Reconstruction of Cooperite (PtS) Surfaces: A DFT-D plus U Study

Cooperite (PtS) is one of the main sources of platinum in the world and has not been given much attention, in particular from the computational aspect. Besides, the surface stability of cooperite is not fully understood, in particular the preferred surface cleavage. In the current study, we employed computer modeling methods within the plane-wave framework of density functional theory with dispersion correction and the U parameter to correctly predict the bulk and surface properties. We reconstructed and calculated the geometries and surface energies of (001), (100), (101), (112), (110), (111), and (211) cooperite surfaces of stoichiometric planes. The Pt d-orbitals with U = 4.5 eV and S p-orbitals with U = 5.5 eV were found optimum to correctly predict a band gap of 1.408 eV for the bulk cooperite model, which agreed with an experimental value of 1.41 eV. The PtS-, Pt-, and S-terminated surfaces were investigated. The structural and electronic properties of the reconstructed surfaces were discussed in detail. We observed one major mechanism of relaxation of cooperite surface reconstructions that emerged from this study, which was the formation of Pt-Pt bonds. It emanated that the (110) and (111) cooperite surfaces underwent significant reconstruction in which the Pt2+ cation relaxed into the surface, forming new Pt-Pt (Pt22+) bonds. Similar behavior was perceived for (101) and (211) surfaces, where the Pt2+ cation relaxed inward and sideways on the surface, forming new Pt-Pt (Pt22+) bonds. The surface stability decreased in the order (101) > (100) approximate to (112) > (211) > (111) > (110) > (001), indicating that the (101) surface was the most stable, leading to an octahedron cooperite crystal morphology with truncated corners under equilibrium conditions. However, the electronic structures indicated that the chemical reactivity stability of the surfaces would be determined by band gaps. It was found that the (112) surface had a larger band gap than the other surfaces and thus was a chemical stability competitor to the (101) surface. In addition, it was established that the surfaces had different reactivities, which largely depended on the atomic coordination and charge state based on population atomic charges. This study has shown that cooperite has many planes/ surface cleavages as determined by the computed crystal morphology, which is in agreement with experimental X-ray diffraction (XRD) pattern findings and the formation of irregular morphology shapes.