Pre-phase transition of a Cu2−xS template enables polymorph selective synthesis of MS (M = Zn, Cd, Mn) nanocrystals via cation exchange reactions

Abstract

Utilization of copper-deficient Cu_2−xS nanocrystals (NCs) with diverse crystal phases and stoichiometries as cation exchange (CE) templates is a potential route to overcome the current limitations in the polymorph selective synthesis of desired nanomaterials. Among the Cu_2−xS NCs, covellite CuS is emerging as an attractive CE template to produce complicated and metastable metal sulfide NCs. The presence of a reducing agent is essential to induce a phase transition of CuS into other Cu_2−xS phases prior to the CE reactions. Nevertheless, the effect of the reducing agent on the phase transition of CuS, especially into the hexagonal close packing (hcp) phase and the cubic close packing (ccp) phase, has been scarcely exploited, but it is highly important for the polymorphic production of metal sulfides with the wurtzite phase and zinc blende phase. Herein, we report a reducing agent dependent pre-phase transition of CuS nanodisks (NDs) into hcp and ccp Cu_2−xS NCs. 1-Dodecanethiol molecules and oleylamine molecules selectively reduced CuS NDs into hcp djurleite Cu_1.94S NDs and ccp digenite Cu_1.8S NCs. Afterward, the hcp Cu_1.94S NDs and ccp Cu_1.8S NCs were exchanged by Zn²⁺/Cd²⁺/Mn²⁺, and the wurtzite phase and the zinc blende phase of ZnS, CdS, and MnS NCs were produced. Without the pre-phase transition, direct CE reactions of CuS NDs are incapable of synthesizing the above wurtzite and zinc blende metal sulfide NCs. Therefore, our findings suggest the importance of the pre-phase transition of the CE template in polymorphic syntheses, holding great promise in the fabrication of other polymorphic nanomaterials with novel physical and chemical properties.