Charge- and Size-Complementary Multimetal-Induced Morphology and Phase Control in Zeolite-Type Metal Chalcogenides

Zeolite-type chalcogenides are desirable due to their integration between porosity and semiconductivity. CPM-120, with super-sodalite topology (Zeolite Structure Code: RWY), is among the few zeolite-type chalcogenides with permanent porosity, and is the only chalcogenide with a zeolite code. Importantly, the RWY-type has evolved into a platform for studying properties of porous chalcogenides. Yet so far, few studies have been made to probe the effects of synthetic parameters and framework compositions on this platform. Here, we probe the effects of the third metal type (Ga³⁺ , In³⁺ , Cd²⁺ , and Sn⁴⁺ ) on the Zn²⁺ /Ge⁴⁺ /S^2- platform. We find that charge-complementary and size-compatible Ga³⁺ leads to the synthesis of CPM-120-ZnGaGeS which is the first trimetallic zeolite-type chalcogenide, with improved crystal morphology and reproducibility. We also find that charge-compatible and size-complementary cations (Cd²⁺ or Sn⁴⁺ ) can induce an abrupt phase transition from super-sodalite to super-diamond, also with unprecedented trimetallic T2 clusters. For In³⁺ , which is dual-complementary (charge and size), a gradual phase transition is observed with increasing In³⁺ amount. Furthermore, by controlling the cluster composition, tunable band gaps can be realized. These materials show promising properties such as high CO₂ uptake (4.32 mmol cm^-3 , 298 K, 1 bar) and high photocatalytic activity.