ACS Appl Mater Interfaces. 2010 Jul;2(7):1817-23. doi: 10.1021/am100390u.
Monodispersed highly ordered and homogeneous ZnS microsphere with precisely controlled hierarchical and non-hierarchical surface structure was successfully fabricated in water-ethanol mixed solvent and in water without using any catalysts or templates in a hydrothermal process. The microsphere formation has been facilitated by self-assembly followed by Ostwald ripening process. The products were characterized by field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and energy-dispersive X-ray spectrometry (EDX). The XRD results indicated that the cubic phase ZnS formed in hydrothermal process at various reaction times. Introducing ethanol as a co-solvent with water facilitated hierarchical porous surface structure. The influences of various zinc and sulfur precursors, various alcohols as co-solvent, and solvent ratio on the formation of specific surface structured microsphere was investigated. The water-ethanol (1:1) solvent ratio is the minimum required to facilitate hierarchical porous surface structure. The by-products formed during the hydrothermal process are induced specific surface structure in ZnS microsphere. This is the first report on in situ generated by-products being used as a reagent to facilitate surface structured material fabrication. The formed by-products could be used as recyclable reagents to fabricate hierarchical porous ZnS in three consecutive cycles. A plausible growth mechanism of by-product-induced surface structure in different solvent was discussed. The research results may lay down new vistas for the in situ generated by-product-assisted specific surface structured ZnS fabrication.
在水-乙醇混合溶剂中和水相中,无需使用任何催化剂或模板,通过水热过程成功制备了具有精确控制的分级和非分级表面结构的单分散高度有序和均匀的 ZnS 微球。微球的形成是通过自组装和奥斯特瓦尔德熟化过程促进的。通过场发射扫描电子显微镜 (FE-SEM)、透射电子显微镜 (TEM)、X 射线衍射 (XRD) 和能谱 (EDX) 对产物进行了表征。XRD 结果表明,在不同反应时间的水热过程中形成了立方相 ZnS。引入乙醇作为与水的共溶剂促进了分级多孔表面结构的形成。研究了各种锌和硫前体、各种醇作为共溶剂以及溶剂比对形成特定表面结构微球的影响。水-乙醇(1:1)溶剂比是促进分级多孔表面结构形成的最小要求。水热过程中形成的副产物在 ZnS 微球中诱导了特定的表面结构。这是首次报道原位生成的副产物用作促进表面结构材料制备的试剂。形成的副产物可在三个连续循环中用作制备分级多孔 ZnS 的可回收试剂。讨论了不同溶剂中副产物诱导的表面结构的可能生长机制。研究结果可能为原位生成的副产物辅助特定表面结构 ZnS 制备开辟新的前景。