Department of Chemistry, University of California, Riverside, 900 University Ave, Riverside, CA, 92521, USA.
Department of Chemistry and Biochemistry, California State University Long Beach, 1250 Bellflower Boulevard, Long Beach, CA, 90840, USA.
Chemistry. 2018 Jul 25;24(42):10812-10819. doi: 10.1002/chem.201801571. Epub 2018 Jun 27.
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 (Ga , In , Cd , and Sn ) on the Zn /Ge /S platform. We find that charge-complementary and size-compatible Ga 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 (Cd or Sn ) can induce an abrupt phase transition from super-sodalite to super-diamond, also with unprecedented trimetallic T2 clusters. For In , which is dual-complementary (charge and size), a gradual phase transition is observed with increasing In amount. Furthermore, by controlling the cluster composition, tunable band gaps can be realized. These materials show promising properties such as high CO uptake (4.32 mmol cm , 298 K, 1 bar) and high photocatalytic activity.
沸石型硫属化合物由于其具有孔隙率和半导体性而备受关注。具有超方钠石拓扑结构（沸石结构代码：RWY）的 CPM-120 是少数具有永久孔隙率的沸石型硫属化合物之一，也是唯一具有沸石代码的硫属化合物。重要的是，RWY 型已发展成为研究多孔硫属化合物性质的平台。然而，到目前为止，很少有研究探讨合成参数和骨架组成对该平台的影响。在这里，我们研究了第三金属类型（Ga、In、Cd 和 Sn）对 Zn/Ge/S 平台的影响。我们发现，电荷互补且尺寸匹配的 Ga 导致合成了 CPM-120-ZnGaGeS，这是第一个具有改进的晶体形态和重现性的三金属沸石型硫属化合物。我们还发现，电荷兼容且尺寸匹配的阳离子（Cd 或 Sn）可以诱导从超方钠石到超金刚石的急剧相转变，同时具有前所未有的三金属 T2 簇。对于具有双重互补性（电荷和尺寸）的 In，随着 In 含量的增加，观察到逐渐的相转变。此外，通过控制簇的组成，可以实现可调谐的带隙。这些材料表现出高 CO 吸收（4.32 mmol cm，298 K，1 bar）和高光催化活性等有前途的性质。
