Constructing heterojunctions and designing advanced structures are effective approaches to enhancing the photoelectrochemical performance of semiconductor photocatalysts for solar energy conversion. Here, we have developed a sequential chemical etching, sulfidation, and cation-exchange strategy for preparing multi-shelled ZnS-CdS rhombic dodecahedral cages (RDCs) with tunable compositions and shell numbers from 1 to 5. Yolk-shelled Zn-based zeolitic imidazolate (ZIF-8) RDCs are first synthesized by chemical etching of ZIF-8 rhombic dodecahedrons. Sulfidation of the yolk-shelled ZIF-8 RDCs leads to the formation of multi-shelled ZnS RDCs, which are further converted into multi-shelled ZnS-CdS RDCs via a cation-exchange reaction. The composition of the multi-shelled ZnS-CdS RDCs can be tuned by varying the cation-exchange reaction time, and the shell number can be adjusted by changing the size of ZIF-8 precursors. Because of the heterojunction formed and the unique hollow structure, these triple-shelled ZnS-CdS RDCs with optimized composition show enhanced photoelectrochemical performance for solar water splitting.

构建异质结和设计先进的结构是增强半导体光催化剂用于太阳能转化的光电化学性能的有效方法。在这里，我们已经开发了一种顺序化学蚀刻，硫化和阳离子交换策略，以制备组成可调且壳数为1至5的多壳ZnS-CdS菱形十二面体笼（RDC）。 （ZIF-8）RDC首先通过ZIF-8菱形十二面体的化学蚀刻合成。蛋黄壳ZIF-8 RDC的硫化导致形成多壳ZnS RDC，它们通过阳离子交换反应进一步转化为多壳ZnS-CdS RDC。可以通过改变阳离子交换反应时间来调节多壳ZnS-CdS RDC的组成，可以通过改变ZIF-8前体的大小来调整壳数。由于形成的异质结和独特的空心结构，这些具有优化成分的三壳ZnS-CdS RDC显示出增强的光电化学性能，可用于太阳能水分解。