Da Pengfei, Zheng Yao, Hu Yang, Wu Zelong, Zhao Hongyu, Wei Yicheng, Guo Linchuan, Wang Jingjing, Wei Yanping, Xi Shibo, Yan Chun-Hua, Xi Pinxian
State Key Laboratory of Applied Organic Chemistry, Frontiers Science Center for Rare Isotopes, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000, China.
School of Chemical Engineering and Advanced Materials, The University of Adelaide, Adelaide, South Australia, 5005, Australia.
Angew Chem Int Ed Engl. 2023 Apr 24;62(18):e202301802. doi: 10.1002/anie.202301802. Epub 2023 Mar 24.
Oriented synthesis of transition metal sulfides (TMSs) with controlled compositions and crystal structures has long been promising for electronic devices and energy applications. Liquid-phase cation exchange (LCE) is a well-studied route by varying the compositions. However, achieving crystal structure selectivity is still a great challenge. Here, we demonstrate gas-phase cation exchange (GCE), which can induce a specific topological transformation (TT), for the synthesis of versatile TMSs with identified cubic or hexagonal crystal structures. The parallel six-sided subunit (PSS), a new descriptor, is defined to describe the substitution of cations and the transition of the anion sublattice. Under this principle, the band gap of targeted TMSs can be tailored. Using the photocatalytic hydrogen evolution as an example, the optimal hydrogen evolution rate of a zinc-cadmium sulfide (ZCS4) is determined to be 11.59 mmol h g , showing a 36.2-fold improvement over CdS.
长期以来，定向合成具有可控组成和晶体结构的过渡金属硫化物（TMSs）在电子器件和能源应用方面一直很有前景。液相阳离子交换（LCE）是一种通过改变组成进行深入研究的方法。然而，实现晶体结构选择性仍然是一个巨大的挑战。在此，我们展示了气相阳离子交换（GCE），它可以诱导特定的拓扑转变（TT），用于合成具有确定立方或六方晶体结构的通用TMSs。定义了一个新的描述符——平行六面体亚基（PSS），以描述阳离子的取代和阴离子亚晶格的转变。在此原理下，可以调整目标TMSs的带隙。以光催化析氢为例，确定硫化锌镉（ZCS4）的最佳析氢速率为11.59 mmol h g ，比CdS提高了36.2倍。
