Wang Qun, Li Jianhuan, Li Jianjun
MIIT, Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, 92 West Dazhi Stree, Harbin 150001, P. R. China.
Phys Chem Chem Phys. 2018 Jan 17;20(3):1460-1475. doi: 10.1039/c7cp06465a.
In this work, CuSbS hierarchical flower-like microspheres composed of chlorine (Cl)-doped CuSbS nanoflakes are realized via a one pot solvothermal ion exchange reaction. The kinetic factors including the duration time, the ratio of source materials, and the KOH concentration, are systematically investigated. Using a suite of analytical techniques, including SEM, XRD and FTIR, the mechanism of the two stage in situ chemical transformation of CuS flower-like microspheres consisting of nanoflake intermediates to the target product CuSbS is elucidated. The difference in solubility between reactants and products (Ksp(CuS) > Ksp(CuSbS)) determines that the ion-exchange reaction from transition binary to ternary metal chalcogenides is favorable under the impetus of a thermodynamic driving force. In addition, the optical and enhanced thermoelectric transport properties are investigated. The results revealed that Cl-doped CuSbS exhibited an improved power factor, which was 8 times higher than that of undoped CuSbS at 500 K. The current study not only provides a facile and economical way to synthesize high-quality Cl-doped Cu-Sb-S three dimensional (3D) hierarchical nanostructures, but also opens up a new route for preparation of other I-V-VI multicomponent chalcogenide NCs, such as Cu-Bi-S and Cu-Pb-S systems, which would be difficult to obtain otherwise.
在这项工作中，通过一锅溶剂热离子交换反应实现了由氯（Cl）掺杂的CuSbS纳米片组成的CuSbS分层花状微球。系统地研究了包括持续时间、原料比例和KOH浓度在内的动力学因素。使用包括扫描电子显微镜（SEM）、X射线衍射（XRD）和傅里叶变换红外光谱（FTIR）在内的一系列分析技术，阐明了由纳米片中间体组成的CuS花状微球向目标产物CuSbS的两步原位化学转化机制。反应物和产物之间的溶解度差异（Ksp（CuS）>Ksp（CuSbS））决定了在热力学驱动力的推动下，从过渡二元金属硫族化物到三元金属硫族化物的离子交换反应是有利的。此外，还研究了其光学和增强的热电传输性能。结果表明，Cl掺杂的CuSbS表现出改善的功率因数，在500 K时比未掺杂的CuSbS高8倍。当前的研究不仅提供了一种简便且经济的方法来合成高质量的Cl掺杂的Cu-Sb-S三维（3D）分层纳米结构，而且还为制备其他难以通过其他方式获得的I-V-VI多组分硫族化物纳米晶体（NCs），如Cu-Bi-S和Cu-Pb-S系统，开辟了一条新途径。
