Location-selective immobilisation of single-atom catalysts on the surface or within the interior of ionic nanocrystals using coordination chemistry

Single-atom catalysts dispersed on support materials show excellent heterogeneous catalytic properties that can be tuned using the interactions between the single atoms and the support. Such interactions depend on whether the single atoms are located on the surface or within the interior of the support. However, little is known about immobilising single atoms on the surface or within the interior of supports deliberately and selectively. Herein, such location-selective placement of single atoms is achieved through the choice of metal complex precursor, solvent, and workup procedure. Using CdSe nanoplatelets as a support, a cis-[PtCl(2)(SO(CH(3))(2))(2)] precursor in an aprotic solvent exclusively attaches single Pt atoms on the surface of the support. In contrast, a [PtCl(4)](2−) precursor in a protic solvent followed by amine treatment places 60% of the single Pt atoms inside the support by cation substitution. The surface-adsorbed single Pt atoms show higher stability in photocatalytic hydrogen evolution than the substituted ones, and the preclusion of substitution as internal Pt maximises the activity. Thus, this study provides a viable strategy for the structurally precise synthesis and design of single-atom catalysts.