Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei 230026, China.
Langmuir. 2011 Jan 18;27(2):665-71. doi: 10.1021/la104475s. Epub 2010 Dec 15.
The morphological evolution of uniform Cu(2)O nanocrystals with different morphologies in a weak acetic acid solution (pH = 3.5) has been studied for cubic, octahedral, rhombic dodecahedral, {100} truncated octahedral, and {110} truncated octahedral nanocrystals. Cu(2)O nanocrystals undergo oxidative dissolution in weak acid solution, but their morphological changes depend on the exposed crystal planes. We found that the stability of Cu(2)O crystal planes in weak acid solution follows the order of {100} ≫ {111} > {110} and determines how the morphology of Cu(2)O nanocrystals evolves. The stable {100} crystal planes remain, and new {100} facets form at the expense of the less stable {111} and {110} crystal planes on the surface of Cu(2)O nanocrystals. Density functional theory calculations reveal that the Cu-O bond on Cu(2)O(100) surface has the shortest bond length. These results clearly exemplify that the morphology of inorganic crystals will evolve with the change of local chemical environment, shedding light on fundamentally understanding the morphological evolution of natural minerals and providing novel insights into the geomimetic synthesis of inorganic materials in the laboratory.
在 pH 值为 3.5 的弱乙酸溶液中,研究了具有不同形貌的立方、八面体、菱形十二面体、{100} 截断八面体和{110} 截断八面体的均匀 Cu2O 纳米晶体的形态演变。Cu2O 纳米晶体在弱酸溶液中发生氧化溶解,但它们的形态变化取决于暴露的晶面。我们发现,Cu2O 晶体在弱酸溶液中的稳定性顺序为{100}≫{111}>{110},并决定了 Cu2O 纳米晶体的形态如何演变。稳定的{100}晶面保持不变,新的{100}面在 Cu2O 纳米晶体表面上不太稳定的{111}和{110}晶面的消耗下形成。密度泛函理论计算表明,Cu2O(100)表面上的 Cu-O 键具有最短的键长。这些结果清楚地表明,无机晶体的形态将随着局部化学环境的变化而演变,这为从根本上理解天然矿物的形态演变提供了启示,并为实验室中无机材料的地质模拟合成提供了新的见解。