Straightforward High-Pressure Synthesis and Characterization of Indium-Based Thiospinels: Photocatalytic Potential for Hydrogen Production

Abstract

Ternary chalcogenides (AB2X4) based on the spinel structure are gaining a great deal of attention because of the possibility of tuning their magnetic and optoelectronic properties not only by changing chemical composition but also by altering their degree of inversion. Here we report a rapid high-pressure synthetic method for the synthesis of MIn2S4 powders starting from commercially available solid sulfides. We prove the versatility of our method by reporting the synthesis of six members of the MIn2S4 family (M = Mn, Fe, Co, Ni, Zn, and Cd) under high-pressure conditions (3.5 GPa); these compounds show complete to moderate degrees of inversion. Furthermore, this family covers a spectral region that includes visible band gaps. Interestingly, the structural refinement carried out by X-ray and neutron diffraction allows one to establish positive correlations between the gap and different parameters, including the degree of inversion. Finally, as a proof-of-concept, these ternary chalcogenides show moderate photocatalytic hydrogen production from aqueous solutions.