Department of Chemistry, National Tsing Hua University, Hsinchu 30013, Taiwan.
Chemistry. 2010 Dec 17;16(47):14167-74. doi: 10.1002/chem.201000563.
We report the development of a facile method for the synthesis of Ag(2)O crystals with systematic shape evolution from cubic to edge- and corner-truncated cubic, rhombicuboctahedral, edge- and corner-truncated octahedral, octahedral, and hexapod structures by mixing AgNO(3), NH(4)NO(3), and NaOH at molar ratios of 1:2:11.8. A sufficient volume of NaOH solution was first added to a mixture of AgNO(3) and NH(4)NO(3) solution to promote the formation of Ag(NH(3))(2)(+) complex ions and the growth of Ag(2)O nanocrystals with good morphological control. The crystals are mostly submicrometer-sized. X-ray diffraction, scanning electron microscopy, and transmission electron microscopy characterization has been performed to determine the crystalline surface facets. A band gap value of approximately 1.45 eV has been found for the octahedral Ag(2)O crystals. By changing the molar ratios of AgNO(3)/NH(4)NO(3)/NaOH to 1:2:41.8, corner-depressed rhombicuboctahedra and elongated hexapods were obtained as a result of enhanced crystal growth along the [100] directions. Smaller nanocubes with average sizes of approximately 200 and 300 nm and octapods can also be prepared by adjusting the reagent molar ratios and their added volumes. Both the octahedra and hexapods with largely silver atom-terminated {111} surface facets responded repulsively and moved to the surface of the solution when dispersing in a solution of positively charged methylene blue, but can be suspended in a negatively charged methyl orange solution. The cubes and octapods, bounded by the {100} faces, were insensitive to the molecular charges in solution. The dramatic facet-dependent surface properties of Ag(2)O crystals have been demonstrated.
我们报告了一种简便的方法来合成 Ag(2)O 晶体,通过混合 AgNO(3)、NH(4)NO(3)和 NaOH,其摩尔比为 1:2:11.8,可以使 Ag(2)O 晶体从立方体形到棱边和顶角截断的立方体形、菱方八面体体形、棱边和顶角截断的八面体形、八面体形和六足结构进行系统的形状演变。首先将足够体积的 NaOH 溶液加入到 AgNO(3)和 NH(4)NO(3)溶液的混合物中,以促进 Ag(NH(3))(2)(+)配合物离子的形成和 Ag(2)O 纳米晶体的生长,从而实现良好的形态控制。这些晶体大多为亚微米级。通过 X 射线衍射、扫描电子显微镜和透射电子显微镜的表征,确定了晶体的表面晶面。发现八面体 Ag(2)O 晶体的带隙值约为 1.45 eV。通过将 AgNO(3)/NH(4)NO(3)/NaOH 的摩尔比改为 1:2:41.8,可以获得具有角凹陷的菱方八面体和拉长的六足结构,这是由于沿[100]方向增强了晶体生长。通过调整试剂的摩尔比及其加入量,还可以制备更小的纳米立方体,平均尺寸约为 200 和 300nm 以及八足体。当在带正电荷的亚甲基蓝溶液中分散时,具有大量银原子终止的{111}表面晶面的八面体和六足体表现出强烈的排斥性并移动到溶液表面,但可以悬浮在带负电荷的甲基橙溶液中。由{100}面围成的立方体和八足体对溶液中的分子电荷不敏感。Ag(2)O 晶体的显著的晶面依赖性表面性质已经得到了证明。