State Key Laboratory for Physical Chemistry of Solid Surfaces and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, PR China.
Langmuir. 2010 Feb 16;26(4):2745-50. doi: 10.1021/la902765p.
Higher-ordered architectures self-assembly of nanomaterials have recently attracted increasing attention. In this work, we report a spontaneous and efficient route to simultaneous synthesis and self-assembly of 3D layered beta-FeOOH nanorods depending on a pH-induced strategy, in which the continuous change of pH is achieved by hydrolysis of FeCl(3).6H(2)O in the presence of urea under hydrothermal conditions. The electron microscopy observations reveal that the square-prismic beta-FeOOH nanorods are self-assembled in a side-by-side fashion to form highly oriented 2D nanorod arrays, and the 2D nanorod arrays are further stacked in a face-to-face fashion to form the final 3D layered architectures. On the basis of time-dependent experiments, a multistage reaction mechanism for the formation of the 3D layered beta-FeOOH nanorods architecture is presented, involving the fast growth and synchronous self-assembly of the nanorods toward 1D, 2D, and 3D spontaneously. The experimental evidence further demonstrates that the urea-decomposition-dependent pH continuously changing in the solution, spontaneously altering the driving force competition between the electrostatic repulsive force and the attractive van der Waals force among the nanorods building blocks, is the essential factor to influence the self-assembly of the beta-FeOOH nanorods from 1D to 3D.
近年来,人们对纳米材料的高级有序结构自组装越来越关注。在这项工作中,我们报告了一种自发且高效的方法,可在水解氯化铁六水合物和尿素的水热条件下,通过 pH 诱导策略,同时合成和自组装 3D 层状β-FeOOH 纳米棒。电子显微镜观察表明,四方棱柱状β-FeOOH 纳米棒以并排的方式自组装成高度取向的二维纳米棒阵列,二维纳米棒阵列进一步面对面堆叠形成最终的 3D 层状结构。基于时间依赖性实验,提出了形成 3D 层状β-FeOOH 纳米棒结构的多阶段反应机制,涉及纳米棒向一维、二维和三维的快速生长和同步自组装。实验证据进一步表明,溶液中尿素分解依赖性 pH 的连续变化,自发改变了纳米棒构建块之间静电斥力和吸引力范德华力之间的驱动力竞争,是影响β-FeOOH 纳米棒从一维到三维自组装的关键因素。