戊土矿的不同结构，并在 Ni 和 Fe 的四面体（T）位上掺杂了 Mn、Co、Cu 和贵金属（Ru、Rh、Pd、Os、Ir 和 Pt）。团簇扩展（CE）显示，富含铁的 Fe5Ni4S8 结构最稳定，其空间群为 P42/nmc（四方）。在 Fe（T）上掺入 Mn、Cu、Rh、Pd、Ir 和 Pt 后，Fe5Ni4S8 结构从四方结构变为立方结构，而掺入 Co、Ru 和 Os 后则保持四方结构。在 Ni（T）中掺入 Co 后，其结构从四方结构变为立方结构，而掺入 Mn、Cu、Ru、Rh、Pd、Os、Ir 和 Pt 后，其结构仍为四方结构。研究发现，在铁(T)上掺入钯会产生热力学上最稳定的化合物（Fe3Pd2Ni4S8），其形成热为-130.24 meV。状态密度（DOS）显示，钯和铂是戊兰特结构中最优选的铁（T）取代位，而钴则优选镍（T）位。此外，在铁(T)上掺杂锰和在镍(T)上掺杂钌也会使结构产生磁性。这项研究预测了掺杂剂在戊兰特上的各种组成，为使用 DFT-CE 方法预测新的矿物化合物奠定了基础。

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来源期刊

Materials Chemistry and Physics 工程技术-材料科学：综合

CiteScore

8.70

自引率

4.30%

发文量

1515

审稿时长

69 days

期刊介绍： Materials Chemistry and Physics is devoted to short communications, full-length research papers and feature articles on interrelationships among structure, properties, processing and performance of materials. The Editors welcome manuscripts on thin films, surface and interface science, materials degradation and reliability, metallurgy, semiconductors and optoelectronic materials, fine ceramics, magnetics, superconductors, specialty polymers, nano-materials and composite materials.